Encyclopedia of Chemical Processing and Design Volume 69 Supplement 1 PDF

Encyclopedia of
Chemical Processing and

Design: 69 Supplement 1
Rayford G. Anthony
John J. McKetta
Marcel Dekker, Inc.

Encyclopedia of
Chemical Processing
and Design
EDITOR Rayford G. Anthony
SENIOR ADVISORY EDITOR John J. McKetta
69 Supplement 1
Library of Congress Cataloging in Publication Data
Main entry under title:
Encyclopedia of chemical processing and design.
Includes bibliographic references.

1. Chemical engineering—Dictionaries 2. Chemistry,
Technical—Dictionaries. I. McKetta, John J.
II. Cunningham, William Aaron.
Tp9.E66 660.2′8′003 75-40646
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Contributors to Volume 69
Steve Chum, Ph.D. Research Fellow, The Dow Chemical Company, Polyolefins
Research, Freeport, Texas: Structure, Properties, and Applications of Polyolefins
Produced by Single-Site Catalyst Technology
Ray A. Cocco, Ph.D. Senior Specialist, The Dow Chemical Company, Midland,
Michigan: Circulating Fluidized Bed Reactors: Basic Concepts and Hydrody-
namics
David M. Fishbach, P.E. Senior Consulting Engineer, Starfire Electronic Devel-

opment & Marketing, Ltd., Bloomfield Hills, Michigan: Nanophase Materials in
Chemical Process
Avery N. Goldstein, Ph.D. Research Director, Starfire Electronics Develop-

ment & Marketing, Ltd., Bloomfield Hills, Michigan: Nanophase Materials in
Chemical Process
Manfred Grove Senior Partner, Intermacom A.G., Technology Consultants,

Auerich, Switzerland: Introduction to the Selective Catalytic Reduction Tech-
nology
Dennis Hendershot Rohm and Haas Company, Bristol, Pennsylvania: Funda-

mentals of Process Safety and Risk Management
Trevor A. Kletz Process Safety Consultant, Cheshire, United Kingdom: Funda-

mentals of Process Safety and Risk Management
Fu-Ming Lee, Ph.D. Director of Technology, GTC Technology Corporation,

Houston, Texas: Recent Development of Extractive Distillation: A Distillation Al-
ternative
Jim Makris Director, Chemical Emergency Preparedness and Prevention Office,

U.S. Environmental Protection Agency, Washington, D.C.: Process Safety and
Risk Management Regulations: Impact on Process Safety
M. Sam Mannan, Ph.D., P.E. Associate Professor of Chemical Engineering,

Mary Kay O’Connor Process Safety Center, Texas A&M University, College Sta-
tion, Texas: Fundamentals of Process Safety and Risk Management; Process Safety
and Risk Management Regulations: Impact on Process Industry
Rajen M. Patel, Ph.D. Technical Leader, The Dow Chemical Company, Polyo-
lefins Research, Freeport, Texas: Structures, Properties, and Applications of Polyo-
lefins Produced by Single-Site Catalyst Technology
H. James Overman Dow Chemical Company, Freeport, Texas: Process Safety

and Risk Management Regulations: Impact on Process Industry
iii
iv Contributors to Volume 69
Michael V. Pishko, Ph.D. Assistant Professor, Department of Chemical Engi-

neering, Texas A&M University, College Station, Texas: Recent Advances in Bio-
materials
Alan W. Weimer, Ph.D., P.E. Professor of Chemical Engineering, University

of Colorado, Boulder, Colorado: Effect of Pressure and Temperature in Bubbling
Fluidized Beds
CONTENTS OF VOLUME 69
Contributors to Volume 69 iii
Conversion to SI Units vii
Bringing Costs up to Date ix
Circulating Fluidized Bed Reactors: Basic Concepts and

Hydrodynamics
Ray A. Cocco 1
Effect of Pressure and Temperature in Bubbling Fluidized Beds

Alan W. Weimer 35
Fundamentals of Process Safety and Risk Management

M. Sam Mannan, Dennis Hendershot, and Trevor A. Kletz 49
Introduction to the Selective Catalytic Reduction Technology

Manfred Grove 94
Nanophase Materials in Chemical Process

Avery N. Goldstein and David M. Fishbach 150
Process Safety and Risk Management Regulations: Impact on

Process Industry
M. Sam Mannan, Jim Makris, and H. James Overman 168
Recent Advances in Biomaterials

Michael V. Pishko 194
Recent Development of Extractive Distillation: A Distillation

Alternative
Fu-Ming Lee 207
Structure, Properties, and Applications of Polyolefins Produced by

Single-Site Catalyst Technology
Rajen M. Patel and Steve Chum 231
v
Conversion to SI Units
To convert from To Multiply by
acre square meter (m 2 ) 4.046 ⫻ 10 3

angstrom meter (m) 1.0 ⫻ 10⫺10
are square meter (m 2 ) 1.0 ⫻ 10 2
atmosphere newton/square meter (N/m 2 ) 1.013 ⫻ 10 5
bar newton/square meter (N/m 2 ) 1.0 ⫻ 10 5
barrel (42 gallon) cubic meter (m 3 ) 0.159
Btu (International Steam Table) joule (J) 1.055 ⫻ 10 3
Btu (mean) joule (J) 1.056 ⫻ 10 3
Btu (thermochemical) joule (J) 1.054 ⫻ 10 3
bushel cubic meter (m 3 ) 3.52 ⫻ 10⫺2
calorie (International Steam Table) joule (J) 4.187
calorie (mean) joule (J) 4.190
calorie (thermochemical) joule (J) 4.184
centimeter of mercury newton/square meter (N/m 2 ) 1.333 ⫻ 10 3
centimeter of water newton/square meter (N/m 2 ) 98.06
cubit meter (m) 0.457
degree (angle) radian (rad) 1.745 ⫻ 10⫺2
denier (international) kilogram/meter (kg/m) 1.0 ⫻ 10⫺7
dram (avoirdupois) kilogram (kg) 1.772 ⫻ 10⫺3
dram (troy) kilogram (kg) 3.888 ⫻ 10⫺3
dram (U.S. fluid) cubic meter (m 3 ) 3.697 ⫻ 10⫺6
dyne newton (N) 1.0 ⫻ 10⫺5
electron volt joule (J) 1.60 ⫻ 10⫺19
erg joule (J) 1.0 ⫻ 10⫺7
fluid ounce (U.S.) cubic meter (m 3 ) 2.96 ⫻ 10⫺5
foot meter (m) 0.305
furlong meter (m) 2.01 ⫻ 10 2
gallon (U.S. dry) cubic meter (m 3 ) 4.404 ⫻ 10⫺3
gallon (U.S. liquid) cubic meter (m 3 ) 3.785 ⫻ 10⫺3
gill (U.S.) cubic meter (m 3 ) 1.183 ⫻ 10⫺4
grain kilogram (kg) 6.48 ⫻ 10⫺5
gram kilogram (kg) 1.0 ⫻ 10⫺3
horsepower watt (W) 7.457 ⫻ 10 2
horsepower (boiler) watt (W) 9.81 ⫻ 10 3
horsepower (electric) watt (W) 7.46 ⫻ 10 2
hundred weight (long) kilogram (kg) 50.80
hundred weight (short) kilogram (kg) 45.36
inch meter (m) 2.54 ⫻ 10⫺2
inch mercury newton/square meter (N/m 2 ) 3.386 ⫻ 10 3
inch water newton/square meter (N/m 2 ) 2.49 ⫻ 10 2
kilogram force newton (N) 9.806
kip newton (N) 4.45 ⫻ 10 3
knot (international) meter/second (m/s) 0.5144
league (British nautical) meter (M) 5.559 ⫻ 10 3
league (statute) meter (m) 4.83 ⫻ 10 3
vii
viii Conversion to SI Units
To convert from To Multiply by
light year meter (m) 9.46 ⫻ 10 15

liter cubic meter (m 3 ) 0.001
micron meter (m) 1.0 ⫻ 10⫺6
mil meter (m) 2.54 ⫻ 10⫺6
mile (U.S. nautical) meter (m) 1.852 ⫻ 10 3
mile (U.S. statute) meter (m) 1.609 ⫻ 10 3
millibar newton/square meter (N/m 2 ) 100.0
millimeter mercury newton/square meter (N/m 2 ) 1.333 ⫻ 10 2
oersted ampere/meter (A/m) 79.58
ounce force (avoirdupois) newton (N) 0.278
ounce mass (avoirdupois) kilogram (kg) 2.835 ⫻ 10⫺2
ounce mass (troy) kilogram (kg) 3.11 ⫻ 10⫺2
ounce (U.S. fluid) cubic meter (m 3 ) 2.96 ⫻ 10⫺5
pascal newton/square meter (N/m 2 ) 1.0
peck (U.S.) cubic meter (m 3 ) 8.81 ⫻ 10⫺3
pennyweight kilogram (kg) 1.555 ⫻ 10⫺3
pint (U.S. dry) cubic meter (M 3 ) 5.506 ⫻ 10⫺4
pint (U.S. liquid) cubic meter (m 3 ) 4.732 ⫻ 10⫺4
poise newton second/square meter (N ⋅ s/m 2 ) 0.10
pound force (avoirdupois) newton (N) 4.448
pound mass (avoirdupois) kilogram (kg) 0.4536
pound mass (troy) kilogram (kg) 0.373
poundal newton (N) 0.138
quart (U.S. dry) cubic meter (m 3 ) 1.10 ⫻ 10⫺3
quart (U.S. liquid) cubic meter (m 3 ) 9.46 ⫻ 10⫺4
rod meter (m) 5.03
roentgen coulomb/kilogram (c/kg) 2.579 ⫻ 10⫺4
second (angle) radian (rad) 4.85 ⫻ 10⫺6
section square meter (m 2 ) 2.59 ⫻ 10 6
slug kilogram (kg) 14.59
span meter (m) 0.229
stoke square meter/second (m 2 /s) 1.0 ⫻ 10⫺4
ton (long) kilogram (kg) 1.016 ⫻ 10 3
ton (metric) kilogram (kg) 1.0 ⫻ 10 3
ton (short, 2000 pounds) kilogram (kg) 9.072 ⫻ 10 2
torr newton/square meter (N/m 2 ) 1.333 ⫻ 10 2
yard meter (m) 0.914
Bringing Costs up to Date
Cost escalation via inflation bears critically on estimates of plant costs. Historical
costs of process plants are updated by means of an escalation factor. Several pub-
lished cost indexes are widely used in the chemical process industries:
Nelson Cost Indexes (Oil and Gas J.), quarterly

Marshall and Swift (M&S) Equipment Cost Index, updated monthly
CE Plant Cost Index (Chemical Engineering), updated monthly
ENR Construction Cost Index (Engineering News-Record), updated weekly
Vatavuk Air Pollution Control Cost Indexes (VAPCCI) (Chemical Engineering),
updated quarterly
All of these indexes were developed with various elements such as material
availability and labor productivity taken into account. However, the proportion
allotted to each element differs with each index. The differences in overall results
of each index are due to uneven price changes for each element. In other words,
TABLE 1 Chemical Engineering and Marshall and Swift Plant and Equipment Cost
Indexes since 1950
Year CE Index M&S Index Year CE Index M&S Index

1950 73.9 167.9 1973 144.1 344.1
1951 80.4 180.3 1974 165.4 398.4
1952 81.3 180.5 1975 182.4 444.3
1953 84.7 182.5 1976 192.1 472.1
1954 86.1 184.6 1977 204.1 505.4
1955 88.3 190.6 1978 218.8 545.3
1956 93.9 208.8 1979 238.7 599.4
1957 98.5 225.1 1980 261.2 659.6
1958 99.7 229.2 1981 297.0 721.3
1959 101.8 234.5 1982 314.0 745.6
1960 102.0 237.7 1983 316.9 760.8
1961 101.5 237.2 1984 322.7 780.4
1962 102.0 238.5 1985 325.3 789.6
1963 102.4 239.2 1986 318.4 797.6
1964 103.3 241.8 1987 323.8 813.6
1965 104.2 244.9 1988 342.5 852.0
1966 107.2 252.5 1989 355.4 895.1
1967 109.7 262.9 1990 357.6 915.1
1968 113.6 273.1 1991 361.3 930.6
1969 119.0 285.0 1992 358.2 943.1
1970 125.7 303.3 1993 359.2 964.2
1971 132.3 321.3 1994 368.1 993.4
1972 137.2 332.0 1995 381.1 1027.5
1996 381.7 1039.2
1997 386.5 1056.8
ix
x Bringing Costs up to Date
TABLE 2 Nelson-Farrar Inflation Petroleum Refinery Construction Indexes since 1946

(1946 ⫽ 100)
Nelson
Materials Labor Miscellaneous Inflation
Date Component Component Equipment Index
1946 100.0 100.0 100.0 100.0
1947 122.4 113.5 114.2 117.0
1948 139.5 128.0 122.1 132.5
1949 143.6 137.1 121.6 139.7
1950 149.5 144.0 126.2 146.2
1951 164.0 152.5 145.0 157.2
1952 164.3 163.1 153.1 163.6
1953 172.4 174.2 158.8 173.5
1954 174.6 183.3 160.7 179.8
1955 176.1 189.6 161.5 184.2
1956 190.4 198.2 180.5 195.3
1957 201.9 208.6 192.1 205.9
1958 204.1 220.4 192.4 213.9
1959 207.8 231.6 196.1 222.1
1960 207.6 241.9 200.0 228.1
1961 207.7 249.4 199.5 232.7
1962 205.9 258.8 198.8 237.6
1963 206.3 268.4 201.4 243.6
1964 209.6 280.5 206.8 252.1
1965 212.0 294.4 211.6 261.4
1966 216.2 310.9 220.9 273.0
1967 219.7 331.3 226.1 286.7
1968 224.1 357.4 228.8 304.1
1969 234.9 391.8 239.3 329.0
1970 250.5 441.1 254.3 364.9
1971 265.2 499.9 268.7 406.0
1972 277.8 545.6 278.0 438.5
1973 292.3 585.2 291.4 468.0
1974 373.3 623.6 361.8 522.7
1975 421.0 678.5 415.9 575.5
1976 445.2 729.4 423.8 615.7
1977 471.3 774.1 438.2 653.0
1978 516.7 824.1 474.1 701.1
1979 573.1 879.0 515.4 756.6
1980 629.2 951.9 578.1 822.8
1981 693.2 1044.2 647.9 903.8
1982 707.6 1154.2 622.8 976.9
1983 712.4 1234.8 656.8 1025.8
1984 735.3 1278.1 665.6 1061.0
1985 739.6 1297.6 673.4 1074.4
1986 730.0 1330.0 684.4 1089.9
1987 748.9 1370.0 703.1 1121.5
1988 802.8 1405.6 732.5 1164.5
1989 829.2 1440.4 769.9 1195.9
1990 832.8 1487.7 797.5 1225.7
1991 832.3 1533.3 827.5 1252.9
Bringing Costs up to Date xi
TABLE 2 Continued
Nelson
Materials Labor Miscellaneous Inflation
Date Component Component Equipment Index
1992 824.6 1579.2 837.6 1277.3
1993 846.7 1620.2 842.8 1310.8
1994 877.2 1664.7 851.1 1349.7
1995 918.0 1708.1 879.5 1392.1
1996 917.1 1753.5 903.5 1418.9
1997 923.9 1799.5 910.5 1449.2
the total escalation derived by each index will vary because different bases are
used. The engineer should become familiar with each index and its limitations
before using it.
Table 1 compares the CE Plant Index with the M&S Equipment Cost Index.
Table 2 shows the Nelson-Farrar Inflation Petroleum Refinery Construction In-
dexes since 1946. It is recommended that the CE Index be used for updating total
plant costs and the M&S Index or Nelson-Farrar Index for updating equipment
costs. The Nelson-Farrar Indexes are better suited for petroleum refinery materials,
labor, equipment, and general refinery inflation.
Since
C B ⫽ C A (B/A) n (1)
Here, A ⫽ the size of units for which the cost is known, expressed in terms of
capacity, throughput, or volume; B ⫽ the size of unit for which a cost is required,
expressed in the units of A; n ⫽ 0.6 (i.e., the six-tenths exponent); C A ⫽ actual
cost of unit A; and C B ⫽ the cost of B being sought for the same time period as
cost C A .
To approximate a current cost, multiply the old cost by the ratio of the current
index value to the index at the date of the old cost:
C B ⫽ C A I B /I A (2)
Here, C A ⫽ old cost; I B ⫽ current index value; and I A ⫽ index value at the date
of old cost.
Combining Eqs. (1) and (2),
C B ⫽ C A (B/A) n (I B /I A ) (3)
For example, if the total investment cost of plant A was $25,000,000 for 200-
million-lb/yr capacity in 1974, find the cost of plant B at a throughput of 300
million lb/yr on the same basis for 1986. Let the sizing exponent, n, be equal to
0.6.
From Table 1, the CE Index for 1986 was 318.4, and for 1974 it was 165.4.
Via Eq. (3),
xii Bringing Costs up to Date
TABLE 3 Vatavuk Air Pollution Control Cost Indexes (VAPCCI). First Quarter 1994
⫽ 100.0 (index values have been rounded to the nearest tenth).
1994 1995 1996

Control Device (Avg.) (Avg.) (Avg.)
Carbon adsorbers 101.2 110.7 106.4
Catalytic incinerators 102.0 107.1 107.0
Electrostatic precipitators 102.8 108.2 108.0
Fabric filters 100.5 102.7 104.5
Flares 100.5 107.5 104.9
Gas absorbers 100.8 105.6 107.8
Mechanical collectors 100.3 103.0 103.3
Refrigeration systems 100.5 103.0 104.4
Regenerative thermal oxidizers 101.4 104.4 106.3
Thermal incinerators 101.3 105.9 108.2
Wet scrubbers 101.3 112.5 119.8
C B ⫽ C A (B/A) n (I B /I A )
⫽ 25.0 (300/200) 0.6 (318.4/165.4)
⫽ $61,200,000
Table 3 shows the Vatavuk Air Pollution Control Cost Indexes (VAPCCI) since
1994. For details, see the Vatavuk Air Pollution Control Cost Indexes article in
volume 61.
Editor’s note: For a more thorough explanation of updating costs, see the arti-
cle, ‘‘Tower Cost Updating’’ in volume 58.
john j. mcketta
Encyclopedia of
Chemical Processing
and Design
69
Circulating Fluidized Bed Reactors:
Basic Concepts and Hydrodynamics
Introduction
Circulating fluidized beds (CFBs) consist of two basic designs, as shown in Fig. 1.
One design involves a fast-fluidized bed where high gas velocities convey a sub-
stantial amount of solids to one or more cyclones. The separated particles are fed
back to the fluidized bed using a standpipe. The second basic design uses a riser
to convey solids to one or more cyclones. The separated particles are fed to an
optional fluidized bed and then back to the riser. Solids flow rates can be controlled
using nonmechanical L- and J-valves or using a mechanical slide valve.
The large-scale commercial realization of CFBs occurred in the early 1940s,
although some coal gasification was done in a fluidized bed as early as 1926 [1].
With the increased demand for gasoline during World War II, major efforts were
underway to develop reactors to crack petroleum feedstocks into usable fuels more
productively than the moving bed or snake reactors (i.e., the Houndry Process)
used at that time. The result was a fluidized catalyst cracker (FCC), where high
catalyst circulation rates allowed a balance between the exothermic burning of
coke on the catalyst in the regenerator and the endothermic hydrocracking of petro-
leum in the reactor. The continuous circulation or regeneration of catalyst provided
fresh catalyst for petroleum cracking and thereby resulted in high sustainable pro-
ductivities. With the addition of a stripping section after the reactor, even higher
yields were obtained. The addition of steam, CO 2, or other inerts would remove
the product from and around catalyst particles flowing toward the regenerator.
Today, the evolution of the FCC unit has results into several basic designs, as
shown in Fig. 2.
In 1960, circulating fluidized beds contributed to another breakthrough process
for the petroleum and chemical industry. Standard Oil of Ohio (SOHIO) developed
a fluidized-bed reactor for the ammoxidation of propene to acrylonitrile. Previous
technology was done in tube-and-shell fixed-bed reactors. However, the high heat
of reaction of 160 kcal/mol limited the economic feasibility of those units. The
high heat transfer characteristic of fluidized-bed reactors made them ideal for the
production of acrylonitrile. Today, nearly all large-scale acrylonitrile plants are
based on the SOHIO design, with capacities up to 180,000 tons per year [4].
The greatest challenge in developing the SOHIO process was in the manage-
ment of backmixing. The inherent hydrodynamics of fluidized beds, where solids
and, to a lesser extent, gas circulate from the top of the bed to the bottom, then
to the top again, would have a deleterious effect on acrylonitrile selectivity. To
overcome backmixing, SOHIO developed sieve trays to compartmentalize the gas
flow in the fluidized-bed reactor to resemble a more plug-flow characteristic [5].
In 1979, SOHIO redesigned the acrylonitrile reactor to more of a ‘‘tube-and-shell’’
fluidized-bed unit [6], as shown in Fig. 3.
1
2 Circulating Fluidized Bed Reactors
FIG. 1 Basic design of circulating fluidized beds.
FIG. 2 Typical FCC units based on the designs of (a) Standard Oil Development, (b) UOP, (c) Kel-
logg, and (d) Exxon. (Adapted from Refs. 2 and 3.)
Circulating Fluidized Bed Reactors 3
FIG. 3 Two-dimensional schematic of the SOHIO acrylonitrile processes. (Adapted from Ref. 5.)
During the late 1970s and early 1980s oil crisis, circulating fluidized beds found
applications in coal combustion. The high-heat-transfer capabilities of these re-
actors resulted in lower operating temperatures, thereby reducing NO x and SO 2
emissions. In addition, the high gas velocities resulted in significant turbulence,
which provided uniform temperatures in the combustor. With the surplus of oil
starting in the late 1980s, fluidized-bed combustors became economically less at-
tractive. As of the early 1990s, only Dynergy (via the Destec process) and Lurgi
and Ahlstrom are practicing this technology [7].
Today, circulating fluidized beds are used in a wide array of chemical pro-
cesses, as shown in Table 1. With fluidized beds having the unique distinction of
excellent heat transfer and continuous in situ regeneration, the economic attrac-
tiveness of processing thermally sensitive chemicals or using catalysts that require
TABLE 1 Some Fluidized and Circulating Fluidized Bed Reactor Processes
Product Process Developer

Acrolynitrile Propene ammoxidation SOHIO
Aniline Nitrobenzene hydrogenation BASF, Cyanamid, Lonza
Chloromethanes Cat. oxidaton of methane Asahi Glass
Goal gasification Oxidation Winkler
Hydrocyanic acid Ammono-dehydrogenation Shawinigan
Maleic anhydride Butane oxidation Alusuisse & Lummus (Alma Process)
Maleic anhydride Butane oxidation DuPont
Maleic anhydride Butene oxidation Mitsubishi
Perchlorethlyene Chlorination Diamond Shamrock
Phthalic anhydride Naphthalene oxidation Badger/Sherwin-Williams
Polyethylene Ethlyene polymerization Union Carbide (Unipol)
Synthesis gas Fisher–Tropsch SASOL, Kellogg
Vinyl chloride Ethylene chlorination, Ethyl, Hoechst, Mitsui, Toatsu, Mon-
oxychlorination santo
frequent regeneration are more realized. Once the obstacles of backmixing, mass
transfer, and attrition have been addressed, these reactors often set the standards
in reactor design.
Basic Concepts
As the gas velocity through a bed of solids increases, the bed undergoes several
regimes, as shown in Fig. 4. At first, the gas velocity is insufficient to fluidize
the particles and the bed remains fixed. With increasing velocity and under ideal
conditions, the fixed bed expands smoothly and uniformly. Particles move in a
limited fluidlike fashion and the bed pressure drop becomes constant. At this point,
the bed is commonly referred to as undergoing minimum fluidization.
Further increases in gas velocity results in further bed expansion and particles
appear to freely move throughout the bed. The gas permeates through the bed
without the formation of bubbles. This regime is referred to as smooth fluidization
and is only observed for Geldart Group A powders (see Appendix A). These pow-
ders require noticeably higher gas velocities to promote the formation of gas bub-
bles after minimum fluidization. In contrast, Group B powders begin bubbling
shortly after minimum fluidization. Group C powders, being cohesive, may even
show signs of bubbling prior to minimum fluidization; however, this is usually the
result of channeling.
The onset of bubbles in the fluidized bed is commonly referred to as bubbling
fluidization. Here, gas bubbles form at or near the distributor and grow to a maxi-
mum bubble size as they propagate through the bed. The top of the fluidized bed
is still well defined, as it was in the minimum and smooth fluidization regimes.
The pressure drop across the bed is still constant, on average, but starts exhibiting
large, but regular, fluctuations with time.
As the gas velocity continues to increase, the top of the bed becomes less
defined. Large amounts of particles are ejected into the freeboard region above
the bed. Concurrently, sizeable regions of voidage and particle clusters are seen
FIG. 4 Various fluidization regimes with increasing superficial gas velocity.

in the bed itself. For Group A and B powders, this transition from the bubbling
fluidized-bed regime is called the onset of turbulent fluidization. Group C and D
powders may show a slugging behavior prior to the turbulent fluidization regime.
During fast fluidization, the gas velocity is sufficient enough that the surface
of the bed can no longer be discerned. Particle density is still higher at the bottom
of the unit compared to the top, suggesting that some sort of bed exists. Particle
clusters and streamers are readily observed and, in some cases, a core–annulus
radial variation in particle density begins to take shape. Particle entrainment is high
and the total disengagement height may be well beyond the physical dimensions of
the fluidized-bed unit. To overcome the losses of particles due to entrainment,
cyclones may be used to capture entrained particles and recirculate them back into
the bed.
At very high gas velocities, nearly all the particles are entrained from the bed.
This regime is commonly referred to as pneumatic conveying. In this regime, axial
variation in particle density is no longer observed, except maybe in entrance and
exit regions. Radial variation in particle density can vary dramatically and range
from a core–annulus profile to a uniform profile. For dense systems, clusters and
streamers are readily observed.
Thus, for gas–solid systems, increases in the gas velocity results in dramatic
and sometimes sharp transitions in the hydrodynamics. In the design of fluidized
beds, it is crucial that one knows the fluidized regime that will exist at operating
conditions. The simple transition from one regime to another can have significant
impacts on reaction, heat transfer, attrition, and entrainment rates. For circulating
fluidized beds, where several regimes may exist in a single unit (i.e., from con-
veying in the riser to a bubbling fluidized-bed regime in the regenerator), knowl-
edge of the fluidization regimes is paramount.
In order to gain better understanding of these regimes, the methodology used
to determine the onset of each fluidization regime is discussed in the following
sections. Keep in mind that most of the correlations are empirical and may not
fully represent every system. With the cost of these units running in the tens of
millions of dollars for large-scale plants, experimental validation of the expected
regimes is critical when designing these processes.
Minimum and Smooth Fluidization
As a gas permeates through a fixed or packed bed, the pressure drop can be de-
scribed by the Ergun equation [8]:
∆P (1 ⫺ ε bp )2µu g (1 ⫺ ε bp )ρ g u 2g
g c ⫽ 150 ⫹ 1.75 (1)
L ε 3bp (Φd p ) 2 ε 3bp (Φd p ) 2
With increasing gas velocity, the bed reaches a point where the drag force exceeds
the force of gravity on the particles. The particles become mobile and the bed
becomes fluidized. The gas velocity at the onset of this type of fluidization is
referred to as the minimum fluidization velocity or u mf. Assuming that the weight
of the particles in the fluidized bed corresponds to ∆P/L, the Ergun equation can
be written as
冢冣冢冣
2
1.75 d p u mf ρ g 150(1 ⫺ ε mf ) d p u mf ρ g d 3 gρ (ρ ⫺ ρ g )
⫹ ⫽ p g 2s (2)
ε 3mf Φ µ ε mf Φ
3 2
µ µ
or
1.75 2 150(1 ⫺ ε mf )
Re p,mf ⫹ Re p,mf ⫽ Ar (3)
ε 3mf Φ ε 3mf Φ 2
where the Archimedes number, Ar, is defined as
d 3pgρ g (ρ s ⫺ ρ g )
Ar ⫽ (4)
µ2
and Re p is the particle Reynolds number having the expression
d p u mf ρ g
Re p,mf ⫽ (5)
µ
Equation (3) can be written as a quadratic with the coefficients K 1 and K 2 having
the form
K 1 Re 2p,mf ⫹ K 2 Re p, mf ⫽ Ar (6)
By solving for Re p, mf, Eq. (6) can be rewritten as
冤冢冣冢冣冥 ⫺ 冢2KK 冣
2 0.5
K1 Ar
Re p, mf ⫽ ⫹ 1
(7)
2K 2 K1 2
where the particle Reynolds number at minimum fluidization is a simple function

of the Archimedes number and two constants (K 1 /2K 2 and 1/K 1 ).
Many correlations for the minimum fluidization velocity are based on Eq. (7)
TABLE 2 K1 and K2 Values for Eq. (7)

Reference K2 /2K1 1/K1 Comments
Wen and Yu [9] 33.7 0.0408 For fine particles
Richardson [10] 25.7 0.0365
Saxena and Vogel [11] 25.3 0.0571 Dolomite at high temperature and pressure
Bubu et al. [12] 25.3 0.0651
Grace [13] 27.2 0.0408
Chitester et al. [14] 28.7 0.0494 For large particles
Source: Adapted from Ref. 7.
for the constants K 1 /2K 2 and 1/K 1. These constants are presented in Table 2 for
a wide range of studies. For typical Geldart Group A powder, the constants of
Wen and Yu are most often used. However, these correlations are specific to a
group of particles with common characteristics and may not represent a less-than-
ideal particle morphology and texture.
The minimum fluidization velocity can be experimentally determined by mea-
suring the pressure drop across a bed of particles with increasing superficial gas
velocity. For smooth, round, and noncohesive particles, the pressure drop increases
linearly with gas velocity until the minimum fluidization velocity is reached. With
further increases in the gas velocity, the pressure drop remains constant. Hence,
the minimum fluidization velocity is the intersection of the linearly increasing line
with the constant-pressure-drop line.
Figure 5–8 demonstrate the results of such an experiment. Figure 5 is the
pressure-drop curve for alumina particles with a mean particle diameter of 60 µm
in a 4.5-in.-inner diameter fluidized bed unit. The minimum fluidization velocity
for these particles was determined to be 6.5 cm/min. When measuring the mini-
mum fluidization velocity, less scatter in the data is obtained from larger or higher
beds. The scatter in Fig. 5 suggests that perhaps a higher bed should have been
used. The diameter of the fluidized bed used in this type of experiment is also
FIG. 5 Minimum fluidization curve for smooth and round alumina particles, d p,ave ⫽ 60 µm.
FIG. 6 Minimum fluidization curve for smooth and round alumina particles, d p,ave ⫽ 60 µm, with
increasing and decreasing gas velocities.
critical to obtaining accurate data. For Geldart Group A powders, bed diameters
less than 3 in. can result in experimental data that are influenced by frictional
effects at the wall. For the coarser Group B powders, the minimum diameter is
much larger.
Figure 6 shows two pressure drop versus superficial gas velocity curves for
the same particles used in Fig. 5. The black data points are the pressure drop with
increasing gas velocity and the gray data points are the subsequent pressure-drop
measurements with decreasing gas velocities. For round, smooth, and noncohesive
particles, the two curves should overlap each other, as shown in Fig. 6. However,
for irregular, rough, or cohesive particles, a hysterisis effect is typically observed.
This is obvious in Fig. 7 for rough and irregularly shaped alumina particles with
FIG. 7 Minimum fluidization curve for rough alumina particles, d p,ave ⫽ 92 µm.
FIG. 8 Minimum fluidization curve for cohesive iron catalyst particles, d p,ave ⫽ 68 µm.
a mean particle diameter of 92 µm. This resulted in higher solid shear forces during
fluidization such that the pressure drop is dependent on previous conditions or is
path dependent. Figure 8 shows the pressure-drop curve for a catalyst supported
on alumina with a mean particle diameter of 68 µm. Here, it is almost impossible
to detect the minimum fluidization velocity. High cohesive forces result in a fluid-
ized bed prone to channeling. Each peak or spike in Fig. 8 is the result of another
channel achieving fluidization while the majority of the bed remains fixed. This
behavior is typically of Group C powders.
Bubbling Fluidization
As discussed earlier, beds with Group A powders pass from minimum fluidization
to smooth fluidization to bubbling fluidization with increasing gas velocity. Group
B and D powders exhibit bubbling fluidization at the onset of minimum fluidiza-
tion. Oddly enough, gas bubbles in all fluidized beds behave similarly to gas bub-
bles in low-viscosity liquids [7]. Large gas bubbles are typically spherical on top
and flattened or even inverted on the bottom; smaller bubbles tend to be completely
spherical. As in liquid systems, gas bubbles in fluidized beds can coalesce into
larger bubbles or split into smaller bubbles, depending on bed conditions. Also,
as gas bubbles approach the top of a fluidized bed, they collapse such that solids
are propagated into the freeboard region. Higher pressures or temperatures result
in a decrease in the maximum bubble size (due to changes in the gas physical
properties) and tend to make fluidization smoother [1].
The minimum velocity for bubble formation is referred to as the minimum
bubbling velocity or U mb. For Geldart Group A and C powders, Abrahamsen and
Geldart [15] proposed that the minimum bubbling velocity can be calculated from
u mb 2300ρ 0.13 0.52

g ug
⫽ 0.8 exp(0.72P 45 µm ) in SI units (8)
u mf d p,ave (ρ s ⫺ ρ s )0.93
This expression is based on observations that the minimum bubble velocity is

strongly dependent on P 45 µm, the probability of finding a particle with a diameter
less than 45 µm. For calculations where less information regarding the system is
known, Eq. (8) can be simplified into the form
冢冣
0.1
ρ
u mb ⫽ 33d p g in SI units (9)
µg
For Geldart Group B and D powders, the minimum bubbling velocity is near the
minimum fluidization velocity. Thus, the onset of fluidization and the formation
of gas bubbles nearly coincide and
u mb ⫽ u mf (10)
As gas bubbles rise through the fluidized bed, the bubble size increases until a
maximum or equilibrium size is achieved, provided that the bed is high enough.
For Group A and B powders, Davidson and Harrison [16] proposed that the maxi-
mum stable bubble size can be determined from
2u t
d b,max ⫽ (11)
g
where u t is the terminal free-fall velocity of the particle (see Appendix B). Geldart
[1] found that Eq. (11) provided a better fit to experimental data if an effective
diameter, d′p, was used to calculate the terminal velocity [i.e., u t ⫽ f(d′p )]. The
effective diameter is defined as
d′p ⫽ 2.7d p (12)
For Group D powders, the maximum stable bubble size is so large that in realistic
fluidized-bed applications the bubbles size is restricted by the bed diameter.
Turbulent Fluidization
Further increases in the gas velocity result in a slugging or turbulent fluidized bed.
If the bed diameter is small and the bed is sufficiently high, the fluidized bed will
slug before entering the turbulent fluidization regime. For Group A, B, and D
powders, slugging is basically the result of a bubble diameter that exceeds about
two-thirds the bed diameter. The wall stabilizes the bubble such that almost the
entire bed is translated up to the top of the bed or even higher. Group C powders
may also exhibit slugging behavior even in large-diameter beds due to the cohesive
forces. Thus, the larger and more cohesive the particles or the smaller the bed
diameter, the higher the probability of a bed exhibiting slugging. For these cases,
the minimum slugging velocity, U ms, can be estimated using the expression of
Stewart and Davidson [17], where
u ms ⫽ u mf ⫹ 0.07(gD)0.5 (13)
For Group A or B powders in large-diameter beds, where the maximum bubble

diameter is smaller than two-thirds the bed diameter, higher gas velocities result
in the onset of turbulence fluidization directly from the bubbling bed regime. The
onset of turbulent fluidization is defined as the point where the standard deviation
of the pressure fluctuations reaches a maximum [18]. Grace and Bi [19] noted
that fluidization at this point reflects the balance between bubble coalescence and
breakup. Higher velocities cause this balance to shift toward a dominating bubble
breakup mechanism. The minimum velocity for the onset of turbulence fluidiza-
tion, u mt, can be calculated using the expression of Bi and Grace [20]:
u mt ⫽ 1.24 Ar 0.45
冢冣
µ
ρg dp
(14)
where 2 ⬍ Ar ⬍ 1 ⫻ 108 or, in terms of dimensionless numbers,
Re mt ⫽ 1.24 Ar 0.45 (15)
where 2 ⬍ Ar ⬍ 1 ⫻ 108.
Fast-Fluidization Regime
Detecting the point of transition between the turbulent fluidized bed and the fast-
fluidized bed regimes has been under debate for many years. Yerushalmi [21]
proposed that this transition occurs when a significant number of particles become
entrained from the fluidized bed. This transition can be observed by detecting a
sudden change of pressure drop with respect to entrainment rate for increasing
superficial velocities. The superficial gas velocity corresponding to this point is
referred to as the minimum transport velocity or u mr. Schnitzlein and Weinstein
[22], however, were unable to determine u mr using Yerushalmi’s method. Their
observations suggested that the value of u mr was strongly dependent on the location
and the distance separating the two pressure taps used to measure the pressure
drop.
Bi and Grace [20] measured the entrainment rate versus superficial velocity for
a wide range of fluidized-bed systems. They noted that the onset of fast fluidization
correlated to the point where significant particle entrainment was observed. For
Groups A and B powders, this minimum transport velocity can be estimated with
the expression
u mr ⫽ 1.53 Ar 0.45
冢冣
µ
ρgdp
(16)
where 2 ⬍ Ar ⬍ 4 ⫻ 106. For the larger Group D powders, Eq. 16 may underpredict
u mr compared to using the terminal velocity as the minimum transport velocity.
Under these conditions, the minimum transport velocity should be set to equal the
terminal velocity [19].
Pneumatic Conveying
As the velocity continues to increase in a fast-fluidized bed, the axial transition

between the dense and lean regions disappears. This transition marks the onset of
the pneumatic conveying regime and the superficial velocity corresponding to this
point is called the minimum conveying velocity or u mc. The onset of pneumatic
conveying is readily measured by starting with a high superficial gas velocity and
decreasing its value while holding the entrainment rate constant. The superficial
gas velocity where the suspension collapse (i.e., choking) is observed corresponds
to the minimum conveying velocity [19]. Yang [23] proposed that this velocity
can be estimated with the equation
冢冣
2.2
mc ⫺ 1)
2gD(ε ⫺4.7 ρ
⫽ 681,000 g (17)
u mc /ε mc ⫺ u t ρs
Regime Map
The bed hydrodynamics associated with each powder classification used in fluid-
ized beds are summarized in Fig. 9. Increasing the gas velocity through a powder
bed results in the transition of several regimes, which are dependent on the particle
properties. For Group A powders, increasing the gas velocity results in bed hydro-
dynamics that start in the fixed-bed regime and continue through smooth fluidiza-
tion, bubbling fluidization, turbulent fluidization, fast fluidization, and, finally,
pneumatic transport. Group B powders exhibit the same types of transition, with
the exception that smooth fluidization is typically not observed; the onset of fluid-
FIG. 9 Flow regime map for various powders. Slugging for Group A and B powders depend on
vessel diameter. Group C powders tend to slug and Group D powders almost always exhibit
slugging.
ization corresponds with the onset of bubble formation. For Group C powders,
smooth and bubbling fluidization are often replaced by channeling due to large
solid stresses or large cohesive forces on these particles. Group C powders also
have a higher tendency to exhibit slugging prior to turbulent fluidization. Group
D powders often exhibit slugging during the onset of fluidization. The large particle
sizes and/or high densities of Group D powder result in the formation of large
maximum bubble diameters that often exceed the diameters of commercial-scale
fluidized beds. In contrast, slugging for Group A, B, and, to a lesser extent, C
powders may not be observed in large commercial units where the effective bed
diameter often exceeds the maximum stable bubble size.
In an effort to develop a design guide for fluidized unit operations, various
attempts have been made to quantify the flow regimes for gas–solid flow. Reh
[24] first made the attempt for a unified flow regime map by comparing the parti-
cle’s Reynolds number, Re p, to the inverse of the drag coefficient, 1/CD. Further
modification to Reh’s map were made by Werther [25]. Li and Kwauk [26] and
Avidan and Yerushalmi [27] took a different approach to developing a unified flow
regime map by comparing the relationship of the superficial gas velocity to solids
voidage. This approach was further modified by Rhodes [28]. Yet, another ap-
proach was taken by Leung [29], Klinzing [30], and Yang [23], who compared
the superficial gas velocity to the solid flux.
In each of these cases, however, the transition from the fast-fluidized bed to
a pneumatic transport regime was not well defined. Grace [31] resolved this prob-
lem by generating a unified flow regime map based on the dimensionless variables
d*p and u* of Zenz and Othmer [32]. By comparing the dimensionless particle
diameter, d *p ⫽ Ar 1/3, with the dimensionless gas velocity, u* ⫽ Re p /Ar 1/3, Grace
was able to discern the transition to pneumatic conveying. Kunii and Levenspiel
[7] further modified Grace’s work by including the observations of van Deemter
[33], Horio et al. [34], and Catipovic et al. [35]. Figure 10 shows the result of this
effort. It is interesting to note that Kunii and Levenspiel’s [7] demarcation from
fast fluidization to pneumatic conveying is not identical to that first proposed by
Grace. Kunii and Levenspiel describe this transition as not being well defined.
With the aid of Fig. 10 and the relatively simple calculation of d*p and u*, the
flow behavior of most gas–solid systems can be readily obtained. Keep in mind,
however, that the boundary for each regime shown in Fig. 10 should not be consid-
ered as sharp transitions, but more of a gray area between two adjacent regimes.
Pressure Balance in a CFB
In designing a circulating fluidized bed (CFB), special attention needs to be given

to the pressure-loop calculations. This is especially true in the proper design of
standpipes and mechanical or nonmechanical valves (i.e., L-valves, J-valves, slide
valves). The bed height in a standpipe counterbalances the dynamic pressure drop
occurring in the riser or fast-fluidized-bed section. Mechanical or nonmechanical
valves provide better response for this counterbalancing. For instance, an increase
in the gas flow rate in a riser would require a constriction in a slide valve or less
aeration in a L- or J-valve to prevent backflow. This correction results in a higher
standpipe bed height and pressure drop. The higher pressure in the standpipe coun-
FIG. 10 Flow regime diagram proposed by Kunii and Levenspeil. (From Ref. 7.)
terbalances the increased pressure in the riser. Counterbalancing can also happen
without the aid of mechanical or nonmechanical valves, but the response time is
slow and the probability for backflow is much greater.
Figures 11–13 give qualitative examples of the pressure-loop behavior in the
CFBs shown in Fig. 1. The pressure drop in the riser or fluidized-bed section must
equal the pressure drop in the cyclone, fluidized bed, standpipe, and control valve
sections. For example, in Fig. 11, the pressure loop is defined as
[(P 4 ⫺ P 3 )] fluid bed ⫹ [(P 5 ⫺ P 4 )] freeboard

⫽ [(P 6 ⫺ P 7 ) ⫹ (P 5 ⫺ P 6 )] cyclone (18)
⫹ [(P 8 ⫺ P 9 ) ⫹ (P 7 ⫺ P 8 )] standpipe
or
∆P| fluid bed ⫹ ∆P| freeboard ⫽ ∆P| cyclone ⫹ ∆P| standpipe (19)
Assuming that particle frictional (both particle–particle and particle–wall) and par-
ticle acceleration effects are negligible, the pressure drop in the fluidized bed can
be approximated by
∆P| fluid bed ⫽ L bρ s g(1 ⫺ ε) (20)
where L b is the height of the fluidized bed. Similarly, the freeboard can be described
FIG. 11 Pressure loop for a CFB of Design I in Fig. 1.
using
冮
Lu
∆P| freeboard ⫽ ρ s g [1 ⫺ ε(z)] dz ⬇ ρ s g(1 ⫺ ε)(L u ⫺ L b ) (21)
Lb
where L u is the height of the unit. Because the voidage profile, ε(z), in the freeboard
region is rarely known, Eq. (21) can be approximated by using the average voidage
in the freeboard ε.
For the right-hand side of Eq. (18), the pressure drop in the cyclone can be
determined using the expression described by Muschelknautz and Greif [36],
where
∆P| cyclone ⫽ ∆P| wall friction ⫹ ∆P| vortex losses (22)
The first term of this expression corresponds to the friction losses at the wall due
to gas. The second terms accounts for momentum losses in the vortex. Under the
assumption that the flow over the wall of the cyclone is similar to flow over a flat
plate, the pressure drop due to wall friction in a cyclone can be calculated using
ρ g A surface
∆P| wall friction ⫽ λ p (u 0 u b )0.67 in SI units (23)
1.8Q g
The pressure drop in the vortex depends on the average velocity in the vortex tube
and the tangential velocity in the vortex tube or exit. This pressure drop can be
calculated from
冤冢冣冢冣冥
1.33 2
u0 u0
∆P| vortex losses ⫽ ρ g v 20 2 ⫹ 3 in SI units (24)
v0 v0
where the average velocity in the vortex tube is
V̇ g
v0 ⫽ (25)
πr 20
For the standpipe, the pressure drop is determined in a method similar to that used
for the fluidized bed under the same assumptions. The pressure drop in the lean
phase of the standpipe can be estimated as
冮
Ls , 0
∆P| standpipe, lean phase ⫽ ρ s g [(1 ⫺ ε)(z)] dz ⬇ ρ s g(1 ⫺ ε)(L s , 0 ⫺ L s,b ) (26)
L s,b
where L s,0 and L s,b are the height of the standpipe and the dense-phase bed in the
standpipe, respectively. For the dense-phase region of the standpipe, the pressure
drop is approximated as
∆P| standpipe, dense phase ⫽ ρ s g(1 ⫺ ε)L s,b (27)
For the CFB in Fig. 12, the pressure loop has the expression
FIG. 12 Pressure loop for CFB with a fluidized bed as shown in Design II of Fig. 1.
FIG. 13 Pressure loop for CFB with no fluidized bed as shown in Design III of Fig. 1.
(P 4 ⫺ P 3 ) riser ⫽ [(P 5 ⫺ P 4 ) ⫹ (P 6 ⫺ P 5 )] cyclone

⫹ [(P 7 ⫺ P 6 ) ⫹ (P 8 ⫺ P 7 )] 1st Standpipe (28)
⫹ [(P 9 ⫺ P 8 ) ] 2nd standpipe ⫹ [(P 10 ⫺ P 9 ) ⫺ (P 3 ⫺ P 10 )] L-valve
or
∆P| riser ⫽ ∆P| cyclone ⫹ ∆P| 1st standpipe ⫹ ∆P| 2nd standpipe ⫹ ∆P| L-valve (29)
Similarly, the pressure loop for the CFB in Fig. 13 can be described as
(P 4 ⫺ P 3 ) riser ⫽ [(P 5 ⫺ P 4 ) ⫹ (P 6 ⫺ P 5 )] cyclone

⫹ [(P 7 ⫺ P 6 ) ⫹ (P 8 ⫺ P 7 )] standpipe (30)
⫹ [(P 9 ⫺ P 8 ) ⫹ (P 3 ⫺ P 9 )] L-valve
or
∆P| riser ⫽ ∆P| cyclone ⫹ ∆P| standpipe ⫹ ∆P| L-valve (31)
A similar set of expressions can be obtained for the CFB in Fig. 13. Compared
to the pressure-loop calculations used for the system in Fig. 11, the only new
expressions needed to complete the pressure-loop calculations in Figs. 12 and 13
are the pressure drop across the L-valve. Yang and Knowlton [37] noted that the
pressure drop across an L-valve is similar to that used by Jones and Davidson [38]
for a mechanical valve where
冢冣
2
1 Ws
∆P| mechanical ⫽ (32)
2ρ s (1 ⫺ ε mf ) C D A 0
For mechanical valves, the valve opening area, A o, may vary during operation but
is always known. For an L-valve, however, the opening area, A o, depends on the
amount of aeration and is not known. Yang and Knowlton [37] found an empirical
expression for this opening area of the L-valve based on 158 experimental data
points. Their results showed that the opening area can be expressed as
Q aeration πD 2L-valve L L-valve

A o ⫽ 1.41 ⫺ 0.0623 in Foot Pounds Seconds (FPS) units
ut ut
(33)
Thus, pressure drops through a CFB can be estimated and can provide the basic
foundation for design. However, as these units become more complicated or are
operated at higher and higher solid circulation rates, this procedure may not be
enough. Indeed, the pressure-drop calculations presented assume that frictional and
acceleration effects are negligible. Although this may be a safe assumption for
rough estimates of the pressure loop, detailed design calculations cannot neglect
these effects. In addition, particle properties such as roughness, sphericity, and
particle size distribution can also have a significant effect on the pressure drop.
Indeed, the addition of fines to a Group A powder can result in reduced pressure
drops for fluidized beds and risers. Using computation fluid dynamics, Sinclair
and Mallo [39] demonstrated that this may be due to the fact that smaller particles
dampen the wakes generated by larger particles or bubbles. Hence, a clear under-
standing of the hydrodynamics is needed to fully describe pressure loss in CFBs.
Fortunately, this has been the focus of intensive research in the last few years.
Gas–Solid Hydrodynamics
In general, the hydrodynamics of a riser can be divided into macro-scale and meso-
scale flow behavior. Macro-scale behavior is mostly concern with solids concentra-
tion profiles and solids velocity on a large scale. Risers typically exhibit a wide
and diverse range of axial and radial solids profiles that are highly dependent on
operating and design conditions. For instance, the design of the entrance and exit
regions of a riser can influence the solid profile throughout the riser. Hence, it is
important to understand this macro-scale behavior in order to provide the correct
riser design for the desired solids concentration and velocity profiles.
To make matters even more complicated, fast-fluidized beds and risers have
shown evidence of dynamic meso-scale flow behavior in the form of particle ag-
glomeration called clusters and streams. The size and frequency of these clusters
and streams are also highly dependent on operation and design conditions. Both
the cluster size and frequency have a substantial impact on both catalytic reaction
rates and heat transfer.
Fortunately, a clearer understanding of these macro-scale and meso-scale be-
haviors are under intensive investigations. Today, fast-fluidized beds and risers
can be designed with the solids concentration and radial profile in mind. However,
this can only be achieved if one has an understanding of gas–solid hydrodynamics.
Macro-Scale Behavior: Solids Profile

Axial Profile of Solids in a Fast-Fluidized Bed and Riser
In 1971, Reh noted that there exists an axial gradient of solids concentration in a
riser similar to that observed in a fast-fluidized bed. Figure 14 illustrates these
subtitle differences in the axial solids concentration profile commonly observed
throughout a fast-fluidized bed and riser. As the gas velocity increases through a
fluidized bed, the boundary between the dense fluidized-bed region and the lean
freeboard region becomes indistinguishable. Indeed, having a distinguishable bed
height is one of the indicators for fast fluidization (see the subsection Fast-Fluid-
ized Regime). However, it was surprising that this axial gradient also exists in a
riser (i.e., pneumatic conveying region) where higher gas velocities are used.
This behavior was later quantified by Li and Kwauk [26], Weinstein et al. [40],
Hartge et al. [41], and Rhodes et al. [42], who found that the axial gradient of the
solids concentration exhibited an S-shaped curve. Horio [43] suggested that this
S-shaped curve is restricted to units with a large L/D, riser length to diameter ratio.
Large-scale units, such as atmospheric fluidized-bed combustors, may not exhibit
this axial profile. Unfortunately, data on large units are limited and the solids con-
centration profiles in these units are still a subject of debate.
FIG. 14 Axial solids concentration profile in (a) a fast-fluidized bed and (b) a riser.
FIG. 15 Length-normalized pressure drop in a riser with increasing solids flux.
Recent studies have shown that the design of the entrance and exit region in
a riser can have a substantial effect on the resulting performance. As illustrated
in Fig. 15, the pressure drop, normalized by the distance between pressure taps,
versus the riser length to diameter ratio, L/D, can be affected by the entrance design
for 20 to 30 L/D’s. Furthermore, this effect becomes more pronounced with higher
solids fluxes. Using an x-ray absorption technique, Kostazos et al. [44] were able
to further substantiate this effect by examining the radial profile in a riser at varied
feed ports. Their results showed that an asymmetric position of the feed manifested
itself in the asymmetry of the radial profile at an axial position of up to 30 L/D’s.
Radial Profile of Solids in a Fast-Fluidized Bed and Riser
The radial profile of solids that exists in fast-fluidized beds and risers is even more
surprising. At some point beyond the entrance region of the fast-fluidized bed or
riser, particles segregate toward the wall to form a core–annulus profile, as illus-
trated in Fig. 16. Studies using kinetic sampling probes, a γ-ray densitometer, and
fiber optic probes were able to resolve this core–annulus profile [1,45–48]. Their
results showed that the core consists of a lean concentration of solids moving up
the riser, whereas the annulus consists of a dense concentration of particles. At
moderate solids fluxes, particles in the annulus region actually exhibit a downward
velocity, as shown in Fig. 16 [46,48,49]. Karri and Knowlton were able to quantify
this downflow as a function of radial profile by measuring the solid mass fluxes
in a 20-cm-diameter by 14-m-high riser [49]. Figure 17 presents their results where
downflow in the annulus regions was observed for solid mass fluxes of 49 and 93
FIG. 16 Representation of the core–annulus profile in a riser where downflow is observed near the
walls. (Adapted from Ref. 48.)
kg/m2 s. Miller and Gidaspow [50] showed that the largest magnitude of annular
downflow flux at and near the wall was near the bottom of the riser. At less than
2 m from the inlet of Miller’s 7.5-cm-diameter riser, downward fluxes were several
times the average feed flux [51].
The implications of this behavior can be substantial. For many catalytic reac-
tions, backmixing near the feed region and, to a lesser extent, up throughout the
riser can have a significant impact on productivity. Fortunately, many of these
reactions require very high solids fluxes where downflow may be less of an issue.
For example, Fig. 17 shows that operating Karri and Knowlton’s riser [49] at or
above solid fluxes of 195 kg/m2 s, results in a core–annulus profile where particles
at the wall move in the same direction as those in the core region (positive solids
mass flux of ⬃1 kg/m2 s). In this case, backmixing was limited. Similar findings
FIG. 17 The effects of solids mass flux on the radial net solids mass flux profile. (Adapted from
Ref. 49.)
FIG. 18 Representation of the core–annulus profile in a riser where upflow is observed near the
walls. (Adapted from Ref. 49.)
have also been reported by Issangya et al. [52]. A representation of this behavior
is presented in Fig. 18.
Particle segregation appears also to be influenced by the core–annulus profile
in a riser. Karri and Knowlton [49] observed that in the presence of downflow,
the particle size distribution in the annulus region was larger than that found in
the core. In contrast, this effect appears to only occur for downflow operations.
Particle segregation was not observed for core–annulus upflow profiles for either
very high or low solid mass fluxes [49]. Jones et al. [53] examined this phenomena
using, the Laser Doppler Velocimetry (LDV) of particle-laden jets. Their results
showed that eddies or recirculation zones were responsible for this particle segrega-
tion. Hence, the high shear and resulting recirculation zones generated from the
solids downflow near the wall may be responsible for the segregation effect ob-
served by Karri and Knowlton [49]. With upflow at the wall, the low shear may
not generate strong enough eddies to effect the particle size distribution across the
riser diameter.
There are also design features that can reduce backmixing in risers. Baffles
can induce wakes and turbulence, which limit the core–annulus profile. Of course,
the added attrition caused by baffles needs to be factored into the design process.
Another option is to use secondary feeds to produce a higher plug flow or uniform
solids velocity profile at the entrance region. A core–annulus profile may still
develop further up the riser, but backmixing is less severe in this region.
As with the axial profile, the design of the entrance and exit region can have
a substantial effect on the solid radial concentration profile. Rhodes et al. [42] used
a nonisokinetic sampling probe to examine the radial solids loading in a 0.09-m-
inner diameter by 7.2-m-high riser. Their results showed that a side solids feed
resulted in a nonuniform radial distribution of solids beyond 40 L/D’s, as depicted
in Fig. 19. In addition, Rhodes et al. noted that the asymmetries in solids radial
distribution were more noticeable in the interphase between the dense and dilute
regions. Thus, depending on the design of the feed region, a nonuniform radial
profile may exist throughout many industrial risers.
In a similar fashion, the exit configuration of a riser can have an impact on
the solids profile for several L/D’s below the exit region. Brereton and Grace [54]
observed this effect for smooth and abrupt riser exits. As shown in Fig. 20, using
FIG. 19 Illustration of the nonuniform solids radial profile in a riser due to solids feed on the side
of the riser (not drawn to scale). (Adapted from Ref. 28.)
FIG. 20 Effect of exit configuration on solids volume fraction for a 0.15-m-diameter by 9.3-m-high
riser with a superficial gas velocity of 7.1 m/s, initial solids flux of 73 kg/m2 s, and 148-
µm sand particles. (From Ref. 54).
FIG. 21 Solids flux ratio with respect to radial position for a riser with a smooth, rounded exit at a
superficial gas velocity of 4.2 m/s, solids flux of 50 kg/m2 s, and 80-µm sand particles.
(From Ref. 55.)
a smooth, wide-radius bend to terminate the riser resulted in little deviation in the
axial solids concentration profile. However, an abrupt bend, such as a square bend
or tee, resulted in backmixing, which affected the overall riser solids volume frac-
tion profile up to 20 L/D’s below the exit region.
Similar effects for solids fluxes are reflected in the data of Kruse and Werther
[55] who compared normalized solid fluxes to radial solids loadings for a 0.4-m-
diameter by 15.1-m-high riser, as shown in Figs. 21 and 22. For smooth bends,
substantially less downflow is observed compared to the abrupt exit configurations.
In addition, the region of downflow for the abrupt exit configuration was over
twice the size of that observed for the smooth configuration.
These results provide a good example of the importance of riser design for
chemical production. For combustors, where backmixing is tolerable and some-
times even desired, asymmetric feed designs and abrupt exits are less critical. How-
FIG. 22 Solids flux ratio with respect to radial position for a riser with an abrupt, squared exit at a
superficial gas velocity of 4.2 m/s, solids flux of 71 kg/m2 s, and 80-µm sand particles.
(From Ref. 55.)
FIG. 23 Illustration of riser entrance region for a more uniform solids loading profile.
ever, in chemical production such as in oxidation and chlorination, asymmetric

solids profiles and backmixing can seriously reduce selectivity and activity. Fortu-
nately, both the entrance and exit can be designed such that minimal asymmetric
solids profiles and backmixing ensues. For the entrance region, care needs to be
taken such that entering solids are well mixed with the entraining gas. One such
design is shown in Fig. 23. A fluidizing gas is used to distribute incoming solids,
and one or more jets are used to entrain catalyst into the riser. Similarly, the exit
region should have either a long radius bend or a disengagement section. Typically,
industrial risers have a stripper section at the top of the riser to not only strip gas
but also minimize exit effects on the riser, as shown in Fig. 24.
Meso-Scale Behavior: Clusters and Streamers
Riser sections in circulating fluidized beds exhibit a core–annulus profile with

downward flow resulting in the formation of clusters and streamers of particles.
FIG. 24 Illustration of riser exit region (i.e., stripper) for a more uniform solids loading profile.
This phenomenon was proposed by Squires et al. [56] and Yerushalmi and Avidan
[21,57]. Under the assumption that the pressure drop equals the weight of the solids
in suspension, the resulting slip velocity, calculated as
Gs
v slip ⫽ v g ⫺ (34)
ρs εs
was found to be several times larger than the terminal velocity [51]. Because the
slip velocity cannot exceed the terminal velocity, it was postulated that the particles
must be forming clusters that effectively act as larger particles. Today, cluster and
streams are frequently observed. High-speed movies [24], laser sheet [58], infrared
imagining [59], and fiber-optic probes [60–62] all reveal the presence of wave
packet of particles near the riser wall moving with the downward annulus flow in
continuous but dynamic and unstable sheets. These sheets of particles (commonly
called clusters, streamers, swarms, strings, or strands) are represented in Fig. 25.
Laser sheet and fiber-optic studies of Horio [43] and Rudnick and Werther
[61] have further demonstrated that these clusters are three dimensional in nature
and can be found in the annulus and core regions. In general, it was observed that
clusters move in a direction parallel to the flow of the suspension phase. In other
words, in a core–annulus profile with downward flow at the walls, clusters in the
annulus region flow downward and clusters in the core region flow upward.
Soong et al. [63] experimentally measured the cluster length and time-averaged
local solid volume fraction in riser flow. Their results were in agreement with
Yerushalmi and Avidan’s [57] earlier empirical correlation of
d c ⫹ d p ⫹ ε s (0.027 ⫺ 10 d p ) ⫹ 32 ε 6s (35)
However, Soong et al. replaced the average local solids volume fraction of parti-
cles, ε s, by the solids volume fraction of a cluster, ε cl, as
d c ⫹ d p ⫹ ε cl (0.027 ⫺ 10d p ) ⫹ 32 ε 6cl (36)
FIG. 25 An illustration of the cluster or streamers often observed in risers.

Gu and Chen [64] further correlated Soong’s data such that the solids volume
fraction of a cluster can be related to the local solids volume fraction of particles
using the expression
冤冢ε 冣冥
3.4
εs
ε cl ⫽ ε s,max 1 ⫺ (37)
s,max
where the maximum local solids volume fraction, ε s,max, is 0.57. Tsuo and Gidaspow
[65] observed that, for Group A powders, the clusters were 2–3 cm in length
in the down-flowing annulus region. Furthermore, cluster density increased with
increasing solids flux, decreasing gas velocity, or decreasing pipe diameter.
The mechanism for the formation and degeneration of clusters in a riser is still
under some dispute. Tsuo and Gidaspow [65] proposed that clusters are the result
of partially inelastic collision with the walls. Particles hit the wall, lose energy,
and fall, to collide with another particle. This process continues until a cluster is
formed.
Senior and Grace [66] proposed that inelastic wall collisions cannot account
for all the energy loss needed to form clusters. For this to happen, wall collisions
would need a coefficient of restitution of less than 0.1, which is unlikely. Perfectly
elastic collisions have a coefficient of restitution of 1. Instead, Senior and Grace
proposed that the balance between shear-induced lift and drag forces on a particle
act to momentarily detain particles at the wall region of the riser. After a particle
collides with the wall, it has insufficient momentum to counteract the lift force.
As a result, the particle continues to hit the wall, each time losing more lateral
velocity. When the particle-to-wall friction slows the particle below the local gas
velocity, lift forces acting in the opposite direction move the particle away from
the wall to the near-wall regions. Clusters form when many particles undergo this
lateral-velocity-reduction process. The downward motion of a cluster is caused by
the net lift forces on a cluster being less than the sum of the forces on each individ-
ual particle.
Particle migration to the wall is not only dependent on axial and lateral veloci-
ties but also on the particle diameter. Lee and Durst [67] found that 100- and 200-
µm-diameter glass beads readily accumulated at the wall, whereas larger particles,
with a 400–800-µm diameter, did not. The larger particles were traveling at sig-
nificantly lower axial velocities and were less influenced by lift forces directed to
the wall. Tsuji et al. [68] was also able to measure this crossover of particles to
the wall for smaller particles. Senior and Grace [66] were able to model these
trajectories and found similar conclusions. For particles larger than 500 µm in
diameter, no range of lateral velocities was found that slowed the particle signifi-
cantly enough for crossover to the wall. Yet, for 230-µm particles, a significant
concentration of particles was predicted to accumulate near the wall for initial
lateral velocities of 4.5–5.5 cm/s. For 40-µm particles, concentrations were found
to be an order of magnitude larger at the wall than that found for 230-µm particles
with lateral velocities ranging from 3 to 22 cm/s.
What is interesting here is that if particle collisions with the wall help create
the formation of clusters, how do cluster form in the core region as observed by
Horio [43] and Rudnick and Werther [61]. Furthermore, Karri and Knowlton [49]
observed that particles in the annulus region with a downward flow had a larger
particle size distribution than that in the core. In a core–annulus profile where both
regions have an upflow profile, no particle size distribution effects were observed.
Both of these results contradict the above postulate of Senior and Grace in which
a wall is needed for cluster formation and larger particles prefer the core region.
Most likely, the magnitude of the solids flux or solids concentration may have a
significant impact on the locality of cluster formation and particle-size-segregation
effects. These macroscopic properties may also need to be considered.
Horio [43] proposed that another mechanism may be responsible for cluster
formation. A particle in flight can have either attractive or repulsive forces with
nearby particles. Two particles traveling perpendicular to the gas flow tend to re-
peal each other, whereas two particles aligned parallel with the flow tend to attract
each other due to the nearest-neighbor effect on lift and drag. Yet, in riser flow,
particle alignment is not stable, as particles undergo collisions, bumping, tumbling,
and other nonelastic processes. This may be the very mechanism to ensure cluster-
ing. The combination of nonelastic processes and the parallel-aligned particle flow
may provide the attractive force needed to promote clustering.
Furthermore, Horio noted that buoyancy forces dominate in lean-phase regions,
whereas gravitational forces dominate in dense-phase regions. This results in a
shear between clusters and the lean-phase region. The interaction of these forces
controls the development of particle groups to form steady but turbulent structures
of a certain characteristic length. Two-dimensional simulations of particles show
this very event, where a homogeneous suspension evolved into clusters [69].
Closing Remarks
To date, a complete description of the CFB hydrodynamics is not possible even

after decades of intensive research. Hence, predicting accurate pressure profiles,
reaction productivities, heat transfer, and gas and solid residence times is still more
art than science. Yet, circulating-fluidized-bed reactors have been in productive
use for more than 50 years. Indeed, a broad knowledge base exists for the design
of fluidized catalyst crackers using empirical-based models. Even though a funda-
mental understanding of the physics behind gas–solid flow is limited, the design,
construction and operation of these units can be done in a relatively short period
of time.
For the design, construction, and operation of CFBs in the chemical industry,
this is not the case. Unlike the petroleum industry where FCC catalysts have similar
properties, the physical properties of the catalyst commonly used in the chemical
industry are diverse. Thus, it is more important to understand and apply at least
the known physics in gas–solid flow. This is not a daunting task; just careful con-
sideration of each design aspect of the CFBs needs to be addressed.
Nomenclature
Ar Archimedes’ number
A surface Surface area
db Bubble diameter
d b,max Equilibrium bubble diameter
dc Cluster diameter
dp Particle diameter
d p′ Effective particle diameter
d p,ave Average particle diameter
d *p Dimensionless particle diameter
D Vessle diameter
D L-valve Diameter of an L-valve
g Acceleration of gravity
gc Newton’s law proportionality factor, 9.8 m/s2 or 32.2 ft/s2
Gs Solids flux rate
L Length
Lb Height of fluidized bed
L L-valve Height of L-valve (distance between L-valve feed and horizontal leg into
reactor)
Lu Height of fluidized-bed vessel
P 45µm Proportion of particles with a diameter less than 45 µm
Q aeration Volumetric flow rate of the gas for L- or J-valve
Qg Volumetric flow rate of the gas
r Radius
R Vessel radius
Re p Particle Reynolds number
Re pmf Particle Reynolds number at minimum fluidization
ug Superficial gas velocity
u mc Superficial gas velocity at the onset of pneumatic conveying in a fluid-
ized bed
u mb Superficial gas velocity at the onset of bubbling in a fluidized bed
u mf Superficial gas velocity at minimum fluidization
u mr Superficial gas velocity at the onset of fast fluidization in a fluidized bed
u ms Superficial gas velocity at the onset of slugging in a fluidized bed
u mt Superficial gas velocity at the onset of the turbulence regime in a fluid-
ized bed
ui Inlet velocity of a cyclone
u0 Tangential velocity at the wall of a cyclone
u* Dimensionless gas velocity
ut Particle terminal velocity
V̇ g Volumetric gas flow rate
v slip Slip velocity
z Distance
ε Solids void fraction
ε bp Solids void fraction for a packed bed
ε cl Average solids void fraction of a cluster
ε ms Solids void fraction at the onset of pneumatic conveying in a fluidized

bed
ε mf Solids void fraction for a bed at minimum fluidization
εs Average solids void fraction
∆P Pressure drop
λp Dimensionless solids friction coefficient
µ Gas viscosity
ρg Gas density
ρs Solids density
Φ Sphericity
Appendix A: Geldart Powder Classification
Simpson and Rodger [70], Jackson [71], and Verloop and Heertjes [72] suggested
that the fluidization of particles can be classified into two categories: particulate
and aggregative. The particulate category pertains to powders that fluidize in a
liquidlike fashion. As the superficial gas velocity increases, these particles move
further apart in an independent fashion. In contrast, particles in the aggregates
catagory would exhibit bubble formation with increasing gas velocities. For the
aggregate particles, the resulting dense phase remains unchanged in terms of solids
concentrations after initial fluidization. Most particles adhere to the aggregative
behavior.
Unfortunately, this two-category methodology falls short in adequately describ-
ing fluidization behavior. The particulate category is limited to a small group of
particles leaving the aggregative category to describe everything else. To address
this shortcoming, Geldart and Rhodes [1,73] demonstrated that particles could be
classified into four distinct categories or groups. Today, these groups are referred
to as Geldart Group A through D.
Figure A1 illustrates how the fluidization behavior of a particular powder can
be predicted using the Geldart Group classification. This graph is the basic founda-
tion of modern-day fluidization engineering. By comparing the particle density
(less the gas density) with the mean particle diameter, the ‘‘type’’ of fluidization
can be determined. In general, Group A powders undergoing fluidization behave
significantly different than the other groups. Thus, the design and operation of a
fluidized-bed unit containing a Group A powder would not be the same as that
used for a Group B powder. To better clarify these differences, a description of
the fluidization behavior is presented in the order of increasing particle size.
Geldart Group C powders are typically less than 50 µm in diameter and are
the most difficult to fluidize. These particles are considered cohesive and almost
always exhibit significant channeling during fluidization. To limit this effect,
Group C powders are usually fluidized with the aid of baffles and/or mechanical
vibration. Sometimes, larger particles, such as Group B powders, are added to the
bed to promote smoother fluidization.
Geldart Group A powders are the most common type of powder used in fluid-
ization. For example, most FCC units are designed for Group A powders, which
FIG. A1 Geldart powder classification at ambient conditions. (Adapted from Ref. 7.)
typically have a mean particle diameter of 75 µm and a particle density of 1.0 g/

cm3. At low gas velocities, Group A powders tend to exhibit significant bed expan-
sion without the formation of bubbles (i.e., smooth fluidization). At higher gas
velocities (i.e., greater than u mb ), bubbles appear and rise more rapidly than the
gas in the rest of the bed. Gas in the dense or emulsion phase tend to percolate
through the bed compared to the residence time of the gas in the bubbles. Typically,
Group A powders do not promote maximum bubble size greater than 10 cm [7].
Geldart Group B powders have particle diameters typically ranging from 200
to 800 µm. Unlike Group A powders, where smooth fluidization is observed, these
powders exhibit the formation of bubbles at the onset of fluidization. The bubble
size in Group B powders can be large, on the order of feet in some cases. Group
B powders fluidize easily and are used in a wide range of fluidization unit opera-
tions with little difficulties. Care should be taken that slugging does not occur in
smaller fluidized beds.
Geldart Group D powders have the largest particle diameters of all other Geld-
art groups. As a result, gas requirements for fluidization are large. These powders
are typically processed in spouting beds where gas requirements are less than that
needed in standard fluidized beds. During fluidization, Group D powders have
enormous bubble diameters and slugging is commonly observed even in large flu-
idized beds.
It should be noted that Figure A1 was developed for particles at ambient condi-
tions. Under high pressures, a Group B powder may behave as a Group A powder
Furthermore, the transition from one group to another is not well defined. In some
cases, the behavior of a powder can be classified under more than one group. For
example, some powders fluidize well as a Group A powder, but become perma-
nently defluidized as a Group C powder in nonaerated horizontal sections of a
CFB. These powders are sometimes referred to as Group AC powders.
Appendix B: Terminal Velocity
The velocity of a free-falling particle will increase according to the acceleration

of gravity. At some point, the drag on the particle will reduce the acceleration to
zero and the particle reaches its terminal velocity. Haider and Levenspiel [74]
defined the terminal velocity of a single particle as
⫺1
u *t ⫽
冢18
(d*p ) 2
⫹
2.335 ⫺ 1.744Φ
(d*p )0.5 冣 (B1)
where
冢冣
1/3
ρ 2g
u*t ⫽ u t
µ(ρ s ⫺ ρ g )g
Thus, to avoid significant carryover in a fluidized bed, the superficial gas velocity
should be less than the terminal velocity, u t.
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RAY A. COCCO
Effect of Pressure and Temperature in Bubbling

Fluidized Beds
Introduction
Typical commercial gas fluidized-bed processes operate at up to 7.1 ⫻ 106 Pa

(⬃70 atm) pressure and 1273 K (1000°C). Hence, an understanding of the effect
of pressure and temperature on hydrodynamics is critical for propert fluidized-bed
system design.
Temperature and pressure affect fluidized-bed systems because they affect the
gas density and gas viscosity, two critical parameters impacting bed operation.
These effects cannot be considered independently of particle size, as particle size
dramatically impacts fluid–particle interactions. In this section, we will summarize
the impact of pressure and temperature on the critical hydrodynamic parameters
of minimum fluidization velocity, u mf, bed voidage at minimum fluidization veloc-
ity, ε mf, minimum bubbling velocity, u mb, bubble diameter, d b, bubble frequency,
f, dense phase voidage, ε D, and particle entrainment and elutriation rates, K *i ∞. We
will also summarize the reported effect of pressure on chemical reaction conversion
because reactor performance is the result of all combined effects the pressure and
temperature may have on hydrodynamics as well as on the reaction. The reader
is referred to two in-depth reviews of the subject [1,2].
36 Pressure and Temperature in Fluidized Beds
Two-Phase Flow Model
A bubbling fluidized bed can be considered as consisting of two phases (Fig. 1):
(1) a dense (or emulsion) phase of solid particles with a surrounding interstitial
dense (or emulsion) phase gas and (2) a dilute phase consisting of gas jets which
protrude up through a perforated gas distributor or series of nozzles, and gas bub-
bles that form at the top of the jets. The gas that enters a fluidized bed at the
volumetric flow rate q G(in) enters in the form of gas jets. At the top of the jets, this
gas is distributed between bubbles that form (q B) and the interstitial dense phase
gas (q D) that flows through the solid particles. Mass and heat transfer (interchange)
occur between the jets and the dense phase gas, between the bubbles and the dense
phase gas, and between the dense phase gas and solids. Heat is also transferred
by the dense phase to internal heat-exchange surfaces.
A critical factor affecting the overall performance of a fluidized bed is the
interchange between the dilute and dense phases. Interchange rates can be in-
creased by (1) increasing the ratio of the gas jet volume to the bubble volume in
the bed (i.e., VJ /VB), (2) increasing the ratio of the gas flowing through the dense
phase to the gas flowing as bubbles (i.e., q D /q B), and (3) maintaining a small bubble
size throughout the bed. Small bubbles provide higher mass-transfer rates and in-
creased residence time in the bed. It is imperative to note that although we want
bubbles to be small, bubbles must not disappear. Bubbles must be present in order
to achieve rapid mixing in the reactor, contributing to high heat-transfer rates to
internal surfaces.
FIG. 1 Transport, phases, and pressure in fluidized beds.

Pressure and temperature can have a significant effect on the distribution of

gas between the bubble and dense phases and the mass- and heat-transfer rates.
Minimum Fluidization Conditions
The minimum fluidization velocity, u mf, is a fundamental characteristic of a fluid-

ized bed. Its accurate prediction is important for the successful design and opera-
tion of a fluidized-bed process. At minimum fluidization conditions, the drag force
by upward-moving gas equals the weight of particles lifted in the fluidized bed.
The following relationship can be shown to hold (see the Nomenclature section
for terms):
1 ⫺ ε mf 1.75
Ar ⫽ 150 Re mf ⫹ 3 Re 2mf (1)
φ ε mf
2 3
φε mf
or
2C 1 1
Ar ⫽ Re mf ⫹ Re 2mf (2)
C2 C2
where
d 3p ρ g(ρ p ⫺ ρ g)g d p u mf ρ g
Ar ⫽ , Re mf ⫽
µ 2g µg
42.86(1 ⫺ ε mf)
C1 ⫽ (3)
φ
φε 3mf
C2 ⫽ (4)
1.75
Working on the assumption that the particles constituting the bed can be approxi-
mated by a constant value of φ and that ε mf remains constant over the entire range
of operating conditions of temperature and pressure, various investigators have
proposed values of C 1 and C 2 on the basis of experimental results to be in the
range 18.75–33.7 and 0.0313–0.0651, respectively [3].
The first terms on the right-hand sides of Eqs. (1) and (2) are important if
laminar, or viscous, flow predominates in the system, whereas the second terms
are important if turbulent, or inertial, flow predominates.
For small particles (Re mf ⬍ 20), the simplified form of Eqs. (1) and (2) is
冢冣冢冣
C2 d 2p (ρ p ⫺ ρ g)g
u mf ⫽ (5)
2C 1 µg
For large particles (Re mf ⬎ 1000), the simplified form becomes
冢冣
d p (ρ p ⫺ ρ g)g
u 2mf ⫽ C 2 (6)
ρg
With gas viscosity, µ g, almost independent of pressure and because ρ p ⬎⬎ ρ g for

most materials, Eq. (5) indicates that u mf is relatively unaffected by changes in
pressure for fine particles. On the other hand, according to Eq. (6), u mf for larger
particles will vary with (1/ρ g)0.5, indicating that u mf decreases for increasing pres-
sure.
For changes in temperature, Eq. (5) indicates that u mf varies with 1/µ g . Because
the gas viscosity, µ g, increases with temperature, u mf decreases with an increase
in temperature for fine-particle systems in which viscous forces dominate. For
large particles, Eq. (6) indicates that u mf will increase with temperature because
an increased temperature results in a decreased ρ g.
For systems in the intermediate regime (20 ⬍ Re mf ⬍ 1000), Eq. (2) can be
rearranged and used:
u mf ⫽
冢冣µg
dpρg
[(C 21 ⫹ C 2 Ar)0.5 ⫺ C 1] (7)
The trends that u mf is relatively unaffected by changes in pressure and decreases

for increases in temperature for fine-particle systems and that u mf decreases for
increases in pressure and increases for increases in temperature for large-particle
systems are consistent with those reported experimentally. However, the absolute
values of the predictions may be incorrect because of the difficulty in determining
a representative value for d p and φ, or estimating ε mf.
In the absence of reliable data, use C 1 ⫽ 33.7 and C 2 ⫽ 0.0408 [4] for fine-
particle systems and C 1 ⫽ 28.7 and C 2 ⫽ 0.0494 [5] for coarse-particle systems.
A recommended method for improving the accuracy of u mf is to first determine
u mf experimentally at ambient conditions and to back-calculate an effective particle
diameter (i.e., d eff) from Eq. (5), (6), or (7), using fixed C 1 and C 2. Using this
effective particle diameter, calculate u mf at the desired conditions of temperature
and pressure. This method substitutes an effective value for d p and φ, which are
independent of temperature and pressure; however, it does not account for any
changes in ε mf which might occur for changes in temperature and pressure.
The effect of temperature and pressure on ε mf has been studied by a number
of investigators. Several studies [5,6] have indicated that pressure has essentially
no effect on ε mf for fine particles and a slight increasing effect on ε mf for larger
particles. The effect of temperature on ε mf has been reported to be much more
significant [7–10] and to affect fine-particle systems more than coarse-particle sys-
tems. The temperature effect appears to be the result of interparticle forces which
affect packing properties [8,10]. The dependence of ε mf on temperature can be
expressed in linear form as [8]
ε mf ⫽ ε mf(amb) ⫹ k(T ⫺ T (amb) ) (8)
where the parameter k is a function of particle properties.

Although substantial data have been reported in the literature, no reliable correla-
tions are available for predicting ε mf for a given system. However, it is clear that
incorporating an accurate value of ε mf with an effective particle size, d eff, in Eq. (1)
will allow an accurate calculation of u mf. Without experimental data, the use of Eq.
(7) with the recommended values for C 1 and C 2 is suggested for calculating u mf.
Minimum Bubbling Velocity, umb and Dense Phase

Voidage, εD
As the gas velocity is increased above that required to incipiently fluidize the bed
of particles, gas bubbles eventually form (at u 0 ⫽ u mb) and rise through the dense
phase. In fine-particle systems at high pressures, it is possible to observe a particu-
lately (or homogeneously) fluidized bed without bubbles for intermediate gas ve-
locities between u mf and minimum bubbling, u mb (i.e., for u mf ⬍ u 0 ⬍ u mb). The
minimum gas velocity at which bubbles appear, u mb, has been found to equal u mf
for coarse-particle systems [11]. However, for fine-particle systems, there is a range
of velocities between u mf and u mb over which the bed expands uniformly. The
velocity range over which this ‘‘delayed bubbling’’ occurs can be extended with
an increase in operating pressure.
Abrahamsen and Geldart [12] observed that u mb and, hence, the region of partic-
ulate expansion is increased by adding fines (increased F, weight fraction of parti-
cles ⬍45 µm) to a fluidized bed of fine Group A powders:
u mb 2300ρ 0.126 µ 0.523 exp(0.716F)u mf

⫽ g g
(9)
u mf d p g (ρ p ⫺ ρ g)0.934
0.8 0.934
Equation (9) indicates that u mb will increase for an increase in gas temperature and
pressure (via increased u g and ρ g) and that the sensitivity to viscosity is more
significant than the sensitivity to pressure. This equation has been shown to be
valid over a wide range of pressures for fine-particle systems [13].
For fluidized beds of fine Group A powders that particulately fluidize (i.e.,
u mb ⬎ u mf), the voidage of the dense phase, ε D, exceeds ε mf. This voidage has
been shown to be adequately described for high-pressure systems of fine powders
[14] by the empirical correlation of Kmiec [15]:
(18Re ⫹ 2.7Re1.687)0.209
εD ⫽ (10)
Ar 0.209
It is important to note that an increase in ε D results in a decrease in dense phase

viscosity, µ D.
The effect of u mb ⬎ u mf and ε D ⬎ ε mf is to increase the interchange between
feed gases and solid particles because more feed gas flows directly through the
dense phase (i.e., ⬎ q D /q B). Hence, overall reaction rates for catalytic and gas–
solid fluidized-bed reaction processes involving fine particles will increase with
increased pressure due to the effect of pressure on fluidization hydrodynamics

alone.
Jetting Region
As gas flows through a perforated or multinozzle distributor plate, it enters a fluid-

ized bed in the form of gas jets. This jetting region (Refs. 16 and 17, among others)
has high gas–solid contacting efficiencies relative to the bubbling region above.
Several investigators [18,19] have shown that the penetration of the gas jets into
the fluidized bed increases substantially with an increase in operating pressure.
The effect of gas viscosity was not found to be significant [20]. The contribution
of pressure and temperature impacting the jet length, h j, is through their effect on
gas density via the equation [19]:
冢冣冢冣
0.68 0.24
hj ρg dp
⫽ 21.2Fr 0.37 Re0.05 (11)
do ρp do
Bubbling Region
Bubble size is one of the most important parameters of conventional gas–solid

fluidized beds. Overall reaction rates depend on the size of bubbles because bubble
size is a primary contributor to bubble rise velocity, gas rate of exchange between
phases, heat transfer, and fine-particle elutriation.
Fine-Particle Systems
For fine-particle Group A systems, increased pressures yield smaller-sized bubbles.

Studies have indicated [21] that the smaller bubbles result from a decrease in the
stability of bubbles leading to their breakup into smaller voids. X-rays [22] of gas
bubbles in fluidized beds have shown that an initial disturbance, indenting the
upper surface of a bubble, grows to split it from above. It has been suggested that
this splitting results from a Taylor instability [23] wherein a heavy fluid overlies
a lighter one [24].
In applying the Taylor theory to bubbles in fluidized beds, the dense phase
over the bubble is the heavy fluid and the gas in the bubble is the lighter fluid.
An initial, random, small disturbance with amplitude η 0 is assumed to perturb the
essentially horizontal upper surface of the bubble and to grow according to
η ⫽ η 0 exp(nt) (12)
where n is a parameter depending on the physical properties of the system and on

the wavelength of the disturbance. In gas fluidized beds, n may be obtained from [25]
g
R 4 ⫹ 2R 2 ⫺ 4R ⫹ 1 ⫺ ⫽0 (13)
(k 3ν 2p)
where
2π
k⫽ (14)
λ
is the wave number of the disturbance and
R ⫽ 1 ⫹ n(ν p k 2) (15)
A numerical solution for Eq. (13) has been presented elsewhere [25]. For each ν p,
there is a specific wavelength called the ‘‘most dangerous’’ wavelength, λ max,
which exhibits the maximum growth rate.
Clift et al. [25] have noted that disturbances initiated on the roof of a bubble
are swept around the periphery. In practice, a bubble does not split unless the
disturbance has grown sufficiently before the tip of the growing spike reaches the
side of the bubble. The likelihood of splitting can be estimated by comparing the
time constant for the growth of a disturbance (i.e., t e ⫽ 1/n) with the maximum
time available for growth [25]:
冢冣冢冣
0.5
R0 1
t am ⫽ ln (16)
g tan(θ/2)
If the time available for growth, t am, is greater than the required growth time, t e,
the bubble is liable to split. Otherwise, the disturbance grows so slowly that it
does not achieve an amplitude large enough to cause splitting before it is swept
around the bubble equator.
Observations of splitting bubbles suggest that disturbances usually develop in
a regular pattern on either side of the node. Assuming a node is located λ/4 from
the bubble nose so that the node is an antinode in the initial disturbance,
λ π
θ⫽ ⫽ (17)
2θ kR 0
The relationship between the stable bubble frontal diameter, d f , and the correspond-
ing ν p is shown in Fig. 2. It is clear from Eq. (13) and from Fig. 2 that ν p is the
dominant factor determining the growth of the instabilities, the most dangerous
wavelength, λ max, and, hence, the maximum stable bubble size, d bmax. Thus, the pre-
diction of the effect of system properties on the bubble stability depends on the
prediction of the effect of system properties on ν p. Smaller particles and higher
pressures are known to lower ν p [26] and thus, according to the Taylor instability
theory, result in smaller d f . The major difficulty in testing the ability of using the
FIG. 2 Effects of kinematic viscosity on stable bubble frontal diameters.
Taylor instability theory to explain observed limited bubble growth in high-pressure

fluidized beds is the lack of data, correlations, and theory relating the kinematic
viscosity of the dense phase, ν p, to system parameters. The relationship between
the stable bubble frontal diameter, d f , and the corresponding ν p is shown in Fig. 2.
The actual bubble volume is approximately 75% of that of a sphere of diameter
equivalent to d f [22]. Hence, d f and d b are related:
d f ⫽ 1.1d b (18)
For Taylor instabilities governing the maximum stable bubble size in fluidized
beds, d bmax is dependent on ν p. Because ν p decreases with an increase in ε D and
ε D increases with an increase in pressure and temperature, particularly for fine-
particle systems, increased pressure and temperature result in a decrease in d bmax.
However, the effect of particle size must be taken into consideration because the
effect of pressure and temperature on d bmax is minimal for coarse-particle systems
compared to fine-particle systems.
A suitable relationship for estimating µ D from variations in ε D for gas fluidized
beds is needed in order to predict d bmax a priori. Although such a relationship is
not currently available, calculations using equations developed for systems of solid
spheres in liquids have been shown to be consistent with µ D needed to limit bubble
growth in high-pressure systems [14]. Hence, no suitable relationship exists today
to allow the calculation of d bmax for fine-particle systems as impacted by tempera-
ture and pressure. Nonetheless, experimentally determined values for d b indicate
that higher pressures and temperatures yield smaller-diameter bubbles in gas fluid-
ized beds, particularly for fine-particle systems.
It has generally been reported that the bubble frequency, f, increases with in-
creases in temperature [27–29] and pressure [30]. These results are consistent with
decreases in bubble size for increases in temperature and pressure.
Coarse-Particle Systems
A generalized correlation for bubble size has been developed by Cai et al. [31]
for pressurized fluidized-bed combustors (PFBC) on the basis of a comprehensive
analysis of previous work. The correlation takes into account the different flow
regimes at different pressures and gas velocities, as well as the special variation
of bubble size within the lower-pressure range of the bubbling regime.
For PFBC (P in Pa),
d b ⫽ 0.1905h0.8P 0.06(u 0 ⫺ u mf)0.42

⫻ {exp[⫺1.4 ⫻ 10⫺14P 2 ⫺ 0.25(u 0 ⫺ u mf)2 ⫺ 1 ⫻ 10⫺6P(u 0 ⫺ u mf)]} (19)
The equivalent bubble size of the entire bed is
d be ⫽ 0.1002L 0.8
f P
0.06
(u 0 ⫺ u mf)0.42
⫻ {exp[⫺1.4 ⫻ 10⫺14P 2 ⫺ 0.25(u 0 ⫺ u mf)2 ⫺ 1 ⫻ 10⫺6P(u 0 ⫺ u mf)]} (20)
Particle Entrainment and Carryover
Entrainment occurs when gas bubbles break at the top of the fluidized bed and
throw particles up into the freeboard region above the bed surface. At low gas
velocities, these particles quickly fall back into the bed and are retained, but as
the fluidizing velocity is increased, more and more particles are transported to
greater heights above the bed surface and there exists a particle density gradient
extending some distance above the surface. For sufficiently tall freeboards, there
will be a certain height at which the density gradient eventually falls to zero, and
above this height, the entrainment flux will be constant. This height is called the
transport disengagement height (TDH). If the bed solids have a wide size distribu-
tion and the gas velocity in the freeboard exceeds the terminal fall velocity of the
smaller ones, then these will be carried out of the system or elutriated.
Entrainment from fluidized beds is affected by changing pressure and tempera-
ture. An increase in the operating pressure increases the carrying capacity of the gas
and increases the amount of solids carried over [32,33]. Chan and Knowlton [32]
also found that the TDH increased linearly with pressure in the range 1–30 atm.
Findlay and Knowlton [20] studied the effect of increasing temperature on
entrainment. They investigated temperatures in the range of ambient to 1033 K
while maintaining the system pressure constant; thus, the dominant effect was the
increase in gas viscosity. The increased gas viscosity decreased the terminal fall
velocity and increased the rate of entrainment for a given fluidizing velocity.
For the discharge point exceeding TDH, Geldart [11] recommended various
elutriation rate constants for particle size fraction d pi. The Zenz–Weil [34] equation
is recommended for particles of diameter d p ⬍ 100 µm and superficial gas veloci-
ties u 0 ⬍ 1.2 m/s when the entire bed is potentially entrainable (even the largest
particles have a terminal velocity u t ⬍ u 0). Some of the applicable materials include
cracking catalyst, coal char, and other low-density solids:
冢冣
B
K*i ∞ u 20
⫽A (21)
(µ gu 0) gd pi ρ 2p
where
A ⫽ 1.26 ⫻ 107 and B ⫽ 1.88 when [(u 20 /(gd pi ρ 2ρ) ⬍ 3 ⫻ 10⫺4

A ⫽ 4.31 ⫻ 104 and B ⫽ 1.18 when [(u 20 /(gd pi ρ 2ρ) ⬎ 3 ⫻ 10⫺4
Geldart [11] proposed that
K*i ∞
(ρ gu 0)
⫽ A′ exp
冢冣
⫺B′u t
u0
(22)
where
A′ ⫽ 23.7 and B′ ⫽ 5.4 for higher velocities and coarser particles

A′ ⫽ 31.4 and B′ ⫽ 4.27 for beds consisting largely of 1-mm solids
A′ ⫽ 49.1 and B′ ⫽ 4 for 2.5-mm coarse particles in the bed
It is clear that the elutriation rate constants will increase for increases in gas viscos-
ity and gas density according to Eqs. (21) and (22).
Also, the elutriation rate will increase for a decrease in the particle terminal
velocity, u t, according to Eq. (22). Increasing the temperature will cause a reduction
in the terminal velocity for particles in the Stokes region (small particles) and
an increase for those in Newton region (large particles). Terminal velocities are
unaffected by the gas density in the Stokes region (small particles), slightly in the
transition region, and in the Newton region (large particles) according to (1/ρ g)0.5.
Hence, as the gas pressure is increased at constant gas velocity, the size of the
particles carried over will increase slightly.
Effect of Hydrodynamics on Reaction Conversion
Because the conversion of fluidized-bed chemical reactors depends on the contact

of solids (either catalyst or reacting) with reactant gases, it is advantageous to be
able to improve the amount of feed gas contacting the solids. This contacting can
be improved by forcing more feed gas to flow directly into the dense phase (i.e.,
increasing q D relative to q B) and to keep the bubbles, which do form, small (im-
proved mass transfer between dilute and dense phases). Because higher pressures
increase gas–solid contacting for fine-particle systems, one would expect that
higher pressures would result in improved reactor conversions.
Weimer et al. [21] presented the only comparative results ever reported for a
pilot-scale tubular fixed-bed (3.8 cm inner diameter ⫻ 22 cm long) and fluidized-
bed (15 cm inner diameter ⫻ 2.7 m long) catalytic process operating at comparative
gas hourly space velocities (GHSV) and temperatures. They investigated the exo-
thermic Fischer–Tropsch synthesis of syngas at pressures of P ⫽ 3549 and 6996
kPa and temperatures between T ⫽ 613 and 663 K. The fluidizable particle size
was measured to be around d p ⫽ 100 µm.
Their results showed that for nominal pressures of P ⫽ 3549 kPa, the conver-
sion of carbon monoxide (X CO) was noticeably higher for the fixed-tube reactor.
For GHSV ⬃1000 h⫺1 and T ⫽ 623 K, X CO ⫽ 0.7 in the pilot fixed bed versus
X CO ⫽ 0.55 for the pilot fluidized bed. At nominal P ⫽ 6996 kPa, the fixed-bed
conversions were only slightly higher than those in the fluidized bed were. For
GHSV ⬃1600 h⫺1 and T ⫽ 621 K, X CO ⫽ 0.74 in the fixed bed versus X CO ⫽ 0.71
in the fluidized bed.
The better agreement between results at nominal P ⫽ 6996 kPa versus P ⫽
3549 kPa was believed due to smaller bubbles at the higher pressures. Bubbles
were reported to be d b ⬃5 cm in diameter for the P ⫽ 3549 kPa operation and to
be d b ⬍ 2 cm in diameter for the P ⫽ 6996 kPa operation. The number of gas
interchanges for bubbles traversing the bed (i.e., the number of times the bubble
gas was exchanged with the dense phase gas as bubbles rise in the bed) was calcu-
lated to be between 5 and 6 for the smaller bubbles at higher pressures versus 1
for the larger bubbles at lower pressures. The investigators believed that even better
results could have been achieved if finer particles were being fluidized (⬍100
µm).
These results indicate that the smaller bubbles resulting from higher pressures
in fine-particle systems contribute to substantial improvement in mass interchange,
allowing fixed-bed-type conversions. The scale-up of high-pressure, fine-particle
fluidized beds from laboratory data is simplified because bubble growth is limited
by hydrodynamics. Normally, fluidized-bed scale-up is complicated by the fact
that the wall for small-particle systems limits bubble growth and that bubbles grow
as the bed gets larger. Results reported in the literature indicate that the high-
pressure, fluidized-bed bubble size can be controlled by proper selection of fine-
particle size.
Nomenclature
A Constant in Eq. (21)

A′ Constant in Eq. (22)
Ar Archimedes number ⫽ d 3pρ g(ρ p ⫺ ρ g)g/µ 2g
B Constant in Eq. (21)

B′ Constant in Eq. (22)
db Bubble diameter (m)
C1 C 1 ⫽ 42.86(1 ⫺ ε mf)/φ
C2 C 2 ⫽ φε 3mf /1.75
d bmax Maximum bubble diameter (m)
df Frontal bubble diameter (m)
do Jet nozzle or distributor orifice diameter (m)
d be Equivalent bubble diameter, averaged over bed height (m)
dp Particle diameter (m)
d eff Effective particle diameter based on experimental u mf calculation (m)
d pi Diameter of particle size fraction I (m)
F wt fraction of fine particles ⬍45 µm in diameter
Fr Froude number ⫽ u 20 /gd p
f Bubble frequency (1/s)
g Gravitational force (m/s2)
h Distance up the bed axially (m)
hj Distance the jets protrude up the bed (m)
K*i ∞ Elutriation rate constant for size fraction d pi(kg/m2 s)
k Linear slope for rate of change of ε mf with temperature (l/K)
Lf Expanded bed height (m)
n Parameter used in Eq. (12)
P Pressure (Pa)
qB Volumetric flow rate of gas as bubbles (m3/s)
qD Volumetric flow rate of dense phase gas (m3/s)
q G(in) Volumetric flow rate of gas (m3/s)
R Defined by Eq. (15)
R0 Frontal radius of a bubble (m)
Re mf Particle Reynolds number ⫽ d pu mf ρ g/µ g
T Temperature (K)
T (amb) Ambient temperature (K)
t am Time available for growth (s)
te Required growth time (s)
u0 Superficial gas velocity (m/s)
u mf Minimum fluidization velocity (m/s)
ut Terminal velocity (m/s)
VB Bubble phase volume (m3)
Vj Jet phase volume (m3)
X CO Conversion of carbon monoxide
Greek
εD Dense phase voidage

ε mb Voidage at minimum bubbling
ε mf Voidage at minimum fluidization
ε mf(amb) Voidage at minimum fluidization at ambient temperature
η Amplitude of disturbance for Taylor theory [Eq. (12)]

η0 Initial amplitude of disturbance for Taylor theory [Eq. (12)]
φ Particle sphericity
λ Wavelength of disturbance for Taylor theory [Eq. (12)]
λ max Maximum wavelength of disturbance
µg Gas viscosity (kg/m s)
νp Kinematic dense phase viscosity
θ Angular position where disturbance originates
ρg Gas density (kg/m3)
ρp Particle density (kg/m3)
References
1. T. M. Knowlton, ‘‘Pressure and Temperature Effects in Fluid-Particle Systems,’’ in

Fluidization VII (O. E. Potter and D. J. Nicklin, eds.), Engineering Foundation, New
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ALAN W. WEIMER
Process Safety and Risk Management 49
Fundamentals of Process Safety

and Risk Management
Introduction
The growth of industry and, as a result, the economy are dependent on technology
advances and innovations. However, these same activities often lead to more com-
plex processes, especially in the chemical industry, which is using comparatively
severe operating conditions (temperature, pressure, flow rate, etc.), more reactive
chemicals, and exotic chemistry. These more complex processes require in-depth
analysis and knowledge of process chemistry and hazards. It is even more impor-
tant now to design the process and equipment to precise standards based on a
complete understanding of the underlying hazards, process chemistry, and the im-
pact of operating conditions. Recently, much attention has been paid to human
factors and its impact on chemical plant incidents. However, one can also say that
process knowledge and understanding is the most human factor. This is based on
the concept that inadequate knowledge, information, and understanding of the pro-
cess hazards, chemistry, and impact of operating conditions are the root cause of
many process plant incidents.
Managing safety is no easy task, but it makes bottom-line sense. There is a
direct payoff in savings on a company’s workers’ compensation insurance, whose
premiums are partly based on the number of claims paid for job injuries [1]. The
indirect benefits are far larger, for safe plants tend to be well run in general and
more productive. The recipe for safety is remarkably consistent from industry to
industry. It starts with sustained support of top management followed by imple-
mentation of appropriate programs and practices that institutionalize safety as a
culture as compared to add-on procedures. The ingraining of safety as second na-
ture in day-to-day activities requires a paradigm shift and can only be accomplished
when safety is viewed as an integral and comprehensive part of any activity as
compared to being a stand-alone or add-on activity.
Accident Process and Multiple Barrier Concept
Most chemical plant accidents follow a typical pattern. It is important to study

these patterns in order to be able to develop management systems to prevent these
accidents. Also, many accidents occur as a result of the failure of multiple systems
or ‘‘barriers.’’ In fact, it can be argued that many of these accidents may not have
occurred, had at least one of the ‘‘barriers’’ not failed. Thus, it is important to study
the concept of multiple barriers and its role in preventing process plant accidents.
50 Process Safety and Risk Management
The Accident Process
Most chemical accidents follow a three-step process, as described by Crowl and

Louvar [2]:
• Initiation: the event, which starts the accident process

• Propagation: the event, series of events, or condition which allows the accident
process to continue, or which expands the magnitude of the accident
• Termination: the event or events, which stop the accident
The following is an example of the process:
• A seal on a sulfuric acid pump leaked, requiring replacement (initiating event).

• The pump was drained and washed, but some time passed before maintenance
began (propagating event).
• An isolation valve between the pump and the sulfuric acid supply was leaking
(propagating event).
• The mechanic wore most of the required personal protective equipment, but
failed to wear rubber boots (propagating event).
• When the mechanic began to work on the pump, he was splashed on the foot
when a small amount of sulfuric acid was released, resulting in an acid burn
(terminating event—all of the acid in the pump was released).
To prevent accidents, we must modify this accident process. This can be done
by eliminating or reducing the likelihood of initiating events or propagating events,
reducing the ability of propagating events to increase the magnitude of the accident,
or by providing terminating events to interrupt the accident sequence before unac-
ceptable consequences can occur. For the example described, some corrective ac-
tions might include the following:
• Using a pump with an improved design, which would require less frequent seal
repair (reducing the likelihood of the initiating event)
• Providing a double block between the sulfuric acid supply and the pump, and
improving procedures and training to ensure timely washing of equipment and
use of protective equipment (reducing likelihood of propagating events)
• Training the mechanic to assume the pump contains sulfuric acid and to drain
it to a safe place before he begins his work (provide a safe terminating event
by safely removing the acid)
Multiple Barrier Concept (Layers of Protection)
Chemical processes traditionally rely on multiple layers of protections, or barri-

ers, between a hazardous agent and the people, environment, and property which
might be adversely impacted by an incident. This concept is illustrated in Fig. 1
FIG. 1 Typical layers of protection for a chemical process. (Based on Fig. 2.2 of Ref. 3.)
[3]. The layers of protection might include the basic process design, basic process
controls and operating procedures, critical alarms and process shutdown proce-
dures, safety interlocks, emergency equipment such as rupture disks and pressure
relief valves, physical containment systems such as catch tanks and spill con-
tainment dikes, emergency response equipment and services such as sprinkler sys-
tems and fire-fighting equipment and personnel, and personnel evacuation proce-
dures.
Multiple barriers are generally required because no barrier will be perfect—
all are subject to potential failure. An inherently safer process (discussed elsewhere
in this article) will reduce or eliminate the hazard and will require fewer or less
robust layers of protection—and, if the hazard is sufficiently small, there may be
no need for additional protective layers at all. This is highly desirable because the
layers of protection may require significant initial capital investment and ongoing
operating costs to ensure their continued effectiveness. Also, although the layers
of protection may be highly reliable and the risk of an accident may be small, it
can never be zero—there is always a possibility that all of the layers of protection
will fail simultaneously and the accident will occur.
The number and required reliability of the barriers or layers of protection must
be established through the use of the various hazard and risk analysis techniques
described in the following sections. This requires a complete understanding of the
hazards of the process and plant-hazard identification, and an understanding of the
mechanisms or scenarios by which those hazards might result in harm to people,
the environment, or property—hazard analysis or hazard evaluation.
Regulations
During the past 15 years, a number of chemical or related incidents in the petro-
chemical industry have adversely affected surrounding communities. A few of
these incidents, such as the vapor cloud explosion in Flixborough in 1974, the
liquefied petroleum gas explosion in Mexico City in 1984, the toxic material re-
lease in Bhopal in 1984, and the fire and radiation release in Chernobyl, were
reported worldwide. Both governmental agencies and trade organizations re-
sponded by developing standards and regulations to improve process safety. The
American Petroleum Institute (API) and the American Chemistry Council (ACC)
started to work with their members to develop organizational guidelines. The U.S.
Department of Labor directed the Occupational Safety and Hazard Administration
(OSHA) to develop federal standards for managing process safety.
A consensus started to emerge in 1990. Although the language, application,
and extent of each document differed, the contents and objectives were almost the
same. The API published Recommended Practice 750: Management of Process
Hazards [4] in January 1990. OSHA published the proposed federal process safety
rule [5] in July 1990. In October 1990, the ACC published its Resource Guide for
Implementing the Process Safety Management Code of Practices [6]. In addition,
the Clean Air Act Amendments of 1990 directed OSHA and the Environmental
Protection Agency (EPA) to develop process safety management regulations to
protect workers and the environment. The final OSHA rule on Process Safety Man-
agement of Hazardous Chemicals (29 CFR 1910.119) was published in the Federal
Register [7] on February 24, 1992. A matrix showing the relevance of OSHA
Process Safety Management (PSM) elements to the Center for Chemical Process
TABLE 1 Summary Comparison of OSHA Elements with CCPS Elements

CCPS 12 elements of chemical process
safety management Relevant paragraphs of OSHAs PSM rule
1. Accountability: Objectives and
Goals
2. Process Knowledge and Documenta- Process Safety Information § 1910.119 (d)
tion
3. Capital Project Review and Design Pre-Startup Safety Review § 1910.119 (i)
Procedures (for new and existing
plants, expansions, and acquisi-
tions)
Mechanical Integrity § 1910.119 (j)
4. Process Risk Management Process Hazard Analysis § 1910.119 (e)
Pre-Startup Safety Review § 1910.119 (i)
5. Management of Change Management of Change § 1910.119 (l)
6. Process and Equipment Integrity Process Hazard Analysis § 1910.119 (e)
Operating Procedures § 1910.119 (f )
Mechanical Integrity § 1910.119 (j)
7. Human Factors Process Hazard Analysis § 1910.119 (e)
Operating Procedures § 1910.119 (f )
8. Training and Performance Operating Procedures § 1910.119 (f )
Training § 1910.119 (g)
Pre-Startup Safety Review § 1910.119 (i)
Emergency Planning and Response
§ 1910.119 (n)
9. Incident Investigation Incident Investigation § 1910.119 (m)
10. Standards, Codes, and Laws
11. Audits and Corrective Actions Compliance Audits § 1910.119 (o)
12. Enhancement of Process Safety
Knowledge
Safety’s (CCPS) chemical process safety management elements is given in Table 1.

EPA published the Risk Management Program in June 1996.
The international chemical and petroleum community has also been addressing
process safety management through regulations and recommended practices. The
Norwegian Petroleum Directorate issued rules [8] in 1981 requiring quantita-
tive hazard analyses for offshore petroleum operations. In response to the 1976
chemical dioxin release in Seveso, Italy, a European Directive [9] (commonly
called the Seveso Directive) on process safety management was issued in 1982.
More recently, the British government has issued process safety management
regulations [10] for North Sea petroleum operations, following the recommenda-
tions of the widely distributed Cullen Report, which investigated the 1985 Piper
Alpha offshore platform tragedy. Outside of Europe, the World Bank [11] has
provided process safety management guidance for third-world projects. Similarly,
the International Labor Office in Geneva has issued hazard analysis recommenda-
tions [12].
The Process Safety Management Program
The 14 elements of the OSHA Process Safety Management (PSM) regulation (29
CFR 1910.119) were published in the Federal Register on February 24, 1992 [7].
The objective of the regulation is to prevent or minimize the consequences of
catastrophic releases of toxic, reactive, flammable, or explosive chemicals. The
regulation requires a comprehensive management program: a holistic approach that
integrates technologies, procedures, and management practices.
The process safety management regulation applies to processes that involve
certain specified chemicals at or above threshold quantities, processes that involve
flammable liquids or gases on-site in one location, in quantities of 10,000 lbs, or
more (subject to few exceptions), and processes that involve the manufacture of
explosives and pyrotechnics. Hydrocarbon fuels, which may be excluded if used
solely as a fuel, are included if the fuel is part of a process covered by this regula-
tion. In addition, the regulation does not apply to retail facilities, oil or gas well
drilling or servicing operations, or normally unoccupied remote facilities.
The process safety management regulation requires a systems approach for
managing safety. Segments of the hazardous chemicals industry have for sometime
practiced some or all of the required programs. The promulgation of the regulation
formalized the requirements and established a minimum criterion. This is both
good and bad. The regulation now requires everyone to establish the management
systems and apply the technologies needed to comply with the regulation. How-
ever, because of the same reason, there is a tendency to look for ‘‘paper compli-
ance’’ as compared to making real improvements in safety programs and technolo-
gies.
The Risk Management Program
In 1996, the EPA promulgated the regulation for Risk Management Programs for
Chemical Accident Release Prevention (40 CFR 68). This federal regulation was
mandated by section 112(r) of the Clean Air Act Amendments of 1990. The reg-
ulation requires regulated facilities to develop and implement appropriate risk
management programs to minimize the frequency and severity of chemical plant
accidents. In keeping with regulatory trends, EPA required a performance-based
approach toward compliance with the risk management program regulation.
The EPA regulation also requires regulated facilities to develop a Risk Manage-
ment Plan (RMP). The RMP includes a description of the hazard assessment, pre-
vention program, and the emergency response program. Facilities submit the RMP
to the EPA and, subsequently, it is made available to governmental agencies, the
state emergency response commission, the local emergency planning committees,
and communicated to the public.
The risk management program regulation defines the worst-case release as the
release of the largest quantity of a regulated substance from a vessel or process
line failure, including administrative controls and passive mitigation that limit the
total quantity involved or release rate. For gases, the worst-case release scenario
assumes the quantity is released in 10 min. For liquids, the scenario assumes an
instantaneous spill and that the release rate to the air is the volatilization rate from
a pool 1 cm deep unless passive mitigation systems contain the substance in a
smaller area. For flammables, the scenario assumes an instantaneous release and
a vapor cloud explosion using a 10% yield factor. For alternative scenarios (note:
EPA used the term alternative scenario as compared to the term more-likely sce-
nario used earlier in the proposed regulation), facilities may take credit for both
passive and active mitigation systems.
Appendix A of the final regulation lists endpoints for toxic substances to be
used in worst-case and alternative scenario assessment. The toxic endpoints are
based on ERPG-2 (Emergency Response Planning Guidelines—Level 2) or level
of concern data compiled by the EPA. The flammable endpoints represent vapor
cloud explosion distances based on overpressure of 1 psi or radiant heat distances
based on exposure to 5 kW/m2 for 40 s.
Hazard and Risk

Hazard
A hazard is a physical or chemical characteristic of a material or process which

has the potential to cause harm to people, the environment, or property. A hazard
can be a characteristic property of a material, it can be a result of the conditions
of use of the material, or it can be the result of an interaction among two or more
materials or sources of energy. Some examples of hazards include the following:
• Chlorine is a toxic gas.

• Gasoline is a flammable liquid.
• Sulfuric acid is corrosive.
• A cylinder containing compressed air contains significant potential energy from
the pressurized gas.
• A mixture of a vinyl monomer and a peroxide initiator has significant potential
chemical energy of reaction.
• A 600 psig steam pipe is at elevated temperature and also contains a lot of
energy from the pressure of the steam.
These hazards cannot be changed; they are intrinsic to the material or its conditions
of use. The only way to eliminate or reduce hazards is to change the material or
conditions of use. Although it is generally preferable to eliminate or reduce hazards
(see later discussion on inherent safety), this is not always possible. The properties
of a material or system, which create a hazard, may be the same as the properties,
which make the material or system useful. A highly reactive monomer, when poly-
merized under controlled conditions, will produce a valuable product. However,
if the polymerization is not controlled, the result could be overpressurization of a
reactor and a possible explosion. Therefore, it is often necessary to manage and
control the hazards of a process and plant. To do this, you must first identify and
understand the hazards—hazard identification. Then, you must understand how
the harm to people, the environment, or property can be realized from the hazard-
ous material or condition—hazard evaluation or hazard analysis.
Risk
Risk is a measure of human injury, environmental damage, or property loss ex-

pressed in terms of both the likelihood of the incident and the magnitude of the
injury, damage, or loss. Risk can be considered to be a function of the potential
incident occurrence, incident consequence, and incident likelihood:
Risk ⫽ f (incident, consequence, likelihood)
There can be many different kinds of risk associated with a chemical process or
plant; for example, safety risk to plant workers, health risk to workers, health risk
to neighbors, risk of various kinds of environmental damage, risk of damage to
the plant or other property, risk of producing product which does not meet specifi-
cations and cannot be sold, risk of loss of business due to a plant outage, business
risk that the product cannot be sold, and others. All of these risks must be under-
stood and managed to successfully operate a profitable plant and business over the
long term.
There are many different measures for each of the risks associated with a chem-
ical manufacturing facility. For example, some measures of risk to employees in
a plant include the following:
• Average risk of fatality from a process accident to an employee in the plant

• Maximum risk of fatality from a process accident to the employee at greatest
risk
• Average risk to a specific employee in a plant over the course of a normal
working day as he does various specific jobs
• An estimate of the distribution of likelihood of accidents of various size (im-
pacting one employee, two employees, three employees, etc.)
• Average risk of injury to an employee
The CCPS Guidelines for Chemical Process Quantitative Risk Analysis [13] de-
scribes many different measures of safety risk which might be used in understand-
ing the risk of a chemical plant and also provides quantitative methodologies for
calculation.
Hazard Identification and Hazard Evaluation

Objective of Hazard Identification and Evaluation
The objective of hazard identification is to fully understand the hazards of a chemi-

cal process, including the hazards associated with the following:
• Materials; for example, toxicity, reactivity

• Process conditions; for example, high temperature, high pressure
• Potential interactions among one or more materials; for example, chemical reac-
tion, decomposition, corrosion
A full understanding of all hazards of a process is the essential first step in eliminat-
ing, minimizing, or managing those hazards.
The objective of hazard evaluation is the identification of specific mechanisms
by which the potential harm associated with the process hazards can be realized.
Hazard evaluation techniques can also include the identification of protective mea-
sures which have been incorporated into the process design to manage the hazards,
qualitative assessment of the risk of the specific incident scenarios identified, and
evaluation of the adequacy of existing protective features or recommendation for
additional safeguards.
Hazard Identification
Hazard identification is based on a complete knowledge of the properties of the

materials being handled and the chemical and physical processes used. Hazards
of materials can be identified from literature searches, publications such as Sax’s
Dangerous Properties of Industrial Materials [14], and libraries of Material Safety
Data Sheets. The best source of hazard information for raw materials is often the
material supplier. Bretherick’s Handbook of Reactive Chemical Hazards [15] pro-
vides a comprehensive summary of reactive chemical hazard literature. Checklists
are a good mechanism for identifying process hazards (checklists as a hazard evalu-
ation technique will be discussed later). Two specific tools for hazard identification,
which are particularly useful in understanding chemical reaction hazards, are dis-
cussed in more detail in the following sections.
Interaction Matrix
The interaction matrix (Fig. 2) is intended to identify chemical reaction hazards

among materials and energy sources in a chemical process. This tool is particularly
useful early in the development of a new chemical process. To create an interaction
matrix, list all of the materials, materials of construction, likely contaminants, po-
tential sources of energy, process utilities (such as steam, water, nitrogen, com-
pressed air, ethylene glycol coolant, and heat transfer oil), and other relevant pa-
rameters along each axis of the matrix. It is a good idea to also include ‘‘people’’
on one of the axes, to prompt questions about toxicity and other adverse impacts
of materials on people. Then, ask what happens for each interaction where the
matrix columns and rows intersect. The matrix should go beyond a simple yes–
no answer, but rather should provide some detailed information on the nature of
the interactions identified. Often an interaction matrix will generate more questions
than answers, particularly early in development. In this case, it may be appropriate
to recommend a literature search or laboratory experiments to understand potential
interactions.
FIG. 2 Example interaction matrix.
Chemistry Hazard Analysis
The Chemistry Hazard Analysis (CHA) is derived from the Hazard and Operability
(HAZOP) study methodology. The thought process of a HAZOP study can be
applied at any stage in process development. The CHA is a HAZOP applied to a
chemical reaction, without the detailed plant design information required for a
traditional HAZOP study. For the CHA, the chemist or engineer usually assumes
that the deviation identified by the application of the guide word to the chemical
reaction does occur for some reason, not developing specific causes, and investi-
gates the consequences. If the consequences are known, the designer should deter-
mine if they represent a hazard which must be understood and managed as a part
of the process development, and document this information for future action or
reference. In many cases, early in process development, the consequences may not
be known, and additional research or experiments may be needed.
Hazard Evaluation: Selection of Procedure
A number of different hazard evaluation techniques are in common use in the

chemical industry, as listed in Table 2. Some techniques, particularly those based
on logic models, require more detailed plant design information and it may not
be possible to apply them early in process development. Table 3 provides some
TABLE 2 Process Hazard Analysis Tools Commonly Used in the Chemical Process Industries
Category Process Hazard Analysis Tool Description and Comments
Brainstorming tech- Safety review Relatively unstructured brainstorming
niques Preliminary hazard analysis techniques to identify hazards and po-
What If tential accident scenarios.
Hazard and Operability Study (HAZOP) A structured analysis procedure that fo-
Failure Mode and Effect Analysis cuses brainstorming activities, includ-
(FMEA) ing use of a specific set of guide words
or knowledge and checklists of known
equipment failure modes.
Checklist techniques Checklist Predefined checklists based on previ-
What If/checklist ous experience compare a design to
specific standards or good practice.
When combined with What If analysis,
the checklists are used to prompt brain-
storming activities.
Risk-ranking techniques Relative ranking A general category that includes a
large number of quantitative and semi-
quantitative techniques which use
checklists or equations based on mate-
rial properties, quantities, and handling
conditions to numerically rank risk. Ex-
amples include the Dow Fire and Ex-
plosion Index and the Dow Chemical
Exposure Index.
Logic model techniques Fault-tree analysis Logic models which identify specific
Event-tree analysis causes combinations of events which
lead to a potential accident scenario.
These techniques require much detailed
design information and usually focus
on analyzing a few specific accident
scenarios in detail. These techniques
can be quantified and are important
tools in quantitative risk analysis
guidance on how the various techniques have commonly been applied through the
life cycle of a chemical process.
What-If Analysis
What-If Analysis is a brainstorming technique in which a team with expertise on

the process asks ‘‘what-if ’’ questions about the process to identify potential haz-
ards or incident scenarios. The Preliminary Hazard Analysis and Safety Review
techniques are forms of What-If Analysis. In a What-If Analysis, a team of experts
on the process and plant meet in a free brainstorming session to ask ‘‘what-if ’’
questions to identify what can go wrong. The technique is very flexible and can
60
TABLE 3 Process Hazard Evaluation Techniques
Process Hazard Analysis Technique

Failure Hazard
Mode and and
Preliminary Effect Operability Fault- Event-
Chemical Process Safety Relative Hazard What-If/ Analysis Analysis Tree Tree
Life-Cycle Stage Review Checklist Ranking Analysis What-If Checklist (FMEA) (HAZOP) Analysis Analysis
Research and development 䊊䊊䊉䊉䊉䊊䊊䊊䊊䊊
Conceptual design 䊊䊉䊉䊉䊉䊉䊊䊊䊊䊊
Detailed engineering 䊊䊉䊊䊉䊉䊉䊉䊉䊉䊉
Construction 䊉䊉䊊䊊䊉䊉䊊䊊䊊䊊
Start-up 䊉䊉䊊䊊䊉䊉䊊䊊䊊䊊
Routine operation, modifi- 䊉䊉䊉䊉䊉䊉䊉䊉䊉䊉
cations, and expansions
Decommissioning 䊉䊉䊊䊊䊉䊉䊊䊊䊊䊊
Demolition 䊉䊉䊊䊊䊉䊉䊊䊊䊊䊊
Note.—䊉: PHA technique commonly used; 䊊: PHA technique rarely used or not appropriate.
Source: Based on Ref. 5.
Process Safety and Risk Management
TABLE 4 Example of the Results of a What-If Analysis for a Batch Process

Hazard or
What-If...? consequence Safeguards Recommendations
1. Reactant feed 1. Heat generation 1. High reactant 1. Establish preven-
rate is too high? rate exceeds heat flow rate inter- tive maintenance
removal capabil- lock shuts down and testing pro-
ity, increased tem- feed. High reactor gram for flow
perature, poten- temperature in- and temperature
tial runaway terlock shuts interlocks.
reaction. down feed. Rup-
ture disk sized ad-
equately to pro-
tect reactor for
maximum feed
rate with no cool-
ing.
2. Reactor tempera- 2. Reaction may 2. Low reactor tem- 2. Evaluate rupture
ture is too low? stall, resulting in perature alarm disk size relative
a buildup of re- warns operator. to potential pool-
actants. This pool ing of unreacted
of unreacted mate- material. Based
rial has signifi- on result, deter-
cant potential en- mine if additional
ergy, possible protection is
runaway reaction needed.
if temperature is
subsequently in-
creased.
be applied at any stage in the process life cycle. The unstructured nature of What-
If Analysis can be both an advantage and a disadvantage. With an experienced and
knowledgeable team, the technique can be powerful. The discussion and interaction
among team members in the meeting can enhance the identification of hazards.
However, the unstructured nature may result in an incomplete analysis by an inex-
perienced team. Table 4 is an example of the results of a What-If Analysis. What-
If is often combined with a checklist to ensure that a minimum set of ‘‘What-If’’
questions are covered by the review team.
Checklist Analysis
A checklist is a list of items used to verify that a plant or process is designed and
operated consistently with a predetermined set of good practices defined by the
checklist. A checklist is often used to confirm that a plant complies with codes,
standards, or regulations. Checklists vary from general lists of questions describing
common chemical hazards and processing concerns to detailed lists of specific
requirements of a standard. Many checklists are simple, requiring only ‘‘yes, no,
not applicable’’ answers. The use of checklist analysis depends on the availability
of suitable checklists for the plant being reviewed. Good checklists are most likely
to be available for common types of installation, such as flammable-solvent storage
facilities, and are unlikely to be available for unique process operations. Checklist
completeness depends on the experience of the checklist authors. The output of a
checklist analysis is a list of responses to the checklist questions, with areas of
noncompliance highlighted and recommendations for bringing the facility into
compliance.
Combining a What-If Analysis with a checklist can be a very effective hazard
identification and evaluation technique. The What-If allows creative brainstorming
of a team to identify hazards, and the checklist ensures that the team considers a
specified list of hazards based on prior experience, addressing the concern about
completeness of the What-If analysis.
Hazard and Operability Study
A Hazard and Operability Study (HAZOP) is a guide word hazard evaluation tech-
nique normally done by a review team. HAZOP begins with the premise that the
process is safe if operated, as intended, and the team must agree that this is true.
Incidents are assumed to result from deviation from intended operation. Guide
words are used in conjunction with the process operating parameters to identify
potential deviations, and the review team determines the consequences of those
deviations.
A Hazard and Operability Study is best applied when specific process and plant
information is available (e.g., a detailed plant design or an operating plant). To
do a HAZOP, the process is first divided into sections, or nodes, which are analyzed
individually. A node might be a transfer line from one vessel to another, a piece
of process equipment such as a reactor or heat exchanger, or a step in a batch
process. The team states the intended operation of each process node, including
values of the process parameters—the process intention. The team then applies
guide words to the parameters to identify potential deviations from intended opera-
tion. The following are basic guide words:
• No
• More
• Less
• Part Of
• Reverse
• As Well As
• Other
As an example, the guide word ‘‘less’’ can be combined with a specified reactor
temperature intention to arrive at the deviation ‘‘less (lower) reactor temperature.’’
Once a deviation has been identified, the team determines as many potential causes
of the deviation as possible. For the deviation ‘‘less reactor temperature,’’ causes
might include a cooling water control valve stuck open, incorrect temperature set
point, and others. The team determines the consequences of each deviation, cause
combination, and existing safeguards. It then qualitatively judges the effectiveness

of the safeguards to determine if they are adequate. A semiquantitative risk-ranking
system is often used to aid the team in evaluating the significance of the hazards
identified. If the existing safeguards are judged to be inadequate, the team should
recommend appropriate action to mitigate the potential hazard. The team continues
to apply the guide words to each node until no additional deviations can be identi-
fied. These steps are repeated for each process node, until the entire process has
been reviewed. Table 5 shows a part of the output of a typical HAZOP study.
Fault-Tree Analysis
A fault tree is a logic model which identifies the multiple ways in which equipment
and human failures in a system can combine to cause an undesired event (the ‘‘Top
Event’’). The analyst begins with a specific undesired event and develops a model
using Boolean ‘‘AND’’ and ‘‘OR’’ logic gates to identify the immediate causes.
These immediate causes can then be further developed to identify their causes,
also using Boolean logic gates. The development of the tree continues until it
reaches a level of resolution judged to be adequate for understanding potential
incident sequences and identifying system improvements. These events are not
further developed and are called basic events. Normally, basic events are at the
level of failure of individual plant components (e.g., a shutoff valve stuck in the
open position, a pump failure to run, a pressure sensor failing to detect high pres-
sure). Human error can be incorporated into a fault tree by including specific opera-
tor actions (e.g., opening the wrong manual valve) or errors (e.g., failure to act in
response to a high temperature alarm). Figure 3 is an example of the top levels
of a fault tree for a fire.
A fault tree can be solved using Boolean algebra techniques to identify specific
combinations of individual equipment failures and human errors, which can cause
the undesired top event. These combinations of failures and errors describe specific
potential incident scenarios and are called minimal cut sets. The cut sets can be
used to identify areas where the system can be improved. Fault trees can also be
quantified by assigning failure rate and probability data to the basic events. These
data can be mathematically manipulated to estimate the likelihood of the top event
and to understand the relative contribution of individual basic events and cut sets
to the total probability of failure.
Event-Tree Analysis
An event tree is a graphical logic model which shows the possible outcomes
resulting from an initiating event. An event tree describes the response of a sys-
tem to a disturbance created by the initiating event. For example, Fig. 4 shows an
event tree for the sulfuric acid splash incident used to describe the accident pro-
cess. An event tree describes a number of potential outcomes from a single initiat-
ing event. These outcomes may vary in severity, and the event tree is useful in
understanding the full range of possible outcomes that can result from a single
system failure. Event trees are very useful in understanding the effectiveness of
64
TABLE 5 Example of Partial Results of a HAZOP
Deviation Causes Consequences Safeguards Recommendations

1. MORE than 160 lbs/h A. Wrong set point (too A. Reactor R-310 tempera- A. 1. High flow alarm on A. Confirm that operator
Raw Material A flow high) on FIC-301-01 ture increases, heat bal- FIC-301-01 warns opera- training includes proper
B. FIC-301-01 control value ance indicates there is no tors. response to FIC-301-01
stuck open potential for runaway re- 2. High temperature and TAH-310-05 high
C. FIC-301-01 flow sensor action, even for maxi- alarm TAH-310-05 on Re- alarms.
miscalibrated—reads low mum possible flow rate; actor R-310 warns oper-
product will not meet ator.
specifications if R-310 B. Same as A.
temperature increases C. A-2 only applies. A-1
above 90°C. will not provide an alarm
B. Same as A. because the flow sensor is
C. Same as A. miscalibrated. Plant expe-
rience indicates this is not
likely.
Note.—Intention: Feed 150–160 lbs./h of 42–44% aqueous Raw Material A solution from Feed Tank F-101 using Pump P-110 through line 10436 and flow controller FIC-
301-01 to Reactor R-310. Raw Material A solution temperature is 20–35°C. While feeding, Reactor R-310 agitator is running at 50 rpm.
FIG. 3 Top levels of a fault tree for a fire.
the multiple layers of protection, which are often present in a chemical process.
Each independent layer of protection is a branch point in the event tree, with the
branches corresponding to the success or failure of the layer of protection. An
event tree, like a fault tree, can also be quantified by estimating a frequency
for the initiating event and the probabilities of success and failure at each branch
point in the event tree. Quantitative event tree analysis is often combined with
fault-tree analysis: Fault trees are used to quantify the frequency of the initiating
event and the probability of failure of the protective systems at the event-tree
branch points.
Failure Mode and Effect Analysis
A Failure Mode and Effect Analysis (FMEA) lists the known failure modes of
specific pieces of equipment in a plant and determines the impact of those failures
on the plant. FMEA and HAZOP are similar; the main difference is the starting
point for identifying potential hazardous incident scenarios. HAZOP starts by pos-
tulating a deviation in the value of a process parameter (e.g., more flow) and asking
what kind of equipment failures or operating errors might have caused that devia-
FIG. 4 Example event tree.
tion and what the process impact will be. FMEA starts by postulating a known
equipment failure mode (e.g., control valve stuck open) and asks what impact this
failure will have on the operation of the process.
The FMEA starts with a functional description of each piece of process equip-
ment and identifies ways in which that piece of equipment might fail to perform
as designed. A good understanding of the equipment and potential failure modes
is required. The FMEA determines how the process will respond to the potential
equipment failure, determines if a potentially hazardous incident will result, identi-
fies existing safeguards, evaluates their effectiveness, and develops recommenda-
tions for action where appropriate. These steps are very similar to the correspond-
ing step in a HAZOP study. Table 6 shows a part of the output from a typical
FMEA study.
Risk-Ranking Techniques
Risk-ranking techniques such as the Dow Fire and Explosion Index [16] and the
Dow Chemical Exposure Index [17] develop a numerical risk-ranking index based
on various process characteristics such as material properties, chemical reactions,
unit operations, operating conditions, and other factors. These risk indices provide
a relative ranking of specific types of process hazards (e.g., fire and explosion
hazards) and are useful for comparing alternate process or plant designs (including
location and siting), understanding the parts of a plant or process which are the
major sources of risk, and prioritizing other hazard evaluation and risk management
activities.
TABLE 6 Example of Partial Results of a Failure Mode and Effects Analysis
Item and Description Failure mode Effects Safeguards Recommendations

1. Cooling Water Control A. Valve stuck in closed A. Unable to increase flow A. High temperature inter- A. Confirm that there is no
Valve FIC-301-10. Pneu- position of cooling water to reac- lock TAH-310-08 on Re- buildup of unreacted ma-
matically operated valve, tor to control tempera- actor R-310 closes raw terial and stopping feed
fails closed on air supply ture of batch during exo- material feed valve. will stop reaction. Re-
failure thermic reaction. view maintenance proce-
Possible uncontrolled re- dures and make sure
action generating high Valve FIC-301-10 is reg-
temperature and pressure. ularly inspected and
tested.
B. Air failure to FIC-301- B. Valve will open, putting B. Full cooling is sufficient
10 full cooling on the reac- to control temperature at
tor. maximum raw material
feed rate.
67
Summary of Hazard Identification and Evaluation
This section has briefly described a number of commonly used hazard identification
and evaluation tools. Most of these tools are best used in a multidisciplinary team
environment, providing a wide variety of plant and process experience and interac-
tive discussion to understand the process and identify potential hazards and inci-
dent scenarios. CCPS [18] and Wells [19] provide more information on the applica-
tion of these and other hazard evaluation tools in the chemical industry.
Consequence Analysis
As mentioned earlier, risk is defined as a function of incident occurrence, fre-

quency, and consequence. Consequence analysis is the quantitative estimation of
the consequence of a chemical process incident—an estimate of the magnitude of
the potential harm to people, the environment, or property. Because there is a
wide range of potentially harmful impacts of chemical process incidents, there is
a number of different tools which may be useful in analyzing these impacts. In
this discussion, the consequence analysis tools described will be limited to those
commonly used to estimate the potential for injury or fatality to people as an imme-
diate result of exposure to harmful materials or energy. However, it is recognized
that there is a wide variety of other potential consequences of incidents and a
correspondingly wide variety of tools used to understand these consequences.
Consequence models can be quite complex and can only be described in general
terms in this discussion. A number of publications by the Center for Chemical
Process Safety [20–24] describe specific types of consequence analysis models in
detail. Les [25] also provides a detailed description of incident consequence mod-
els. There are also a number of public domain and proprietary commercial com-
puter-modeling systems available for chemical release consequence analysis.
Source Models
Source models quantitatively estimate the magnitude, rate, duration, physical state
(solid, liquid, gas, or a combination), and temperature or other physical condition
of a chemical release based on the physical and chemical parameters associated
with a particular release scenario.
Most source models are well developed in chemical engineering theory and
are essentially the same as the models used for similar material flow scenarios
used to design plant equipment. These include single-phase and multiphase flow
models for flow-through holes, orifices, and pipes, which are readily adapted to
describe flow from a leaking pipe or vessel. Two-phase flashing flow models are
based on technology developed by the Design Institute for Emergency Relief Sys-
tems (DIERS) [26]. Two-phase or flashing jet release models must also consider
the formation of fine aerosols in the discharge and the potential for the small drops
to remain suspended in the atmosphere rather than ‘‘raining out’’ into an evaporat-
ing pool on the ground. For a discharge of material from a reactive system, the
models required to fully understand the system may be quite complex and data
from reaction calorimetry tests may be required.
If a release is wholly or partially in the form of a liquid, it will form a pool
on the ground. The evaporation of vapor from this pool is another potential source
term for atmospheric dispersion models, which estimate the downwind concentra-
tion of the vapor. The first step in estimating evaporation from a liquid pool is to
estimate the size of the pool. Pool size models consider the momentum of the
liquid stream entering the pool, gravity spreading resulting from the depth of the
pool, and the liquid physical properties (e.g., viscosity, surface tension, and surface
wetting properties). Physical constraints such as dikes and containment systems
may also determine the size of a pool of spilled liquid.
There are three major pool evaporation situations, which are typically modeled:
boiling liquid pools, volatile liquid pools, and relatively nonvolatile liquid pools.
• Boiling liquid pools occur when the pool liquid boils at a temperature below
that of its surroundings (the ground and atmosphere). In this case, vapor genera-
tion is controlled by heat transfer into the liquid pool, both from the ground
and from the surrounding atmosphere. The vapor release rate is determined from
an estimate of the total heat transfer into the pool and the heat of vaporization
of the liquid.
• Volatile liquid pools exert a significant vapor pressure but are at a temperature
below the liquid boiling point. Evaporation models for volatile liquid pools
consider both heat transfer into the pool and mass transfer rates into the atmo-
sphere from the pool surface.
• The evaporation of relatively nonvolatile liquid pools is primarily determined
by mass transfer at the surface of the pool. Because the evaporation rate is low,
the pool temperature will be essentially the same as the temperature of the
surroundings after any initial temperature differences equilibrate. Evaporation
models are based on standard methodologies for estimating convective mass
transfer from a liquid into a gas.
Vapor Cloud Dispersion
Vapor cloud dispersion models estimate the area covered by the vapor cloud from
a chemical release as it disperses in the atmosphere, and they estimate the vapor
concentrations at specific locations in the cloud. Some of the data required for a
vapor cloud dispersion model include the following:
• Characteristics of the release, including rate, total quantity released, location of

the release
• Characteristics of the release (phase, direction, velocity, composition, tempera-
ture, pressure)
• Atmospheric conditions, including wind speed, atmospheric stability, tempera-

ture, pressure
• Characteristics of the surface, including surface roughness
Some of the complex vapor cloud dispersion models may require additional infor-
mation to characterize the release, the atmospheric conditions, and surface condi-
tions.
Vapor cloud dispersion models consider three typical types of behavior:
• Neutrally buoyant gases (having a density close to the density of air)

• Positively buoyant gases (having a lower density than air)
• Dense or heavy (negatively buoyant) gases
Two major types of releases must also be considered:
• Instantaneous (puff releases)

• Continuous releases (plumes)
The CCPS [20] describes vapor cloud models in detail, including all of the
major types of dispersion models and release types. The CCPS [22] provides a
more condensed summary of some of these models. The output of these models
describes the concentration of the released material in both time and space as the
vapor cloud travels downwind.
Fires
Incident consequence analysis may require consideration of one or more of several

different types of fire:
• Pool fire: a burning pool of a flammable or combustible liquid

• Jet fires: burning of a flowing jet of flammable liquid or gas, usually from a
pipe or vessel
• Flash fire: nonexplosive combustion of a flammable mixture of a combustible
vapor in air
Pool Fire
The primary mechanism of damage from a pool fire is thermal radiation from the
flame. Pool fire models estimate the thermal effects based on the properties of the
material burning in the pool, the geometry of the pool, atmospheric characteristics,
and geometry of the fire relative to the receiving source. Pool fire models are
well developed. They are based on empirically determined characteristics such as
burning rate, flame height, surface emissive power, and atmospheric transmissivity,
all of which are well established in the literature. Pool fire models provide an
estimate of the thermal radiation at locations of interest surrounding the fire.
Jet Fire
Many jet fire models are based on models used for the design of flare systems.
As for pool fires, the damage from a jet fire results primarily from thermal radiation
from the fire. Jet fire models require an understanding of the characteristics of the
jet (discharge rate and velocity, material burning properties) and, like pool fires,
characteristics of the atmosphere. Jet fire models are primarily empirical but are
derived from much data and experience. The models produce an estimate of the
thermal radiation at locations surrounding the jet fire.
Flash Fire
A flash fire results from the ignition of a cloud of flammable gas (a cloud containing
a flammable material at a concentration between its lower and upper explosive
limits in air). Such a cloud can explode under the proper conditions (size and
degree of confinement), resulting in a vapor cloud explosion. If the conditions
required for a vapor cloud explosion are not present, the cloud may still ignite and
burn. In this case, the burning cloud will not generate pressure and an explosion,
but the flash fire is still capable of causing significant damage. The primary hazard
is from direct contact with the flame and from thermal radiation, which is normally
for a brief time of a few tenths of a second. Flash fires are normally modeled by
determining the dimensions of the flammable cloud using vapor dispersion models
and estimating the thermal radiation resulting from combustion of the cloud.
Explosions
Chemical incident consequence analysis may need to consider four types of explo-
sion:
• Physical explosions: the failure of a vessel containing material under pressure

without chemical reaction (e.g., due to a vessel defect or excess pressure in the
vessel).
• Vapor cloud explosions: explosion of a cloud of flammable vapor dispersed in
the atmosphere.
• Confined explosions: explosion resulting from a rapid chemical reaction gener-
ating high temperature and pressure inside a confined space such as a vessel
or a building.
• Boiling liquid expanding vapor explosions (BLEVE): the catastrophic failure
of a vessel containing a superheated liquid. If the liquid is flammable, ignition
may result in a fireball.
The CCPS [20,22] describes commonly used explosion models in detail.

Physical Explosions
Physical explosion models generally estimate the amount of energy which would
be released by the sudden expansion of the material contained in a vessel from its
initial temperature, pressure, and volume to atmospheric pressure. This estimated
energy is then converted to an equivalent amount of TNT. A number of correlations
of explosion pressure as a function of distance from a TNT explosion have been
published, and these can be used to estimate damage. It may also be necessary to
consider the potential impact of the vessel fragments, which result from a vessel
explosion. Empirical models to estimate the number and size of fragments, their
travel distance, and energy are available.
Vapor Cloud Explosions
If ignited, a flammable vapor cloud can burn as a flash fire, or, if the flame speed
accelerates sufficiently, it can produce significant blast pressure from a vapor cloud
explosion. A number of factors have been found to be important in determining
whether a vapor cloud explosion occurs when a flammable vapor cloud is ignited.
These include the following:
• Turbulence in the vapor cloud. This turbulence may arise from the energy from
the release of the fuel itself (from a jet or catastrophic loss of containment) or
from the interaction of the cloud with its surroundings during the combustion
process.
• Partial confinement of the vapor cloud as a result of obstacles, structures, or
other factors, which could cause local partial confinement. The explosive com-
bustion in the locally confined cloud can propagate into the rest of the cloud.
• Mass of the cloud. Experimental studies have demonstrated that there is a mini-
mum mass of flammable material required to transition to a vapor cloud explo-
sion. The CCPS [21] reports studies indicating that this minimum mass is in
the range of 1 to 15 tons for typical hydrocarbons.
• Combustion properties of the fuel. Materials with a high fundamental burning
velocity such as ethylene oxide and ethylene are reported to be more readily
inclined to propagate to a vapor cloud explosion.
Vapor cloud explosions are modeled using three types of model:
• TNT Equivalency Models. The total energy available from the combustion is
estimated from the mass of fuel in the cloud and the heat of combustion of the
fuel. This combustion energy is then converted to an equivalent mass of TNT
and reduced by an ‘‘explosion efficiency’’ factor, which is empirically esti-
mated. The explosion overpressure and other characteristics can then be esti-
mated as a function of distance from the cloud using readily available experi-
mental data for TNT explosions. TNT equivalency models are empirical, and
the results are strongly dependent on the explosion efficiency, which may not
be known for a particular material or cloud configuration. TNT equivalency
models also do not characterize the vapor cloud explosion well in the area close
to the cloud, where they may predict much higher pressure than typically result
from the combustion of a flammable cloud.
• Multienergy Method. This model is based on the assumption that the blast char-
acteristics of a flammable vapor cloud depend more on the level of congestion
and confinement than on the fuel. The models require dispersion models to
determine the size of the cloud. Then, areas with different confinement and
congestion characteristics are identified and considered to be sources of strong
blasts. The energy from each blast source is estimated, and the potential damage
is estimated from empirically derived correlations.
• Baker–Strehlow Method. This model also considers confinement as the basis
for the size of the flammable vapor cloud. It also considers burning characteris-
tics and reactivity of the fuel, geometry of the confined volume, and the degree
of confinement created by the obstacles in the confined volume. Blast character-
istics are then estimated using a set of correlations and charts.
These models are discussed in detail in Refs. 20 and 22.
Confined Explosions
Confined explosions result from combustion or another rapid chemical reaction

in a confined vessel or building. Confined combustion reactions may occur with
flammable vapor–air mixtures or from the dispersion of a cloud of combustible
dust in air. The combustion or reaction products are often gases, and pressure is
generated by the gas and also the elevated temperature resulting from the heat of
combustion or reaction. Confined explosions are modeled by estimating the peak
pressure that can be generated from the chemical reaction. The models are specific
to the reaction and may require considerable reaction thermodynamic and kinetic
data. The maximum pressure resulting from the reaction model is then compared
to the failure characteristics of the confining vessel or building. If the pressure
exceeds the expected failure pressure of the vessel, the damage resulting from
vessel failure and the potential for damage or injury from fragments can be esti-
mated using the methods for physical explosions discussed earlier.
Boiling Liquid Expanding Vapor Explosions
A BLEVE is the rapid release of a large amount of superheated liquid to the atmo-
sphere. It often occurs as a result of weakening of a pressure vessel caused by
direct flame impingement on the vessel above the liquid level. This weakens the
metal vessel and it can fail rapidly and catastrophically. The sudden loss of con-
finement allows the superheated liquid to rapidly flash, increasing its volume sev-
eral hundred times and generating a pressure wave and fragments. If the released
liquid is flammable, it can also ignite, resulting in a fireball. BLEVE models are
based on the expansion energy of the flashing liquid. Blast effects tend to be local,
and the impact of the fireball, which usually accompanies a BLEVE of a flammable
material, is the more important source of damage. BLEVE fireball models empiri-
cally estimate the fireball dimensions based on the quantity of material released.
Thermal radiation characteristics of the fireball are then modeled using a combina-
tion of empirically derived relationships and fundamental models for the geometry
of the fireball with respect to the receptor and atmospheric transmission of the
thermal radiation. The result is an estimate of the radiant energy flux level and
duration at various locations surrounding the BLEVE.
Effect Models
The result of the application of the models discussed in this section so far is an
estimate of some type of physical parameter at various locations surrounding a
chemical release: a concentration of toxic gas in the atmosphere, the amount of
radiant energy at a specific location from a fire, and the peak pressure and impulse
duration from an explosion. Effect models estimate the damage, which results from
these physical effects. There are a wide range of possible effect models correspond-
ing to the wide range of potential damage to people, the environment, and property,
which can result from exposure to toxic materials, fires, and explosions.
The CCPS [22] provides a summary of effect models commonly used to esti-
mate the impact of toxic vapors, fires, and explosions on people. These models
are generally empirical and are based on experimental data and evaluation of the
consequences of past incidents. Models are available to estimate the impact of a
hazardous agent using the dose-response relationship (e.g., relating probability of
fatality to concentration and duration of exposure by inhalation of a toxic gas,
relating severity of burns to intensity and duration of exposure to thermal radiation,
or estimating damage to structures based on peak overpressure and duration).
Risk Assessment
However many the resources we devote to the prevention of accidents, we can

never eliminate every risk. We have to decide our priorities: Which risks should
we deal with first? Which are so small compared with the other risks to which we
are exposed that we should tolerate them, at least for the time being? Often, the
judgment is qualitative: Some risks are illegal; some are obviously intolerable large
or acceptably small; sometimes a generally accepted standard or code of practice
tells us what to do. In other cases, the decision is not obvious and we use a numeri-
cal method known as quantitative risk assessment (QRA), probabilistic risk assess-
ment (PRA), or, in the chemical industry, hazard analysis (Hazan).
Stages of Risk Assessment
Before carrying out a risk assessment, we have to identify the hazards (i.e., the
substances, objects, or situations that can give rise to injury or damage) using one
of the methods described earlier. (A risk, in contrast, is the probability that injury
or damage will occur.) There are then three questions to answer:
• How often will injury or damage occur?

• What is the extent of the injury or damage?
• What action should we take?
Whenever possible, the answer to the first question should be based on experi-
ence, but often there is no experience, as the equipment is new or failure has never
occurred. We then estimate a failure rate for the equipment as a whole, based on the
known failure rates of its components, as described earlier. Similarly, the answer to
the second question should be based on experience whenever possible but can be
estimated as by one of the methods described earlier. The answer to the third
question depends on the nature of the consequences. If damage is possible but
injury is not, then the average cost of the damage (including consequential loss)
is compared with the cost of prevention.
If injury is possible, then the QRA approach is to set a target or criterion,
usually based on the risk to life. Risks above a certain level should be removed
or reduced as a matter of priority. Those below this level can be left alone, at least
for the time being. Thus, QRA is a method for determining priorities. In a later
development, there are two levels of risk. Risks above an upper level are considered
intolerable; if they cannot be reduced, the plant should not be built (or should not
be operated if it is already built). The risk considered tolerable for members of
the public is much lower than that considered tolerable for employees. Risks below
a much lower level are considered acceptable and need not be reduced. In between
the two levels, we reduce the risks if we can, but we tolerate them if it is impractica-
ble or very expensive to do so. The pressure to reduce them is great if the risk is
near the intolerable level and reduces as we approach the acceptable level.
The extent to which this approach is used and the risk levels are made explicit
differs from country to country. The United Kingdom has long accepted the princi-
ple that we should compare the size of a risk with the cost, in money, time, and
trouble, of removing it (although the ability to pay is not a deciding factor). If
there is a gross disproportion between them, the risk being insignificant in relation
to the cost, the risk can be tolerated. QRA was therefore accepted readily and the
regulatory authority has suggested figures for the tolerable and acceptable risk
levels. Other governments have been reluctant to admit that even trivial and infre-
quent risks should be tolerated and this has hindered the use of QRA.
The actual risk levels suggested for the United Kingdom are as follows. They
are similar to those used by many organizations elsewhere.
Risk of death per

person per year
Maximum tolerable risk (employees) 10⫺3
Maximum tolerable risk (public) 10⫺4
Maximum tolerable risk (public—nuclear risks) 10⫺5
Broadly acceptable risk (employees and public) 10⫺6
The maximum tolerable risk to employees seems rather high, but this risk is, in
fact, tolerated in some industries.
For comparison, the annual risk of death from all causes is about 10⫺4 for
someone aged 20 years and about 10⫺3 for someone aged 60 years.
Public Attitudes
Quantitative risk assessment is difficult to explain to the public. They pick on the
fact that a number of people could be killed in an industrial accident but ignore
the fact that the probability that this will occur is extremely low. The death of 10
people once in 10 years is given far more publicity than the death of 1 person per
year for 10 years. As a result, public pressure often compels industry and govern-
ment to reduce risks which are already low but which the public perceives as high.
At its best, this is democracy in action; at its worst, it is giving the most to those
that shout the loudest.
The public tends to oppose risks with the following traits:
• Imposed rather than accepted voluntarily

• Not under the individual’s control
• Of no obvious benefit to them
• Man-made rather than natural
• Unfamiliar
• Dreaded (e.g., cancer is more dreaded than heart disease though the latter kills
far more people)
• Immoral (e.g., crime is feared more than road accidents)
• Associated with unpleasant events (e.g., nuclear power reminds us of atomic
bombs)
When the public cannot judge the message, they judge the messenger. Unfortu-
nately, most of these concerns make the man in the street oppose the chemical
industry: The risks are imposed, not under his control, man-made, unfamiliar, and
dreaded; past experience has been unpleasant; the industry does not obviously
benefit him; and the spokesmen for the industry are often outsiders. There is no
easy way of countering this perception. We try to explain the benefits of the indus-
try and the low levels of risk, but we cannot say that accidents will never happen.
Incident Investigation
The purpose of incident investigation is to find out why the incident occurred so
that we can prevent it from happening again. The purpose is not to find out who
should be blamed. Many people have an opportunity to prevent almost every inci-
dent. Figure 5 shows by example the opportunities that are available to prevent a
fire or minimize the consequences of an apparently simple incident: An expansion
joint (bellows) was incorrectly installed in a pipeline so that it was distorted. After
some months, it leaked and a passing vehicle ignited the escaping vapor. Damage
FIG. 5 An example of an accident chain. An expansion joint (bellows) was incorrectly installed so
that it was distorted. After some months, it leaked and the escaping vapor was ignited by a
passing vehicle. Damage was extensive, as the surrounding equipment had not been fire-
protected to save the cost. Many people in various functions could have prevented the incident
or minimized the consequences.
was extensive, as the surrounding equipment had not been fire-protected to save
the cost.
Many people could have prevented the fire, not just the fitter who installed the
expansion joint incorrectly. The fire could have been prevented by better detailed
design (not using expansion joints for hazardous materials), by better design meth-
ods (using HAZOP, consulting experts, better design standards, better training of
designers), by better training of the fitter, by better inspection of workmanship,
by keeping eyes open on plant visits, and by not tolerating poor workmanship in
the past.
We should investigate all incidents, including those, which, by good fortune,
caused no injury or damage, but might easily have done so. Next time, they may.
Finding the Facts
• Include people with a variety of experience on the investigating panel. It should

not be too large; four or five people are usually sufficient.
• Do not disturb evidence that may be useful to experts who may be called in
later.
• Draw up a list of everyone who may be able to help, such as witnesses, experts,
designers, and people on other shifts.
• Be patient when questioning witnesses. Valuable information may be missed
if we try to take police-type statements. Do not put ideas into people’s minds.
Avoid questions to which the answer is ‘‘yes’’ or ‘‘no.’’
• Make it clear that the objective of the investigation is to find out the facts, so
that we can prevent the incident happening again, not to establish blame.
• Inform any authorities who have to be notified.
• Record information on damage and injuries so that others can use it for predic-
tion.
Drawing Conclusions from the Facts
Accident investigation is like peeling an onion. Beneath the immediate technical

causes, look for ways of avoiding the hazard, such as inherently safer design. Look
also for weaknesses in management, such as poor training or instructions or turning
a blind eye to previous failures to follow instructions.
Concentrate on prevention rather than causes. Look for causes that lead to
actions. Do not, for example, quote corrosion as a cause and stop there. Ask if it
was foreseen. If not, why? If it was foreseen, why did it occur? Was the right
material of construction used? Were operating conditions outside the design range?
Was monitoring carried out? If so, were the results followed up?
Preventing leaks is a more effective way of preventing liquid and gas fires than
removing sources of ignition (although we should also do what we can to remove
known sources of ignition). Avoid the use of the term ‘‘human error’’ and never
recommend someone to take more care. Instead, ask if we need better training,
better instructions, or better compliance with instructions and, if so, say how this
will be achieved. If an error was due to a slip or lapse of attention, inevitable from
time to time, look for ways of removing opportunities for error.
It is often useful, especially when investigating fires and explosions, to ask
why it occurred when it did and not at some other time. It is also useful to ask
if similar incidents, perhaps with less serious results, have occurred before,
what recommendations were then made, and if they were effective or allowed to
lapse.
Avoid long shopping lists of possible recommendations. Ask if the cost of each
recommendation is proportional to the size of the risk. Consider alternative solu-
tions as well as the obvious ones.
For each recommendation, make it clear who will carry it out and when. Bring
the report forward at that time. Otherwise, nothing will happen except a repeat of
the incident.
Managers should not accept reports that fall short in any of these respects.
They should look out for what is not said. For example, writers of accident reports
are naturally reluctant to draw attention to similar incidents that had occurred else-
where and, if they had been followed up, could have prevented the accident.
Spreading the Message
Many companies restrict the circulation of incident reports, but this will not prevent
the incident from happening again. We should circulate the essential messages
throughout the company. There is no need to say where the incident occurred.
Remember that incident reports grab people’s attention and are read, whereas ad-
vice and instruction are put aside to be read when we have time (if we ever do).
Having paid the high price of an accident, we can recover some of the cost by
turning it into a learning experience.
Circulate reports containing new or forgotten information throughout the indus-
try, so that others can learn from them. There are several reasons for doing so.
• Moral: If we have information that might prevent another accident, we have a

duty to pass it on.
• Pragmatic: If we tell other organizations about our accidents, they may tell us
about theirs.
• Economic: We would like our competitors to spend as much as we do on safety.
• The industry is one: Every accident affects its reputation.
Remembering the Message
Incident reports are written, acted on, and then filed and forgotten. After a few
years, people forget the reasons for the changes that were made. Procedures lapse
or the equipment falls out of use and the incident happens again, even in the plant
where it happened before. To prevent this from happening we should do the fol-
lowing:
• Include in every instruction, code, and standard a note on the reasons for it and
accounts of accidents that would not have occurred if the instruction, code, or
standard had been followed.
• Never remove equipment before you know why it was installed. Never abandon
a procedure before you know why it was adopted.
• Describe prior accidents as well as recent ones in safety bulletins and discuss
them at safety meetings. Giving the message once is not enough.
• Follow up at regular intervals to see that the recommendations made after acci-
dents are being followed, in design as well as operations.
• Remember that the first step down the road to an accident occurs when someone
turns a blind eye to a missing blind.
• Include important accidents of the past in the training of undergraduates and
company employees.
• Keep in every control room a folder of reports on past accidents. It should be
read by all new arrivals and others should browse it during quiet shifts.
• Devise better retrieval systems so that we can find, more easily than at present,
details of past accidents in our own and other companies and the recommenda-
tions made afterward.
The Management of Safety

Inherently Safer Design
The first step in the management of safety, after the hazards have been identified
(see the section Hazard Identification and Hazard Evaluation), is to see if they can
be removed. Only when we cannot do so, should we look for ways of keeping
them under control or mitigating their consequences. When we remove a hazard,
the safety is inherent in the design and cannot be lost. When we control a hazard,
the protective equipment may fail, or be neglected, or the safety procedures may
lapse.
Note that we refer to inherently safer, not safe, design as we can rarely, if ever,
remove every hazard. The principle routes to inherently safer design are as follows:
• Intensification or minimization: Using so little hazardous material that it does

not matter if it all leaks out. ‘‘What you don’t have, can’t leak.’’ This may
seem obvious but until the explosion at Flixborough, UK in 1974 little thought
was given to ways of reducing the amount of hazardous material in a plant.
Engineers simply designed a plant and accepted whatever inventories the design
required, confident that they could keep it under control. Flixborough weakened
that confidence, and 10 years later, Bhopal almost destroyed it.
Microreactors promise much greater intensification than has been possible in

the past. Intensification, when it is practicable, is the first choice, as it brings about
greater reductions in cost. If less material is present, we need smaller pipes and
vessels and smaller structures and foundations.
• Substitution: If intensification is not possible, then an alternative is substitution,

using a safer material in place of a hazardous one. Thus, it may be possible
to replace flammable solvents by nonflammable ones and processes that use
hazardous raw materials or intermediates by processes that use safer ones.
• Attenuation or moderation: Another alternative to intensification is attenua-
tion—using a hazardous material under the least hazardous conditions. Thus,
liquefied chlorine and ammonia can be stored as refrigerated liquids at atmo-
spheric pressure instead of storing them under pressure at ambient temperature.
The lower pressure results in smaller leaks through a hole of a given size leak
and the lower temperature results in less evaporation.
• Limitation of effects, by changing designs or reaction conditions rather than by
adding on protective equipment, which may fail or be neglected. For example,
it is better to prevent overheating by using steam or oil at a safe temperature
than by using a hotter medium and a control system.
• Simplicity: Simpler plants are safer than complex plants, as they provide fewer
opportunities for error and contain less equipment that develop faults. They are
usually also cheaper.
Defense in Depth
The hazards that cannot be removed have to be controlled. Because we depend

on equipment and people, both of which may fail, we use defense in depth. If we
handle flammable liquids or gases and an inherently safer design is not possible,
we use some or all of the following:
• Prevent leaks by good design, construction, maintenance, and operation.

• Install automatic detectors so that leaks are detected promptly and people not
required to deal with the leak can leave the area.
• Install remotely operated emergency isolation valves in places where leaks are
most likely to occur or where a large quantity could leak.
• Remove all known sources of ignition.
• Minimize damage by installing fire protection. Passive equipment such as fire
insulation is usually better than active equipment such as water spray turned
on by automatic equipment. This is better than active equipment turned on by
people.
• Provide fire-fighting equipment.
It is essential to carry out regular audits—tests and inspections to make sure

that automatic equipment is in working order and those procedures have not lapsed.
Human Factors
Engineers are interested in equipment, its failures, and ways of preventing them
and often less interested in people. However, all systems involve both equipment
and people. Engineers, whether they are designers, supervisors, or managers, there-
fore, should understand the way people react with equipment and why they some-
time fail to act in the way we instruct them or expect them to act.
• Some errors, usually called mistakes, occur because people do not know what
to do. The intention was wrong. Employers should provide adequate training
and instructions and should not write the sort of instructions that are designed
to protect the writer rather than help the reader. However, for many instructions
we write, problems will arise that are not covered by them and so people, partic-
ularly operators, should be trained in flexibility (i.e., the ability to diagnose and
handle unforeseen situations). If instructions are not being followed, are they
too complex? Can the job be simplified?
• Some errors, usually called violations or noncompliances, occur because some-
one knows what to do but makes a deliberate decision not to do it. Some viola-
tions occur because all people carrying out routine tasks tend to cut corners
after a while. Many more occur because people think they know a better way
of doing the job. Note that if the instructions are wrong, noncompliance may
achieve the intention. There is a fine line between showing initiative and break-
ing the rules.
To prevent or reduce violations, we should do the following
• Explain the reasons for the instructions. We do not live in a society in which
people will simply do as they are told. They want to know the reason why.
• If possible, simplify the job. If the correct method is difficult, an incorrect
method will be used.
• Carry out checks from time to time to see that instructions are being followed
and do not turn a blind eye if they are not.
• Some errors (mismatches) occur because the job is beyond the physical or men-
tal ability of the person asked to do it, sometimes beyond anyone’s ability. For
example, errors occur if people are overloaded, or underloaded, or asked to
break well-established habits. We should change the plant design or method of
working.
• The fourth category is the commonest—a momentary slip or lapse of attention.
People know what to do, intend to do it, and are able to do it, but it slips their
mind. Compared with mistakes, the intention is correct but is not fulfilled. They
happen to everyone from time to time and cannot be prevented by telling people
to be more careful or by telling them to keep their minds on the job. All we
can do is to change the plant design or method of working so as to remove
opportunities for error (or minimize the consequences or provide opportunities
for recovery). We should, whenever possible, design inherently safer plants
which can withstand errors (and equipment failures) without serious effects on
safety (and output and efficiency).
Managers and designers as well as operators make errors, but because they
usually have time to check their work, slip and lapses of attention are infrequent.
Most of their errors are mistakes or violations.
Management Systems
Some management systems have been discussed in earlier sections on risk assess-
ment, hazard identification, and accident investigation. The following are also im-
portant:
The preparation of equipment for maintenance: Many accidents have occurred

because equipment was not isolated correctly, was not freed from hazardous
materials, or was not correctly identified and the wrong equipment was opened
up. Sometimes, procedures were poor; sometimes, they were not followed.
The management of change: Many accidents have occurred because a change to
plant, process, or organization had unforeseen effects. Before any change is
made, it should be examined by professionally qualified people using HAZOP
(or a simpler technique if the change is minor) and then inspected after comple-
tion to make sure that the intention has been followed and that the modification
looks right. What does not look right is often wrong and should always be
checked.
Testing and inspection of equipment: All protective equipment is liable to fail and
should be tested or inspected at regular intervals. When active equipment such
as relief valves and interlocks fails, the failure is usually hidden and regular
testing is necessary. If passive equipment such as fire insulation is missing,
this is visible, but, nevertheless, it should be checked regularly. If 10% of the
fire insulation on a vessel is missing, the rest is useless. The following equip-
ment is often overlooked but should be tested or inspected regularly:
• Drain holes in relief valve tailpipes. If they choke, rainwater will accumulate
in the tailpipe.
• Drain valves in tank bunds. If they are left open, the bund is useless.
• Emergency equipment such as diesel-driven firewater pumps and genera-
tors.
• Earth connections, especially the moveable ones used for earthing road
tankers.
• Fire and smoke detectors and fire-fighting equipment.
• Flame arrestors.
• Hired equipment. Who will test it, the owner or the hirer?
• Labels are a sort of protective equipment. They vanish with remarkable
speed and regular checks should be made to make sure that they are still
there.
• Mechanical protective equipment such as overspeed trips.
• Nitrogen blanketing (on tanks, stacks and centrifuges).
• Nonreturn valves and other backflow prevention devices, if their failure can
affect the safety of the plant.
• Open vents. These are the simplest possible sort of relief device and should
be treated as relief valves.
• Spare pumps, especially those fitted with auto-starts.
• Steam traps.
• Trace heating (steam or electrical).
• Valves, remotely operated and hand-operated, which have to be used in an
emergency.
• Ventilation equipment.
• Water sprays and steam curtains.
All protective equipment should be designed so that it can be tested or inspected.
Test results should be displayed for all to see, for example, on a board in the
control room.
Operators sometimes regard tests and inspections as a nuisance, interfering

with the smooth operation of the plant. Training should emphasize that protective
equipment is there for their protection and they should ‘‘own’’ it.
Remembering the past: A most important system, discussed in the subsection Re-
membering the Message, is one to ensure that the lessons learned from past
accidents, in our own and other companies, is not forgotten and that the infor-
mation can readily be retrieved.
Introducing and maintaining systems: When systems are introduced or changed,

they should be discussed with those who will have to operate them and not
just sent to them through the mail. Discussions should start with descriptions
of incidents that would not have occurred if the systems had been in operation
at the time. These have much more impact than mere procedures and bring
out the need for the changes. Discussions will allow the manager to check that
the message has been received and understood and he may discover that it is
impracticable or difficult to use in its present form.
All systems are subject to a form of corrosion more rapid than that which
affects the steelwork and can vanish without trace once managers lose interest.
Continuous monitoring is necessary to make sure that systems continue in use.
Limitations of systems: Some managers seem to believe that good safety manage-
ment systems will ensure a safe plant. All the systems can do, however, is
ensure that people’s knowledge and experience are applied systematically. If
the staff lack knowledge and experience, then the systems are empty shells.
People will go through the motions, but the output will be poor. Without a
system, people will not achieve their full potential. Without knowledge and
experience, systems will achieve nothing. This is a particular danger at times
when companies are reducing manpower and experienced people are leaving.
Senior managers should systematically assess the levels of knowledge and ex-
perience needed and ensure that they are maintained.
Audits
We need audits of equipment and procedures by outsiders because of the following:
• Those who work in a plant do not notice the hazards they see everyday.
• Auditors may have specialized knowledge and thus see hazards not apparent
to others.
• Auditors have more time for investigation in depth than those who work regu-
larly on a plant.
Safety auditing should not be a police activity; it is intended to help the local
management, who may miss hazards through familiarity, ignorance, or lack of
time.
Auditors should pay particular attention to the following:
• The quality of the training and instructions and the knowledge and experience
of employees.
• The procedures for preparing equipment for maintenance, controlling modifica-
tions, and testing protective equipment and whether or not these procedures are
actually followed.
• Procedures for investigating accidents, passing on the lessons learned, and en-
suring that they are not forgotten.
• Process hazards as well as mechanical ones.
• Places where others do not look, behind, and underneath equipment.

• Although it may be a separate exercise, process hazards should be reassessed
every few years in the light of new knowledge and new techniques.
Auditors (and managers) should visit the plant at night and at weekends, not just
during the day.
The Measurement of Safety
Whenever possible, we should provide a numerical measure of the success of each

management function. Accident rates in good companies are now so low that the
usual measure of safety, the lost-time accident rate, merely measures luck and the
willingness of injured people to remain at work. In any case, it never measured
process safety. Possible additional or alternative measures are as follows:
• An index based on audit results. Unlike many other measures of safety, this
one tries to detect falling standards before an accident occurs.
• A monthly summary of the cost of incidents.
• An annual report of the progress made in reducing inventories of hazardous
substances.
• The number of faulty permits-to-work found by routine inspection.
• The number of faulty protective systems found by routine testing.
Mitigation
Mitigation is the cornerstone of emergency management. It is the ongoing effort

to lessen the impact disasters have on people and property. Mitigation involves
keeping homes and populated areas away from industry, engineering process plants
to be inherently safer, and creating and enforcing effective engineering codes to
protect employees, the public, and the environment from potential process plant
upsets and incidents.
Mitigation is defined as ‘‘sustained action that reduces or eliminates long-term
risk to people and property from hazards and their family and belongings are better
protected from floods, earthquakes, hurricanes, and other natural hazards. They
can be utilized to help business and industry avoid damages to their facilities and
remain operational in the face of catastrophe. Mitigation technologies can be used
to strengthen hospitals, fire stations, and other critical service facilities so that they
can remain operational or reopen more quickly after an event. In addition, mitiga-
tion measures can help reduce disaster losses and suffering so that there is less
demand for money and resources in the aftermath.
In practice, mitigation can take many forms. It can involve actions such as the
following:
• Promoting sound land use planning based on known hazards

• Buying flood insurance to protect your belongings
• Relocating or elevating structures out of the floodplains

• Having hurricane straps installed to more securely attach a structure’s roof to
its walls and foundation
• Developing, adopting, and enforcing effective engineering codes and standards
• Engineering process plants to be inherently safer
• Using fire-retardant materials in new construction
• Developing and implementing a plan in your business or community to reduce
your susceptibility to hazards
In the multiple-barriers concept and development of inherently safer layers of

protection, mitigation is a much lower-level activity and should be looked at only
when all other measures in the inherently safer hierarchy are exhausted. For exam-
ple, mitigation should be addressed only after the following options have been
exhausted:
• Inherent safety: These include inventory reduction (i.e., less chemicals stored
or less in process vessels), substitution of a less hazardous chemical for one
more hazardous, and use of lower temperatures and pressures.
• Engineering design: Examples are use of better seals or materials of construc-
tion, ensuring proper operating conditions and material purity, and installing
dikes and spill vessels.
• Management: Examples include consistent operating policies and procedures,
training for vapor release prevention and control, audits and inspections, equip-
ment testing, maintenance program, management of modification and changes
to prevent new hazards, and general plant security.
Some of the common mitigation techniques employed by process plants are

as follows:
• Early vapor detection and warning: Detection by sensors or personnel. De-

pending on the nature and extent of the chemical hazards, some plants may
choose to employ very sophisticated sensor systems. For example, a pipeline
company handling sour gas mixtures with very high H2S content decided to
install an early warning H2S-sensing system. The system known, in the industry
as Teledyne Geotech’s ‘‘LASP’’ [27,28] (Leak Alarm System for Pollutants)
consisted of a semipermeable tubing which is laid above the sour gas pipeline
under the ground. The tubing is capable of drawing air through it, which is
analyzed for H2S contamination at regular intervals. Another common technique
utilized to protect high-hazard pipelines is the installation of labeled warning
ribbons approximately 1 ft below grade over the pipeline.
• Use of engineered and management systems to impede the progress of the re-
leased chemicals. Some of the engineered systems, which have been very effec-
tive in mitigation, include water sprays, water curtains, steam curtains, and air
curtains. Management systems may include standing procedures to deliberately
ignite explosive clouds, procedures for forced dilution of contaminant, and pro-
cedures to mitigate or suppress released chemicals by the use of foams and
other suppressants.
Isolation by distance of a chemical process from on-site and off-site sur-

rounding populations is generally a very effective consequence–mitigation mea-
sure. Separating the process from vulnerable populations affords both attenuation
of the effects and time to provide emergency response. The isolation distances
needed to appreciably reduce blast effects and impact from toxic releases is sig-
nificantly large, whereas this type of mitigation measure is not useful for the protec-
tion of on-site personnel. Other hazard mitigation measures should be used for
protection of on-site personnel. For example, explosion hazards may warrant the
construction of blast-resistant buildings or blast walls. Toxic release hazards may
require the availability of shelter-in-place facilities or escape respirators. Some
process plants use consequence modeling in deciding the layout of the plant. For
example, a hazards analysis early in the design stage may identify one particular
unit as having the greatest potential for a toxic release and that unit may then be
located on the site as far as possible from off-site neighbors, perhaps considering
prevailing directions as well.
Process integrity may also be addressed in the engineering design. Process
integrity involves the chemistry of plant design and operation. Mitigation after loss
of containment can also be effective and usually must be provided for in the process
design stage. Secondary containment by double-walled piping or double-walled
vessels may be needed. Dikes, curbs, and trenches leading away from storage ves-
sels to strategically located impoundments can be used to reduce the rate of evapo-
ration, help keep the liquid source of the vapor away from the most sensitive areas
of the plant, and limit the extent of emergency response activities.
Mitigation measures such as active and passive scrubbers, stacks, flares, catch
tanks for vapor–liquid separation, incinerators, absorbers, adsorbers, and condens-
ers are used widely for reducing the impact after loss of containment. CCPS’s
Guidelines for Vapor Release Mitigation [29] provides detailed discussions on
these mitigation techniques.
Response
Emergency response plans for process plants should be developed in accordance

with applicable governmental regulations and operating company requirements.
Written emergency response procedures, accident investigation protocol and proce-
dures, and repair procedures should be prepared, and the appropriate operating
personnel should be trained in their proper use. Results or risk assessment studies
and hazard zone calculations should be used in the formulation of emergency re-
sponse actions contained in the emergency plans.
In addition to being quickly and effectively warned of a dangerous situation,
personnel need to know ahead of time the best response to minimize their chances
of being affected by the vapors. Questions that should be settled in advance include
emergency shutdown criteria, incident commander designation, and the roles of
incident commander and other emergency personnel. Other issues that should be
settled in advance include circumstances which would warrant shelter-in-place for
the employees and the affected public.
Communicating warnings to potentially exposed personnel is essential in an

emergency. Warnings can be communicated through the use of public address
systems, alarm systems, and sirens. Recently, many companies are also moving
toward the installation of automatic telephone dialing and alerting systems or com-
municating hazard warnings to downwind personnel. Preprogrammed computers
can be used to dial thousands of preselected numbers in very short periods of time.
Every plant should establish clearly defined procedures for emergency shut-
down of equipment. The procedures should clearly indicate what constitutes an
emergency situation. The extent and nature of steps taken to bring the process
back under control should also be clearly indicated. Finally, the conditions which
would unambiguously require a shutdown should be spelled out. Personnel author-
ized to make the decision to shutdown should be aware of their responsibilities
and the role of other personnel.
Technology Advances
Advances in the understanding of chemical hazards have led to the development

of new technology in the arena of process design, equipment, and risk management.
A discussion of three major areas of development is given here.
Relief Valve Sizing and Overpressure Alternatives
Recent research on relief valve sizing and overpressure protection alternatives has
focused on the development of validated engineering design procedures for the
proper sizing of safety relief valves for systems, which involve two-phase flows
of viscous fluids. Systems which are being considered include single-phase viscous
liquids and gas flows, ‘‘frozen’’ (e.g., air–liquid) two-phase flows of gases and
viscous liquids, and flashing flows of viscous and nonviscous liquids.
Reactive Chemistry
In the Reactive Chemistry arena, calorimeters are being used increasingly for
studying the thermal behavior of reactive systems. One such calorimeter is the
Reactive Systems Screening Tool (RSST), which is designed for rapid measure-
ment of thermal behavior of small samples (10 cm3) for temperatures up to 400°C
and pressures to 500 psia. Another apparatus is the Automatic Pressure Tracking
Adiabatic Calorimeter (APTAC) for detailed analyses of thermal behavior of larger
samples (up to ⬃130 cm3) for temperatures up to 450°C and pressures up to 2000
psia. In this calorimeter, closed-cell sample pressures are continuously matched
by an external pressure of nitrogen so that sample cells of low mass and therefore
low thermal inertia can be used for highly sensitive measurements of sample ther-
mal behavior. Other advanced features of the APTAC include in situ additions to
the sample cell of reactants or catalysts with a high-pressure syringe pump.
During typical experiments with each calorimeter, the sample temperature is

measured during temperature scans when the temperature is increased at a steady
rate or held isothermally (in the APTAC). Thermal energy released or absorbed
by the sample (as defined by sample temperature changes of ⱖ0.04°C/min) is
measured by the calorimeter as a nearly adiabatic excursion from the thermal scan
baseline. For each sample, the thermal peaks can be identified and measured from
ambient up to 450°C (up to 400°C in the RSST). With this experimental capability,
investigations of thermal behavior of wide ranges of reactive systems and systems
of questionable chemical compatibility can be performed, which, in turn, is used
to design safe processes and choose safe operating conditions.
Safety Integrity Levels
Industry is moving toward the use of high-integrity protection systems to reduce

flare loading and alleviate the need to upgrade existing flare systems when expanding
facilities. In the process industry, a key safety consideration is the control and re-
sponse to overpressure situations. Industry standards from the American Petroleum
Institute (API) and American Society of Mechanical Engineers (ASME) provide
criteria for the design of vessels and the protection of these vessels from overpres-
sure. Traditionally, pressure relief valves and flares were used to handle the relieving
of vessels in the worst credible scenario. Flare loading calculations gave no credit
for operator intervention, fail-safe equipment operation, or trip systems.
In many communities and countries around the world, the belt is tightening
on the venting and combustion of gases. It is simply not acceptable to flare large
volumes of gas. In addition, the cost of designing and installing large flare systems
has continued to rise. API 521 and Case 2211 of ASME Section VIII, Division 1
and 2, provide alternatives in the design of overpressure protection systems. These
alternatives revolve around the use of an instrumented system that exceeds the
protection provided by a pressure relief valve and flare system.
ASME Code Case 2211, approved in 1996, sets the conditions under which
overpressure protection may be provided by an instrumented system instead of a
pressure relief valve (PRV). The ruling is intended to enhance the overall safety
and environmental performance of a facility by utilizing the most appropriate engi-
neered option for pressure protection. Although there are no specific performance
criteria in the Case Code, the substitution of the high-integrity protection systems
for the pressure relief valve should provide a safer installation. Consequently, the
substitution is generally intended for limited services where the PRV may not
work properly due to process condition (e.g., plugging, multiple phases, etc.). The
overpressure protection can be provided by a safety instrumented system in lieu
of a pressure-relieving device under the following conditions:
One of the most important criteria for safety instrumented system (SIS) design
is the requirement that the User assign and verify the safety integrity level (SIL)
for the SIS [30]. The assignment of SIL is a corporate decision based on risk
management philosophy and risk tolerance. The SIS should be designed to meet
a safety integrity level, which is appropriate for the degree of hazard associated
with the process upset. Safety integrity levels per draft IEC 61508 [31,32] and
ANSI/ISA S84.01 [33–37] are designated in Table 7.
TABLE 7 Safety Integrity Levels

Availability Probability to fail
Safety integrity level required on demand 1/PFD
IEC 61508:
4 ⬎99.99% 10⫺5 to 10⫺4 100,000–10,000
ISA S84:
3 99.90–99.99% 10⫺4 to 10⫺3 10,000–1,000
2 99.00–99.90% 10⫺3 to 10⫺2 1,000–100
1 90.00–99.00% 10⫺2 to 10⫺1 100–10
Industrial Hygiene and Toxicology
As the world becomes more industrialized in an attempt to increase the quality of

life, more and more environmental problems will require the attention of engineers,
managers, and planners. In the coming years, findings and advances on chemical
toxicity will require the implementation of stringent industrial hygiene standards.
Although there are many toxic effects, both acute and long term associated with
chemicals, one of the most dreaded is cancer. It is quite apparent that industrial
hygiene requirements in the coming years will be dictated to a large extent by the
upcoming findings on carcinogenesis and mutagenesis. By one estimate, there are
500 new chemicals marketed each year [38]. Thus, determining the toxicological
effects of these chemicals and, as a result, developing industrial hygiene programs
to protect people from these effects will command significant attention and re-
sources from process safety personnel.
Although workers are often exposed to contaminant mixtures, exposure regula-
tions do not take into account the effects of the various types of contaminant inter-
actions capable of modifying toxicity. To remedy this situation, the scientific re-
search and development of databases on the toxicity of mixtures are needed. With
this information, health and safety specialists will be able to quantify contaminant
interactions for any given situation.
Although substantial progress has been made in the United States toward im-
proving worker protections since 1970 (largely a result of occupational safety and
health research), workplace hazards continue to inflict a tremendous toll in terms
of human and economic costs. Clearly, there is much work to be done.
The practical impact of the toxicological and industrial hygiene research pro-
grams on the workplace largely depends on the actions of employers, employees,
and partners in governmental agencies, industry, labor, academia, and community
organizations. The stated objectives in this area include target levels of improve-
ments in work-related conditions. Examples are reducing work-related deaths and
injuries, reducing lost work days and incidences of cumulative trauma and skin
disorders, and increasing the number of workplaces with rehabilitation and safety
and health programs. The work of governmental agencies and research organiza-
tions has had and will continue to have an impact on improving health and safety
at the workplace; therefore, it will help address many of the issues related to work-
related hazards, injuries, illnesses, and deaths (such as musculoskeletal problems,
skin diseases, violence in the workplace, employee stress, and back injuries) as
well as categories of workers and prevention strategies for mine workers, farm
workers, and adolescents. In addition, surveillance efforts will assist the develop-
ment of comprehensive databases, thereby helping to establish baseline and trend
information in the occupational safety and health area.
Future Developments
Increasingly, the process safety requirements for chemical plants will become more
and more stringent. In addition, the pressure to operate safely from the point of
view of competitiveness and profitability will also keep increasing. Finally, the
public outcry for improved safety performance also creates significant pressure on
the industry. In fact, in future processes, safety performance will quite likely be
dictated by national goal setting. This would require the establishment of a baseline
assessment of the status of process safety incidents. Given a baseline assessment,
National Chemical Safety Goals can be established, with the identification of activ-
ities necessary to accomplish the goals and the development of a measurement
system to measure progress toward the goals.
Regulatory programs and industrial standards and practices in the United States
have quite often been reactive (i.e., in response to catastrophic accidents or other
events). The pros and cons of establishing national process safety goals and evalua-
tion approaches include the following:
1. Stakeholder consensus on national chemical (process) safety goals

2. Identification of where we want to be and by when in relation to national
chemical safety goals
3. List of activities that need to be implemented to accomplish Step 2 above
4. Agreement on some common metrics for measurement of progress toward
national chemical safety goals
Summary and Conclusions
The industrial revolution brought prosperity and, along with it, the use of hazardous
processes and complex technologies. Growing economies and global competition
has led to more complex processes involving the use of hazardous chemicals, ex-
otic chemistry, and extreme operating conditions. As a result, a fundamental under-
standing of the hazards and associated risks is essential. Process safety and risk
management requires the application of the basic sciences and a systematic ap-
proach. Recent advances, such as overpressure protection alternatives and reactive
chemistry, allow safer design and operation of processes.
In the multiple-barriers concept, plants are designed with several layers, so that
an accident would require the failure of several systems. Another novel approach to
process safety and risk management is to consider various actions in a descending

hierarchical order. Inherently safer design consideration should be first in the hier-
archy, followed by prevention systems, mitigation, and response. The success of
these systems is dependent on the fundamental understanding of the process and
the associated hazards. Chronic as well as catastrophic consequences resulting
from toxic and flammable substances can be reduced and/or eliminated through
appropriate design and operating practices.
In the end, progress toward the improvement in safety performance can be
measured only by a reduction in occupational injuries, illnesses, and fatalities. In
fact, measurable progress has been made in the period 1970 to 1995, during which
the rate of workplace fatalities fell by 78% and the number of workplace deaths
has declined by 62%. We have also seen a 25% decline in the rate of occupational
injuries and illnesses from 1973 through 1994. These reductions are the result of
the combined efforts of all the partners in occupational safety and health: industry,
labor, academic researchers, National Institute of Occupational Safety and Health,
Occupational Safety and Health Administration, Mining Safety and Health Admin-
istration, state and local agencies, and others. No single partners can claim exclu-
sive credit for the progress. Thus, if further progress is to be made, all of the
partners must act—from identifying the causes of disease and injury through con-
trolling or eliminating the hazards or exposures at the worksite.
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M. SAM MANNAN
DENNIS HENDERSHOT
TREVOR A. KLETZ
Introduction to the Selective Catalytic

Reduction Technology
Introduction
Overview
The selective catalytic reduction (SCR) process has been originally developed for
reducing oxides of nitrogen (NOx). The process is being discussed within the frame-
work of air-pollution control policies and practices of industrialized countries, ac-
counting for about 20% of the world population and generating 80% of the global
combustion air-pollution. The United States with approximately 5% of the world
population accounts for about 28% of the world’s fossil fuel consumption (Interna-
tional Energy Agency, Paris, France), more than twice the per-capita consumption
of other major industrial countries. Stringent Energy Conservation and Emission
Reductions Policies have a much longer tradition in Europe and Japan than in the
United States. In the United States, due to low-cost energy, excess fuel is often
used to reduce NOx of IC engines, which accounts for over 50% of the United
States’ total NOx inventory, by a 4-degree time-retard timing. This at the expense
of major increases in CO emissions, fuel consumption, and carcinogenic particulate
matter (PM) emission. (Source: BACT best available control technology of U.S.
EPA, Cal.-ARB, and SCAQMD).
The SCR process has been designed to reduce oxides of nitrogen (NOx), a
precursor of regulated low-level ozone (O3) emission. The ozone is formed primar-
Selective Catalytic Reduction 95
ily by the two precursor NOx and volatile organic compounds (VOC) in the pres-
ence of sunlight through photosynthesis. However, advanced SCR developments
have been achieving VOC/HC (hydrocarbons) and particulate matter (PM) emis-
sion reductions simultaneously with the NOx reduction. Also, in recent years, Euro-
pean application engineering technology developments have broadened the appli-
cation of SCR technology. Originally developed in the 1970s for stationary utility
power generation equipment, the SCR process can be used to reduce emissions of
practically all types of combustion equipment, including mobile applications such
as heavy-duty diesel (HDD) trucks, portable generation sets, diesel locomotives,
coastal and ocean-going vessels, earth-moving equipment, and so forth. Today,
SCR technology is being used in retrofit and integrated emission control systems.
The SCR combustion pollution control technology is able to overcome the target
conflict of IC combustion equipment, increasing the NOx emission by reducing
the fuel consumption or increasing the PM and CO emission by increasing fuel
consumption through fuel-based emission controls (see Fig. 1).
The earliest SCR applications were located primarily in oil-burning utility
boiler facilities in Japan in the 1970s. Then, in the 1980s, European SCR applica-
tions for hard-coal-burning utility and oil- and gas-burning industrial boilers, and
stationary gas, diesel, and dual-fuel IC engines were added. In the United States,
gas turbine applications were introduced in the 1980s and many coal-burning utility
power plants require SCR retrofit system installations by 2004. Figure 2 shows
high-dust and low-dust utility boiler applications.
However, because the number of utility plants are relatively few in comparison
to the number of other nonutility SCR applications to be considered for OEM and
retrofit applications in future, accounting for over half of the total U.S. NOx pollu-
tion inventory, the nonutility and the new mobile combustion sources are being
emphasized in this article.
The SCR utility applications have to compete with pollution control processes,
FIG. 1 The target conflict of IC equipment emission reduction versus fuel consumption. (Source:
German Engineering Society (VDI), May 1993.)
96 Selective Catalytic Reduction
FIG. 2 Utility boiler applications. (Courtesy of Siemens.)
such as the selective noncatalytic reduction process (SNCR), featuring low capital
investment but high operating costs. This process is limited to a small operating
temperature window of usually 1350–1550 F (750–900°C) and requires an ammo-
nia or urea consumption of up to four times the stoichiometric requirements of the
SCR process.
In the United States, natural-gas- and fuel-oil-burning industrial boilers and IC
engines and turbines were equipped with SCR systems in a few regional nonattain-
ment areas for ozone since the 1980s and gas- and coal-burning utility boilers since
the 1990s.
In Europe, due to the development of a diesel SCR catalyst with an operating
temperature window of 300–1020 F (150–550° C), air quality regulators cooper-
ated with the trucking industry and the SCR equipment industry in the development
and field testing of SCR systems for heavy-duty diesel truck engine applications
in the 1990s. These truck field tests have lasted for some 4 years, accumulating
approximately 3 million road and highway miles with 20 Class 8 type HDD trucks.
The SCR systems will go to market in 2002. Today, the range of SCR applications
is rather broad, as shown by Fig. 3: From (clockwise) a coal-burning utility plant
to HDD truck, portable generator set, vessel, railroad, construction equipment,
pipeline pump station, and gas turbine applications.
Today, the SCR technology allows the simultaneous reduction of combustion
emission of 70–95% NOx, 20–50% PM, and 85–95% VOC/HC at minimum fuel
consumption and CO2 emission. It may be interesting to note that the emission
reduction of VOC include air toxins such as aldehydes and polycyclic aromatic
hydrocarbons (PAH), which are almost completely oxidized in the SCR process.
Hence, SCR technology is considered the most promising, cost-effective technol-
ogy available to reduce combustion emissions, enabling air quality regulators
worldwide to achieve more drastic emission reductions of combustion equipment
than thought possible just a few years ago.
Various cost-effectiveness calculations showed annualized costs of ⬍$500 to
⬃1500 per annual ton of NOx reduction, depending on the type and size of the
SCR equipment. The capital investment cost of SCR systems are ⬃US$ 10 to 50
per BHP h, depending on custom engineering requirements and the number of
systems of the same design fabricated (Siemens).
FIG. 3 The Range of SCR applications. (Courtesy of Siemens.)
Environmental Policies
After the United Nations summits on the environment in the 1990s in Rio, Brazil
and Kyoto, Japan, environmental policy-makers around the world have been focus-
ing on the reduction of emission generated by combusting fossil fuel.
• Health effects of NOx, PM, and VOC/HC have been the driving force for air
quality legislation in the past. The air quality regulations, however, were devel-
oped in a piecemeal approach: first NOx, then VOC/HC to reduce ground-level
ozone, and, finally, PM. This has been a major disadvantage for SCR technology
applications, as no considerations were given to the capability of reducing VOC
and PM simultaneously with NOx at no extra cost.
• Global warming is becoming an increasing concern domestically and interna-
tionally, considering changes in weather pattern, shorelines of the ocean, and
so forth. The industrialized countries must reduce their fossil-fuel combustion
emission substantially to allow developing nations to generate more power for
their growing economies. The various emission inventory data for the United
States for NOx indicate that the leading sources of combustion emission are from
on-road and off/nonroad emission sources. Gasoline engines, at the expense of
higher fuel consumption and N2O (laughing gas) secondary emission, have been
equipped with three-way catalyst systems for many years. For the most fuel-
efficient device in converting fossil fuel into useful energy and power, the diesel
engine, no cost-effective, commercially available solution to reduce NOx, PM,
and VOC/HC emissions substantially and simultaneously existed until the early
1990s. Therefore, as mentioned above, fuel is often used today to reduce emis-
sions, increasing the fuel consumption of engines and other combustion equip-
ment and, with it, global warming gas emissions. Increases of 10–13% in CO2
FIG. 4 Target conflict: reduction of NOx versus increase in fuel consumption, CO2, and PM. (Courtesy
of Siemens.)
and up to 70% of PM emission of diesel engines were reported at public Cal.

ARB meetings in 1999 and 2000.
• Combustion emission reductions through fuel savings and internal combustion
equipment design modifications such as electronic engine management systems,
unit electronic–hydraulic injection, intercooling, and exhaust gas recycling is
limited. In Fig. 4, the target conflict of the U.S. EPA NOx emission reductions
versus exponential increases in fuel consumption, CO, VOC/HC, and PM emis-
sion of Class 8 HDD truck engines, is shown by reducing NOx emissions of
engines by modifications such as U.S. EPA’s BACT mentioned earlier. There-
fore, to avoid higher fuel cost and to achieve future U.S. EPA emission reduc-
tion goals beyond 2002 and 2004, exhaust gas aftertreatment technologies will
be required in mobile and other applications.
Environmental Regulations
In 1970, the U.S. Ambient Air Quality Act was passed and then amended in 1990,
allowing a maximum ground-level ozone concentration of 0.12 parts per million
(ppm). The U.S. National Ambient Air Quality Standard (NAAQS), however, was
never met throughout the United States. Serious nonattainment areas for ozone
(O3) such as in the Northeast and in California still exist and new ones were added
recently. In 1997, the U.S. EPA further reduced the ground-level ozone standard
due to late health data and increased health concerns to 0.08 ppm ozone at an 8-h
average and introduced a new PM 2.5 standard of 65 µm/m3 at a 24-h average.
That increased the nonattainment areas in the United States substantially (Fig. 5).
The various state implementation plans for combustion emissions in the United
States, therefore, call for substantial further NOx reductions of the U.S. inventory
of approximately 25 million tons of NOx per year (U.S. EPA).
FIG. 5 Nonattainment areas in the United States for ozone (dark areas) based on the EPA’s new
standards for ground-level ozone and PM 2.5.
In addition to major cities in California and the Northeast, cities such as At-
lanta, GA, Chicago, IL, Dallas, TX and Houston, TX became serious or extreme
nonattainment areas. East coast states, after years of complaining about Mid-west
combustion pollution transfers to the East, finally received an ozone transfer regu-
lation for about 20 states, requiring midwest states to reduce NOx substantially.
According to NESCAUM data presented at the ICAC Forum 1998, the NOx emis-
sion in the midwest was caused by utilities (⬃33%), by independent power produc-
ers (14%), and by mobile equipment (on-road 34% and off/nonroad 14%). Other
estimates (i.e., California) are more like 30% each for stationary, on-road, and
nonroad combustion equipment after 20 years of stationary emission source regula-
tions in that State. Figure 6 shows the different emission source categories by area
in Texas in 1996.
Technology
As stated earlier, SCR technology has been advanced considerably in Europe in

recent years; however, the basic SCR process is still the same. The SCR process
equipment layout is pictured in Fig. 7, using an engine as an example for combus-
tion equipment.
FIG. 6 NOx emission by source category in tons per year at selected areas of Texas in 1996. Example:
Houston, clockwise: 2% area, 20% nonroad, mobile, 25% on-road, and 53% stationary emis-
sion sources. (Source: TNRCC, 2000.)
FIG. 7 The SCR process, using a diesel engine SCR application as an example. (Courtesy of Siemens.)
The exhaust gas generated by a diesel engine passes from the engine through
the exhaust pipe or duct, through the SCR reactor and other exhaust gas system
components such as the muffler into the atmosphere. The exhaust gas duct, leading
to the reactor, houses the gas flow straightener, turning vanes, static mixers, and
some sensor probes. The SCR reactor houses the SCR catalyst and other sensor
and instrumentation probes. Depending on the exhaust gas temperature, mass flow,
raw or uncontrolled, and permitted or controlled NOx concentration and other vari-
ables, a certain amount of a reducing agent is injected and homogenously mixed
upstream of the catalyst bed.
There are several reducing agents in use today. Anhydrous ammonia (NH3),
a toxic, hazardous, and flammable gas, is used primarily in stationary industrial
and utility applications. A safer ammonia reducing agent, aqueous ammonia, con-
taining 25–29% ammonia gas in demineralized water, was introduced to SCR ap-
plications in the 1980s. The mobile SCR system application developments of the
1990s, however, required a much safer reducing agent, aqueous urea, from which
ammonia is generated through hydrolysis, yielding two NH3 and one CO2 in the
exhaust duct upstream of the SCR catalyst. When subsequently passing through
the SCR catalyst bed, the reducing agent NH3 reacts with the NOx to yield molecu-
lar nitrogen (N2) and water vapor (H2O) with very limited ammonia slip, typically
in the 2–30-ppm range as secondary emission. Some typical chemical reactions
of the SCR process are shown by Fig. 8a. Figure 8b shows the reversible side
reactions and their equilibrium at threshold temperatures (EESI/Steuler, a leading
SCR system supplier) at a specific chemical exhaust gas composition.
Secondary Reactions and Emissions
The effects of high SOx levels in the exhaust gas is given in Fig. 8b.
A European university study on the effects of high SOx levels in the exhaust
gas duct concluded that temperature and SO2 ⬎ SO3 control is key to avoid ammo-
nia salt emissions. Figure 8b shows a few of the reversible side reactions and
their equilibrium threshold temperatures (EESI/Steuler), using an exhaust gas of
a specific chemical composition: 72% N2, 15% CO2, 10% H2O, 3% excess O2, 200
ppm NO, 10 ppm NO2, 1000 ppm SO2, 50 ppm SO3, and 200 ppm HCL.
Ammonia slip has been a concern of health experts and air quality regulators
when considering SCR exhaust emission reductions. United States air quality regu-
lators for gas turbine SCR applications have imposed extremely costly low levels
of NH3 slip emission limits of 2–5 ppm. However, pollution control experts point
out that this ‘‘NH3-slip hype’’ is not based on facts: European and U.S. NH3 Emis-
sion Inventory Studies in the Netherlands, Germany, and California show that,
depending on the life stock concentration, 60–75% of the total local NH3 emission
is caused by animal droppings. Also, depending on weather conditions and the
type and intensity of fertilizer usage, the area NH3 emission may be as high as 5–
30%. The industrial applications such as air conditioning, nitric acid production,
and SCR-based NH3 slip emission do not account for more than 0.5–2% of the
total NH3 emission inventory (Bavarian-EPA, Cal. ARB, and other studies). In a
U.S. study, a well-supported estimate of a SCR-based NH3 slip rate of 2–5 ppm
for 200,000 MW utility applications would just cause an NH3 emission increase
Reducing Agent Urea: Ammonia generation through hydrolysis in the exhaust or flue gas, upsteam
of the SCR catalyst.
1. (NH2)2 CO ⫹ H2O → 2 NH3 ⫹ CO2
NOx Reduction with Ammonia
2. 4NO ⫹ 4NH3 ⫹ O2 → 4N2 ⫹ 6H2O
3. 6NO ⫹ 4NH3 → 5N2 ⫹ 6H2O
4. 2NO2 ⫹ 4NH3 ⫹ O2 → 3N2 ⫹ 6H2O
5. 6NO2 ⫹ 4NH3 → 7N2 ⫹ 12H2O
(a)
Effects of high SOx levels in the exhaust gas

Temperature (°C) Chemical Reactions
1. 22 2NH3 ⫹ H2O ⫹ SO2 i (NH4)2SO3
2. 219 2NH3 ⫹ H2O ⫹ SO3 i (NH4)2SO4
3. 209 NH3 ⫹ H2O ⫹ SO3 i NH4HSO4
4. 113 NH3 ⫹ HCl i NH4Cl
5. 88 NH3 ⫹ H2O ⫹ (1/2)O2 ⫹ 2NO2 i 2NH4NO3
(b)
(c)
FIG. 8 (a) Typical chemical reactions of the SCR process. (b) Equilibrium threshold temperatures
at which ammonia salts is formed/dissolved. (c) NH3 /NOx ratio and the effects of overinjection
and underinjection of ammonia. (Courtesy of L. Pruce.)
of less than 10,000 tons per year equal to less than 1% of the total U.S. NH3
emission inventory.
System Controls
The component selection will vary depending on the type of combustion equip-
ment, emission reduction, control/monitoring system requirements, and so forth.
Basically, two types of reducing agent injection control are being used. The first
is the open-loop, feed-forward control with a computer-based ‘‘map,’’ a correlation
function of NOx emission generated at certain combustion equipment loads, re-
quiring a calculated amount of reducing agent to achieve the permitted NOx emis-
sion rate. Such a system is also called a Predictive Emission Monitoring System
(PEMS). Maximum reduction rates at minimum unreacted ammonia (slip) can be
achieved by adding to the rapidly responding open-loop system a slower closed-
loop system. The feedback systems are, in most cases, certified systems, incorpo-
rating continuous emission monitoring systems (CEMS) or sensors.
SCR System Design Considerations
The following basic design considerations are common to all SCR systems:
• Proper exhaust gas flow and temperature distribution at the front face of the
catalyst bed
• Proper selection of the catalyst material formulation, the catalyst bed, and hous-
ing design
• Proper selection of materials, system components, and control system design
The SCR system component selection and system configuration may vary con-
siderably depending on the application. Utility applications for large boilers or gas
turbines are therefore custom engineered. Also, Independent Power Producer (IPP)
and industrial applications such as cogeneration and standby generation sets are
still primarily custom engineered. However standardized, volume-produced small
gas turbine and engine SCR applications will be more cost-effective and thus more
common in future. The new mobile SCR applications for diesel and lean-burn
gas engines will be such standardized and volume-produced SCR systems. This
industrial approach, developed and adopted for the first time in the HDD truck
program by Siemens and the European trucking industry, is already benefiting the
custom-engineered SCR systems as well.
SCR System Component Summary

The Exhaust or Flue Gas Piping or Duct
This is usually heat insulated, made of heat-resistant nonscaling steel such as mo-
lybdenum alloys, and connects the combustion equipment with the SCR reactor.
Such inlet ducts with the SCR reactors downstream are pictured in Fig. 9.
The inlet duct or piping houses the gas flow straightener, flow turning vanes,
sensor probes, and injection spray heads or nozzle as well as the static mixers.
Only in very special cases, bypass valves are incorporated in ducts to cope with
certain operating conditions such as cold start-ups, alternate fuels, and so forth,
which could harm the SCR catalyst of earlier developments. An even flow rate
(a)
(b)
FIG. 9 (a) SCR inlet duct and catalyst location, gas turbine application. (b) SCR inlet duct and catalyst
location, stationary engine application.
and temperature distribution at the front face of the catalyst bed are most crucial
and prerequisites of any well-performing SCR system design. As a case in point,
in a gas turbine project in southern California, even major improvements in the
ammonia/exhaust gas mixing system and a major increase in the catalyst volume
could not solve the original problem. The uneven gas flow rate and temperature
distribution at the front face of the catalyst still deviated by 20–40% due to im-
proper turning vanes and lack of static mixers that the contractor had refused to
install. To obtain a Permit to Operate, the permitted NOx reduction rate was finally
negotiated and increased by the local regulator without hearing expert witnesses.
Figure 10 pictures such a flow modeling case and how an even gas flow can be
achieved through turning vanes and a static mixer in front of the SCR catalyst
bed.
The Reactor Housing and Stack Duct
These are normally heat insulated, made of heat resistant nonscaling molybdenum
alloy steel rather than stainless steel, which is sensitive to stress corrosion in
welded areas. They house the SCR catalyst and any oxidation catalyst or sound
deadening material as may be required by the specific application. In addition, they
house instrumentation probes for monitoring operating conditions and emission
FIG. 10 Flow modeling: before and after computer and scale modeling, improving the uneven (32%)
to a more acceptable (9%) flow rate deviation at the front face of the catalyst bed.
reductions. Manholes, loading and unloading equipment, and excess doors for han-
dling catalyst modules are required in larger, stationary SCR applications as well.
Most custom-engineered SCR systems have space available for adding a row or
layer of catalyst at a later date to reduce the emission even further or to meet
certain catalyst replacement strategies. (See Fig. 11.)
The SCR Catalyst
This is the ‘‘heart’’ of SCR systems and much research and development work
went into catalyst material formulations, structures, and production processes over
the last 20 years. Initially, catalyst ‘‘fouling’’ was a major problem, with the fol-
lowing concerns:
• Masking, washable flue gas deposits reduce the reactive catalyst surface tempo-
rarily
• Poisoning, an irreversible degradation of the catalyst surface
• Plugging, dust clogging of the catalyst, causing an increase in back pressure
and/or reducing catalyst reactivity/ performance.
The operating temperature window was limited to 570–850°F (300–450°C)

to avoid ammonia sulfate formations at low reactivity and ammonia combustion
problems at high temperature. These problems gave the SCR technology in the
early developments prior to the 1990s a bad name. Since then major R&D and
FIG. 11 Reactor housing with SCR catalyst in shelf system. (Courtesy of EESI/Steuler.)
application engineering work was carried out in Europe. Also, a pollution con-
trol industry, trucking industry and air quality regulator partnership conducted
lab/bench and field tests with several technical universities and certified test labs
in Europe. Various catalysts from different European and U.S. manufacturers were
evaluated in late 1980s to early 1990s Some test results from the technical univer-
sity RWTH-Aachen, Germany of 1989–1991 are shown in Table 1 and Fig. 12.
Upon the completion of these tests, the best performing ‘‘Catalyst A,’’ the diesel
catalyst from Siemens was selected by the European trucking industry for the field
tests in the early 1990s.
Today, several different types of SCR catalyst are commercially available from
several suppliers. The diesel SCR catalyst did overcome past SCR problems related
to high-sulfur fuel, a phosphorus and zinc compound containing lubricating oils,
arsenic resistance, and high-dust loads and allows operating temperatures as low
as 300°F (150°C) and as high as 1020°F (550°C).
Like most oxidation catalyst guaranties today, the SCR catalyst service life
was guaranteed for 1 year only during early developments. Today, the standard
process or performance guarantee for SCR systems worldwide is 20,000 operating
hours or 3 years, whichever occurs first, in stationary and several hundred thousand
kilometers in mobile, on-road applications, maintaining the emission reduction,
ammonia slip, and so forth.
Tank and Piping System for the Reducing Agent Anhydrous Ammonia,
Aqueous Ammonia, or Aqueous Urea
Anhydrous ammonia, a hazardous, toxic, and flammable gas, requires professional

handling. The operator of supply piping and anhydrous ammonia storage tanks is
Selective Catalytic Reduction
TABLE 1 European HDD Truck Tests, Catalyst Selection
Cpi SV(m3 /hm3) AV(m3 /hm2) A/V(m2 /m3)

A. Homogeneous, extruded V2O5 /TiO2 /WO3 45 5100 6.0 850
B. Coated substrate (CS-based) V2O5 /TiO2 100 8200 5.8 1400
C. CS based V2O5 /TiO2 100 8200 6.8 1250
D. CS based V2O5 /TiO2 /WO3 100 8200 6.8 1250
E. Homogeneous extruded zeolite Fe/molecular sieve 21 4000 7.0 570
F. CS based Cu/zeolite 100 8200 6.8 1250
Note: Cpi ⫽ Channels per inch, SV ⫽ space velocity, AV ⫽ area velocity, A/V ⫽ area/volume.
107
(a) (b)
FIG. 12 NOx (a) and VOC/HC (b) reduction rates at different temperatures during 30–50 operating
hours with NH3 slip of ⬍30 ppm.
required to strictly adhere to safety instruction of the manufacturers as well as to

local, state, and federal regulations.
Aqueous ammonia is safer but requires the same handling and storage precau-
tions as for anhydrous ammonia. In Europe, 25% ammonia concentration in demin-
eralized water is standard. In the United States, sometimes 27–29% ammonia
concentrations are common, requiring pressurized tank certifications and routine
maintenance in some states (i.e., New Jersey). Ammonia with a concentration of
20%, however, usually does not require such certified tanks.
Engineers with little or no corrosion engineering experience sometimes specify
carbon steel rather than SS316 for piping and lower-grade stainless steel for storage
tanks in case aqueous ammonia is used, not realizing that aqueous ammonia is
highly corrosive in the vapor phase. This tank corrosion has been causing extensive
downtime due to rust particles, clogging valves, spray nozzles, and so forth. Again,
this gave the SCR technology a bad name in the United States. Examples of SCR
systems with anhydrous and aqueous ammonia are shown in Fig. 13.
Aqueous urea, as salt dissolved in demineralized water, is nonhazardous, non-
toxic, and nonflammable and is primarily used as fertilizer and animal feed. It
required extensive R&D and application engineering development to make urea
SCR systems work properly and reliably. The urea SCR system engineering devel-
opment work in Europe was a prerequisite for applying the SCR technology to
mobile, on-road, and off/nonroad applications, now benefiting the new and retrofit
stationary combustion applications as well. Data on aqueous urea is presented in
Fig. 14.
The Ammonia and Urea Supply, Metering, and Injection Systems
These systems are due to the corrosive nature of the reducing agents made of
SS316 steel. To achieve proper mixing of the reducing agent into the flue gas, the
reducing agent is heated and diluted with hot air or recycled exhaust gas prior to
(a) Anhydrous Ammonia Tank
(b) Aqueous Ammonia Tank

FIG. 13 (a) Gas turbine application with PEMS and CEMS controls. (b) Gas/diesel (dual fuel) 4.8-
MW engine cogeneration plant. (Courtesy of EESI/Steuler.)
being injected into the exhaust gas stream in front of the catalyst bed. Alternately,
aqueous ammonia and aqueous urea may be co-injected and atomized with com-
pressed air directly into the exhaust pipe. Because the dissolved urea salt may
crystallize again and deposit around the spray nozzles, temperature control and
other design considerations have to be met. Also, aqueous urea requires a certain
reaction time to convert to ammonia in the exhaust duct, determining the injection
nozzle location upstream of the static mixer.
Aqueous Urea: (NH2)2 CO ⫹ H2O, industrial grade

Safety Aspects: Virtually nonodorous, nonhazardous, and nonflammable
Consumption: Molecular weight ratio NO2: Urea ⫽ 1:0.87
NO: Urea ⫽ 1:1.00
Concentration: Urea in demineralized water (%) 30 – 40%
Crystallization: ⫺11.4°C or ⫹11.5 F at 32.5% concentration
Salting-out temperature: ⫹ 0.6°C or ⫹33.0 F at 40% concentration
Specification:
Typical industrial grade Value Dimension
Example, Urea 40 ⫾ 0.5 %
pH 8.0–9.0
Density at 15°C 1105–1125 g/cm3
Viscosity (at 25°C) 1.38 mPa s
Specific heat (at 25°C) 3.26 kJ/kg K
Electrical conductivity (1.2–1.3) ⫻ 10⫺4 m S/cm
Temperature range without 0–35°C (32–95 F)
temperature control
Biuret ⬍0.5 %
Fe ⬍0.1 mg/kg
PO4 ⬍0.5 mg/kg
Mg ⬍0.1 mg/kg
Ca ⬍0.1 mg/kg
FIG. 14 Aqueous urea data. (Courtesy of Siemens.)
There are basically two types of supply, metering, and injection system designs
currently being used. The first is a constant high-pressure common rail piping
system with needle valves or unit electronic hydraulic injectors. The alternate sys-
tem incorporates corrosion-resistant, variable speed or variable stroke metering
pumps of different designs.
The reducing agent is metered and injected continuously in accordance with
the signals received from the microprocessor or Process Logic Controller (PLC)-
based SCR electronic operating control system. Such system may feature either
a feed-forward PEMS-based injection control, operating on historical computer
memory data, or the feed-forward control plus a slower, but fine-tuning feedback
control. The feedback system incorporates either a Continuous Emission Monitor-
ing System (CEMS) or sensors. Such custom-designed SCR systems used to oc-
cupy an entire row of control cabinets. The mobile SCR system developments re-
duced such controls to less than laptop computer size. (See Fig. 15.)
The Integrated, On-Line SCR Operating Control

and Emission Monitoring System
This features a Predictive Emission Monitoring System (PEMS), which operates

on historical emission data measured at different loads of the combustion equip-
ment during (for example, engine bench tests or gas turbine, engine, or boiler SCR
system) start-ups.
The correlation function of engine-load values versus NOx emission values
generated is combined with an algorithm in the software of the SCR control system,
calculating the amount of reducing agent required to reduce the NOx to the specified
(a)
(b)
FIG. 15 (a) SCR control system cabinets with PEMP and CEMS. (Courtesy of EESI/Steuler.)
(b) Laptop-size SCR operating and injection control system. (Courtesy of Siemens.)
permitted emission rate. An example of this ‘‘mapping’’ process is shown in Fig.

16a–16c.
Figure 16a shows the highest temperature of 900–950 F at 1000 rpm and me-
dium torque, a typical truck operating condition. Figure 16b shows that the highest
NOx emission is generated at medium speed and torque as well.
(a) (b)
(c) (d)
FIG. 16 (a,b) PEMS mapping: correlation functions of uncontrolled NOx and operating temperatures
of a 12-L HD diesel truck engine rated 400 HP. (c, d) PEMS mapping: correlation functions
of NOx reduction rates and break-specific fuel consumption. (Courtesy of Siemens.)
Figures 16c and 16d show that the highest NOx reduction takes place at medium
speed and medium torque (Fig. 16c), where the lowest fuel consumption is
achieved (Fig. 16d) as well. Engine test standards should therefore emphasize those
operating conditions.
The control system monitors all SCR system functions such as tank level con-
trol with high, reordering, and low limit, operating parameters such as exhaust gas
temperature and pressure drop of the SCR catalyst as well as all required mainte-
nance and trouble-shooting management functions. Thereby, the system communi-
cates with, for example, the electronic engine management system and the remote
central control panel or On-Board Diagnostic (OBD) system by CAN bus or via
4–20-mA or 0–5 V analog signals.
In many stationary applications, the local air quality regulator requires the use
of certified CEMS in accordance with U.S. EPA regulations such as 40 CFR Part
60, Appendix B for IC engines. Thereby, the accurate but expensive gas-analyzer-
based CEMS are often more capital-intensive than the SCR emission reduction
equipment, achieving NOx reductions of up to 90%. Again, this gave the SCR
technology a bad name.
Catalyst Selection Process
The type of SCR application determines the material and component selection.
Not all SCR catalysts and system components perform well in all SCR applications.
The SCR catalyst selection begins with a careful analysis of the performance and
guarantee requirements. Then, the SCR catalyst meeting the performance charac-
teristics best is selected. In some cases, this is not sufficient and the SCR catalyst
is optimized through changes in catalyst material formulations; for example, reduc-
ing the reactivity to avoid exhaust duct corrosion through SO2 ⬎ SO3 conversion
(SO3 ⫹ H2O ⬎ H2SO4), or changing the catalyst structure such as the cell density
of honeycomb catalyst from i.e. 200 to 300 cells/in.2, to reduce the weight and
the size of the SCR catalyst for a mobile on-road application where it matters most.
In several cases, oxidation catalyst manufacturers in the United States also included
oxidation catalysts upstream of the (SCR) catalyst, causing high corrosion through
up to 80% SO2 ⬎ SO3 conversion and reducing the NOx emission reduction by
converting more than 50% of NO ⬎ NO2, as shown in Fig. 17a–c.
SCR Catalyst and System Performance Parameters
Depending on the application, different operating conditions and performance re-

quirements have to be met. The following is a partial list of parameters that may
have to be considered while designing a SCR system:
• Fuels and fuel analysis: No. 1, 2, 3, and 6 fuel oil, natural gas, digester or
landfill gas, wood chips, chemical waste, liquid or gas, as well as the chemical
analysis thereof
• Fuel operation: different fuels as percentage of total operating time
• Flue gas analysis: NO/NO2 ratio, uncontrolled NOx and emission such as CO,
VOC/HC, PM and NH3-slip as well as the emission reduction requirements
• NOx —in: raw/uncontrolled emission at different loads of the combustion equip-
ment
• NOx —out: reduced, permitted NOx rate [kg or lb. per hour, ppm vd (dry by
volume)] at stack or tail pipe
• Exhaust gas mass flow rate (kg or lb. per hour, N m3 per hour or scfm) and gas
density
• Flow rate (m/s) and uneven gas flow and temperature deviations (%) at front
face of catalyst bed, requiring computer and/or scale-flow-modeling and static
mixer applications
• Maximum allowable pressure drop of the catalyst bed
• Pressure drop, total from combustion equipment to stack or tail pipe exit
• Sound attenuation requirements (dB A)
• Free-flow, area-, and space-velocity data
• Catalyst space availability: maximum cross section and length
• Temperature range, max. and min. at front face of catalyst at different loads
• H2O concentration in the flue gas
• O2 concentration in flue gas
(a)
(b)
(c)
FIG. 17 (a) Metal-substrate based noble metal oxidation catalysts. (Courtesy of Miratech/Hug.) (b)
Catalytic reactivity of noble metal catalyst for SO2 ⬎ SO3. (Courtesy of Dudoco 1995.) (c)
NOx reduction rate at increased pre-oxidized NO ⬎ NO2 at ⬃500 F (250°C). (VDI-Report
1995.)
• O2 concentration of air quality regulator’s standard for emission rate calcula-

tions at 5%, 7%, or 15% O2
• Acceptable process guaranties and equipment warranties
• Calculated catalyst bed dimensions and number of catalyst modules
• Oxidation catalyst requirements
• Particulate filter requirement
• Other
There are several SCR and Oxidation Catalyst and Application Engineering
Calculations required to layout a SCR system. For some basic calculations equa-
tions are provided in Fig. 18.
SCR Catalyst Material
There are basically three types of material used for SCR catalysts, noble, base
metal, and zeolite. The material formulations and manufacturing processes are usu-
ally proprietary developments of the manufacturers. The reaction of NOx with am-
monia takes place at the catalyst macropore surface, which may amount to 60 m2 /
per gram of material of noble or base metal catalyst materials. In the case of the
ceramic-zeolite-type catalysts, the exothermic reaction takes place inside the vast
micropore structure of over 200 m2 per gram of zeolite.
Noble catalyst metals are platinum, rhodium, and palladium. They can be used
for both NOx reductions and for the oxidation of VOC/HC, CO, PM. Due to the
high cost, primarily oxides of base metal are being used for SCR catalysts. Noble
metal oxidation catalysts may be used upstream and/or downstream of the SCR
catalyst: for upstream, to enhance the SCR NOx reduction by partially oxidizing
NO to NO2, which in some cases, however, is counterproductive if SO2 is converted
to SO3 as well; for downstream, to reduce possible ammonia slip spikes and CO/
HC not oxidized by the SCR catalyst. In HD diesel engine SCR applications using
the Siemens diesel SCR catalyst, oxidation catalysts are generally not recommended
because additional PM would be generated when burning sulfur fuel. Also, today’s
efficient HD diesel engines emit only minimal amounts of CO and VOC/HC.
Base-metal-based SCR catalysts contain oxides of base metals such as titanium
(TiO2), vanadium (V2O5), tungsten (WO3), and additive and ceramic binders. V2O5
is highly reactive and used in small amounts of up to ⬃2% only. Catalysts with
a high V2O5 content are used in the production of sulfuric acid (H2SO4) as well,
which would also form in exhaust gas ducts if SO2 oxidizes to SO3 catalytically
(SO3 ⫹ H2O ⬎ H2SO4). Base-metal-type SCR catalysts have nondiscrete mac-
ropores and channels, adsorbing ammonia, which is desorbed in a subsequent oper-
ation. This allows the adsorption of unreacted ammonia spikes (ammonia slip)
rather than passing through the stack as secondary emission. Ammonia slip rates
as low as 3–10 ppm have been achieved in continuous operations. The advanced
diesel SCR catalyst development allows NOx emission reductions at temperatures
as low as 300 F (150°C). Although originally developed for NOx reduction only,
the advanced SCR catalysts is able to simultaneously reduce VOC/HC by up to
95%, PM by up to 50% and NOx by up to 95% at no extra cost. In Fig. 21, the
plate-type and the extruded-type base metal catalyst packaging are pictured.
(a) The K values, the reactivity value of catalysts, may vary greatly, depending on type, material,
and structure of catalyst
SV
Keff. ⫽ ⫻ ln(1 ⫺ n), (1)
AV
where SV is the space velocity, the volume of the exhaust gas flow (N m3) per hour at normal conditions
divided by the volume of the catalyst (m3) resulting in (1/h), AV is the area volume, the catalyst surface
area per catalyst volume (m2 /pm3), ln is the natural logarithm, and n is the emission reduction rate (i.e.
95% ⫽ 0.95).
(b) Catalyst Volume (Vcat.)
VEGF (N m3 /h)
Vcat. ⫽ (m3) (2)
SV (1/h)
AV
SV ⫽ Keff. ⫽ see Eq. (1)
ln(1 ⫺ n)
where VEGF is the total exhaust gas flow at standard or normal condition (N m3 /h) and SV is the space
velocity. [For each proprietary catalyst formulation and structure variation, the manufacturer has devel-
oped proprietary space velocity table values for reactivity and NOx reduction rate (1/h).]
(c) Exhaust Gas Flow, (VEGF)
VEGF ⫽ VEGF min. ⫹ NGcons. (N m3 /h) (3)
VEGF min. ⫽ VAIR min. ⫻ NGcons. (N m3 /h) (4)
2(Cx ⫻ Hx)
VAIR min. ⫽ (N m3 /h) (5)
21
21
l⫽ (%) (6)
(21 ⫺ O2act.)
where VEGF min. is the volume of air consumption times O2 content times NG consumption (N m3 /h),
VAIR min. is the volume of air with 21% O2 required to oxidize total HC (N m3 /h), l is the percentage
O2 in the air used during combustion, Cx Hy is the various hydrocarbons (HC) of the NG analysis
making up the total HC, O2 act. is the actual oxygen (O2) concentration of the exhaust gas, and NGcons.
is the natural gas consumption (N m3 /h).
(d) Reducing Agent Consumption, Example Aqueous NH3 Consumption
NH3 cons. ⫽ VEGF(N m3) ⫻ NOx reduction (ppm)

⫻ 3.3/1,000,000 (kg/h) using aqueous (7)
ammonia with a 25% ammonia concentration,
NOx —Reduction ⫽ (NOx in ⫺ NOx out)(ppm), (8)
ppm NO ⫽ ppm NO ⫻ 30 (molecular weight)/22.4 (mg/N m ) 3
ppm NO2 ⫽ ppm NO2 ⫻ 46 (molecular weight)/22.4 (mg/N m3), (9)

ppm NH3 ⫽ ppm NH3 ⫻ 17 (molecular weight)/22.4 (mg/N m ), 3
ppm SO2 ⫽ ppm SO2 ⫻ 64 (molecular weight)/22.4 (mg/N m3),
21 ⫺ O2 stand.
O2act vs. stand ⫽ (ppmvd compound) (ppm vd) (10)
21 ⫺ O2 actual.
FIG. 18 (a) Reactivity of SCR catalysts; (b) catalyst volume calculation; (c) Exhaust gas flow calcula-
tions, natural gas combustion; (d) reducing agent consumption.
FIG. 19 Pellet-type catalyst. (Courtesy of SCAQMD.)
Zeolite, also called molecular sieve, is a ceramic material. Some zeolite struc-
tures occur naturally; others like the ZSM5 of Mobile Oil is produce synthetically.
Oil refineries heavily depend on them for their gasoline cracker, synthetic lubrica-
tion oil, and gasoline from natural gas processes. The extruded honeycomb-type
zeolite-based SCR catalyst has a very large micropore structure of over 2000 ft2
or 200 m2 per gram of material. NOx and NH3 are attached to the micropore surface
upon passing through the discrete pore openings of ⬃6–10 Å in size. This enor-
mous sponge effect compensates for major spikes of NH3 and NOx during rapid
load changes. The exothermic reaction of ammonia and NOx takes place inside the
micropore structure through electrostatic forces. The reaction products, N2 and H2O
vapor, are disposed of, back into the exhaust gas. This reaction is relatively slow,
requiring a higher volume of catalyst than, for example, base metal catalysts. How-
ever, the zeolite catalyst has superior resistance to many compounds such as heavy
metals, which are unable to enter the micropore structure through the discrete open-
ings, and thereby extending the service life of the SCR catalyst considerably. One
example of the over 1000 known different zeolite crystals is shown in Fig. 20.
Some other more novel combinations of zeolite with noble or base metal mate-
rials are presently being researched for PM and other emission reductions.
SCR Catalyst Structure
There are three types of SCR catalyst structure. The pellet-type catalyst, the ex-
truded monolithic, honeycomb-type catalyst using either oxides of base metals or
zeolite, and the coated-substrate-type catalyst, incorporating either corrugated foil
FIG. 20 A zeolite crystal.
or plate-type stainless-steel sheet metal or extruded Corderite ceramic substrates.

There is also a novel catalyst development incorporating fiber-based substrates.
(See Figs. 20–22).
Pellet-type catalysts are filled in containers through which exhaust gas is
passed. The pulsing exhaust gas flow, however, cause the pellets to vibrate, abrade/
erode, and dust. The dust settles, clogging the catalyst bed and prevents an even
gas flow. Due to the erosion of the pellets, the catalyst bed shrinks and unreacted
exhaust gas will bypass together with the injected ammonia over the top of the
catalyst bed into the atmosphere. Thus, pellet catalysts do not work most of the
time and were replaced as soon as the honeycomb-type catalysts became available.
However, there are still several such reactors operating in southern California
today.
FIG. 21 Left: Coated stainless-steel mesh/expanded metal-substrate-based plate-type catalyst for

high-dust applications; right: extruded, honeycomb, monolithic, base metal diesel catalyst.
(Courtesy of Siemens.)
FIG. 22 Macropore structure of extruded base metal catalyst.
The extruded, monolithic, honeycomb-type SCR catalyst has low back pressure
and is widely used for gas turbines and boilers, engines, and other applications.
The higher the number of extruded channels per square inch (cps), the higher the
reactivity/active surface area and the smaller the catalyst for a specific application.
Advanced base-metal-type SCR catalysts are available with 14–300 cps with chan-
nel wall thicknesses of 0.3–1.08 mm containing the macropore structure. This
advanced catalyst development allows NOx emission reductions at temperatures
as low as 300 F (150°C). The lack of a ‘‘sponge effect’’ may also be the reason
for the lower emission reduction rates achieved by the coated-substrate-based cata-
lyst at temperatures below 480 F (250°C); see Fig. 23.
The coated-type SCR and oxidation catalyst has usually three layers: the corro-
sion-resistant substrate (such as the extruded Corderite monolith, corrugated stain-
less-steel foil or mesh plates, the aluminized washcoat to which the third layer,
the catalytically active material, is bond. The corrugated foil substrate is primarily
used for noble metal catalysts, whereas the Corderite monolith is used for noble
and base metal. The plate-type catalyst has been developed for flue gases, con-
taining high-dust loads, such as the hard coal utility boiler, industrial and municipal
solid-waste incineration, and other industrial applications. Long-term operating
experiences in Europe showed that the erosion of the reactive catalyst material at
the face of the SCR catalyst bed will terminate upon the exposure of the stainless-
steel substrate, extending the service life. Due to the smaller macropore structure
and surface area and thus absorption capability, the coated-type catalyst is less
reactive.
Conclusion
It would be beyond the scope of this introduction to the SCR technology to go

into further details of the process and the application engineering (i.e., review
basically 10–20-year-old designs for coal and gas utility boilers). The future of
(a)
(b)
FIG. 23 (a) Extruded monolithic honeycomb catalyst macropore structure versus the reduced coated-
metal substrate-based macropore structure. (b) Standardized test: relative reactivity of ex-
truded (⫽1) versus coated-catalyst structures depending on thickness of coating (⫽0.6 and
0.2) at space velocity of 60,000/h. (Courtesy of Siemens.)
the SCR technology lies in distributed power generation applications such as gener-
ation sets, cogeneration sets, and mobile on-road and non-road applications. There
are already close to 1000 IC engine and turbine applications in service worldwide
today (Intermacom AG). This number could multiply when HDD trucks and other
mobile SCR applications come to market in 2001 through 2010. In the following
section, a few examples of SCR projects are summarized. However, because some
past design, application engineering, and operation deficiencies gave the SCR tech-
nology a bad name in the United States, SCR systems engineers will have to pay
more attention to design and application engineering details in future (Table 2).
TABLE 2 Why Certain SCR Systems Have Not Performed in the United States
Advanced (SCR)
Failure Cause Technology Solutions
Catalyst
1. Clogging and bypass of Pellet type catalyst Honeycomb or plate-type
NOx and NH3 slip catalyst
2. Reactivity loss Masking, poisoning, or de- Special lean burn/diesel cat-
lamination of catalyst alyst, homogeneous ma-
coating with metal or terial, allowing up to 3%
Corderite-based sub- sulfur fuel and an op-
strates erating temperature win-
dow of 300–1020 F
3. Emission spikes at rapid Little to no adsorption/ Diesel catalyst with micro-
load changes desorption capability of pore structure/‘‘sponge
catalyst (nonmonolithic effect’’ with adsorption/
catalysts) at ⬍500 F desorption features
(250°C)
System Design
1. Clogging of injection Heavy corrosion/particle All stainless-steel storage,
system valves or noz- volume due to carbon delivery and injection
zles steel aqueous ammonia system
tank and piping material
2. Clogging of catalyst Carbon steel reactor hous- Heat-resistant steel such as
ing, scaling/ particles low Molly steel
due to temperature
cycling
3. Low emission reduction Uneven gas flow at front Gas flow modeling, scale
face of catalyst bed or in- model tests, and low
sufficient mixing of ex- back-pressure static mix-
haust gas/NH3 ers such as Parmix TM/
TM Siemens
Controls and Other
1. High emission spikes at Relying only on a down- Feed-forward PEMS-based
load changes stream CEMS with long control with optional
feedback/response time feed back CEMS or
sensor-based control
2. Not cost effective Including a fully certified Electric–chemical sensor-
CEMS, which is often based accurate spot
more costly than the check analyzer with peri-
SCR emission reduction odic emission testing by
system for NOx, VOC, third party
and PM itself
3. Politics: Operator’s Operators avoiding fines, Independent test lab certifi-
good references but bad shutdowns, and lawsuits cation, confirming equip-
performance of air pollu- of poorly maintained sys- ment manufacturer’s
tion control equipment tem or new/unproven long-term performance
in actual operation technology, ‘‘pro- claims during a 3-year
moted’’ by the regulator performance guarantee
Summary of SCR Application Case Studies

Diesel/Coal-Slurry Fueled Diesel Engine Cogeneration Plant,
University of Alaska, 1999
System Overview
The University of Alaska, Fairbanks (UAF) has a 9000-kW electric Fairbanks–

Morse reciprocating engine, which currently is fueled on No. 2 diesel fuel upon
start-up in Summer 2000. UAF, in partnership with Fairbanks–Morse and the De-
partment of Energy (DOE), has been constructing a demonstration project to test
the feasibility of pulverized coal mixed in water, a coal slurry as an alternative
fuel. Fairbanks–Morse had already developed and tested the engine modifications
in their research facility in Wisconsin so that the long-term field tests could com-
mence in 2000. The engine will provide electrical power for the campus. Power
not used by the campus is sold to the local electric utility. An exhaust waste heat
recovery system generates steam, which is used for heating and cooling campus-
wide.
An SCR system was proposed to reduce NOx emission. Because of the rela-
tively high sulfur content of the fuel and the required low SO2 to SO3 conversion,
a zeolite catalyst was selected. When operating on coal slurry, the engine produces
large amounts of particulate matter (PM). In order to deal with the high-PM load,
the extruded monolithic honeycomb SCR catalyst was designed with a larger than
normal pitch or channels per square inch (CPSI). This allows the PM to pass
through more easily. The system was designed with a vertical exhaust flow, from
top to bottom, allowing the PM to pass through and being collected in an ash
hopper below the catalyst housing. A soot-blowing system has been installed above
the catalyst. The soot blower automatically blows down the PM from the catalyst
at regular intervals when the engine is running on coal slurry. When running on
diesel, the exhaust gas PM or soot concentration is low enough to operate without
the soot blower.
The SCR system is designed to reduce NOx emissions independently of the
fuel used. Because there is a large difference in NOx emission, exhaust temperature,
and exhaust flow rate between the two fuels, the system had to be designed with
a wide operating range. When running on diesel fuel, exhaust temperature and
flow, and NOx emissions are higher than when running on coal slurry. A system
of duplex metering pumps was furnished. The reducing agent flow is adjusting by
varying the speed of the metering pumps. When operating on coal slurry, only one
pump is required. When operating on diesel, both pumps will run.
The system is designed to use aqueous ammonia (20% NH3 in demineralized
water by weight) as the reducing agent. Ammonia was selected over urea because
it is easier to source in the region, and because urea would require a great deal of
temperature control during winter operation. Injection rate control utilizes a feed-
forward system, which sets pump speed based on engine load. A control feedback
is used which measures NOx emissions upstream and downstream of the catalyst;
this data are then used to ‘‘trim’’ or fine-tune the reducing agent injection. The
continuous emission monitoring system (CEMS) analyzer (furnished by UAF) al-
ternately reads emissions upstream and downstream of the catalyst and thereby
provides the feedback necessary to ensure that the SCR system is operating at peak
emission reduction with minimal ammonia slip.
The system is designed to reduce NOx emissions by 90%, with ammonia slip
of 10 ppm or less. Currently, since the system start-up in Summer 2000, the system
is operating within these parameters, on diesel fuel.
During commissioning, a 90% NOx reduction and almost zero ammonia slip
was measured. The construction on the coal–water slurry production facilities will
start in 2001. The engine is scheduled to run primarily on coal slurry by late 2001
or early 2002.
In Fig. 24, the process and instrumentation diagram (P&ID) and modified sum-
mary excerpts of the operating and maintenance manual are presented. Figure 25
shows the Table of Contents of the summary excerpt of the Operating and Mainte-
nance Manual.
Design Parameters
The SCR system is designed based on the parameters shown in Fig. 26.
SCR Catalyst and Housing

CER-NOx (SCR) Abatement Catalyst. The CER–NOx* (SCR) NOx abate-
ment catalyst is a honeycomb-type, molecular sieve, all-zeolite catalyst. Zeolites
are crystalline microporous ceramic solids with pore openings of 3–10 Å. The
micropores provide over 1500 ft2 of surface area per gram of zeolite material.
The SCR catalyst is located in the exhaust gas stream downstream of the Fair-
banks–Morse engine, before the heat recovery boiler. Each catalyst module has
dimensions of ⬃152 mm ⫻ 152 mm ⫻ 1000 mm long, without wrapping. Each
module has openings with a 6-mm pitch/cps (channels per square inch) to allow
particulate matters (PM) to pass through without plugging. Seventy-two modules
are wrapped in a stainless-steel cartridge, which protects them from mechanical
damage. The catalyst cartridge weight is 1510 kg (3329 lbs.) and its dimensions
are 1920 mm ⫻ 960 mm ⫻ 1365 mm height.
Chemical Process. Ammonia reacts with NO and NO2 within the zeolite cata-
lyst micropore structure to form nitrogen gas (N2) and water vapor (H2O). Nitrogen
oxides and the injected aqueous ammonia are removed from the exhaust gas
through adsorption into the catalyst micro pores of the zeolite, based on the concen-
tration gradient. Electrostatic forces generated inside the micropores decrease the
activation energy for the reduction process, thus allowing reactions to occur in a
temperature range of 300° C/570° F to 480° C/900° F.
The reaction releases energy, which forcibly expels the reaction products N2
and H2O from the micropores.
* CER-NOx is a trademark of EEST/Steuler.

124
FIG. 24 Process and instrumentation diagram (P&ID) of the Alaska cogeneration plant. (Courtesy of EESI/Steuler.)
Selective Catalytic Reduction
CER-NOx (SCR) NOx ABATEMENT SYSTEM

Overview and Component Description
Table of Contents
1. Design Parameters
2. (SCR) Catalyst & Housing
a) CER-NOx (SCR) Abatement Catalyst
b) Chemical Process
c) (SCR) Reactor Housing
3. Aqueous Ammonia Supply & Injection System
a) General Description
b) Ammonia Metering Panel
c) Compressed Air Subsystem
d) Electric Sub-panel
e) Ammonia Injection Lance Assembly
f) Static Mixer
g) Ammonia Pump Station
h) Ammonia Storage Tank
i) Ammonia Tank-Truck Unloading Station
4. Operating System Control
a) Condition
b) Analysis
c) Action
5. Operating Routines
a) Start Up
b) Normal Operation
c) Shut Down
6. Maintenance Routines
7. Daily Log, Visual Inspection
FIG. 25 Table of Contents of the CER–NOx SCR system.
SCR Reactor Housing. The housing is fabricated of A36 carbon steel. It in-
cludes the following:
• A 90° inlet transition from the exhaust duct to a turning vane assembly to distrib-
ute the exhaust gas evenly across the catalyst bed
• A shelf system with one row for catalyst
• One soot-blowing system to blow ash off the catalyst bed during coal–water
fuel operation. The system includes control valves, isolation valves, and drive
motors, controlled from the Co-gen plant control system
• Bolt-on access doors provided in order to load and unload catalyst; catalyst is
loaded into the housing after the housing has been installed
Aqueous Ammonia Supply and Injection System

General Description. The reducing agent supply and injection system consists
of a storage tank, an ammonia pump station, a metering panel, an injection spray
nozzle, and interconnecting piping. A static mixer is welded into the inlet of the
reactor housing to properly mix the reducing agent and to evenly distribute the
• Emission source: Fairbanks–Morse dual-fuel engine, 9000 kW(e)/ ⬃12,500 BHP

• Fuel type: either diesel fuel or coal–water slurry fuel
Combustion Process Information:

Diesel Fuel Coal Slurry Fuel
Exhaust flow rate, lb/hr 155,800 105,400
Exhaust temp., max, °F 837 800
Exhaust temp., design, °F 665 765
CO2, weight % 8.6 11.3
O2, weight % 13.3 11.9
H2O, weight % 3.5 6.6
N2, weight % 74.4 70.2
NOx, volume 0.18 vol.%, wet 600 ppmv
SO2 0.016 vol. %, wet 79 ppmv
Ash/particulate, lb/hr 2.2 350
—SCR System Performance
NOx Reduction, % 90% —
Ammonia slip 10 ppmvd (15% O2)
SO2 to SO3 conversion 0.1% max
Pressure drop, max., for clean system 1.75″ water column, measured from inlet hood to
end of catalyst bed
—Reducing Agent Aqueous ammonia, nominal 25% in water
Technical grade in demineralized water only!
—Reducing Agent consumption 53.1 gal/h 21 gal/h
—Atomizing Air Requirements
Pressure Minimum 70 psi, maximum 120 psi
Consumption 32 SCFM
FIG. 26 Design parameters for the SCR system. (Courtesy of EESI/Steuler.)
exhaust gas across the front face of the catalyst. The metering panel is controlled
by the Co-gen plant’s Distributed Control System (DCS).
The reducing agent is supplied via stainless-steel pipe to the metering panel.
An ammonia pump station provides pressurized (⬃40 psi) ammonia to the ring
line. The metering panel contains metering pumps, which controls how much re-
ducing agent is injected into the gas stream. Refer also to Fig. 24.
Ammonia Metering Panel. The metering panel is divided into two subsys-
tems: one for reducing agent control, the other for control of atomizing compressed
air. The reducing agent subsystem consists of the following components:
• One fine filter (7 µm) on the pump outlet.

• Two metering pumps (P-103, P-104). During coal–water fuel operation, only
P-103 is operated. When the engine runs on distillate fuel, P-103 is run at full
speed and P-104 is operated at varying speed to provide the balance of the
reducing agent volume required.
• Two variable-speed drives (SIC-103, SIC-104), one for each metering pump
motor. Each drive is controlled by the DCS via a 4–20-mA signal (for speed
setting) and dry contacts (for starting/stopping the drive). A 240-VAC single-
phase input to each drive is converted to a 240-VAC three-phase, variable-

frequency output to the metering pump motor. The drives are located in an
electrical subpanel mounted on the side of the metering panel.
• One normally closed (energized to open) solenoid shutoff valve (FV-101). This
valve gives a positive shutoff of the reducing agent feed when the system is
turned off. The valve is controlled by the DCS. The valve is opened when a
metering pump is started and closed when the metering pump is stopped.
• One pressure gauge (PI-105) on the pump discharge to monitor injection pres-
sure.
• Two relief valves (PSV-103, 104) to protect the metering pumps.
• Two pulsation dampeners to absorb pulsations from the diaphragm pumps.
• One magnetic-inductive flow meter (FE/FIT-101) which provides feedback to
the DCS to close the feed rate control loop.
Compressed Air Subsystem. This subsystem consists of the following com-

ponents:
• One pressure regulator (PCV-201), to maintain air pressure at 43 psig.

• One filter/dryer, to remove particulate matter and moisture from the compressed
air.
• One normally closed (energized to open) solenoid valve (FV-201). This valve
closes off the airflow when the system is not running. It is controlled automati-
cally by the DCS.
• One pressure switch (PSL-201). If the air supply pressure drops below 50 psig,
the pressure switch contacts open, signaling the DCS.
Electrical Subpanel, Mounted on the Metering Panel. This subpanel con-

sists of the following components:
• One 20-A disconnect switch, to provide a local disconnect of the 240-V power
supply to the metering panel
• One 24-VDC power supply to provide power for the solenoid valves and flow
meter
• Three circuit breakers to distribute AC power to the two variable speed drives
(SIC-103 and SIC-104) and 24-VDC power supply
• One circuit breaker to switch on the outlet of the 24-VDC power supply
• Two loop isolators for the variable-speed drives (SIC-103 and SIC-104) speed
setting input
• Four 2PDT pilot relays with 24-VDC coils, to take control inputs from the DCS
for SIC start/stop control.
Ammonia Injection Lance Assembly. The injection lance is inserted into

the exhaust duct upstream of the first static mixer. The lance’s spray head shall
point in direction of flow. The lance consists of an air/liquid atomizing nozzle and
a carrier pipe, which transfers the atomized reducing agent into the exhaust duct.
Static Mixer. One static mixer is provided, which is welded into the duct up-
stream of the reactor-housing inlet. The mixer ensures proper ammonia/exhaust
gas mixing.
Ammonia Pump Station. The ammonia pump station supplies aqueous am-
monia to the ring line feeding the metering pumps. It consists of the following:
• One supply pump, P-102, diaphragm type with fixed speed and capacity of 90
gal/h.
• One motor, M-102, 1/3 hp, 115-VAC single phase, TEFC to drive P-102.
• One pulsation dampener, to remove pulsations from the pump outlet.
• One inlet strainer, 190 µm, to remove larger particle from the aqueous ammonia.
• One pressure relief valve, PSV-101, to protect the pump.
• One pressure/vacuum gauge (PI-103) on the inlet and one pressure gauge (PI-
104) on the pump outlet.
• One back-pressure control valve (PCV-102) to set ring line pressure; the return
side of the ring line is connected to the PCV.
• One control panel, with HOA switch, main disconnect, motor contactor, in
NEMA 4 enclosure. This panel also houses the ammonia tank level indicator/
switch (LIS-101) which indicates the tank level in gallons.
Ammonia Storage Tank. The aqueous ammonia storage tank holds 8000 US
gals, is made of 304 stainless steel, and is resistant to the highly corrosive ammonia
vapor above the liquid. The tank is designed for atmospheric pressure. It is supplied
with ball valves, a safety valve, and a level transmitter, shown on Fig. 24.
Ammonia Tank-Truck Unloading Station. The unloading station is used to

transfer aqueous ammonia from the delivery tank truck to the bulk storage tank.
It consists of the following:
• Centrifugal transfer pump, P-101, with capacity of 100 gal/min.

• A 3 HP, 3450 rpm, 460VAC motor, M-101.
• Flow switch, FE/FS-101, interlocked to the motor, to shut down the pump if
flow is lost.
• One pressure/vacuum gauge (PI-101) on the inlet and a pressure gauge (PI-
102) on the pump outlet.
• Cam-and-groove fittings for the tanker to connect.
• Control panel, NEMA 4 enclosure, with manual start/stop control switch and
interlock with the flow switch above and the ammonia tank level switch (LIS-
101). Upon a ‘‘high tank level’’ alarm, the unloading pump will be shut down.
Operating System Control
The SCR system is controlled by the central DCS of the Co-gen plant. The general
operating sequence should follow the program in Table 3. See the detailed program
description for pin assignments and input/output requirements.
TABLE 3 Operating System Control

Condition Analysis Actions
On start of engine Begin purge of injection Send ‘‘start’’ signal to P-
lance 102
Start pump P-102
Advice from Engine con- DCS decision on which me-
trol if running on distil- tering pump to run
late or coal–water fuel
Exhaust gas temperature Exhaust temperature for Open ammonia valve FV-
(570 F) (from TIT-301) SCR Process OK, ammo- 101
nia injection permitted Start metering pump P-103
(if CWF) and P-104 (if
distillate fuel)
Exhaust gas temperature Exhaust temperature for Stop metering pumps
(896 F) (from TIT-301) SCR Close ammonia valve FV-
Catalyst too high 101
Ammonia storage tank low The ammonia tank empty Stop metering pumps;
level close ammonia valve
FV-101
Atomizing air pressure low Failure of compressed air Stop metering pumps;
system close ammonia valve
FV-101
Ammonia flow below min Failure of metering pump; Stop metering pumps
value (from FIT-101) allow 1 min time delay
and metering pump start from start of pump be-
signal is given, and me- fore writing alarm
tering pump speed signal
above min value
On shutdown of engine Stop metering pumps;
close ammonia valve
FV-101; close air valve
FV-201; stop ammonia
pump P-102
Source: EESI/Steuler.
Operating Routines
Start-up. Upon a complete equipment shutdown, the following restart checks
have to be performed: No maintenance is being performed at the NOx abatement
system, a visual inspection shows no disconnected or broken pipes, wires, and so
forth, and the reducing agent supply is available.
• Open all hand valves in the reducing agent supply and injection lines
• Atomizing compressed air supply (compressor) available
• Open all hand valves of the atomizing compressed air supply and aqueous am-
monia injection lines
• Verify that the DCS available
• Verify power is available to metering panel
• Start the system via the DCS upon determine permissive conditions to start
injection based on temperature, lack of alarm signals, and other operating pa-
rameters
Normal Operation. Under normal operating conditions, the DCS controls the
speed of the reducing agent pumps in accordance with the NOx signal received
from the continuous emissions monitor-based feedback. It is generally not required
to make adjustments or continuously monitor the system.
Shutdown. If the system will be shut down for maintenance, and so forth, the
following steps have to be taken:
• Shut down aqueous ammonia injection and allow system to purge lines and
lances with compressed air
• Shut off power supply to the metering panel
• Close air and ammonia hand valves at inlet and outlet of metering panel
Maintenance Routines
In general, routine maintenance on the CER-NOx SCR system is limited to occa-

sional visual inspections, pump oil changes, and periodic replacement or cleaning
of filters. Usually, the system can be quickly checked out in conjunction with other
maintenance activities. Table 4 outlines how often certain maintenance procedures
should be performed. Note that these intervals assume continuous operation. Under
intermittent operation, these intervals could be extended. The operator shall deter-
mine if the intervals can be lengthened based on operating experience.
Daily Log
Table 5 is the inspection checklist.
Gas Turbine Combined Cycle Power Plant Rated 2 ⫻ 170 MW,

Natural Gas/Liquid Fuel Fired at Bridgeport Harbor, Connecticut
Overview
Cogeneration and distributed power generation will be the preferred and most fuel-
efficient way of the future to generate heat and electricity as fuel cost increases
and the utility industry becomes fully deregulated. Rather than ‘‘destroying’’ the
so-called ‘‘waste heat’’ in cooling systems, the local heat requirement will be the
driving output/product and the by-product, the excess electricity can easily be
wired away. Fuel efficiency has been a driving force of air-pollution control regu-
lator outside the United States in the power generation community, especially
in Japan and Europe. Fuel efficiencies of over 85% versus 50–60% max. in
TABLE 4 Maintenance Routine

Operation Daily Weekly Monthly Biannual Annual
Visual inspection (see: Visual Inspec- X
tion Daily Log)
Check reducing agent supply tank level X
Check/replace metering pump (P-103/ X
104) and ammonia transfer pump
(P-102) oil. Replace every 1000 h
of operation
Drain differential pressure gauge X
(PDIT-301) condensate lines for
SCR reactor
Record differential pressure indication X
for SCR reactor
Clean/replace reducing agent in meter- X
ing panel
Clean atomizing air filter in metering X
panel
Clean reducing agent strainer at ammo- X
nia pump station
Check/replace metering pump and X
transfer pump diaphragms
Check metering panel and pump sta- X
tion pulsation dampener charge
Check/rebuild metering panel solenoid X
valves (FV-101/201)
Check metering panel pressure relief X
valve setting (PSV-103/104)
Check air pressure switch (PSL-201) X
setting
Check injection lance nozzle for X
cleanliness
Calibrate all 4–20-mA loops to DCS X
Source: EESI/Steuler.
combined-cycle, gas/steam turbine projects have been achieved. A Swedish utility

company operates a 1200-MW cogeneration power plant, providing heating to the
town nearby. The Saarbruecken utility company in Germany, reducing CO2 emis-
sion by over 15% in the prior 10 years, primarily through cogeneration, received
the U.N. Environmental Award at the summit of world leaders in Rio, Brazil in
1990.
In the United States, utility companies have rarely opted for the highly fuel-
efficient cogeneration plant alternative yet. The new or upgraded power plants,
however, usually incorporate gas turbines and downstream steam turbines, utilizing
the steam generated from the ‘‘waste heat’’ of the gas turbine for electricity genera-
tion.
TABLE 5 Inspection Checklist

Initial
Inspection check list when done
1 Inspect reducing agent storage tank, and stainer for good physical con-
dition.
Verify no leaks exist.
2 Inspect supply line between reducing agent storage tank and metering
panel.
Verify no leaks exist and that isolation valves are fully open.
3 Inspect atomizing air source. Verify that no leaks exist in air supply
lines between atomizing air source and metering panel, and that iso-
lation valves are open, and correct pressure is available (75–120 psi
4 Check metering panel for proper position of its isolation valves (fully
open), proper draining of condensate drains, that no physical dam-
age exists (internal or external of enclosure), and that no air or re-
ducing agent is leaking inside or outside of enclosure. If system is
running, that it is making normal operation noises, and when fin-
ished; that the door is closed and latched.
5 Inspect air and reducing agent lines between metering panel and injec-
tion lance for good physical condition. Verify no leaks exist and
that isolation valves are fully open.
6 Check that injection lance is in good physical condition (no bent or
cracked hook-up ports).
7 Inspect insulation on exhaust duct and SCR housing for condition and
proper installation. Verify that no obvious exhaust leaks exist (indi-
cated by soot tracks at insulation joints).
8 Check thermocouple probe at inlet of SCR housing that no exhaust
leaks exist and that termination cover is in place.
9 Inspect the SCR differential pressure gauge and its associated block
and bleed valves. Verify that they are not damaged and are properly
positioned (high- and low-pressure input valves open, bypass valve
closed, condensate lines closed).
10 Verify that the DCS is operating normally and that no alarms are dis-
played.
Project Summary
The (2) Siemens V 84.3A gas turbine project is rated 170 MW electric per gas
turbine. The process and instrumentation diagram (P&ID) of the SINOx exhaust
gas cleaning system is shown in Fig. 27. The SCR system design is based on the
exhaust gas data listed in Figs. 28a and Fig. 28b. The system ensures State of
Connecticut EPA compliance with the emission reduction of 91% to 4.5 ppmvd
at 15% O2, dry basis for nitrogen oxides (NOx, as NO2).
The SINOx (SCR) system features the use of either aqueous urea or aqueous
ammonia as the reducing agent to meet future, more restricted safety regulations.
The SINOx system was delivered as two preassembled units.
FIG. 27 P&ID of a (2) gas turbine power generation plant.
A brief technical description of the systems function is provided in Fig. 29 and

a system maintenance schedule is given in Fig. 30.
Mobile, Portable and Other Applications

Background Summary
California ARB (Air Resources Board) Strategy for Additional Emission
Reductions by 2007/2010. During the University of California–Irvine Tech-
nology Meeting on October 6, 1999, the Cal.-ARB presented its objectives to sub-
stantially reduce NOx, HC, and PM emissions. To achieve California SIP (U.S.
EPA’s State Implementation Plan) goals by the year 2007/2010 emission of on-
road and off/nonroad vehicles and equipment could be reduced by market incentive
and monetary incentive programs. Retrofit emission reduction applications for die-
sel locomotives, diesel-powered coastal vessels and construction/mining equip-
ment, portable generation sets, and various agriculture (i.e., irrigation/pump drives)
and garden equipment should be prime targets.
Summary of Recent Market Data on Retrofit Emission Reduction Target

Markets. Over 50% of the total U.S. NOx emission inventory of ⬃25 million
tons per year and close to 60% of PM emissions is generated by portable, on-road,
and off-road vehicles and equipment.
(a)
(b)
FIG. 28 (a) Project data, operating conditions of the (2) gas turbines; (b) project data, system utilities.
FIG. 29 Brief description of the SINOx system process.
• A total of 2.2 million tons/year of NOx from the United States representing
8.6% were assumed from Class 8 HD diesel trucks. However, due to excess
‘‘off-test-cycle’’ emissions of 15.758 million tons during 1988 through 1998,
caused by 1.328 million Class 8 trucks, an additional 1.3 million tons of NOx
per year had to be added, for which engine manufacturers were fined in a con-
FIG. 30 System maintenance schedule.
sent decree. This increased HDD truck NOx emission resulted in over 3.5 mil-
lion tons of NOx emission per year, equal to 12% of the total U.S. NOx inven-
tory.
• The Consent Decree of the U.S. Justice Department and the U.S. EPA, the State
of New York, and Cal.-ARB with the engine manufacturers did not incorporate
any short-term remedies but only engine-rebuilt solutions for this large fleet
of highly fuel-efficient HDD trucks. One reason, according to industry, is the
unrealistic U.S. FTP (Federal Transient Protocol) test cycle with heavy empha-
sis on low torque/low rpm and high rpm, whereas most truck operations take
FIG. 31 Product summary, SINOx SCR System. (From Intermacom AG, Feb. 20, 2000, Draft for
the WebPages of Cal.ARB.)
place in medium torque/rpm. In comparison, Japanese and European tests cycles

emphasize medium torque/rpm, almost neglecting the low torque/low rpm oper-
ation. One of these European tests shall now complement the U.S. EPA FTP
tests. New trucks however, are required to meet NOx ⫹ HC emission levels of
2.4 gr./BHP h by 2002/2004.
• Off-road NOx and PM emission from diesel-powered locomotives, ships, con-
struction, mining, and agriculture equipment as well as portable equipment such
as generation sets have not been a U.S. EPA priority even though they account
for approximately one-quarter of the total U.S. NOx inventory. By 2010, U.S.
diesel locomotives are required to meet 5.6 gr./BHP h. California has an earlier
target date and fleet averaging provisions. Also, marine applications lag behind,
even though less than 2 gr./BHP h NOx emission rates have been demonstrated
in close to 100 marine diesel engine applications (with engines rated 300 to
over 10,000 BHP) in Europe. Portable generation sets are not required to
achieve better than 5.9 gr./BHP h NOx emission rates in California, whereas
some of the same engines in trucks have to meet 2 gr./BHP hr NOx in 2002/
2004. According to Cal.-ARB there are 72,064 portable and stationary diesel
engines without emission controls in California, rated 110–600 BHP.
Reports on Technology Evaluations. In recent publications of UC-Davis’

ITS (University of California, Institute for Transportation Studies) and Diesel Fuel
News, various emission control strategies for HD diesel engines were discussed.
Two most promising retrofit technologies were identified achieving over 70–80%
NOx and VOC/HC and substantial PM emission reduction: The UREA–SCR and
the NOx Absorber Technology. All other retrofit/post treatment technologies are
either years away from any commercialization or achieve only 20–40% NOx reduc-
tion rates.
• The NOx Absorber Technology has been tested by Cummins, using the Euro-3
(13 Mode) Steady State Diesel Engine Tests and 5 ppm sulfur fuel, achieving
80% NOx reduction at a 8.5% fuel penalty. In a Marathon–Ashland Petroleum
commentary to U.S. EPA, it is claimed that only a 20,000-mile service life with
5–15 ppm sulfur fuel could be expected. Currently, no 15 ppm sulfur fuel is
commercially available on a large-scale basis in the United States. The U.S.
EPA does expect that such 15 ppm sulfur fuel will be readily available in the
United States prior to 2007. In addition, lube oils with phosphor and sulfur com-
pounds have to be reformulated and tested to avoid loss in engine service life.
• The UREA SCR Technology for the simultaneous reduction of NOx (70–85%),
VOC/HC/AirToxics (80–95%), and PM (up to 50%) has already been used in
HDD truck field tests in Europe and the United States in the 1990s. The technol-
ogy will be commercially available by 2001, has been field tested for 4 years,
and demonstrate no fuel penalty. The service life is expected to be over 300,000
miles and the initial target price is estimated to be US$ 2000–3000 per HDD
truck. The European truck manufacturers and Siemens pioneered this technol-
ogy. By the end of 2001, Siemens will go into the SCR system production for
Daimler–Chrysler and MAN’s new ultralow-emission HD diesel trucks. The
volume-produced SINOx Systems can then be used for mobile, transportable,
(a)
(b)
FIG. 32 (a) Stationary and mobile applications for the diesel SCR catalyst. (b) Simultaneous reduction
of NOx, VOC/HC, and PM at stationary and mobile applications. (Courtesy of Siemens.)
and stationary engines rated 100–600 BHP. However, to use the prefabricated,
off-the-shelf SINOx products as retrofits kits, engine model/application adapta-
tions through local factory trained and licensed dealers are required.
The SINOx SCR systems are used in coal and gas-fired utility boilers and gas
turbines, stationary and portable generation sets, cogeneration, and various mobile,
on-road and off/nonroad applications. Figure 32 shows the range of SINOx Appli-
cations.
Jet Fuel Pipeline Pump Station for the New York Area Airports, NJ
This SCR application was discussed in two U.S. engineering journals in 1998.
Three 3000-BHP gas engines with low NOx emission exceeded the plants VOC/
HC/AirToxics, CO, and NOx emission limits, set by the State of New Jersey. Figure
33a shows one of the three engine enclosures with the SCR system and exhaust
stack located in front. In Fig. 33b, the engine data are listed. The system design
aspects are listed in Fig. 33c. The process guaranteed emission limits are shown
by Fig. 33d.
(a)
(b)
(c)
(d)
FIG. 33 (a) Engine enclosure with SCR system and stack in front; (b) Data on the three gas engines
of the jet fuel pump station; (c) SCR system design data; (d) Pump station permitting and
process guarantee data. (Courtesy of Siemens.)
Coastal and Ocean-Going Vessels and Other Marine Applications
Two of the vessels equipped with SINOx diesel SCR Systems achieving very low
emission rates of equal or less than 1 gr/pBHP h are pictured in Fig. 34.
Heavy-Duty Diesel Truck Field Tests in Germany and the United States,
1995–1999
SINOx (SCR) System Overview. The SINOx after-treatment system is a fully
developed and tested diesel exhaust emission reduction system. Figure 35 pictures
the first HD diesel truck on the left with a round muffler, replaced by a round
SINOx diesel SCR System in the early 1990s. The right photo shows the Daimler–
Chrysler HD diesel truck barrel-type SCR reactor/muffler, going into production
at the end of 2001.
The UREA–SCR System developed by Siemens (Siemens Westinghouse) and
the European trucking industry uses aqueous urea as a reducing agent for the SCR
process to reduce NOx. The process also reduces VOC/HC, and PM at the same
time. The manufacturer has performed laboratory and fleet tests of the SINOx
system. Approximately 20 European Mercedes Benz (Daimler–Chrysler), IVECO,
and MAN heavy-duty Class 8 trucks were tested in the field. In late 1998, some
of these trucks had accumulated over 300,000 miles in common carrier operations.
The urea infrastructure, the risks of tampering with the UREA (SCR) system, and
other initial operating reliability and other concerns were resolved to the European
trucking industry’s and air quality regulators’ satisfaction. The diesel fuel used
during the tests had a sulfur content of max. 500 ppm (0.05%). Figures 36a and
36b show program objectives and the aqueous urea pump station, respectively.
FIG. 34 SCR marine applications with extremely low NOx emission. (Courtesy of Siemens.)
FIG. 35 Pilot-type and preproduction model SCR system for Class 8 HD diesel trucks. (Courtesy of
Siemens.)
(a)
(b)
FIG. 36 (a) SCR truck program objectives; (b) SCR aqueous urea pump station. (Courtesy of Sie-
mens.)
The SCR system feasibility tests included bench tests using European Station-
ary Cycle (ESC) (⫽OICA) and European Transient Cycle (ETC), and the Federal
Transient Protocol (U.S. FTP) Test Cycle in the United States. NOx, VOC/HC,
and CO of the exhaust gas were measured upstream and downstream of the catalyst,
using sample gas conditioning systems, heated sample gas lines, and various gas
analyzers. The following analyzers were used: chemiluminescent detector (CLD)
for NO and NO2, flame ionization detector (FID) for VOC/HC, a nondisperse infra-
red analyzer (NDIR) for CO and CO2, and a magnetopneumatic analyzer for O2.
Fourier transformation infrared spectroscopy (FTIR) allowed simultaneous, real-
time monitoring for multiple gas components. The FTIR was used downstream of
(a)
(b)
FIG. 37 (a) European steady-state cycle (ESC) test results; (b) European transient cycle (ETC) test
results. (Courtesy of Siemens.)
the catalyst for the exhaust gas and for detecting potential traces of secondary
emissions, such as ammonia slip (NH3), laughing gas (N2O), cyanic acid (HCN),
formaldehyde (CH2O), and so forth. Also, a microwave process analyzer was used
to measure ammonia slip during steady-state tests and for periodic verification/
calibration tests of the FTIR analyzer. For analytical hydrocarbon tests, bag sam-
ples were taken and analyzed with gas chromatographs.
Test results of an European HD diesel engine with a SINOx System are summa-
rized and compared with emission standards, based on the European steady-state
cycle ESC (OICA) and the European transient test cycle (ETC) as shown in Figs.
37a and 37b, respectively. The NOx emission reduction was 80% in steady-state
(a)
(b)
FIG. 38 (a) Urea SCR steady-state/13-mode test results, DDC-S 60, 12 L/400 HP HDD truck; (b)
Urea SCR U.S. EPA’s FTP test results, DDC-S 60 engine. (Courtesy of Siemens.)
and 80% in transient tests. Hydrocarbons are simultaneously reduced by over

80%.
Ammonia slip is limited to single-digit ppm, and no other undesirable second-
ary emissions were detected with the sophisticated analyzer setup described above.
This was confirmed in U.S. bench tests in Detroit in 1998, using the most popular
Class 8 HD diesel truck engine in the United States, the Series 60 Detroit diesel
engine, as shown in Figs. 38a and 38b. The emissions measured downstream of
the SINOx diesel catalyst was approximately 50% lower than the next lower tier
of the European emission limits for NOx, VOC/HC, and PM [18]; that is, the
emission limits achieved in Europe and later in the United States already met the
year 2005 European and the 2002/2004 U.S. EPA emission limits in 1999.
SINOx System Description
The exhaust gas generated by the diesel engine is fed into the SINOx catalyst,
which is integrated into the exhaust gas pipe system (Fig. 39). A certain amount
of the reducing agent, the aqueous urea (30–40%) is injected upstream of the SCR
catalyst. The reducing agent storage tank has a volume of ⬃5% of the fuel tank
volume.
The control system data bus provides the data link between the HDD engine’s
control unit and the SINOx control unit. A flow control unit in the metering panel
meters the amount of reducing agent. The SINOx system is activated by the signals
‘‘engine on’’ (provided by the Engine Management System) and exhaust gas ‘‘tem-
perature above set point’’ (temperature sensor in exhaust pipe). The amount of
reducing agent is metered and in accordance with the computer-memory-based
predicted NOx emission and injected into the gas pipe upstream of the SINOx
FIG. 39 SCR system layout. (Courtesy of Siemens.)

(a)
(b)
FIG. 40 Utility boiler application.

catalyst. The SINOx control system uses a correlation function/map PEMS of the
NOx mass flow, relative to the load, which was generated during engine bench
tests. The reducing agent injection rate can be increased or decreased, depending
on the required NOx yield and/or the measured NOx concentration downstream of
the catalyst via a feedback control.
The SCR Process
Aqueous urea is converted into ammonia through hydrolysis downstream of the

injection nozzle. In the presence of the highly reactive, homogeneous, extruded
SINOx (SCR) diesel catalysts, the nitrogen oxides (NOx) react with the ammonia
(NH3) to yield nitrogen (N2) and water vapor (H2O). The operating temperature
range is approximately 300–1020F. An oxidation catalyst is not required if an
SCR diesel catalyst is used, because the fuel-efficient heavy-duty diesel engines
practically produce no CO and very little VOC/HC and PM, which are further
reduced by 80–90% and 20–30%, respectively. Oxidation catalysts are even unde-
sirable if sulfur-containing fuel is used.
The SINOx system is controlled automatically by a programmable micropro-
cessor-based process logic control system. Active monitoring or supervision of the
system by the operator is not required.
Summary on a Urea SCR Application in a Coal-Burning Utility

Operation, American Electric Power Gavin Plant at Cheshire, Ohio
Rated 2 X 1300 MW
American Electric power (AEP), an international energy company based in Colum-

bus, OH is capable of producing 38,000 MW electricity in 11 U.S. states and has
a customer base of more than 4.8 million. AEP and other power generators in the
Midwest and Southeast are required by court order to reduce their NOx emission
by May 2003. AEP’s Gavin Plant has two 1300-MW generating units and is the
largest utility station in Ohio This AEP Urea SCR project is designed to reduce
NOx by approximately 70% to 0.15 lbs./pBTU of the coal-burning plant’s utility
boilers at a cost of US$ 175 million. This project uses urea rather than anhydrous
or aqueous ammonia as the reducing agent to overcome local safety concerns about
the transport, handling, and storage of ammonia. (See Fig. 40.)
Acknowledgments
The author would like to thank Siemens powergeneration’s KPW Group, Redwitz,
Germany and Alpharetta, GA (USA) for supporting this project. The author is
especially thankful to Dr. Juergen Zuerbig, head of Siemens’ SCR Business world-
wide and Dr. Raimund Mueller,* Head of the U.S. SCR Business and their staff
for the support received and for the permission to incorporate Siemens material,
used in prior papers and public presentations for this project. Without sharing their
inside information about the European advancements in the SCR technology, in
particular in mobile SINOx diesel catalyst applications in recent years, this project
would not have been possible.
Also, the author would like to thank EESI/Steuler for the support received and
the permission to use material from public and internal documentation. The author
is especially thankful to Nick Detor, Engineering and Project Manager of EES
Inc., Cerritos, CA and Hans J. Wagner, Senior Manager of Steuler’s equipment
Division, Hoehr–Grenzhausen, Germany who provided valuable information about
some CER-NOx zeolite SCR catalyst applications.
Furthermore, the author would also like to thank Dr. Ray Anthony, professor
and head of the Chemical Engineering Department, Texas A&M University and
his staff for their valuable guidance and editing effort. Finally, the author would
like to thank the many professionals in the air pollution control community in the
United States and Europe, with whom he has been associated over the years. The
information shared privately, at conferences, and while serving with the author on
committees in California, such as the Scientific Review Committee on Best Avail-
able Control Technology (BACT) at SCAQMD, on IC engines at Cal. ARB, and
at joined projects at the University of California, was most helpful.
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MANFRED GROVE
150 Nanophase Materials in Chemical Process
Nanophase Materials in Chemical Process
Introduction
The selection of construction materials for chemical process equipment is a cri-

tical factor in the efficient operation of a chemical process plant. Engineering
materials must satisfy a variety of criteria in order to operate successfully in a
process environment. The mechanical properties of a material must be satisfactory
with regard to tensile strength, elastic modulus, and resistance to fracture, wear,
fatigue, and creep across a broad range of temperatures and/or pressures. The
chemical property of corrosion resistance is also a significant factor to consi-
der in process material selection. Additionally, the effects of process thermal
conditions and temperature cycling on material properties are relevant to the
durability of the material in a working plant. Beyond these generic material
selection considerations, process-specific material properties are regularly re-
quired.
The demand for new materials with an ever-expanding range of properties has
led to the exploration of nanophase materials. Nanophase materials are in a unique
portion of the ordered length scale of materials between molecular and bulk do-
mains. As the domain size of a given material increases across the nanometer size
regime of between 1- and 100-nm molecular properties become increasing collec-
tive and bulklike in nature. Thus, many bulk properties of a material considered
to be inherent constants are, in fact, size-dependent variables across the nanophase
size regime. The practical effect of material properties being adjustable across
the nanophase size regime is that material domain size becomes another mode
of modifying process material properties, along with the conventional modes of
composition and treatment conditions.
This article highlights nanophase material developments relevant to chemical
process construction and operation. Materials science has experienced substantial
progress in the synthesis and characterization of nanophase materials [1]. Nano-
phase materials have properties which vary from those of the bulk including reac-
tivity [2], magnetism [3], melting temperature [4], and mechanical strength [5].
Although the high surface area of nanophase materials has long been exploited in
catalysis, promising results suggest broad application of nanophase materials in
all aspects of future chemical processes.
Nanophase concepts and technologies can be applied in many different config-
urations, including active nanoclusters, nanocrystalline materials, nanocomposites,
nanotubules, and even ‘‘nanoparticles of vacuum,’’ in which desired materials
properties are obtained by introducing nanometer-scaled voids or pores in materials
[6,7]. These structural configurations combine with the fundamental aspects of
nanophase materials to provide tools for the tailoring of desirable mechanical and
chemical properties.
Nanophase Materials in Chemical Process 151
Nanophase Properties: Origin and Overview
Nanophase properties are largely a function of an incomplete electronic band struc-

ture and surface sites comprising a non-negligible percentage of the total atoms.
These characteristics of nanophase systems will be manifest and helpful in under-
standing the material properties discussed in this article.
Molecular Origin
The central effect of an incomplete electronic band structure in a system is that

the smaller the dimensions, the higher the energy of the lowest excited state. From
a philosophical standpoint, nanocrystals can be examined as either a summation
of a large, but finite, number of interacting atoms or as a small piece of material
excised from a bulk crystal. The former approach relies on atomic orbital hybrid-
ization to build a band structure. Because the evolution from atomic orbitals to
the band structure associated with the bulk follows directly from atomic hybridiza-
tion, a linear combination of atomic orbital–molecular orbitals (LCAO–MO)
method is invoked to explain nanophase behavior.
Changes in electronic structure as a function of size are most easily illustrated
by the use of a one-dimensional system [8]. An infinite chain of N ‘‘atoms,’’ each
possessing one π orbital, containing one electron and separated by a distance, a,
in the absence of any interatomic interactions, has N degenerate orbitals, φ i, each
with an orbital energy, e, given by
e ⫽ ⬍ φ i |H |φ i ⬎ (1)
where H is the electronic Hamiltonian. When the individual units interact, the
resonance energy is given by
β ⫽ ⬍ φ i | H|φ j ⬎ (2)
The result of a unit of the chain interacting with adjacent units is to lift the degener-
acy of orbitals, as shown in Fig. 1.
The energy levels of these one-electron orbitals are derived using the Hückel
approximation of neglecting orbital overlap:
E( j, N)⫽ e ⫹ 2β cos
冢 jπ
(N ⫹ 1) 冣
, j ⫽ 1, 2, . . . , N
(3)
⫽ e ⫹ 2β cos(k j a)
where k j ⫽ j π/(N ⫹ 1) a. As N approaches infinity, k, the wave vector, and E(k)

become continuous variables from 0 to π/a and e ⫺ 2β to e ⫹ 2β, respectively.
FIG. 1 The result of adjacent orbital interactions serves to lift the degeneracy of the orbitals resulting
in the energy levels of N degenerate orbitals splitting into a band.
It is now apparent that π/a is the limit of the Brillouin zone and each ‘‘atom’’ in
the chain is comparable to a unit cell in the semiconductor. For a finite chain, the
eigenvalues are discrete and energetically separated by increasing amounts as the
chain shortens, as shown in Fig. 2. The extreme eigenvalues asymptotically ap-
proach e ⫾ 2β as the chain length increases.
This model system shows how adjacent eigenvalue spacings increase as the
system shrinks, as in the case of a metal, such as Pt [9]. The addition of a two-
unit repetition pair and Jahn–Teller distortion serves to open a gap between the
highest occupied and lowest unoccupied molecular orbitals (HOMO–LUMO) in
the middle of the dispersion curve at k ⫽ π/a′, where a′ is the repetition pair
spacing, as shown in Fig. 3.
The dependence of the electronic properties on particle size shows dramatic
changes between the dimensions of atoms and the bulk material [9]. As the preced-
ing model suggests, the electronic band structure incrementally grows toward the
FIG. 2 The band structure for a one-dimensional chain of N atoms, each with a single electron and
an interatomic separation a. Energy in units of overlap energy. (—): an infinite energy chain;
䊉 N ⫽ 9 eigenvalues; ■ N ⫽ 5 eigenvalues.
FIG. 3 The effect on a uniform chain of the introduction of a two-atom repeat unit and a Jahn–Teller
distortion to produce a HOMO–LUMO gap at k ⫽ π/a′.
bulk as the system size increases. Likewise, one might infer that bulk thermody-
namic characteristics arise from an additive stabilization of atomic properties.
Surface to Volume Ratio
The surface of a nanocrystal contains a non-negligible fraction of the total atoms.

For example, a 1-nm-radius nanocrystal of arbitrary composition contains about
200 atoms, nearly 60% of which occupy surface sites. The effect of a surface can
be incorporated into thermodynamic models to account for the modified behavior
associated with fine particulate metals and molecular clusters. The surface free
energy produces a size dependence in the chemical potential, µ, of the particle.
For a constant density liquid droplet, the chemical potential is given by
2γ
µ ⫽ µ∞ ⫹ (4)
ρR
where γ is the surface tension, ρ is the density, and R is the droplet radius. The
same equation describes crystalline solids with shapes satisfying the Curie–Wulff
equation:
γi
⫽ construction. (5)
hi
where γ i is the surface energy of face i and h i is the distance from that face to the
particle center of mass.
Chemical bond energy and coordination differences also exist between surface
and bulk lattice sites within a material [10,10a]. With the large percentage of con-
stituent atoms or molecules of a nanophase material present on surface sites or
within a few atomic layers of the surface, nanophase materials often are understood
as a manifestation of surface properties which are masked in studies of bulk materi-
als. By way of example, Cu nanoparticles show a significant change in interatomic
spacing, owing to surface tension effects and strained surface geometries associ-
ated with nanophase systems, with the spacing increasing from 2.22 to 2.50 to
2.56 between Cu 2, 0.5-nm nanoparticles, and the bulk, respectively [11].
Properties
Melting
Melting is a fundamental, but not simple, process of a crystalline solid at a distinct

temperature, T m undergoing a phase transformation to a liquid. The complexity in
this seemingly mundane process lies in the atomistic nature of the transformation.
Although thermodynamics rigorously defines T m as the temperature at which the
Gibbs free energy of the solid and liquid phases is equivalent, there is no specifica-
tion as to the mechanism of melting. Thermodynamics is also mute as to the kinetic
issue of the rate at which the transformation occurs. As such, thermodynamic theo-
ries of melting assume a homogenous process occurring simultaneously throughout
the system. Because all real solids contain extrinsic (thermodynamically metasta-
ble) defects such as surfaces, dislocations, and grain boundaries, which often are
both thermodynamically and kinetically more reactive to transformation, it stands
to reason that they play a significant role in melting. The loss of long-range order
is a characteristic of melting, and in the high concentration limit, extrinsic defects
represent a similar disruption of the long-range order.
Metallic and semiconductor nanocrystals have been shown to possess reduced
melting temperatures when compared with the bulk. The depression in melting and
annealing temperature is evident throughout the nanocrystal size regime, but most
profound in the size range from 1 to 6 nm. Melting studies on a range of nanocrystals
have established that the melting temperature is size dependent in the nanometer-size
regime and is approximately proportional to the inverse particle radius, regardless of
the material identity, as shown in Fig. 4. The size-dependent melting temperature of
metallic nanocrystals has included studies of Au [12], Pb and In [13], Al [14], and
Sn [15]. Even though semiconductors have directional and somewhat covalent bonds
and the crystal facets of binary semiconductors do not all exhibit bulk stoichiometry,
the size-dependent melting temperature has been shown in the direct band-gap semi-
conductors CdS [16] and GaAs [17]. Nanocrystals of the indirect semiconductor Si
also exhibit size-dependent melting [18]. The reduction in melting temperature as a
function of nanocrystal size can be enormous. For example, 2-nm Au nanocrystals
melt at about 300°C, as compared to 1065°C for bulk gold [12].
Softening of Nanocrystalline Metals
The properties of bulk materials fail to hold true when dealing with nanophase
materials. For example, nanocrystalline solids often are sought for their increased
FIG. 4 The melting temperature of materials as a function of particle size, plotted as a fraction of
nanocrystal melting temperature T m to the bulk melting temperature T b.
hardness and/or ductility [19]. The Hall–Petch effect is observed in polycrystalline

metals with random grain orientations, where both hardness and yield stress typi-
cally increase as the grain size decreases. Yet contrary to the Hall–Petch effect,
computer simulations of nanocrystalline copper show that as the grain size de-
creases down to values less than approximately 7 nm, hardness and yield decrease
as the grain size decreases [19].
Nanophase Materials
Intermetallic Compounds
Nanophase materials technology can be used to reinforce an intermetallic compound

with a ceramic to obtain desirable characteristics of each type of material. For exam-
ple, the reinforcement of titanium and aluminum intermetallic compounds (Ti 3Al,
TiAl) with TiC improves the toughness and retention of strength across a broad
range of temperatures while continuing to provide a lightweight material with good
oxidation resistance [20]. Mechanical alloying is a viable method for homogeneously
distributing nanophase particles of TiC in an amorphous Ti–Al matrix [20], thereby
creating one such in situ ceramic-reinforced intermetallic compound.
Ceramic reinforcement SiC–Si 3N 4 composite powders have been synthesized
through a sintering process, resulting in nanophase SiC particles distributed inter-
granularly and intragranularly throughout the Si 3N 4 matrix [21]. This resulted in
a dramatic improvement in high-temperature strength and creep resistance [21].
Chemiresistors
High-performance chemiresistors have been developed through the use of a colloi-

dal nanophase structure known as a metal–insulator–metal ensemble (MIME) [22].
The resistance of a chemiresistor changes when the device is placed in the presence
of specific chemicals, as both adsorbed and absorbed vapors affect the transfer of
electrons across the matrix [22]. A thin transducer film having gold nanoclusters
terminated with alkanethiol ligands is deposited onto an interdigital microelectrode
[22]. By selecting the absolute and relative sizes of the gold nanocluster and the
ligand thickness, chemiresistors can be developed to target-specific chemical spe-
cies while ‘‘ignoring’’ others. Thus, one can selectively detect the presence of
various chemicals through changes in electrical resistance.
FIG. 5 Vapor response isotherms of the Au: C 8 (1 : 1) MIME sensor to toluene, tetrachloroethylene
(TCE), 1-propanol, and water, based on 15°C vapor pressures. The inset displays the toluene
response down to a 2.7 ppmv vapor concentration. (From Ref. 22.)
FIG. 6 A simple two-dimensional sketch of the gold cluster film morphology illustrating the gold
core, alkanethiol ligand shell, and region of lower ligand density. (From Ref. 22.)
One such construct has been shown to be extremely sensitive to toluene and
tetrachloroethylene (TCE) vapors, but insensitive to water vapor [22]. Such a
chemiresistor serves as the basis for a new class of miniature chemical sensing
devices that remain unaffected by typical environmental conditions, such as humid-
ity [22].
Polymer Films
Although the coating of lenses is an old practice, high-performance broad-band

antireflection coatings have not been commonplace due to materials limitations
[23]. Antireflective (AR) coatings function through destructive interference of re-
flected light (see Fig. 7A) [23].
The mathematics of this destructive interference, combined with a review of
the available dielectrics, show that single-layer antireflective coatings cannot pos-
sess the desired refractive indices [23]. However, nanoporous films, with pore sizes
much less than the incident light wavelength can be tailored to specific refractive
indices. The refractive index is dependent on the pore volume ratio of the film
[23]. Nanoporous films have been prepared by demixing a binary polymer blend
during spin-coating, and then using a selective solvent to remove one of the source
polymers [23].
Nanocluster technology is being applied to embed metal particles in polymer
FIG. 7 (A) Reflection of light from both interfaces of an AR layer. For a given wavelength and
incidence angle, light transmission is maximized when the two reflected beams interfere de-
structively. (B) Preparation of a binary polymer film. Initially, both polymers (black and gray)
and the solvent form one phase. During spin-coating, phase separation sets in, and after evapo-
ration of the solvent, a lateral phase morphology is obtained. (C) The film is exposed to a
solvent that is selective for one of the polymers, producing a porous film. (From Ref. 23.)
films in order to provide new properties of strength, magnetism, or infrared absorp-

tion capabilities [24]. Iron, iron oxide, silver, and copper have been placed success-
fully into permanent polymer lattice sites [24]. In such constructs, a small quantity
of embedded metal allows the film to remain transparent while still affecting its
performance characteristics [24]. Applications for such materials include magnetic
‘‘watermarks’’ and heat-absorbent window coatings [24].
FIG. 8 Atomic force microscope (AFM) images of two porous PMMA films ⬃110 nm thick. After
spin-casting of a PS–PMMA–THF mixture onto silicon oxide surfaces, the PS phase was
removed by washing the sample in cyclohexane. (A) Films prepared from higher M w PS and
PMMA show average structure sizes of ⬃1 µm. (B) If low M w PS and PMMA are used, the
lateral structure size is reduced to ⬃100 nm. Although the film in (A) appears opaque, the
nanoporous film in (B) is transparent, with a low effective refractive index. (From Ref. 23.)
TABLE 1 Summary of the Magnetic Data Obtained on Four

Different Samples
Sample Tb (K) Hc (G) µ(eff) (emu/g)

Co 70 1800 0.115
Co: Pt 140 2700 0.0598
Co: Pt3 130 2000 0.0357
Au at Co: Pt 30 1000 0.0166
Magnetics
As the information revolution continues, the need for reliable, more compact stor-
age media continues to grow. As researchers look to alloys to improve upon the
magnetic properties of traditional materials, nanophase metallic alloys are viewed
as attractive candidates because of its ability to control properties as a function of
domain size [25]. The magnetic properties of nanophase cobalt, cobalt–platinum,
and gold-coated cobalt–platinum appear to be promising high-performance materi-
als showing dramatic effects in the blocking temperatures (T b ) and coercivities
(H c ) (see Table 1) [25].
High-density media storage requires the nanoparticles to approach monodisper-
sity and a defect-free state. Nanometer-scaled ferromagnetic particle arrays have
reversible rotation and magnetic switching behaviors associated with magnetic
core diameters and shape anisotropy that affords a variety of new device design
options [26]. At temperatures above 30 K, magnetization reversal is dependent on
thermal activation within a volume that increases with particle diameter [26]. Such
a model is useful in predicting blocking temperatures [26].
Catalysts
Properties
The ability to conduct molecular studies of surface behaviors of nanometer-sized

particles and/or nanoporous materials has led to an understanding of surface effects
in catalysis [27]. Improved scanning tunneling microscopy (STM), sum frequency
generation (SFG), vibrational spectroscopy, and atomic force microscopy (AFM)
have provided information about surface reactions and catalysis at relatively high
pressures, as compared to previous instrumentation [27]. The ability to produce
nanometer-scaled ordered arrays and then to conduct detailed studies of their sur-
face behaviors at, or near atmospheric pressures approaching actual catalysis con-
ditions has led to a greater understanding of the pressure dependence of metal
nanocluster catalysis [27]. SFG studies at high pressures reveal that CO molecules
occupy binding states on Pt(111) that are not present at low pressures, whereas
adsorbates that are readily detectable in low-pressure surface studies often are sta-
tionary spectators or totally absent during high-pressure catalytic reactions. Fur-
ther, turnover rates are negligible compared with the overall reaction rate [27].
These findings illustrate the need for pressure-specific studies of the catalytic be-
havior of metal nanoclusters, because the reaction pressures greatly influence the
outcomes in a way that cannot be extrapolated from low-pressure studies [27]. In
additional, the level of surface defects, or other irregularities, can have similarly
profound effects on catalysis behaviors [27].
At the same time, investigations continue into the ‘‘living metal polymer’’
model, in which nanocluster growth is considered analogous to polymer growth
[28] and autocatalytic surface growth once M(0) nanoclusters have been nucleated
[29]. Of interest are the developments in size-control and size-prediction methodol-
ogies, which have been tested successfully in monometallic nanoclusters such as
iridium(0) [29]. Such models are predicted to be applicable to bimetallic, trimetal-
lic, and multimetallic transition metal nanocluster systems [29].
An example of this process of slow, continuous nucleation, followed by auto-
catalytic surface growth, is shown in Scheme 1 and Fig. 9. It is the ratio of the
rate of growth to the rate of nucleation [R ⫽ k 2 (nanocluster active sites)/k] [29]
that can be used to predict, and consequently control, nanocluster size [29]. The
research into these methodologies also has led to an endorsement of the ‘‘magic
(a) Nucleation
k1
A → B
(1) (COD)Ir(P 2W 15Nb 3O 62 )8⫺ ⫹ 2 acetone (COD)Ir(acetone) 2⫹ ⫹ P 2W 15Nb 3O 629⫺

(2) (COD)Ir(acetone) 2⫹ ⫹ 2.5H 2 → Ir(0) ⫹ H⫹ ⫹ S ⫹ 2 acetone
(3) nIr(0) → Ir(0) n
(b) Autocatalytic Surface Growth
k2
A ⫹ B → 2B
(4) (COD)Ir(P 2W 15Nb 3O 62 )8⫺ ⫹ 2.5H 2 ⫹ Ir(0) n → Ir(0) n⫹1 ⫹ H⫹ ⫹

P 2W 15Nb 3O 629⫺ ⫹ S
Net Reaction:
300 [(COD)IR(P 2W 15Nb 3O 62 )8⫺] ⫹ 750H2 →

Ir(0) 300 ⫹ 300 P 2W 15Nb 3O 629⫺ ⫹ 150 H⫹ 300S
SCHEME 1 Minimum mechanism for the formation of Ir(0) nanoclusters, consisting of (a) slow,
continuous nucleation (steps 1–3), rate constant k 1 for the pseudoelementary step,
A → B, followed by (b) fast autocatalytic surface growth (step 4), rate constant k 2 for
the pseudoelementary step A ⫹ B → 2B. Nucleation and growth are separated in time
because k 1 ⬍⬍ k 2 [B], which, in turn, is a key to the observed formation of a near-
monodisperse (⫾ ⱕ15%) particle size distribution. (From Ref. 9.)
FIG. 9 Idealized, roughly-to-scale representation of a P 2W 15Nb 3O 629⫺ polyoxoanion and Bu 4N⫹ stabi-
lized Ir(0) ⬃300 nanocluster, [Ir(0)⬃300(P4W30Nb6O12316⫺)⬃33](Bu4N)⬃300Na⬃228. The Ir(0) atoms are
known (by electron diffraction) to be cubic close packed as shown. For the sake of clarity,
only 17 polyoxoanions are shown, in their monomeric form, and the ⬃300 Bu 4N⫹ and ⬃228
Na⫹ cations have been deliberately omitted. (From Ref. 29.)
number’’ theory of nanoclusters, which states that because closed-shell structures

are stable, they will be more common in the size distribution of completed na-
nocluster formations [29].
Further exploration of the catalysis properties of transition metal colloids indi-
cates that their behavior is extremely reaction-specific and dependent on many
factors. For example, in the synthesis of silicone polymers, the catalytic perfor-
mance of bimetallic colloids of Au(core)/Pt(ligand) and Pd(core)/Pt(ligand) was
compared to the performance of Pt nanoclusters formed during the induction period
of typical industrial reactions [30]. Previously, Au–Pt had been shown to provide
marked improvement over Pt alone in the semihydrogenation of 2-hexyne into cis-
2-hexene [31]. However, in the synthesis of bis(trimethylsiloxyl)octamethylsilane
(BTMOS), the Au–Pt showed no improvement over Pt alone, whereas Pd–Pt
showed marked improvement [30]. These experiments were designed in order to
study the behavior of a bimetallic colloid with a more electronegative core than
the ligand (Au–Pt) and compare it to that of one with a more electropositive core
than ligand (Pd–Pt) [30]. For this particular commercial synthesis, the more elec-
tropositive core seemed to yield superior results. However, in light of the Au–Pt
semihydrogenation mentioned, experimental verification is required before such
findings can be extended to other catalytic systems [30].
Nanocluster agglomeration is prevented through surface stabilization using li-
gands, polymers, or surfactants [32]. Using a combination of STM and transmis-
FIG. 10 A schematic diagram showing how STM and TEM can be used in concert to determine
surfactant stabilizer thickness. Thicknesses observed in this manner are consistent with stan-
dard MM2 force-field calculation theoretical values. (From Ref. 32.)
sion electron microscopy (TEM) to observe and examine the size relationships
between surfactant stabilizers and metal cores, it has been shown that shell thick-
ness is independent of core size and is directly dependent on the size of the surfac-
tant ion, as shown in Fig. 10 [32].
Synthesis
Any discussion of nanophase materials in chemical processes must address the

topic of catalysis. The high surface area to volume ratios associated with nanophase
materials makes them exceptional catalysts as compared to bulk materials. Al-
though nanophase metal catalysts supported on substrata have been industry stan-
dards for high-throughput reactions, in recent years particle size control has strived
to produce stoichiometrically defined particles. Such a well-defined nanophase cat-
alyst offers the prospect of engineering the ratio of edge atomic surface sites on
a particle surface to alter reaction product efficiencies and mixtures. To this end,
transition metal nanocluster systems have been synthesized which behave as isola-
ble and compositionally well-defined soluble heterogeneous catalysts [33]. Further,
new methodologies and a better understanding of nanoclusters in general are call-
ing into question previously identified catalysts in previously explored reactions
[33].
One such example is a hydrogenation of benzene, in which the accepted ion-
pair catalyst, [(C 8H 17 ) 3NCH 3]⫹[RhCl 4]⫺, has been discredited, with the catalyst
shown more likely to be Cl⫺- and [(C 8H 17 ) 3NCH 3]⫹-stabilized Rh(0) nanoclusters
[33]. This indicates that in the cases of other putative homogenous catalysts where
a facile heterogeneous M(0) catalyst is well established, catalysis by even trace
amounts of possibly highly active nanocluster catalysts cannot be ruled out
[33].
The development of industrial catalysts,many of which are composed of metal
particles on oxide substrata, is a topic of great commercial interest [34]. Fabrication
and engineered control in order to deposit tailored metal clusters on oxide surface
with an ordered structure remain a goal of catalyst research [34]. Lithographic
nanostructure fabrication technologies of the semiconductor industry can be ap-

plied to create such engineered clusters and to provide viable model systems for
industrial-supported catalysts [34]. This model of catalytic structure and behavior
has been tested against ethylene hydrogenation on a platinum nanocluster [34].
In a study of the thermal stability of supported silver catalysts, these model
systems and fabrication techniques were used to demonstrate that the presence of
oxygen is the key factor influencing the thermal stability of the silver nanoclusters
[34]. No migration of silver clusters was observed at ⬎700°C in the absence of
oxygen [34]. Yet, with increasing annealing temperature in oxygen, silver cluster
surface oxidation occurs at ⬍200°C [34].
Methods of nanostructure lithographic fabrication also can be applied to other
surface science studies. When combined with AFM, these developments are used
to determine surface mechanical properties, such as the elastic modulus, on nano-
meter-scaled samples [34]. Methodologies also have been developed to measure
the yield of an ion-sputtering process [34].
In addition to the synthesis and use of ligand-stabilized metal clusters, signifi-
cant benefits are realized by polymer stabilization of nanocluster catalysts [35].
The platinum nanoclusters’ catalytic performance on polymer-based supports has
been compared to performance on oxide supports [35]. Polymeric supports show
a marked increase in the stability of the catalysts, especially at room temperatures
[35].
Although stabilizers control particle size and prevent agglomeration, cluster
surface passivation is often the result, with the net effect of reducing catalytic
performance [36]. One proposed solution to this dilemma is the use of dendrimers
to act simultaneously as monodisperse synthesis templates and stabilizers [36].
Researchers have partitioned transition metal ions, such as Pt, into the interior of
polyamidoamine (PAMAM) and have achieved an encouraging combination of
particle size control, particle stability, and electrocatalytic behavior and perfor-
mance [36]. (See Fig. 11.)
Nanophase catalysts also function in decomposition reactions of harmful green-
house gases,such as CO 2[37]. Experiments with different ferrites (XFe 2O 4 ) have
shown that with appropriate selection of X and particle size, CO 2 is broken down
into carbon and oxygen with virtually no CO by-product [37]. The decomposition
of CO 2 also produces quantities of methane. Comparisons of Zn, Ni, and Co ferrites
and of varying particle sizes yielded dramatic results, with ZnFe 2O 4 showing the
most promise [37].
In addition to purely chemical catalysis, nanocluster materials also function as
electrocatalysts. In the synthesis of sodium chlorate, the Dimensionally Stable
Anode (DSA) has realized extensive energy savings on one side of the oxidation
reaction, but high activation overpotentials on the cathodic side still contribute to
large energy losses [38]. The experimental production of a solid Ti 2RuFe nanocrys-
talline cathode has shown promising results. In fact, once the nanocrystalline mate-
rial was pressed into a usable cathode, the activation overpotential was reduced
dramatically when compared to a standard iron electrode [38]. However, this
method of electrode fabrication failed to produce anticipated current density in-
creases expected from the very small crystal size [38].
Template methods, combined with chemical vapor deposition (CVD), also can
be used in the preparation of carbon nanotubules, with diameters ranging from 20
FIG. 11 Schematic illustration of fourth-generation (G4) PAMAM dendrimers having EOH and
NH 2 terminal groups, synthesis of Pt nanoparticles within the hydroxyl-terminated den-
drimer template, and attachment of the composite to an electrode surface. Between 12 and
60 Pt2⫹ ions can be loaded into a single dendrimer and, upon reduction with BH 4⫺, an en-
trapped cluster containing the same number of atoms results. The dendrimer-encapsulated
Pt nanoparticles are electrocatalytically active. (From Ref. 36.)
to 200 nm [39]. Such tubules can be filled with metal catalyst nanoclusters of the
types previously discussed to display interesting and potentially useful electrocata-
lytic properties [39]. A basic method used to synthesize metal-nanocluster-filled
carbon nanotubes includes carbon deposition by CVD onto an alumina template
membrane, followed by immersion in a metal ion solution. Air-drying and reduc-
tion by hydrogen gas completes the formation of the metal nanoclusters within the
nanotubules. Alumina is removed by HF immersion [39]. The mechanical and
electrochemical properties displayed by metal-filled nanotubules hold promise for
the fuel cell industry [39].
Glass Silicates
A physicochemical analysis of nanophase crystalline silicalite-1 shows that it has

many properties in common with micrometer-sized crystalline silicalite-1 [40].
These common properties include a refined structure and concentrations of tetra-
propylammonium species incorporated during the synthesis [40]. Yet, nanophase
silicates have nondegenerate spectroscopic features such as the characteristic
framework infrared (IR) vibration (550 cm⫺1 ) of the micrometer-sized crystal split-
ting into a doublet (at 555 cm⫺1 and 570 cm⫺1 ) in the nanophase material [40]. In
addition, the nanophase material exhibits a high concentration of defect sites, a
FIG. 12 Log-log plot of the bulk (K), shear (G), and Young’s (E) moduli for bulk and nanophase
a-SiO 2, as a function of the density relative to the bulk density. The solid lines are the best
least-squares fits for each of the moduli. (From Ref. 41.)
strain in the crystallites along the a crystallographic direction, as well as a two-

stage dinitrogen physisorption in the low-pressure region [40].
The pore morphologies and mechanical behaviors of nanophase amorphous
SiO 2, investigated by molecular-dynamics (MD) simulations, show that the bulk
amorphous densities of the various nanophase a-SiO 2 glasses are characterized by
different pore sizes and distributions, yet the morphology of the pores, defined in
terms of the fractal dimension of pores and the roughness exponents of pore–silica
interfaces, is similar across various densities [41]. This consistent short-range order
(SRO) of nanophase silica glass of various densities differs little from the SRO
of bulk glass, with both structures consisting of corner-sharing Si(O 1/2 ) 4 tetrahedra
[41]. However, analysis of the first sharp diffraction peak (FSDP) shows a signifi-
cant difference in the intermediate-range order (IRO), dependent on the density,
which is controlled synthetically in the nanophase silica glass [41].
In terms of mechanical properties, the elastic moduli of both the bulk and the
nanophase a-SiO 2 clearly are density dependent [41], as shown in Fig. 12. The
moduli (M) scale as M ⬀ (ρ-bar)3.5 ⫾ 0.2, where ρ-bar is the ratio of the sample
density to the density of bulk silica glass [41]. An understanding of this power-
law dependence can lead to very specific tailoring of physical and mechanical
properties for various uses.
Glass Ceramics
Nanophase glass–ceramic technology also is a rapidly growing field with a wide

variety of commercial applications. Nanophase microstructures composed of crys-
tals ⬍100 nm in size are achieved through efficient nucleation and slow crystal
growth, providing an impressive uniformity of microstructure and the controlled
mechanical properties not available in glass–ceramics of larger crystalline micro-
structures [42].
Transparent nanophase glass–ceramics achieve near-zero coefficients of ther-
mal expansion, along with high thermal stability, high thermal shock resistance,
and, of course, transparency [42]. The requirements to achieve transparency have
previously been recited [42]. Glass–ceramics with these properties typically utilize
lithium-stuffed β-quartz crystals to satisfy scientific and commercial applications,
such as telescope mirror blanks, stove cook tops, cookware, woodstove windows,
fire doors, and other technical devices [42].
Near-zero coefficients of thermal expansion result from adjusting the various
composition components and percentages in stuffed lattices [42]. ‘‘Stuffed’’ β-
quartz crystals are so named because Al3⫹ replaces Si4⫹ in the β-quartz framework
of interlinked helixes of SiO 2 tetrahedra, with the charge balance being maintained
by ions that stuff the interstitial tetrahedral cavities [42].
Other interesting subclasses of transparent glass–ceramics, many of which also
have a ‘‘stuffed’’ microstructure, consist of materials with coefficients of thermal
expansion near that of silicon [42], materials such as transparent mullite or spinel
glass–ceramics that can serve as superior-performance host media for luminescent
transition metal ions such as CR3⫹ [42], and oxyfluoride glass-ceramics used as
hosts for optically active rare earth (RE) cations, because of their low phonon
energies and broad transparency in the IR region of the spectrum, used for the
amplification of light in telecommunications systems [42].
Conclusions
As we have seen, nanophase materials show great promise for many areas of chem-
ical process. Their unique properties, brought about by a high surface area to vol-
ume ratio and incomplete electronic band structures, give them extraordinary flex-
ibility with regard to the desired tailoring of mechanical and chemical properties.
Composition and configuration options offer exciting opportunities to take nano-
phase materials out of the laboratory and into innumerable industrial applications.
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AVERY N. GOLDSTEIN
DAVID M. FISHBACH

Regulations: Impact on Process Industry
Introduction
Chemical accidents have been caused by a number of reasons, including human

error, design flaws, lack of process and engineering knowledge, equipment failure,
and natural disasters. The danger posed to the employees of a chemical plant as
well as the public is illustrated by the accidents that have occurred in onshore as
well as offshore chemical process industries. Figure 1 provides accident statistics
for 1989 from the Accidental Release Information Program (ARIP) of the U.S.
Environmental Protection Agency [1]. ARIP statistics cover catastrophic and un-
planned releases of chemicals into the atmosphere. However, these statistics under-
line the fact that a large number of accidents and catastrophic releases occur be-
cause of design flaws, wrong equipment specifications, and lack of or disregard
of operating and maintenance procedures. The boardroom perspective on the cause
of these accidents and what to do about them varies. The total number of process
plant accidents cannot be estimated accurately because of underreporting. How-
ever, it is clear that the number of accidents is large and many people, both workers
and the public, are affected adversely by these accidents. For example, in 1991,
the National Response Center received over 16,300 calls reporting the release or
potential release of hazardous chemicals [3]. Another study [4] analyzed the EPA’s
Emergency Response Notification System database of chemical accident notifica-
tions. The study found that from 1988 through 1992, an average of 19 accidents
Process Safety/Risk Management Regulations 169
FIG. 1 U.S. Environmental Protection Agency Statistics Accidental Release Information Program—
1989. (Reprinted with permission from Ref. 2.)
occurred each day (i.e., more than 34,500 accidents involving toxic chemicals oc-
curred over the 5-year period). The promulgation of the Toxic Release Inventory
Reporting requirements [5] as part of the Clean Air Act Amendments of 1990 led
to the submittal of toxic release information which clearly delineated the number
and extent of toxic chemical releases and their potential impact on the public and
the environment. In addition to the industry and government agencies, the univer-
sity has a critical role in changing this situation.
In addition to statistics and the sheer number of facilities involved, a number
of highly publicized chemical plant incidents in the 1970s and 1980s focused atten-
tion on management systems and technologies. For example, the 1974 Flixborough
accident occurred because a temporary pipe was used to replace a reactor which
had been removed for repair [6]. The temporary piping was not properly designed
and supported merely on scaffolding. A management of change system could very
well have prevented the incident. The causes behind the 1984 Bhopal accident,
which involved the release of methyl isocyanate and caused thousands of fatalities,
have been investigated quite extensively with varying conclusions. However, the
need for inherently safer design considerations is quite unanimous. Bhopal and
many other process plant incidents including the 1984 Mexico City disaster [7]
also emphasize the need for application of structured management systems for
hazard recognition and identification. According to the official report [8] following
the 1988 Piper Alpha disaster in a North Sea offshore rig, a pump relief valve was
removed for overhaul and the open end blanked. Another shift not knowing the
relief valve was missing, started up the pump. However, this primary reason does
not obviate the fact that a number of other factors contributed to the extensive
damage. Among other things, the Phillips 1989 explosion [9] in the high-density
polyethylene plant demonstrates the need to adhere to operating procedures and
implementing appropriate management systems for contract workers. Many pro-
cess plant accidents in the 1970s and 1980s also exposed the need for management
systems to ensure process and equipment integrity.
Change in population demographics, increasing awareness of process plant
170 Process Safety/Risk Management Regulations
hazards, and, above all, the continuing threat of a chemical catastrophe continue
to provide the impetus for governments to develop legislation for eliminating or
minimizing the potential of such accidents. International efforts include the Seveso
Directive covering members of the European Community. Many other nations also
have similar laws, such as the Sedesol guidelines in Mexico for performing process
risk audits and the post-Bhopal accident prevention law in India. The World Bank
has developed guidelines for identifying and controlling hazards, and the Interna-
tional Labor Organization has developed a code of practice for preventing major
accidents. In 1990, the U.S. Congress enacted the Clean Air Act Amendments
(CAAA) into law. The CAAA directed the Occupational Safety and Health Admin-
istration (OSHA) and the Environmental Protection Agency (EPA) to develop reg-
ulations to reduce the frequency and severity of chemical plant accidents. In keep-
ing with the congressional mandate given in Section 304 of the CAAA, OSHA
promulgated the Process Safety Management (PSM) regulation on February 24,
1992. The PSM regulation is intended to protect workplace employees. Similarly,
as mandated by Section 301(r) of the CAAA, EPA promulgated its risk manage-
ment program regulation in 1996, to protect the public and the environment. In
the United States, federal agencies are not the only government regulators active
in the chemical accident prevention arena. Several states have empowered their
health, safety, and environmental agencies to create regulations requiring compa-
nies to establish and practice specific programs to improve safety.
The Impact of the Industrial Revolution
The eighteenth century was the beginning of technological development, which

affected society and commerce in ways that are felt even today. This technological
development, known as the industrial revolution, was one of the main revolutions
of this era.
The industrial revolution changed manufacturing by changing the way people
worked. For one thing, it brought work out of the home and centralized it in the
beginning to small and simple plant operations and increasingly to large and com-
plex operations. The industrial revolution grew more powerful each year as new
inventions and manufacturing processes added to the efficiency of machines and
increased productivity. The industrial revolution has had far more impact on the
world than the political revolutions of the era, because the Industrial Revolution
effects on society are longer lasting. For example, today we have automobiles,
television, and computers, all made possible by this revolution. Without the indus-
trial revolution, we would not have the technologies that we have today and neither
would we have the standard of living that we enjoy.
Before the introduction of machines and the factory setting, goods were manu-
factured by hand, in single homes or cottages, where the owner worked side by
side with his employees. This changed with the introduction of machines and mass
production. The major advances in technology, particularly in the use of steam,
in the later half of the eighteenth century has its roots in devices that were invented
earlier in the era.
Each advancement in the industrial revolution has brought with it a certain

amount of risk and hazardous activity. Before the industrial revolution, the chemi-
cal hazards we strive to manage safely today did not exist because none of these
chemicals were used. As global competition increased, so did the need for using
increasingly complex processes and new and exotic chemicals at different op-
erating conditions. Demographic changes and the unplanned growth of bedroom
communities around industrial belts have also created a higher risk.
Notwithstanding the benefits of the industrial revolution, there has also been
considerable dialogue about the risks posed by these industrial facilities. The sub-
ject of risk-benefit analysis has been discussed to some extent but is not quite
formalized. Based somewhat on post-accident emotions and partly on a realization
that industry can and should operate safely, there has been a groundswell of opin-
ions from various stakeholders for structured programs to improve safety.
Government Regulations
The history of safety regulations in the United States can be traced back to 1899,
when the United States government issued the River & Harbor Act. This act prohib-
ited the creation of any obstruction not authorized by Congress, to the navigable
capacity of any waters of the United States except on plans authorized by the
Secretary of the Army. The act was promulgated expressly to protect the nation’s
waterways from excessive dumping. Subsequent to the River and Harbor Act,
Congress has passed numerous laws, which impose environmental or safety regula-
tions on businesses.
In 1936, the federal government enacted the Walsh–Healy Act to establish
federal safety and health standards for activities relating to federal contracts. The
Walsh–Healy Act led to early research into the identification and control of occu-
pational diseases. The ideas behind this act are the basis of many of today’s occupa-
tional health and safety regulations.
During the period between 1936 and 1970, a number of other regulations were
promulgated. For example, the Federal Water Pollution Control Act, the Atomic
Energy Act, the Metal and Non-Metallic Mine Safety Act, and the Federal Coal
Mine Health and Safety Act. Although some progress was made, these regulations
were never sufficiently supported to carry out a satisfactory program. This pro-
duced relatively inconsistent and ineffective results.
In 1970, Congress promulgated the Occupational Safety and Health Act
(OSHAct). As a result of this landmark legislation, OSHA and the National Institute
for Occupational Safety and Health (NIOSH) were established within the Depart-
ment of Labor and the Department of Health and Human Services, respectively.
OSHA’s mission is to ‘‘Assure so far as possible every working man and woman
in the nation safe and healthful working conditions.’’ The OSHAct allows OSHA
to set and enforce standards that require employers to maintain safe and healthful
workplaces. NIOSH, on the other hand, does not have any regulatory or enforcement
authority, but it is charged with the responsibility of training professionals and with
the research and recommendation of new regulations to the Secretary of Labor.
Environmental issues affecting the public health and the environment also re-
ceived widespread attention. As a result, the Environmental Protection Agency
(EPA) was established in 1970 to protect the nation’s public health and environ-
ment. The EPA is responsible ‘‘to find ways to clean up and prevent pollution,
ensure compliance and enforcement of environmental laws, assist states in environ-
mental protection efforts, and scientific research and education to advance the na-
tion’s understanding of environmental issues.’’ In 1970, the EPA promulgated the
Clean Air Act, followed by amendments to the act in 1977 and 1990.
The Toxic Substances Control Act (TSCA), passed in 1976, gave the EPA the
ability to track and study the 75,000 industrial chemicals produced or imported to
the United States. The TSCA is a federally enforced law and is not delegated to
the states. Under this act, the EPA has the authority to ban the manufacture or
distribution in commerce, limit the use, require labeling, or place other restrictions
on chemicals that pose unreasonable risk. Asbestos, chlorofluorocarbons, and poly-
chlorinated biphenyls are some of the chemicals regulated by the EPA under
TSCA.
In 1977, the International Safe Container Act established uniform structural
requirements for international cargo containers designed to be transported inter-
changeably by sea and land carriers. In 1983, the Surface Transportation Assistance
Act established protection from reprisal by employers for truckers and certain other
employees in the trucking industry involved in activity related to interstate com-
mercial motor vehicle safety and health.
In December 1984, the release of 40 metric tons of methyl isocyanate from a
pesticide manufacturing plant in Bhopal, India caused the deaths of over 2000
people and injuries to another 100,000 [10]. As a direct consequence of this inci-
dent, the U.S. Congress in 1986 promulgated the Emergency Planning and Com-
munity Right-to-Know Act (EPCRA). The EPCRA requires manufacturers, users,
and storage facilities to keep records about quantity, use, and release of hazardous
materials and make these records available for public record. The EPCRA provided
pathways for better understanding of chemical hazards and called for community
emergency response procedures at the local and state levels. Subsequently, the
EPCRA led to the formation of Local Emergency Planning Committees (LEPCs)
and State Emergency Response Commissions (SERCs). The LEPCs are voluntary
organizations at the local level and are responsible for developing local emergency
response plans in coordination and collaboration with local industry. The SERCs,
on the other hand, are state organizations responsible for coordinating the local
emergency response plans and administering state programs. EPCRA’s reporting
requirements and emergency planning and notification provisions established a
coordinated effort among EPA, state governors, SERCs and LEPCs, owners/opera-
tors of regulated facilities, and local fire departments. LEPCs receive chemical
inventory information, analyze the hazards, and develop local emergency response
plans. The LEPCs are responsible for disseminating this information to the public
and serving as a focus for community awareness and action. The SERCs are ap-
pointed by the governors and consist of state emergency, environmental, and health
agencies, public interest associations, and others with emergency management ex-
perience. The LEPC’s makeup is specified by law, typically consisting of the fol-
lowing:
• Representatives of elected state and local officials

• Law enforcement officials, civil defense workers, and firefighters
• First aid, health, hospital, environmental, and transportation workers
• Representatives of community groups and the news media
• Owners and operators of industrial plants and other users of chemicals, such
as hospitals, farms, and small businesses
The EPCRA extended right-to-know beyond the workplace and into the commu-
nity. This information has stimulated communication between industries and com-
munities and encouraged industries to store smaller inventories of hazardous sub-
stances, discharge less, and substitute less hazardous chemicals. One major
drawback of this initiative is the unfunded and voluntary nature of the LEPCs. As
a result, LEPCs in many counties are marginally active or do not exist at all.
In 1989, OSHA published recommended Safety and Health Program Guide-
lines. These voluntary guidelines identify four general elements that are critical to
the development of a successful safety and health management program. These are
management commitment and employee involvement, worksite analysis, hazard
prevention and control, and safety and health training.
In 1990, EPA analyzed chemical incidents in the early to mid-1980s and com-
pared them to the Bhopal incident. The analysis concluded that 17 incidents re-
leased sufficient volumes of chemicals that could have been more severe than Bho-
pal if the weather conditions and plant location were different. Thus, the Clean
Air Act Amendments of 1990 contained specific mandates requiring OSHA and
EPA to establish regulations to protect workplace employees and the public and
the environment, respectively. OSHA fulfilled its mandate in 1992 by promulgating
the process safety management regulation. The EPA, on the other hand, promul-
gated the Risk Management Program regulation in 1996. The Clean Air Act
Amendments of 1990 also established the Chemical Safety and Hazard Investiga-
tion Board.
State and Local Government Roles
During the late 1800s and early to mid-1900s, the majority of worker-safety laws
were enacted by the state and local governments and thus varied widely in their
extent and enforcement.
By statute, individual states have the option of seeking the delegation of most
federal safety regulations. The state may request delegation from the federal gov-
ernment and submit a state implementation program. The state implementation
program must, in content and enforcement, be, at the minimum, as stringent as
the federal regulation.
Twenty-three states and two U.S. territories operate their own OSHA-approved
occupational safety and health programs. These ‘‘State plan States’’ are integral
partners in OSHA’s mission of assuring the safety and health of the nation’s work-
ers. They are not required to operate programs identical to those of the federal
OSHA, but they have the flexibility to operate programs that reflect their own state-
specific issues and concerns, provided their programs are ‘‘at least as effective’’ as
the federal OSHA program.
States must set job safety and health standards that are ‘‘at least as effective
as’’ comparable federal standards. Most states adopt standards identical to federal
ones. States have the option to promulgate standards covering hazards not ad-
dressed by federal standards.
A state must conduct inspections to enforce its standards, cover public (state
and local government) employees, and operate occupational safety and health train-
ing and education programs. In addition, most states provide free on-site consulta-
tion to help employers identify and correct workplace hazards. Such consultation
may be provided either under the plan or through a special agreement under Section
21(d) of the act.
To gain OSHA approval for a ‘‘developmental plan,’’ the first step in the state
plan process, a state must assure OSHA that within 3 years, it will have in place
all the structural elements necessary for an effective occupational safety and health
program. These elements include appropriate legislation, regulations and proce-
dures for standards setting, enforcement, appeal of citations and penalties, and a
sufficient number of qualified enforcement personnel.
Once a state has completed and documented all its developmental steps, it
is eligible for certification. Certification renders no judgment as to actual state
performance, but merely attests to the structural completeness of the plan.
At any time after initial plan approval, when it appears that the state is capable
of independently enforcing standards, OSHA may enter into an ‘‘operational status
agreement’’ with the state. This commits OSHA to suspend the exercise of discre-
tionary federal enforcement in all or certain activities covered by the state plan.
The ultimate accreditation of a state’s plan is called ‘‘final approval.’’ When
OSHA grants final approval to a state under Section 18(e) of the act, it relinquishes
its authority to cover occupational safety and health matters covered by the state.
After at least 1 year following certification, the state becomes eligible for final
approval if OSHA determines that it is providing, in actual operation, worker pro-
tection ‘‘at least as effective’’ as the protection provided by the federal program.
The state also must meet 100% of the established compliance staffing levels
(benchmarks) and participate in OSHA’s computerized inspection data system be-
fore OSHA can grant final approval.
Rulemaking Process
Regulations by all U.S. federal agencies are developed in a similar manner, with
some minor variations. As an example, the rulemaking process followed by OSHA
is discussed here.
The Occupational Safety and Health Administration can begin standards-set-
ting procedures on its own initiative or in response to petitions from other parties,
including the Secretary of Health and Human Services (HHS), NIOSH, state and
local governments, any nationally recognized standards-producing organization,

employer or labor representatives, or any other interested person.
If OSHA determines that a specific standard is needed, any of several advisory
committees may be called upon to develop specific recommendations. There are
two standing committees, and ad hoc committees may be appointed to examine
special areas of concern to OSHA. All advisory committees, standing or ad hoc,
must have members representing management, labor, and state agencies, as well
as one or more designees of the Secretary of HHS. The two standing advisory
committees are as follows:
• National Advisory Committee on Occupational Safety and Health (NACOSH),

which advises, consults with, and makes recommendations to the Secretary of
HHS and to the Secretary of Labor on matters regarding administration of the
act
• Advisory Committee on Construction Safety and Health, which advises the Sec-
retary of Labor on formulation of construction safety and health standards and
other regulations
Recommendations for standards also may come from NIOSH, established by the
act as an agency of the Department of HHS.
The National Institute for Occupational Safety and Health conducts research
on various safety and health problems, provides technical assistance to OSHA,
and recommends standards for OSHA’s adoption. While conducting its research,
NIOSH may make workplace investigations, gather testimony from employers and
employees, and require that employers measure and report employee exposure to
potentially hazardous materials. NIOSH also may require employers to provide
medical examinations and tests to determine the incidence of occupational illness
among employees. When such examinations and tests are required by NIOSH for
research purposes, they may be paid for by NIOSH rather than the employer.
Once OSHA has developed plans to propose, amend, or revoke a standard,
it publishes these intentions in the Federal Register as a ‘‘Notice of Proposed
Rulemaking’’ or often as an earlier ‘‘Advance Notice of Proposed Rulemaking.’’
An ‘‘Advance Notice’’ is used, when necessary, to solicit information that can
be used in drafting a proposal. The Notice of Proposed Rulemaking will include
the terms of the new rule and provide a specific time (at least 30 days from the
date of publication, usually 60 days or more) for the public to respond.
Interested parties who submit written arguments and pertinent evidence may
request a public hearing on the proposal when none has been announced in the
notice. When such a hearing is requested, OSHA will schedule one, and will pub-
lish, in advance, the time and place for it in the Federal Register. After the close
of the comment period and public hearing, if one is held, OSHA must publish in
the Federal Register the full, final text of any standard amended or adopted and
the date it becomes effective, along with an explanation of the standard and the
reasons for implementing it. OSHA may also publish a determination that no stan-
dard or amendment needs to be issued.
The Occupational Safety and Health Administration continually reviews its
standards to keep pace with developing and changing industrial technology. There-
fore, employers and employees should be aware that, just as they may petition
OSHA for the development of standards, they also may petition OSHA for modifi-
cation or revocation of standards.
Technology and Research Base
The National Institute for Occupational Safety and Health was established by the
Occupational Safety and Health Act of 1970. NIOSH is part of the Centers for
Disease Control and Prevention (CDC) and is the only federal institute responsible
for conducting research and making recommendations for the prevention of work-
related illnesses and injuries. The Institute’s responsibilities include the following:
• Investigating potentially hazardous working conditions as requested by employ-

ers or employees
• Evaluating hazards in the workplace, ranging from chemicals to machinery
• Creating and disseminating methods for preventing disease, injury, and dis-
ability
• Conducting research and providing scientifically valid recommendations for
protecting workers
• Providing education and training to individuals preparing for or actively work-
ing in the field of occupational safety and health
Although NIOSH and OSHA were created by the same act of Congress, they are
two distinct agencies with separate responsibilities. OSHA is in the Department
of Labor and is responsible for creating and enforcing workplace safety and health
regulations. NIOSH is in the Department of Health and Human Services and is a
research agency.
The National Institute for Occupational Safety and Health identifies the causes
of work-related diseases and injuries and the potential hazards of new work tech-
nologies and practices. With this information, NIOSH determines new and effec-
tive ways to protect workers from chemicals, machinery, and hazardous working
conditions. Creating new ways to prevent workplace hazards is the job of NIOSH.
In 1980, the U.S. Congress created the Agency for Toxic Substances and Dis-
ease Registry (ATSDR) to implement the health-related sections of laws that pro-
tect the public from hazardous wastes and environmental spills of hazardous sub-
stances. ATSDR is charged with assessing the presence and nature of health
hazards at specific sites, to help prevent or reduce further exposure and the illnesses
that result from such exposures, and to expand the knowledge base about health
effects from exposure to hazardous substances.
In 1984, amendments to the Resource Conservation and Recovery Act of 1976
(RCRA), which provides for the management of legitimate hazardous waste stor-
age or destruction facilities, authorized ATSDR to conduct public health assess-
ments at these sites, when requested by the EPA, states, or individuals. ATSDR
was also authorized to assist the EPA in determining which substances should be
regulated and the levels at which substances may pose a threat to human health.
With the passage of the Superfund Amendments and Reauthorization Act of
1986 (SARA), ATSDR received additional responsibilities in environmental public

health. This act broadened ATSDR’s responsibilities in the areas of public health
assessments, establishment and maintenance of toxicological databases, informa-
tion dissemination, and medical education.
The Process Safety Management Program
The 14 elements of the OSHA Process Safety Management (PSM) regulation (29
CFR 1910.119) were published in the Federal Register on February 24, 1992 [11].
The objective of the regulation is to prevent or minimize the consequences of
catastrophic releases of toxic, reactive, flammable, or explosive chemicals. The
regulation requires a comprehensive management program: a holistic approach that
integrates technologies, procedures, and management practices.
The process safety management regulation applies to processes which involve
certain specified chemicals at or above threshold quantities, processes which in-
volve flammable liquids or gases on-site in one location, in quantities of 10,000
lbs. or more (subject to few exceptions), and processes which involve the manufac-
ture of explosives and pyrotechnics. Hydrocarbon fuels, which may be excluded
if used solely as a fuel, are included if the fuel is part of a process covered by this
regulation. In addition, the regulation does not apply to retail facilities, oil or gas
well drilling or servicing operations, or normally unoccupied remote facilities.
The management system required by OSHA’s process safety management reg-
ulation envisions a holistic program with checks and balances aimed at creating
multiple barriers of protection. This principle is shown in Fig. 2. The performance-
based approach does not prescribe specific methods and approaches, thus giving
facilities the flexibility for customizing the methods to best meet their needs and
organizational structures. The process hazard analysis (PHA) is the heart of the
FIG. 2 Holistic implementation of the process safety management program.

program and impacts or interfaces with all of the other elements. However, it must
also be pointed out that all elements of the program must be implemented in their
entirety to get the maximum benefit and accomplish the ultimate objective (i.e.,
reduce the frequency and severity of chemical plant accidents). Some of the other
concepts that are apparent from Fig. 2 are as follows:
1. The process safety information and incident history are important inputs to
the PHA and must be compiled before the PHA.
2. Employee participation is important not only for the whole program but also
provides critical information during the PHA.
3. Results of the PHA should be used in modifying and or developing operating
procedures, mechanical integrity program, emergency response program, and
other impacted elements.
4. Irrespective of the PHA done earlier, each process change should be evaluated
by the management of change program, and, if necessary, an appropriate haz-
ard analysis should be done.
5. Pre-start-up safety review is an essential procedure for new or modified pro-
cesses.
Each element of the process safety program is discussed in more detail here and
the interface with other elements of the process safety management is discussed.
Employee Participation
This element of the regulation requires developing a written plan of action regard-
ing employee participation, consulting with employees and their representatives
on the conduct and development of other elements of process safety management
required under the regulation, and providing to employees and their representatives
access to process hazard analyses and to all other information required to be devel-
oped under this regulation.
Process Safety Information
This element of the PSM regulation requires employers to develop and maintain
important information about the different processes involved. This information is
intended to provide a foundation for identifying and understanding potential haz-
ards involved in the process.
The process safety information covers three different areas (i.e., chemicals,
technology, and equipment). A complete listing of the process safety information
that must be compiled in these three areas is shown in Table 1. This information
is intended to provide a foundation for identifying and understanding potential
hazards involved in the process.
The information in Table 1 is essential for developing and implementing an
effective process safety management program. The fundamental concept is that
complete, accurate, and up-to-date process knowledge is essential for safe and
profitable operations. The information contained in the first column of Table 1
should be available from the Material Safety Data Sheets (MSDS) for the hazard-
TABLE 1 Process Safety Information

Chemicals Technology Equipment
Toxicity Block flow diagram or pro- Design codes employed
cess flow diagram
Permissible exposure limit Process chemistry Materials of construction
Physical data Maximum intended inven- Piping and instrumentation
tory Diagrams
Reactivity data Safe limits for process pa- Electrical classification
rameters
Thermal and chemical sta- Consequence of deviations Ventilation system design
bility data Material and energy bal-
Effects of mixing ances
Safety systems
Relief system design and de-
sign basis
ous chemicals, which are used as primary or intermediate feedstocks or are pro-
duced as products at the plant.
The information contained in the second column of Table 1 pertains to the
technology of the process itself. The block flow diagram can be replaced by a
process flow diagram. The process chemistry information must contain the basic
chemical reactions involved and a brief description of the chemistry involved. The
maximum intended inventory refers to the maximum amount of any regulated
chemical that may be expected to be present in the whole facility at any time. The
safe limits for process parameters refer to the upper and lower bounds for the
process parameters outside of which the process would be hazardous. For example,
in the case of a distillation process, the upper and lower limits of the process
parameters outside which the operation of the process could cause significant dam-
age to the tower or other attached equipment would have to be stated. In this
example, the process parameters for which upper and lower bounds are to be speci-
fied are temperature, pressure, composition, and flow rate. The consequence of
deviation from these stated bounds must also be compiled.
Safe upper and lower limits for process parameters and equipment are also
necessary for calibrating instrumentation. It is important to understand the distinc-
tion between process parameter limits and equipment limits. Safe upper and lower
limits for process parameters can be defined as follows:
• For nonreactive processes, process parameter safe limits are defined based on
equipment design ratings, relief device set points, and upstream and downstream
conditions of the process and/or equipment.
• For reactive processes, process parameter safe limits are defined based on the
process chemistry information or any restricted physical conditions for the reac-
tion as well as the criteria used for nonreactive processes.
In contrast, equipment limits are specified by the manufacturer based on materials

of construction and design basis. Processes must be operated and maintained within
both the process parameter and equipment limits.
The final type of information that must be compiled pertains to the equipment
used in the process. The intent is to assure that all equipment used in the process
meets appropriate standards and codes such as those published by the American
Society of Mechanical Engineers (ASME), the American Petroleum Institute (API),
the American Institute of Chemical Engineers (AIChE), the American National Stan-
dards Institute (ANSI), the American Society of Testing and Materials (ASTM), and
the National Fire Protection Association (NFPA). Accepted industry practices can
be used to decide which standards apply. In cases where standards do not exist,
generally acceptable engineering practices can be used. The materials of construction
for each equipment item and the design codes employed can be compiled as separate
lists or may be listed in the Piping and Instrumentation Diagram (P&ID). The P&
IDs must represent the facility exactly as it exists with flanges, valves, and all other
connections shown. The different electrical classifications must also be compiled for
different parts of the facility. A simple plot plan showing the different areas of
electrical classification would be considered to be in compliance with the regulation.
Information must also be compiled on any ventilation system. This information
would indicate the areas in the facility that are ventilated and the nature of ventilation.
A listing of all safety systems must also be compiled that are available to the workers.
This listing should include any and all equipment that is available for protection of
the workers from any hazard or emergency. Information should also be available
on the location of these safety systems and the procedures to use these systems.
As is apparent from the foregoing discussion, compilation of the process safety
information database represents a major challenge. This is complicated even more
because the process safety information must also be kept up-to-date and accurate
and made accessible to employees. Many plants have therefore implemented or
are in the process of implementing electronic data management systems to manage,
access, and use these data. The completion and accuracy of process safety informa-
tion is crucial to the implementation of other PSM elements, including PHAs and
mechanical integrity.
The PSM regulation requires that process equipment should comply with gen-
erally accepted engineering practices. It is therefore not only important to compile
all equipment information but also to ensure that it complies with consensus stan-
dards. OSHA is recognizing that there are consensus standards for design and
fabrication, installation, maintenance procedures, and inspection and testing.
Therefore, equipment constructed in accordance with codes, standards, or practices
no longer in use should be evaluated to ensure that they are compatible with ex-
isting standards. For example, a multilayered vessel built years ago should be eval-
uated to ensure that it complies with today’s engineering standards.
Process Hazards Analysis
This element of the PSM regulation requires facilities to perform a PHA. The PHA
must address the hazards of the process, previous hazardous incidents, engineering
and administrative controls, the consequences of the failure of engineering and
administrative controls, human factors, and an evaluation of effects of failure of
controls on employees. This element requires that the PHA be performed by one
or more of the following methods or any other equivalent method:
• What If
• Checklist
• What If/checklist
• Hazard and operability (HAZOP) studies
• Failure modes and effects analysis (FMEA)
• Fault-tree analysis
The regulation suggests a performance-oriented requirement with respect to

the PHA so that the facility has the flexibility to choose the type of analysis that
will best address a particular process. PHAs may not be performed unless complete
Process Safety Information is available for the process.
Process hazard analyses and the results of PHAs can and will impact the devel-
opment, implementation, and practice of other elements of the PSM regulation. A
PHA would help facilities identify hazards and ways to address them. For example,
a 1989 explosion and fire at a facility in Baton Rouge, Louisiana led to a partial
loss of pressure, power, and fire water because the power, steam, and water lines
were colocated with the lines carrying flammable gases [12]. The losses compli-
cated and prolonged the process of responding to the release, thereby increasing
the damage caused by the release. Similar problems occurred at a facility in Norco,
Louisiana, where an explosion led to the loss of all utilities. A thorough and prop-
erly done PHA should identify these types of potential hazards and allow facilities
to determine how to mitigate the problems. PHAs also identify situations where
major accidents due to control failure (e.g., pressure gauges, overfill alarms) could
be prevented by redundant or backup control or by frequent maintenance and in-
spection practices.
Many other elements of the PSM program should flow from, or at least be
revised based on, the results of the PHA. Existing standard operating procedures,
training and maintenance programs, and pre-start-up safety reviews may need to
be revised to reflect changes in either practices or equipment that derive from
the PHA. The PHA may help define critical equipment that require preventive
maintenance, inspection, and testing programs. It may also help a facility focus
its emergency response programs on the most likely and most serious release sce-
narios.
The PSM regulation also requires that the PHAs be updated and revalidated,
based on their completion date. First, the PSM regulation requires that the process
hazard analysis shall be updated and revalidated. Thus, the whole PHA should not
only be examined to verify that the PHA is consistent with the current process,
but it also should be analyzed to examine if the original analysis is valid. Second,
the PSM regulation requires that the updating and revalidating be done by a team
similar in qualifications to the team that conducted the original PHA. The intent
of a PHA revalidation is to ensure that the PHA team evaluates the previous PHA,
examines the extent of any changes that might have occurred since the PHA was
implemented (or last reviewed), and decides what work is needed to make the
PHA current.
Philosophically, in an ideal process safety management system, the following
process safety concepts should work as checks and balances to accomplish the
PSM program objectives (i.e., minimize the frequency and consequences of cata-
strophic releases):
• Initial process hazards analysis: Identify process hazards and develop mitigation
techniques (technology, equipment, and procedures).
• Management of change: Assess the safety and health impacts of process changes
and ensure that process changes are analyzed (e.g., HAZOPed).
• Revalidation of process hazards analysis: Update and revalidate the PHAs to
assure that the process hazard analysis is consistent with the current process.
Operating Procedures
The operating procedures must be in writing and provide clear instructions for
safely operating processes, must include steps for each operating phase, operating
limits, safety and health considerations, and safety systems. Procedures must be
readily accessible to employees, must be reviewed as often as necessary to assure
they are up-to-date, and must cover special circumstances such as lockout/tagout
and confined space entry. The employer must certify annually that the operating
procedures are current and accurate. The synergism and commonality of operating
procedures to maintenance procedures is in safe work practices. These safe work
practices include lockout/tagout, confined space entry, opening of process equip-
ment or piping (i.e., hot tapping), and control of entrance into the battery limits.
Even though the operations department is involved with all of these practices,
maintenance also plays a very vital role in ensuring that these procedures are fol-
lowed during all maintenance tasks. Many incidents have resulted from inadequate
safe work practices or a failure to follow procedures when they exist.
Training
The regulation requires that facilities certify that employees responsible for op-
erating the facility have successfully completed (including means to verify under-
standing) the required training. The training must cover specific safety and health
hazards, emergency operations, and safe work practices. Initial training must occur
before assignment. Refresher training must be provided at least every 3 years.
Even though this element of the PSM regulation pertains to operations staff
only, it is important to remember that operations and maintenance training should
be coordinated.
Contractors
The PSM regulation identifies responsibilities of the employer regarding contrac-

tors involved in maintenance, repair, turnaround, major renovation or specialty
work, on or near covered processes. The host employer is required to consider
safety records in selecting contractors, inform contractors of potential process haz-
ards, explain the facility’s emergency action plan, develop safe work practices for
contractors in process areas, periodically evaluate contractor safety performance,
and maintain an injury/illness log for contractors working in process areas. In
addition, the contract employer is required to train their employees in safe work
practices and document that training, assure that employees know about potential
process hazards and the host employer’s emergency action plan, assure that em-
ployees follow safety rules of facility, and advise host employer of hazards contract
work itself poses or hazards identified by contract employees.
In the contractor paragraph, OSHA has used a belt and suspender approach.
Both the host employer and contract employer have specific responsibilities that
they must fulfill. The need for flexibility, quick turnarounds, and specialized ser-
vices is the main reason why process plants are contracting out increasingly sig-
nificant portion of their daily work, particularly maintenance work to contractors.
Contractors, in general, receive less training and often perform more hazardous
tasks in process plants as compared to direct-hire workers [13].
Pre-Start-up Safety Review
This element of the PSM regulation requires a pre-start-up safety review of all
new and modified facilities to confirm integrity of equipment, to assure that appro-
priate safety, operating, maintenance, and emergency procedures are in place, and
to verify that a process hazard analysis has been performed. Modified facilities for
this purpose are defined as those for which the modification required a change in
the process safety information.
Usually, changes occur during maintenance and, therefore, maintenance per-
sonnel should be well versed in pre-start-up safety review procedures. Maintenance
should ensure that all necessary procedures have been completed prior to start-up.
Mechanical Integrity
This element of the PSM regulation mandates written procedures, training for pro-
cess maintenance employees, and inspection and testing for process equipment,
including pressure vessels and storage tanks, piping systems, relief and vent sys-
tems and devices, emergency shutdown systems, pumps, and controls such as mon-
itoring devices, sensors, alarms, and interlocks. PSM calls for correction of equip-
ment deficiencies and assurance that new equipment and maintenance materials
and spare parts are suitable for the process and properly installed.
Hot Work Permit
This element of the PSM regulation mandates a permit system for hot work opera-
tions conducted on or near a covered process. The purpose of this element of the
regulation is to assure that the employer is aware of the hot work being performed
and that appropriate safety precautions have been taken prior to beginning the work.
Because welding shops authorized by the employer are locations specifically desig-
nated and suited for hot work operations, the regulation does not require a permit
for hot work in these locations. Additionally, hot work permits are not required in
cases where the employer or an individual to whom the employer has assigned the
authority to grant hot work permits is present while the hot work is performed.
Management of Change
This element of the regulation specifies a written program to manage changes in

chemicals, technology, equipment, and procedures which addresses the technical
basis for the change, impact of the change on safety and health, modification to
operating procedures, time period necessary for the change, and authorization re-
quirements for the change. The regulation requires employers to notify and train
affected employees and update process safety information and operating proce-
dures as necessary.
Incident Investigation
This element of the regulation requires employers to investigate as soon as possible

(but no later than 48 hrs) incidents which did result or could have resulted in
catastrophic releases of covered chemicals. The regulation calls for an investigation
team, including at least one person knowledgeable in the process (a contractor
employee, if appropriate), to develop a written report of the incident. Employers
must address and document their response to report findings and recommendations
and review findings with affected employees and contractor employees. Reports
must be retained for 5 years.
Emergency Planning and Response
This element requires employers to develop and implement an emergency action

plan according to the requirements of 29 CFR 1910.38(a) and 29 CFR 1910.120(a),
(p), and (q).
Compliance Audits
This element of the regulation requires employers to certify that they have evalu-
ated compliance with process safety requirements every 3 years and specifies reten-
tion of the audit report findings and the employer’s response. The employer must
retain the two most recent audits.
Trade Secrets
Similar to the trade secret provisions of the hazard communication regulation, the
PSM regulation also requires information to be available to employees from the
process hazard analyses and other documents required by the regulation. The regu-
lation permits employers to enter into confidentiality agreements to prevent disclo-
sure of trade secrets.
As is apparent from the foregoing discussion, the process safety management

regulation requires a systems approach for managing safety. Segments of the haz-
ardous chemicals industry have for sometime practiced some or all of the required
programs. The promulgation of the regulation formalized the requirements and
established minimum criteria. This is both good and bad. The regulation now re-
quires everyone to establish the management systems and apply the technologies
needed to comply with the regulation. However, because of the same reason, there
is a tendency to look for ‘‘paper compliance’’ as compared to making real improve-
ments in safety programs and technologies.
The Risk Management Program
In 1996, EPA promulgated the regulation for Risk Management Programs for Chem-
ical Accident Release Prevention (40 CFR 68). This federal regulation was mandated
by Section 112(r) of the Clean Air Act Amendments of 1990. The regulation requires
regulated facilities to develop and implement appropriate risk management programs
to minimize the frequency and severity of chemical plant accidents. In keeping with
regulatory trends, the EPA required a performance-based approach toward compli-
ance with the risk management program regulation. The eligibility criteria and re-
quirements for the three different program levels are given in Table 2.
The EPA regulation also requires regulated facilities to develop a Risk Manage-
ment Plan (RMP). The RMP includes a description of the hazard assessment, pre-
vention program, and the emergency response program. Facilities submit the RMP
to the EPA and, subsequently, it is made available to governmental agencies, the
state emergency response commission, and the local emergency planning commit-
tees and is communicated to the public.
The RMP regulation defines the worst-case release as the release of the largest
quantity of a regulated substance from a vessel or process-line failure, including
administrative controls and passive mitigation that limit the total quantity involved
or release rate. For gases, the worst-case release scenario assumes the quantity is
released in 10 min. For liquids, the scenario assumes an instantaneous spill and
that the release rate to the air is the volatilization rate from a pool 1 cm deep unless
passive mitigation systems contain the substance in a smaller area. For flammables,
the scenario assumes an instantaneous release and a vapor cloud explosion using a
10% yield factor. For alternative scenarios (note: the EPA used the term alternative
scenario as compared to the term more-likely scenario used earlier in the proposed
regulation), facilities may take credit for both passive and active mitigation systems.
Appendix A of the final regulation lists endpoints for toxic substances to be
used in worst-case and alternative scenario assessment. The toxic endpoints are
based on ERPG-2 (Emergency Response Planning Guidelines—Level 2) or level
of concern data compiled by EPA. The flammable endpoints represent vapor cloud
explosion distances based on overpressure of 1 psi or radiant heat distances based
on exposure to 5 kW/m2 for 40 s.
Impact on Process Industry
In general, the impact of any regulation on any part of the regulated community
can be related to several factors which include, but are not limited to the following:
TABLE 2 Eligibility Criteria and Compliance Requirements for Different Program

Levels; EPA’s Risk Management Program Regulation
Program 1 Program 2 Program 3

Program Eligibility Criteria
No off-site accident history Process not eligible for pro- Process is subject to OSHA
gram 1 or 3 PSM (29 CFR
1910.119)
No public receptors in
worst-case circle
Emergency response coordi- Process is SIC code 2611,
nated with local re- 2812, 2819, 2821,
sponder 2865, 2869, 2873,
2879, or 2911
Program Requirement
Hazard Assessment Hazard Assessment Hazard Assessment
Worst-case analysis Worst-case analysis Worst-case analysis
5-Year accident history Alternative releases Alternative releases
Certify no additional 5-Year accident history 5-Year accident history
steps needed
Management Program Management Program
Document management Document management
system system
Prevention Program Prevention Program
Safety information Process safety informa-
Hazard review tion
Operating procedures Process hazard analysis
Training Operating procedures
Maintenance Training
Incident investigation Mechanical integrity
Compliance audit Incident investigation
Compliance audit
Management of change
Pre-start-up safety review
Contractors
Employee participation
Hot work permits
Emergency Response Pro- Emergency Response Pro-
gram gram
Develop plan and pro- Develop plan and pro-
gram gram
• The degree to which a particular entity or entities is already attempting to reach

a particular level of achievement
• The additional cost associated with regulatory overhead not directly associated
with the goals of the program (e.g., the cost of record keeping)
• The degree to which already successful programs are compromised by the regu-
lation
• The technical feasibility of compliance

• The impact on compliance with other regulations
• The emphasis on compliance rather than impact
• The ability to maintain a profitable operation
• The ability to absorb the associated overhead cost when offshore competition
does not have those costs
• The degree to which enforcement and other emphasis by the regulating authority
promotes real improvement as opposed to ‘‘paperwork’’ compliance
It must also be noted that painting all industry or even one segment of industry
with one brush is very inappropriate. Many companies and/or groups of companies
are and have been for many years investing considerable time and resources into
process safety and risk management prior to any regulatory requirement to do so.
Also, many companies and industry groups have initiated voluntary programs
which go further than regulations require. In some cases, these efforts have been
in partnership with government and nongovernment groups and in other cases they
have been independent of government participation.
Compliance Programs
At first glance, it would seem that ‘‘compliance’’ must imply compliance with
regulations. However, there are many examples of responsible industry doing
something because it was ‘‘the right thing to do.’’ Following the Texas City disas-
ter in 1949, the industries on the Houston Ship Channel voluntarily formed Channel
Industries Mutual Aid (CIMA) in order to help each other and the public during
emergencies. There were no regulatory drivers. Responsible chemical companies
have been responding to transportation emergencies involving their products for
at least 50 years. Safety programs for worker protection were in place years before
OSHA. For example, dating back to the 1960s and 1970s, Dow Chemical Company
has had an excellent reactive chemicals program. A positive result of regulatory
action has been that companies who have not voluntarily invested in these kinds
of programs are forced to make the investment. Unfortunately, when compliance
with regulation becomes the issue, administrative overhead may increase signifi-
cantly. Furthermore, a one-size-fits-all approach to regulation and compliance may
force a company to abandon a program that has proven successful over time simply
to meet a regulation. It is very difficult to explain to management and workers
that a highly successful, popular program has to be changed or eliminated because
of a rigidly written regulation.
Many companies had employed some form of lockout/tagout procedure for
years that worked. The one size fits all regulatory mentality caused those programs
to be changed at great cost and effort. It can be argued that the cost was not justified
by the result. The changed requirements also caused confusion in the case of some
workers, which might actually have increased the risk. The good news is that those
same responsible companies extend their policies to their facilities wherever they
may be. For example, members of the American Chemistry Council apply the
Responsible Care Code internationally.
Finally, when the ultimate goal becomes compliance rather than results, it is
possible to be in technical compliance and not in functional compliance. For exam-
ple, several persons both in and out of government during work on the National
Response Team’s integrated contingency plan effort commented that in many cases
facility and vessel owners hired contractors to produce response plans under the
Oil Pollution Act of 1990 that were judged by government contractors to meet all
planning requirements but were not useful for response. In other words, compli-
ance, not planning and response, was the goal.
Enforcement
Enforcement can be a two-edged sword. As mentioned earlier, compliance issues

can sometimes outweigh the issues of functionality or statutory and regulatory
intent. Very often, with both government and industry, the issue becomes ‘‘did
you meet the requirements’’ not ‘‘have you increased or reduced the risk.’’ At the
same time, it must also be said that in some cases, the threat of enforcement is
the only leverage regulators have. Sometimes, however, the threat of enforcement
may actually serve to increase overall risk. There is currently a great deal of con-
cern that efforts to mix enforcement and response at the incident command level in
oil spills may discourage the cooperative spirit necessary for an effective response.
Overall, the availability of enforcement has probably had a positive impact on
process safety and risk management. The threat of enforcement has probably had
a chilling effect on cooperative efforts that could possibly make an even larger
impact.
Operational Issues
Operationally, regulations have had a net positive impact in that they have forced
many companies not already committed to environmental and safety excellence
to operate better. In many cases, this improvement has actually been transferred
to the bottom line. Improved operating discipline actually will increase quality,
productivity, morale, and product yield. There are occasional situations, however,
that require procedures that may cause significant problems. For example, there
has never been a catastrophic explosion of an underground fuel tank. That is why
many fire codes prohibit aboveground tanks at retail facilities. The underground
storage tank regulations have made it very expensive to maintain and install under-
ground tanks. In this case, there is an obvious conflict between two competing
interests. Some air regulations require inspection of the seals on floating roof tanks.
It is very difficult to clear those tanks well enough to eliminate emissions during the
inspection process. In this case, one regulation may result in violation of another or
an actual increase in emissions. Elimination of chlorofluorocarbons has caused a
concurrent elimination of Halon-type fire-extinguishing systems. Another example
is the requirement to test marine facility foam systems by actually flowing foam.
These tests have a high likelihood of discharging some foam to the water—a viola-
tion of the Clean Water Act.
Management Systems for Compliance
Management systems for regulatory compliance have evolved over a period of

time. In the early stages, there was a tendency to manage process safety as a sepa-
rate function. With experience, industry has learned that is not the most efficient
or effective approach. In order to gain the most advantage, safety must be inte-
grated into the plant’s everyday activities through each phase of the plant’s life
cycle. The following provides a discussion of some example components of the
management systems necessary for the effective implementation of process safety
and risk management programs.
Integrated Systems Versus Compartmentalized Systems
Management systems for compliance must be integrated and cannot be compartmen-

talized. First, although statutes and the accompanying regulations are often con-
ceived and written as separate entities, they often have impacts on other areas that
may or may not be intentional. One example can be found in the list of chemicals
regulated under the Clean Air Act Amendments that included ethylene glycol. Under
the reportable quantity (RQ) regulations of the Superfund Amendments and Reautho-
rization Act, ethylene glycol defaulted to a 1-lb RQ. This had the effect of creating
a large number of unnecessary and wasteful emergency release reports from people
who understood the regulations and in one sense made criminals out of almost every-
one who had a radiator leak. Only an integrated system could respond to that quirk.
The real thrust of integrated management systems must be to include all safety and
environmental concerns in the entire process from conception to design to construc-
tion and commissioning to start-up and operation to shutdown and demolition. Only
this approach can insure compliance, but more importantly safety and environmental
excellence. Individuals in the organization must understand their respective roles.
Therefore, the management system for compliance should be integrated vertically
within the organization and horizontally across regulatory regimes.
Process Design
It is critical that companies have a system in place that assures compliance from
the time of conception to eventual start-up of any process. There are multiple
regulations that impact every facet of a new process. The process design must
look at air emissions and permitting, wastewater and stormwater handling, waste
handling, generation and reduction, Toxic Substance Control Act implications,
Risk Management Plan implications, and other potential areas of concern. Worker
safety, including repetitive motion injuries, should be an issue from the start. Soft
issues such as public perception must be considered. All of these issues also apply
to modifications to existing facilities. They may also apply to changes in operating
procedures and other ‘‘soft’’ changes. For all of these reasons and for OSHA com-
pliance, a well-conceived management of change (MOC) system must be inte-
grated into the culture.
Very subtle, often seemingly innocuous changes can have significant regulatory
implications. An operator of a water-treatment facility may have several 1-ton
chlorine cylinders on site but never have more than one connected to the process.
That operator may decide that the greatest risk occurs when changing the cylinder
out. The obvious solution would be to manifold several cylinders together. That
change would then make the operator subject to the provisions of Section 112r of
the Clean Air Act.
Equipment Maintenance
For all of the reasons listed earlier, equipment maintenance must be part of the
management system. It is possible that regulatory issues may actually discourage
a good maintenance program. Many maintenance activities, especially in older
plants, require opening processes to the atmosphere in order to make the equipment
safe to work. Air regulations may prohibit, or at least discourage, this activity.
There is no way of quantifying how often needed maintenance is delayed or can-
celed because of environmental concerns. Because of this, a relatively small emis-
sion or environmental upset resulting from maintenance was avoided at the cost
of an eventual catastrophic event.
Prevention and Reduction
Responsible industry has always had prevention and reduction programs. As stated
earlier, regulations have largely served to ‘‘level the playing field’’ between responsi-
ble and irresponsible industry. As early as the 1960s, one chemical company execu-
tive stated on the ‘‘Today’’ show that his company was in the business of making
salable product out of raw materials, and if a molecule left the plant as waste to the
environment, it represented lost profit. Further, in recent years, all companies have
begun to recognize that they must be good neighbors by perception as well as by
reality. Initiatives such as Responsible Care illustrate this recognition.
Response Mechanism
Again, responsible companies have had response systems in place for many years.
Several things have occurred to alter and, in most cases, improve those systems.
The OSHA PSM regulation and the Hazardous Waste Operations regulation
(OSHA 1910.120) have elevated the training requirements for responders. Al-
though experienced responders already had most of the required training and/or
experience, the regulations created minimums that have been very effective. Plan-
ning requirements under a multitude of federal and state regulations have, however
resulted in considerable duplication. PSM, RMP, Community Right to Know,
OPA90, RCRA, and others all mandate response planning. The vessel response
plan requirements proposed by the U.S. Coast Guard will add still further require-
ments. This duplicative regulatory system resulted in numerous plans designed
solely to meet compliance requirements and often had little to do with response.
The good news is that the effort of the National Response Team to publish the
Integrated Contingency Planning Guidance has relieved much of that problem. In

the case of OPA90 in particular, oil spill response is much better than it was during
the Exxon Valdez spill. The most lasting improvement has been in the response
partnerships formed between industry and government at all levels.
Risk Communication
For many years, much of industry did a fairly poor job of telling people about
potential risks. This has been significantly improved by Community Right to
Know, 112r of the Clean Air Act, and voluntary programs such as Responsible
Care. Much remains to be done in this area. Industry and government tend to
respond to public perception of risk without doing a good job of education about
true risk. Very often, uninformed public outcry has forced questionable, if not
totally incorrect, reaction on the part of industry and government. All too often,
groups with hidden agendas have aggravated this process. Fears about dioxins that
have not been scientifically confirmed have resulted in actions like Times Beach;
this is in spite of the record of Seveso in which there are still no documented long-
term effects of the exposure. The challenge is creating an interactive dialogue with
the public to a point where risk perception is based not only on emotion but also
on some level of scientific reality. Zero risk is a myth. However, zero negative
impact is a vision for which industry and government must strive.
Small Business Issues
In the United States, a significant portion of the economy consists of small and mid-
sized companies. We must remember that an accident from such a small facility has
the likelihood of severe consequences and can damage the whole industry ‘‘license
to operate’’ just like an accident in a plant operated by a large multinational com-
pany. However, the large facility probably has resources, training, and equipment
either to prevent the accident in the first place or respond to the consequences if it
does occur. On the other hand, the small facility probably lacks awareness, training,
information, and other things. A recent accident in the United States resulted in
multiple fatalities and total destruction of a small plant. Preliminary investigations
highlight the lack of reactive chemicals knowledge among the plant personnel.
The challenge therefore is to develop collaborative efforts with government agen-
cies (both state and federal), professional and trade organizations, and industry for
safety programs aimed at improving safety in the small and mid-sized companies.
Future Developments
In an increasingly global economy in which the developed nations will compete

even more strongly with the less developed nations, several things must happen.
First, multinational companies must insist that the best practices of worker, public,
and environmental protection be followed throughout the world. Product steward-
ship is one effective method for ensuring the implementation of the same standards
at small and medium-sized businesses in the United States as well as in facilities
overseas. Governments should also promote those best practices. Industries and
governments not doing so should face sanctions in the international marketplace.
It is imperative that those companies trying to do what is right are not penalized
by unfair competition. Partnerships between key players in this arena should be
encouraged and rewarded. Examples include Integrated Contingency Planning and
the OSHA Voluntary Protection Program. The public should be represented in
these programs. All of the stakeholders involved in these issues must work to
identify and eliminate barriers to improvement. These barriers and issues include,
but are not limited to the following:
• Tort regimes that discourage sharing of lessons learned and near-miss informa-
tion
• Regulations and requirements that are duplicative or not based on science
• Public policy that results in ‘‘knee-jerk’’ statutory and regulatory response to
single events
• Companies and industry groups that are willing to conduct meaningful dialogue
with stakeholders
• Most importantly, a willingness to accept and work toward a vision in which
no facility has a negative impact on its workers, the public, or the environment.
Future developments in the United States with regard to process safety and risk
management programs may quite likely be based on risk–benefit analyses. There
is also number of efforts underway to develop stakeholder dialogue and arrive at
consensus opinions regarding national safety goals and targeted improvements
in safety performance. It is quite clear that the need to operate safely is recog-
nized as a competitive advantage and a positive contributor to the bottom line.
The regulatory regime and requirements will also keep changing as more infor-
mation becomes available. Thus, industrial programs and practices will have to
keep pace with the changing clime and consensus standards and targeted safety
goals.
Summary and Conclusions
Safety regulations in the United States have mirrored the industrial revolution. The
industrial revolution brought prosperity along with the use of hazardous processes.
As our understanding of the hazards associated with these processes developed,
procedures and practices were put in place to limit or eliminate the damage. Gov-
ernment programs and industry initiatives spurred improvements in the science
and technology needed for the recognition of hazards and associated risks. Manage-
ment systems have been developed to implement safety programs and industry
practices.
Government regulations continue to be a significant driver for safety programs.

As such, one of the main objectives of the management systems is to ensure com-
pliance. However, it is also quite clear that profitability is directly related to safety
and loss prevention. Thus, the management systems for safety are intricately tied
into the operational management. It is also quite apparent that government regula-
tions alone cannot accomplish our ultimate safety goals. Safety must be tied into
profitability and business objectives. Also, the use of risk assessments and risk–
benefit analysis will play a significant role in the future safety programs.
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EPA, Washington, DC, 1989.
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tem, 1991.
M. SAM MANNAN
JIM MAKRIS
H. JAMES OVERMAN
194 Recent Advances in Biomaterials
Recent Advances in Biomaterials
A vast number of materials (collectively termed biomaterials) are used in clinical

applications, from drug delivery (capsules, transdermal patches) to hip replace-
ments to materials in hemodialysis machines to heart valves. These materials have
had a tremendous impact on patients’ lives, allowing many injured or ill people
to lead a near-normal life in many instances. As one would imagine, these biomate-
rials represent a significant health care cost. The annual sales of medical devices,
diagnostics, and pharmaceutical products using biomaterials in some capacity ex-
ceed $100 billion per year in the United States alone. With new materials and
devices being developed to treat disease and injury, the market for biomaterials
is likely to increase significantly in the next decade.
Specifically, a biomaterial can be classified as a material such as a polymer,
metal, or ceramic that is in intimate contact with a biological environment such
as blood, tissue, or individual cells. The biocompatibility of a biomaterial is defined
as the ability of a material to function with a specific host response. For example,
a blood contacting material should not cause thrombosis or complement activation,
and a hip implant should be load-bearing and non destructive to the surrounding
tissue. The study of biomaterials is a multidisciplinary endeavor, integrating
knowledge from fields such as engineering, chemistry, biology, and medicine. Be-
cause of the high impact of these materials on patient care, this area has been an
intensely researched for the last 20 years.
Although current biomaterials have had a large impact in medicine, they consist
mainly of ‘‘off-the-shelf ’’ materials not originally designed for clinical use. As a
result, complications have and continue to occur. For example, leakage, hardening,
and rupture of silicone gel breast prostheses have lead to billions of dollars in
litigation related to either real or perceived patient health problems attributed to
the material. The early use of cellulose in hemodialysis tubing resulted in anaphy-
lactic shock and death in several patients. As a result of these incidents and numer-
ous others, many materials manufacturers no longer permit the clinical use of their
materials; thus, device manufacturers have feared a shortage of materials. To help
alleviate any future shortage of biomaterials, President Clinton signed the Biomate-
rials Access Assurance Act of 1998 to limit product liability in the biomaterials
area.
To eliminate many of the complications and expand the use of biomaterials in
medicine, research has focused on developing materials specifically designed for
the clinic. These materials are being designed using an advanced knowledge of cell
biology and tissue–material interactions. Many of these new materials represent
chemical and physical modifications of existing materials or are entirely novel in
their chemical structure. Here, we will focus on new material development in three
high-impact areas of biomaterials research: cell–biomaterial interactions, tissue
engineering, and drug delivery. This discussion is by no means exhaustive, as
many significant advances have also been made in other research areas that use
biomaterials.
Recent Advances in Biomaterials 195
Cell–Biomaterial Interactions
Because the lack of biocompatibility of most conventional biomaterials can be

attributed to adverse cell–material interactions, a large amount of research has
been focused on understanding and controlling what happens at the cell–material
and tissue–material interfaces. Most mammalian cells are anchorage dependent;
that is, they must adhere to a substrate to grow and differentiate. Adhesion to a
surface is mediated by protein adsorption onto the surface, followed by cell–
receptor interactions with the adsorbed proteins. As the adherent cells grow and
proliferate, they produce their own extracellular matrix (ECM) on which to adhere.
Surfaces that minimize protein adsorption, such as those modified with poly (ethyl-
ene glycol), also minimize cell adhesion and spreading [1]. Cells on these surfaces
are sparse in number, very loosely attached, and appear rounded.
In addition to purely thermodynamic considerations such as protein adsorption,
cell adhesion is strongly influenced by receptor–ligand interactions between inte-
grins on the cell surface and ECM proteins adsorbed on the substrate. These pro-
teins, examples of which include laminin, fibronectin, and collagen, contain peptide
sequences, such as RGD (R ⫽ arginine, G ⫽ glycine, D ⫽ aspartic acid), specific
for integrin binding. Materials modified with RGD peptide sequences alone are
capable of integrin binding and thus permit cell attachment and growth [2]. Zhang
et al. have used the RAD (A ⫽ alanine) sequence to promote cell adhesion to
oligopeptides terminated with cysteine residues [3]. Via sulfhydryl interactions
with a gold-coated substrate, these oligopeptides can form self-assembled mono-
layers (SAMs) on the surface of the substrate and thus create a good adhesion
substrate for a variety of cell types.
In addition to integrin–cell adhesion, cells such as hepatocytes possess recep-
tors for asialoglycoprotein receptors for β-d-galactose residues present in the ECM
[4,5]. Griffith and colleagues took advantage of these unique interactions to create
an adhesion surface for hepatocytes. Starting with poly (ethylene glycol) or PEG
star polymers (PEG chains radiating from a divinylbenzene core), they added
d-galactose moieties to the hydroxy terminus of PEG and cross-linked the gels
using electron beam irradiation. Hepatocytes readily adhered to these surfaces even
though the ligand density was an order of magnitude lower than in similar galac-
tose-modified polyacrylamide gels. The reason for this strong adhesion was that
the flexibility of the PEG chains allowed necessary multiple ligand–receptor inter-
actions to occur, even though the ligand density was low.
In the past few years, Stupp and colleagues [6–8] have developed a novel class
of block copolymers that self-assemble into highly ordered supramolecular structures
on surfaces. These materials were diblock polymers termed ‘‘rod–coil’’ and are com-
posed of a rigid rod segment of biphenyl esters and a flexible segment (the coil)
composed of a block copolymer of polystyrene and polyisoprene (Figs. 1 and 2).
When cast on surfaces, these polymers self-assembled to form identical nanometer-
scale clusters. The self-organization of the polymers on a surface was based on the
crystallization of the biphenyl ester rod segments, as can be seen in the base of the
structure depicted in Fig. 2. Molecular modeling studies suggested that these aggre-
gates were essentially supramolecular ‘‘mushrooms’’ with the ‘‘stem’’ consisting of
FIG. 1 Structure of self-assembling rod–coil polymer. (Adapted from Ref. 6.)
the crystallized rod segments and the ‘‘head’’ comprised of the coil segments. When
annealed at high temperature, the isoprene segments cross-linked to form films stable
in a variety of solvents. Because of the highly ordered and stable nature of these
clusters, they hold great potential in the design of new biomaterials.
Microfabrication techniques such as photolithography and microcontact print-
ing have also been used to create surfaces with unique topographies and spatially
defined chemistries. Such surfaces have had a profound influence on cell–material
interactions. Researchers at Cornell, for example, have developed micromachined
probes that show minimal adverse tissue response when implanted in the cerebral
cortices of rats [2]. Others have shown that photolithography can define regions
of cell adhesion, controlling both cell position and migration [9].
Microcontact printing or µ-Cp, a soft lithography technique, has received ex-
tensive attention as a method of both chemical patterning [10] and protein pat-
terning surfaces [11] to control cell adhesion and migration. As described earlier,
Whitesides and Lauffenberger used oligopeptide SAMs to create surfaces for cell
adhesion [3]. These peptides can be patterned by µ-Cp, resulting in the spatial
control of cell adhesion and migration and creating unique geometries suitable for
FIG. 2 Molecular graphics of a self-assembled rod–coil polymer structure containing nine layers or
monomer units of isoprene. (From Ref. 6.)
the study of cell–cell interactions on these surfaces. Earlier studies demonstrated

that there are geometric limits to the extent cells can be confined without causing
apoptosis (programmed cell death) [12–14]. Besides µ-Cp, Takayama et al. have
also used the low-mixing laminar-flow conditions in micromachined channels to
pattern cocultures of eukaryotic cells on a single surface [15].
Going beyond SAMs, a four-step soft lithographic process based on microcon-
tact printing (µ-Cp) of organic monolayers, hyperbranched polymer grafting, and
subsequent polymer functionalization has resulted in polymer patterns that direct
the grown of mammalian cells such as IC-21 murine peritoneal macrophages [16],
human umbilical vein endothelial cells, and murine hepatocytes. The functional
units on these surfaces were three-dimensional cell ‘‘corrals’’ that have walls 50
nm in height and lateral dimensions on the order of 60 µm. The corrals have
hydrophobic, methyl-terminated n-alkanethiol bottoms, which promote cell adhe-
sion, and walls consisting of hydrophilic poly(acrylic acid)/poly(ethylene glycol)
(PAA/PEG) layered nanocomposites that inhibit cell growth. Cells seeded on pat-
terned surfaces adhere and grow within the corrals, but they do not span the PAA/
PEG corral walls (Fig. 3). Cell viability studies indicate that cells remain viable
FIG. 3 Murine macrophages cultured on a micropatterned surface of poly(acrylic acid)/poly(ethylene

glycol). (From Ref. 16.)
on the patterned surfaces for up to 21 days, and microscopy studies demonstrate

that cell growth and spreading does not occur outside of the corral boundaries.
Other significant insights have been made in understanding tissue–material
interactions, particularly in influencing the foreign-body response. When a foreign
body such as a medical implant is introduced into a host, the natural tendency of
the surrounding tissue is to degrade or extrude the implant. If the host cannot
eliminate the foreign body, a chronic inflammatory reaction results and the object
is encapsulated in fibrous tissue. This capsule poses a difficult problem in the
development of cell-based therapeutic devices and engineered tissues [17]. It pre-
sents a mass-transfer barrier and therefore limits the concentration of nutrients and
oxygen reaching the transplanted cells. As a result, these cells frequently die from
hypoxia or lack of nutrients, particularly cells that are highly metabolically active
(e.g., pancreatic islets and hepatocytes) [18]. The ability of the capsule to limit
mass transfer has been demonstrated in several studies. In one early study, fibrous
capsules were generated by implanting materials in vivo followed by the harvesting
of the capsule for permeability studies, with results of these studies showing lower
permeability for thicker capsules [19]. In vivo studies of transplanted pancreatic
islets showed that islet viability decreased dramatically with increasing distance
between blood vessels and islets [17,20]. This result is not surprising because in
a healthy pancreas, islets are very closely associated with capillaries [21]. Increased
distance from blood vessels also resulted in lower insulin production from trans-
planted islets [18].
Devices containing transplanted cells must therefore develop capillary net-
works with transcapillary mass-transfer rates high enough to ensure survival of
the cells. Prevascularization of polymer scaffolds for tissue engineering was at-
tempted as a method to develop a vascular network in and around the implant and
promote the survival of cells transplanted into the scaffold at a later date [22]. A
number of studies have also shown that the microarchitecture of an implanted
material has a great influence on its local tissue response [23]. In suture materials,
the topography of the surface affected macrophage involvement, with round su-
tures resulting in less macrophage involvement than sutures with surface irregulari-
ties on the scale of 10–15 µm [24]. In another study, surface features greater than
10 µm appeared to attract foreign-body giant cells to the surface of the implant.
The presence of these inflammatory cells around the implanted material resulted
in thickening of the fibrous capsule [23]. In addition to implant topography, the
anatomical site of implantation influences fibrosis. Acrylic fibers implanted into
the subcutaneous tissue of rats showed a higher degree of fibrosis than those im-
planted into the abdominal fat pad. When islets were introduced, oxygen present
inside these hollow fibers was also consumed by islets in minutes [20].
Studies by Padera and Colton [25] and Brauker et al. [26] have shown that
certain microporous materials will allow blood vessels to grow and be maintained
at the tissue–material interface and in some cases within the pores of the material
(Fig. 4). However, this is not true for all porous polymer membranes, even those
with similar porosities and chemistries. What appears to be driving the host re-
sponse is not necessarily the chemistry of the material, but the microstructure of
individual features within the material onto which host cells can attach. Materials
that are microporous but contain large planar features prompted an avascular host
response while the same material lacking these planar features and having a more
FIG. 4 Top: Micrograph of a tissue section containing a PVDF membrane with a 0.22-µm pore size.
Arrows indicate foreign-body giant cells at the tissue material interface. Note the lack of blood
vessels near the tissue–material interface. Bottom: Micrograph of a tissue section containing
a 5-µm PVDF membrane. Arrows indicate blood vessels either at the tissue–material interface
or within the material.
fibrous structure prompted neovascularization at the tissue–material interface. If

the mechanism of this response can be elucidated, it may then become possible
to fabricate materials with a microstructure designed to promote specific levels of
neovascularization.
Tissue Engineering
Tissue engineering is an interdisciplinary field combining fundamental principles

from biology and engineering to understand the structure and function of tissue.
Tissue failure or loss due to disease or injury accounts for over $400 billion in
total annual health care costs in the United States alone. For some ailments such
as burns, kidney failure, and liver failure, tissue transplantation is the conventional
treatment. However, there exists a serious shortage in available donor tissue. For
example, nearly 40,000 people die each year waiting for a suitable liver for trans-
plantation. To address this need, tissue engineering has developed as a discipline
with the goal of restoring, maintaining, and improving the function of living tissue.
Tissue engineering has taken on three basic forms. The first is the development
of biohybrid artificial organs such as implantable islet-containing bioreactors or
microencapsulated islets for the treatment of diabetes. The second is the controlled
release of growth factors and cytokines to promote tissue repair or regeneration
using existing mechanisms within the body. The third approach, which is addressed
here, uses cells from the desired tissue cultured in vitro on a three-dimensional
biodegradable scaffold. Once these cells have reached a critical density on the
scaffold, they are then transplanted into the subject at the desired location. They
will then hopefully continue to grow and mature into the desired tissue, the scaffold
having degraded with time. This approach has met with some success, particularly
for the generation of skin and cartilage. However, there are several significant
obstacles that must be overcome before it can be used for the repair or replacement
of many types of tissue.
Many of these tissue substitutes take the form of cells from the tissue of interest
cultured on biomaterials, frequently microporous biodegradable polymer scaffolds.
For example, if one wished to form a tissue-engineered liver, hepatocytes (liver
cells) are cultured in vitro on a polymer scaffold to a high cell density. The tissue–
material construct is then implanted into the abdomen of the patient. As the tissue
continues to grow, the polymer scaffold degrades and is eventually replaced by
healthy and functioning liver tissue. Many readers may remember the television
news image of a human ear growing on the back of a rat, an example of tissue
engineering of cartilage. The ear began as cartilage cells (chondrocytes) cultured
on a polymer scaffold in the shape of a human ear.
For some types of tissue such as cartilage and skin, tissue-engineered products
have moved outside the laboratory and into the marketplace. As an example, tissue-
engineered skin developed from biodegradable scaffolds are available from Ad-
vanced Tissue Sciences. Protein Polymer Technologies is developing silk/elastin
gels that can be freeze-dried to form sponges for wound healing and organ-filler
applications. Other tissue-engineered products are currently in development, in-
cluding encapsulated cells and cell-based bioreactors for the treatment of Type I
diabetes and liver failure, vascular grafts, and bone replacement.
For other types of tissue such as liver and nervous tissue, many challenges
are present, including the integration of blood vessels and nerves, adverse tissue
responses to the biodegradable polymer, and engineering tissue containing multiple
cell types. To promote blood vessel growth in engineered tissue, researchers such
as David Mooney of the University of Michigan are developing polymer scaffolds
prepared in supercritical carbon dioxide that release blood-vessel-promoting
growth factors such as vascular endothelial growth factor (VEGF) [27]. VEGF
bioactivity was retained and controlled-release sustained in excess of 30 days.
VEGF, also known as vascular permeability factor (VPF), is a protein composed
of two identical subunits which has a molecular weight of 45 kDa. This protein
is a secreted cytokine that is specific for vascular endothelial cells and has been
shown to have angiogenic activity in vivo [28–31]. Numerous studies have also
shown that VEGF is secreted by macrophages and that VEGF expression is en-
hanced in macrophages under hypoxic conditions [31]. Other researchers such as
Keith Gooch of the University of Pennsylvania are forming capillaries in vitro that
connect to existing blood vessels when implanted.
Significant advances have also been made in the engineering of other tissues.
For nervous tissue, Schmidt and colleagues found that electrically conducting poly-
mers such as polypyrrole aid the reconnecting of severed nerves [32]. For bone,
Anseth and colleagues have developed photo-cross-linkable polyanhydrides that
have excellent mechanical properties and can be fabricated into complex shapes
such as screws [33]. Oberpenning and colleagues recently tested a tissue-
engineered bladder (Fig. 5) that, when implanted in dogs, was able to retain urine
normally for up to 11 months [34]. This bladder, based on smooth-muscle cells and
urethelial cells cultured on a biodegradable poly (lactide-co-glycolide) scaffold,
represents the first construction of a hollow organ by tissue engineering. Finally,
a number of systems have been developed for the in vivo polymerization of a
matrix for tissue engineering, including poly(ethylene glycol) gels that can be inter-
facially polymerized to prevent intimal thickening following ballon angioplasty
[35] and polymer solutions containing chondrocytes that can be polymerized trans-
dermally [36,37].
Drug Delivery
Drug delivery research in the controlled release of proteins has become increasingly
important as many new drugs are either protein or peptide based. Two prime exam-
ples are human growth hormone and erythropoeitin for the treatment of anemia;
both of these proteins are billion dollar drugs. Most of these biomolecules are unsta-
ble in vivo and as a result must be administered by multiple injections. To stabilize
these drugs in vivo and to control the rate at which they are delivered and the
location of delivery, new polymers, both degradable and nondegradable, are being
developed. These materials are designed to control the mass transfer of drug to the
surrounding tissue and to be biocompatible. Many of these materials can maintain a
FIG. 5 Radiographic cystograms of a tissue-engineered bladder implanted in a dog. (From Ref. 34.)
constant release of drug over many days and months. Examples of such degradable
materials include polyesters such as poly(glycolic acid) used in resorbable sutures,
polyanhydrides, and poly(ethylene glycol)–polyester copolymers. These materials
are chemically designed such that their degradation products are nontoxic.
One example is Gliadel, the first new FDA-approved treatment of gliabastoma
(a deadly form of brain cancer) in 20 years [38]. This product is composed of a
biodegradable polymer containing the anticancer drug carmustine. After the brain
tumor is surgically removed, the space formerly occupied by the tumor is lined
with polymer wafers containing the drug. As the polymer degrades over time, the
anticancer drug is released directly to the brain in concentrations that cannot be
achieved by administering the drug via the bloodstream. As a result, the reoccur-
rence of the disease is diminished and chemotherapy side effects are reduced be-
cause the drug is delivered only where it is needed.
Drug delivery products for vaccine delivery, anemia, and cancer treatment are
expected to be available shortly. Other research in drug delivery is currently fo-
cused on developing targeted polymer delivery systems (such as biodegradable
microparticles to the lungs) and developing polymer delivery vehicles for gene
therapy.
Hydrogels, both degradable and nondegradable, have been of particular inter-
est. These materials are highly swollen with water and can possess equilibrium
water content in excess of 90% by weight. With the exception of swelling-con-
trolled or osmotic delivery systems, polymeric materials control drug release by
limiting Fickian diffusion of the drug through the solvent-swollen network. This
process is highly dependent on polymer chain mobility. Mikos and colleagues re-
cently provided a comprehensive review of both nondegradable and degradable
hydrogel systems for drug delivery [39].
Some specific examples are instructive. For example, Khare and Peppas have
described the effects of copolymerization, ionic strength, pH, and buffer composi-
tion on the release of biomolecules [40]. Particularly in the case of anionic gels,
these factors influence the equilibrium water content of the polymer network and
hence the mesh size in the gel. Brannon-Peppas and Peppas describe research on
the effects of comonomer composition and hydrophobicity on swelling [41]. Net-
work hydrophilicity controls swelling via water absorption, and because equilib-
rium water content is directly proportional to biomolecule mass-transfer rates out
of the gel, extended release profiles can be achieved by increasing the hydropho-
bicity of the gel. In polyelectrolytic gels, the ionic character is pH dependent and
can exhibit substantial changes in swelling caused by shifts in pH [41]. Unless
highly localized changes in pH occur, these pH-induced changes in swelling may
not occur in vivo.
DNA–polycation complexes have received extensive attention in recent years
as an alternative to virus-mediated transfection of therapeutic gene therapy vectors
into mammalian cells. Polycations investigated to date include polylysine [42],
cationic liposomes [43], polyethylene imine [44], and poly(amidoamine) (PA-
MAM) dendrimers [45]. PAMAM dendrimers are unidispersed and have a high
positive-charge density at their surface. Electrostatic complexes of DNA and den-
drimers were shown to transfect a variety of cell lines, including fibroblasts, CHO,
Rat2, lymphoma, and hepatoblastoma [45]. In the Rat2 cell line, transfection was
highly dependent on the generation of the dendrimer, which dictates the surface
charge and size of the molecule. Transfection efficiency as compared to simple
exogenous DNA was found to increase exponentially with the generation of the
dendrimer, reaching a plateau after the ninth generation of 20,000 to 40,000 times
more efficient. Although chloroquine and DEAE–dextran enhanced transfection,
they were not required and transfection, as determined from the expression of a
luciferase gene in the vector, occurred at levels easily measured.
Recently, a novel system was described that may have significant applications
in drug delivery. Discher and colleagues [46] described the formation of poly-
mersomes, vesicles made of amphiphilic diblock copolymers of poly(ethylene ox-
ide) and poly(ethylethylene) (Fig. 6). These structures were found to be structurally
FIG. 6 Polymersomes. (A) Schematic representation of diblock copolymer assembly; (B) micrograph
of diblock copolymer vesicles, rodlike structures (black arrow) and micelles (gray arrow).
(From Ref. 46.)
tougher than liposomes and significantly less permeable to water. With further
modification, these materials may be developed into new vehicles for nucleic-
acid- and protein-based drugs.
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Extractive Distillation 207
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MICHAEL V. PISHKO
Recent Development of Extractive Distillation:

A Distillation Alternative
Introduction
Distillation is the most commonly used method for recovering and purifying petro-
chemicals and chemicals in the industry. The difference in boiling points between
the key components to be separated is the means for separation. The ease of separa-
tion is conveniently measured by the relative volatility (α) between the key compo-
nents, which is defined as:
Y 1 /X 1
α⫽
Y 2 /X 2
where X 1 and X 2 are the mole fraction of components 1 and 2, respectively, in the
liquid phase and Y 1 and Y 2 are those in the vapor phase. In fact, α is one of the major
economic factors for distillation. Colburn and Schoenborn [1] gave the following
generalized correlation for the approximate number of theoretical plates required
for a separation of products each of 99% ⫹ purity:
4
Number of theoretical plates ⫽
α⫺1
In general, distillation becomes uneconomical when 0.95 ⬍ α ⬍ 1.05, because a

large number of plates requires very high capital investment and a large reflux
ratio requires very high operating cost. Under this situation, a solvent-enhanced
distillation, such as extractive distillation (ED), becomes economically attractive
and practical.
The basis for ED is to increase α by introducing a high-boiling, polar solvent to
the distillation column. The characteristics, design, and operation of an extractive
distillation column (EDC) have been thoroughly discussed in the literature [2–5].
208 Extractive Distillation
Depending on applications, the solvent-to-feed weight ratio (S/F) can vary from
3 to as high as 20, so the EDC is normally operated using substantially higher amount
of liquid (nonvolatile solvent) than the conventional distillation. Also, due the to differ-
ence in solubility of the key components in the polar solvent, a certain portion of the
EDC may have two liquid phases. Significant progress has been made in the industry
recently in terms of understanding and handling these special situations in the EDC.
Hydrodynamic Behavior of a Packed EDC
The presence of the nonvolatile solvent in the EDC not only substantially increases
liquid flow (L) but also reduces the vapor flow (V) by preferentially absorbing the
more polar components in the vapor stream. Therefore, extractive distillation is
normally operated under significantly higher liquid to vapor ratios (L/V) as com-
pared to conventional distillation.
Depending on applications, the solvent-to-feed weight ratio (S/F) varies from 3/
1 to as high as 20/1. Hydrodynamic behavior of a distillation operation with a high-
L/V condition has not been significantly reported in the literature. Nevertheless, such
information on packed columns used for ED operation was reported by Brown and
Lee [6]. Two types of packing were tested; a random dumped packing [0.63-cm pro-
truded metal packing (Pro-Pak)] and a structured packing (Koch-Sulzer BX).
Shown in Fig. 1, the tests on Pro-Pak random packings were conducted in a 0.15-
FIG. 1 Schematic diagram of ED pilot plant for hydrodynamic study of packings.

Extractive Distillation
TABLE 1 ED Runs with Different Tower Packings
Extract (%) Raffinate (%)

Solvent- Kettle
Run Packing to-feed temp. Reflux Toluene Toluene Heptane Heptane
no. code ratio (°C) ratio recovery purity recovery purity
1 P 6.5 174 4.4 99.6 99.5 95.0 95.4
1 S 6.5 174 3.2 99.1 99.8 98.3 93.3
2 P 6.5 182 2.1 88.8 100.0 100.0 59.8
2 S 6.5 182 3.7 99.3 100.0 100.0 95.3
3 P 10.0 182 3.6 99.2 99.9 99.3 94.4
3 S 10.0 182 3.4 99.1 100.0 100.0 94.0
4 P 10.0 193 1.1 72.8 100.0 100.0 46.7
4 S 10.0 193 1.6 86.7 100.0 100.0 59.3
5 P 6.5 172 4.4 99.7 99.7 96.8 96.5
5 S 6.5 172 3.2 99.1 100.0 100.0 93.4
Notes: Packing codes: P ⫽ protruded packing (ProPak); S ⫽ structured packing (Koch–Sulzer BX). All ratios and percents were measured by weight.
209
m-diameter EDC with 5.7-m total packed height loaded in a duo-column system: The
top and bottom halves of the column were connected in series by insulted vapor
and liquid lines. During the operation, pipe distributors were installed at the top and
at 40% above the bottom of each half-column. The feed (a mixture of 88/12 wt%
toluene/heptane) was fed to the location at 55% above the bottom of the entire EDC,
and the extractive solvent (N-methyl pyrrolidone) was fed at 88% above the bottom
of the EDC. During a normal run, hydrocarbon was introduced into the EDC at a
rate of 0.015–0.022 m3 /h at a temperature slightly below the hydrocarbon bubble
point and a pressure of 35 kPa. Lean solvent was fed to the top of the upper half
of ED tower at a subcooled temperature of 121°C. The solvent-to-feed ratio (S/F)
varied from 6.5 to 10 and the kettle temperature varied between 171°C and 193°C.
Koch–Sulzer BX structured packing was also tested in the same EDC under the
same condition as the Pro-Pak testings. Distributors were placed only at the top of
each half-column. A total of 31 elements with 5.3-m total packing height were fitted
in the duo-column EDC. A summary of the selected runs is presented in Table 1.
To investigate the pressure drop in the EDC under high-L/V condition, a plot of
the difference between the measured pressure drop and the predicted pressure drop is
given in Fig. 2. It was found that the actual pressure drops measured in this study are
significantly higher than the ones predicted by the packing vendor’s correlations [7,8].
The difference between the predicted and actual pressure drop for protruded packing
are at least twice that of the structured packing under the same conditions.
It was also found that the height equivalent to a theoretical plate (HETP) on
both packings was underpredicted by the vendor’s correlations [7,8]. As shown in
Fig. 3, the difference in HETP for the structured packing and protruded packing are
respectively 5 and 10 in. The actual HETP was roughly estimated by the Fenske–
Underwood correlations, utilizing the composition of feed and products, and an
average relative volatility.
Then, computer simulations were run to determine the number of theoretical
stages, using a rigorous computer algorithm capable of simulating distillation pro-
cesses with multicomponents and multiphases. Experimental activity coefficients
FIG. 2 Comparison of predicted and actual pressure drop.

FIG. 3 Comparison of predicted and actual HETP.
for N-methyl pyrrolidone/n-heptane/toluene were used as input to a Renon activity

coefficient model, which was used to determine vapor–liquid equilibrium con-
stants. In the computer simulation, an initial trial solution to the computer algorithm
was made by assuming constant molal overflow and a guessed (assumed) column-
temperature profile. A final solution was then made by convergence on the input
specification values, vapor–liquid equilibria, and heat and material balances. A
Newton–Raphson convergence technique was used.
The gas capacity factor (F s ⫽ the superficial gas velocity times the square root
of the gas density) is an important parameter in determining the loading on the
column. Figure 4 shows that the pressure drop for both packings increase with
increasing F s, but protruded packing consistently shows a pressure drop three times
FIG. 4 Pressure drop versus gas capacity factor.

FIG. 5 HETP versus gas capacity factor.
higher than structured packing. The gas capacity factor is also plotted against
HETP in Fig. 5. It appears that F s has no effect on HETP for both packings over
the range tested. The HETP for protruded packing is slightly higher than that of
structured packing (approximately 1–5 in higher). It is estimated from vendor in-
formation that the column was at 12% of flood, using Koch–Sulzer BX structured
packing [7], and at 32–37% of flood, using the protruded packing [8].
Liquid loading in an EDC is much higher than the conventional distillation
column, so it could be the limiting factor in the design of an EDC. The pressure
drop is plotted against the liquid loading (kg/h/m2 ) in Fig. 6 for both packings.
FIG. 6 Pressure drop versus liquid loading.

FIG. 7 HETP versus liquid loading.
Liquid loading shows a positive linear relationship with pressure drop for the pro-
truded packing and shows a minimum pressure drop at liquid loading around 8070–
8310 kg/h/m2, but otherwise shows little correlation.
Liquid loading is also plotted against HETP for both packings in Fig. 7. Al-
though literature sources predict a decrease in HETP with increased liquid loading
[9,10], the structured packing had a constant HETP and the protruded packing has
little correlation over the liquid loading range investigated. The flow parameter,
(L/V)(ρ v /ρ l )0.5, where ρ v and ρ l are the density of vapor and liquid, respectively,
is an important parameter when considering the flood point or maximum loading
on the column. Assuming the densities (ρ v and ρ l ) to be relatively constant in the
range investigated, L/V is plotted against pressure drop and HETP. Figure 8 shows
the pressure drop against the maximum L/V predicted in the computer simulation
(normally at solvent feed stage).
The column packed with the structured packing shows a constant pressure drop
over a L/V range of 15–27, whereas the column packed with protruded packing
shows a slight decrease in pressure drop with increasing L/V, although the data
points were scattered. A very good linear correlation was found when L/V deter-
mined by the maximum liquid and vapor loadings in the column is plotted against
the pressure drop, as shown in Fig. 9. Both packings show a pressure drop of about
0.1 in. of water per foot of packing for every 0.2 increase in L/V. This is consistent
with established principles, as the stage with the maximum L/V plays the most
important role in determining pressure drop in a column and will be used for sizing
the column.
The HETP is also plotted against L/V for the protruded packing in Figs. 10
and 11 for the solvent feed stage and for the stage with maximum vapor and li-
quid loadings, respectively. Both figures show an increase in HETP with increas-
ing L/V. However, there was no change in HETP with L/V for the structured
packing.
It is concluded that both random and structured packings show a loss of effi-
FIG. 8 Pressure drop versus maximum predicted L/V (on solvent feed tray).
ciency under ED operation (or under very high L/V) as compared to conventional
distillation. Both pressure drop per foot of packing and HETP are underpredicted
by vendor correlations for both types of packings, although the predicted results
for the structured packing is closer to the actual results than those of the protruded
packing. Also, compared to random packing, the structured packing appears to be
less affected by the changes in gas capacity, liquid loading, and L/V. Further litera-
ture data are required to confirm the superiority of the structured packing for extrac-
tive distillation services.
FIG. 9 Pressure drop versus L/V determined by maximum liquid and vapor loadings.
FIG. 10 HETP versus L/V (on solvent feed tray) for protruded packing.
Handling Two Liquid Phases in EDC
One of the considerations in ED technology is the handling of possible formation

of two liquid phases in a certain portion of the EDC where the less soluble compo-
nents are concentrated. The occurrence of a second liquid phase is caused by the
fact that some of the less polar components have significantly lower solubility in
the polar solvent than the more polar components.
One way to solve the problem of two liquid phases in the ED tower is to select
FIG. 11 HETP versus L/V determined by maximum liquid and vapor loadings for protruded packing.
a polar solvent, which has enough solvency to dissolve all the components in the
mixture under process condition. In general, however, solvents with a high selectiv-
ity for compounds to be separated will have a reduced solvency (capacity), and
vice versa. Therefore, in order to eliminate two liquid phases, one may have to
compromise the solvent selectivity, sometimes, to a great extent.
A better way is to cope with two liquid phases in the EDC, without sacrificing
the solvent selectivity, for following reasons:
1. Although two liquid phases normally reduce the solvent selectivity in a three-
phase equilibrium (vapor–liquid–liquid) condition in the EDC, it can be com-
pensated by intrinsic selectivity of a highly selective solvent. For example,
the performance of sulfolane (SULF) was compared with those of N-formyl
morpholine (NFM), N-methyl pyrrolidone (NMP), 2-pyrrolidone (2PD), and
dimethyl sulfoxide (DMSO). The rough comparison was made through their
abilities to enhance the relative volatility of n-heptane over benzene (an aro-
matic and nonaromatic separation) in a one-stage equilibrium cell. Table 2
shows that although two liquid phases were observed using sulfolane as the
solvent, it still gave a better performance than other solvents when a single
liquid phase existed in the mixture.
2. Two liquid phases present no ill effects on the efficiency of small tray or
packed towers with diameter from 0.08 to 0.46 m. However, in a larger tower,
the heavy liquid phase tends to accumulate on the tray if the liquid phases are
not well mixed. This problem can be eliminated by tray designs promoting
gas agitation, causing the two liquid phases to behave as a homogeneous liquid
that followed general correlations for pressure drop, liquid holdup, broth
height, downcomer liquid level, and fractional entrainment. For larger packed
TABLE 2 Comparison of the ED Solvents for n-Heptane and Benzene Separation
Phase composition† (wt%)

Liquid
Solvent S/F X1 Y1 X2 Y2 α1/2 phases
SULF 1.0 16.24 28.94 83.76 71.06 2.10 2
SULF 3.0 16.32 43.76 83.68 56.24 3.99 2
NFM 1.0 16.23 26.39 83.77 73.61 1.85 1
NFM 3.0 16.23 36.84 83.77 63.16 3.01 1
NMP 1.0 18.60 27.74 81.40 72.26 1.68 1
NMP 3.0 18.60 35.71 81.40 64.29 2.43 1
DMSO 1.0 15.21 26.97 84.79 73.03 2.06 1
DMSO 3.0 15.21 37.54 84.79 62.46 3.35 1
2PD 1.0 14.74 24.32 85.26 75.68 1.86 1
2PD 3.0 14.74 34.76 85.26 65.24 3.08 1
Notes: SULF: sulfolane; NFM: N-formyl morpholine; NMP: N-methyl pyrrolidone; DMSO: dimethyl
sulfoxide; 2PD: 2-pyrrolidone.
†
X1 and X2 are the liquid compositions of n-heptane and benzene, respectively, and Y1 and Y2 are the
vapor compositions of n-heptane and benzene, respectively (all in weight% on solvent-free basis).
α1/2 ⫽ (Y1 /X1)/(Y2 /X2), the relative volatility of n-heptane over benzene.
columns, the liquid–liquid redistributor should be specially designed to allow

separate distribution of the two liquid phases [11].
Computer simulations have been developed which are capable of accurately

predicting the development of two liquid phases in the EDC and the summary was
reported [12]. In one approach, the simulation algorithm starts from linearized
pressure, temperature and concentration profiles, and feed conditions given by the
program operator. New estimates of composition are solved using the material
balance and equilibrium relationship for each tray. Then, the equilibrium constants
are reestimated and a new temperature gradient is established to calculate a tray-
by-tray energy balance. Accumulated errors are calculated for the energy, material,
and equilibrium balances. Appropriate column operation restraints are factored in
at this point. A correction factor is found for the temperature, rate profiles, and
liquid composition profile by inverting the accumulated error matrix. These correc-
tion factors are used to form new estimates of composition to start the process again
until the correction factors are small enough to call the components converged.
Multicomponent vapor–liquid and liquid–liquid equilibria solutions are re-
quired for the algorithm. Two activity coefficient models, NRTL and UNIQUAC,
are readily extendable to multicomponent systems and capable of such solutions.
Experimental activity coefficients, γ, at infinite dilution are used for calculating
binary parameters for the NRTL equation. These parameters are then tested using
experimental liquid–liquid ternary data, experimental vapor–liquid equilibrium
data, and data from pilot plant or commercial plant. The NRTL equation is used
in the algorithm to calculate activity coefficients and is given by the following
equations:
冤冢冣冥
2
G 21 τ 12G 12
ln γ 1 ⫽ x 22 τ 21 ⫹
x 1 ⫹ x 2G 21 (x 2 ⫹ x 1G 12)2
冤冢冣冥
2
G 12 τ 21G 21
ln γ 2 ⫽ x 21 τ 12 ⫹
(x 2 ⫹ x 1G 12 ) (x 1 ⫹ x 2G 21 )2
where
ln G 12 ⫽ ⫺β 12 τ 12, ln G 21 ⫽ ⫺β 21 τ 12
η 12 ⫹ S 12T η 21 ⫹ S 21T
τ 12 ⫽ , τ 21 ⫽
RT RT
where G ij , η ij , S ij, τ ij , and β ij are empirical constants, γ i is activity coefficient, R

is the gas constant, T is the absolute temperature, and x i is the liquid-phase mole
fraction of component i. A Newton–Raphson-based flash algorithm checks for two
liquid phases by checking Gibbs free energies for possible second liquid-phase
components. If two liquid phases are indeed present, regular solution theory pro-
vides a method of combining the liquid-phase activity coefficients.
Some Unique Applications of Extractive

Distillation
Extractive distillation technology has been practiced and continuously improved com-
mercially since World War II when it gained commercial recognition in the recovery of
high-purity butadiene, isoprene, and C4 olefins from the C4 and C 5 petroleum streams.
However, ED technology for recovering high-purity heavier petrochemicals from the
petroleum streams has gained commercial importance only recently.
Many ED solvents have been studied during the past 50 years to determine
their selectivity for purifying heavier hydrocarbons. As shown in Table 3, a number
of solvents selective for aromatic recovery from petroleum streams have been listed
in the literature [13]. However, none of the solvents listed in Table 3 have gained
commercial importance for BTX aromatic recovery from the petroleum streams.
The modern state-of-the-art ED technologies for BTX aromatic recovery are
based on several solvent systems: SULF, NFM, and NMP. In most cases, proprie-
tary cosolvents are added to the base solvents to enhance the solvent performance.
The modern ED processes can compete very favorably with, for example, liq-
uid–liquid extraction based on sulfolane, which has dominated the BTX aromatic
recovery field for many years. However, in the following cases, ED technology
may be the preferred or the only choice.
Feeds with High Aromatic Content
The recovery of BTX aromatics from pyrolysis gasoline, which contains 80% ⫹ ar-
omatics is one example. The high aromatic content tends to prevent the interface
formation between the raffinate and the extract phases in the liquid–liquid extrac-
tor, making the process inoperable.
Today, two of the leading ED processes for BTX aromatics recovery are of-
fered by GTC Technology Corporation (GT-BTXSM process) and Krupp Koppers
(Morphylane process) [14,15]. The following is an example using the GT-BTX
process to recover high-purity BTX aromatics from the full-range (C 6 –C 8 ) pyroly-
TABLE 3 ED Solvents for Aromatics Recovery from Petroleum Streams
Furfural Acetonyl acetone Nitrobenzene Nitrotoluene Phenol

Aniline Dichloroethy- Phenyl cellosolve Cresol
lether
Phenol-cresol Nonanoic acid Sodium-o-xylene
sulfonate ⫹
H 2O
Phthalic anhydride 2-Ethylhexanol Propylene glycol
Hexyleneglycol 2-Ethyl hexy- o-Chloroamine o-Phenetidine
lamine
o-Chlorophenol o-Nitrophenol o-Phenyl phenol
Methyl salicylate Dimethyl ani- Dipheyloxide
line–aniline
sis gasoline, which contains around 90% aromatics. This type of feed is unsuitable
for liquid–liquid extraction (LLE), because the aromatic content is so high that it
prevents the formation of the interface between the extract and raffinate phases,
which is necessary for LLE operation. A part of the raffinate stream from the LLE
unit is often recycled to reduce the aromatic content in the feed stream (to ensure
the interface formation) and, thus, reduces the efficiency of the process.
To illustrate the application of ED technology to high aromatic containing feed,
two different feedstocks were tested in a pilot plant consisting of a 60-tray extrac-
tive distillation column and a packed solvent stripper for solvent recovery. The
simplified feed compositions are given in Table 4.
The pyrolysis gasoline feed is introduced to the middle portion of the EDC
near its bubble point. Lean solvent is fed near the top of the EDC at about 10°C
below the column temperature to generate internal reflux to improve the column
performance. The solvent preferentially extracts the more polar components in the
mixture, allowing the nonaromatic components to rise as vapor to the top of the
column as the raffinate product. The bottoms of the column consist of the solvent
and the aromatic components; these are fed to a solvent stripper (containing 9.5
m of random packing) to separate the solvent from the extract products. The lean
solvent is then recycled to the top of the EDC. A schematic diagram is presented
in Fig. 12. The analyses for the product streams are summarized in Table 5.
The solvent-to-feed ratio (weight) for both feeds was 3.0. The recovery for
benzene, toluene, and mixed xylenes, were respectively 96.5–97.0%, 99.0%, and
99.9% by weight. In order to determine the purity of BTX aromatics produced
without fractionating the extract product, a more detailed analysis was carried out
to determine the nonaromatics in the feedstock. Table 6 shows the major compo-
nents and their boiling points in Feed No. 1.
From Table 5, the nonaromatics in the extract (product) stream was 0.54 wt%,
and the split of bottom (extract) to feed in the ED column was 0.87. The nonaromatics
in the extract is equivalent to 0.47 wt% (0.54 wt% ⫻ 0.87) of the heaviest nonaromat-
ics in the feed. According to Table 6, these nonaromatics were iso-nonanes (0.16 wt%)
and the heavy portion of iso-octanes (0.31 wt%). According to material balances,
commercial grade of benzene (with 99.9 wt% purity), toluene (with 99.0 wt% purity),
and mixed xylenes (with 98.5 wt% purity) can be recovered from the extract product
by distillation. The impurities in benzene and toluene products were the 0.31 wt%
heavy iso-octanes in the feed, whereas the impurities in mixed xylenes were the 0.16
wt% iso-nonanes in the feed. These experimental results demonstrate the effectiveness
of a ED process (GT-BTX process) in recovering chemical grade BTX from a full-
range (C 6 –C8 ) pyrolysis gasoline containing high aromatics.
TABLE 4 Composition of Pyrolysis Gasoline for BTX

Aromatics Recovery
Component (wt%) Feed No. 1 Feed No. 2

Nonaromatics 11.50 7.89
Benzene 49.28 48.83
Toluene 27.79 29.38
C8-aromatics 11.35 13.90
C9⫹-aromatics 0.08 0.00
FIG. 12 Schematic diagram of ED process.
Heavy Aromatics Recovery
Liquid–liquid extraction is more effective to extract lighter aromatics, such as

benzene and toleune, but less effective to extract heavier aromatics, such xylenes
and C 9⫹-aromatics. The latter compounds have relatively less solubility in the ex-
tractive solvents than the former compounds. Extractive distillation, on the other
hand, will provide higher recovery for the heavier aromatics, which tend to stay
the solvent at the bottom of the ED column, due to their higher boiling points.
However, the solvent boiling point has to be high enough to allow a clean separa-
tion between the extract product and the solvent by stripping or distillation in the
solvent recovery column. The performance of ED technology for recovering C 8
to C 9⫹ aromatics has not been significantly reported in the literature.
To determine the performance of GT-BTX process, two heavy aromatic feeds
with composition shown in Table 7 were investigated in a pilot plant consisting
TABLE 5 Composition of Product Streams from the ED Unit for High Aromatic Feeds
Feed No. 1 Feed No. 2

Component
(wt%) Raffinate Extract Raffinate Extract
Nonaromatics 84.84 0.54 80.93 0.44
Benzene 13.30 54.66 15.69 52.22
Toluene 1.87 31.66 3.23 32.06
C8-Aromatics 0.11 13.04 0.15 15.31
C9⫹-Aromatics 0.00 0.10 0.00 0.00
TABLE 6 Components and Their Boiling Points of Feed No. 1

Boiling point
Component Wt% (°C)
Cyclopentane 0.22 49.3
2-Methylpentane 0.55 60.3
3-Methylpentane 0.36 63.3
n-Hexane 1.21 68.7
Methyl cyclopentane 3.57 71.8
Benzene 49.65 80.1
Cyclohexane 1.29 80.7
2-Methylhexane 0.30 90.1
2,3-Dimethyl pentane 0.19 89.8
1-cis-3-Dimethyl cyclopentane 0.20 90.8
1-tr-3-Dimethyl cyclopentane 0.12 91.7
1-tr-2-Dimethyl cyclopentane 0.24 91.9
n-Heptane 0.32 98.4
2,2-Dimethylhexane 0.07 106.8
Methyl cyclohexane 0.47 100.9
2,4-Dimethylhexane 0.52 109.4
Toluene 27.50 110.6
n-Octane 0.07 125.7
Iso-octane 1.36 107–119
Ethylbenzene 6.38 136.2
p-Xylene 0.42 138.3
m-Xylene 3.32 139.1
o-Xylene 1.18 144.4
Iso-nonanes 0.16 122–151
C9-aromatics 0.38 152–176
Total 100.26
of a 60-tray extractive distillation column and a packed solvent stripper for solvent
recovery.
The solvent-to-feed ratio (weight) for both feeds was 3.0. Based on the feed
analyses, the kettle temperature and pressure of the ED column were adjusted to
achieve the split of bottom-to-feed ratio of approximately 0.87 for Feed No. 1 and
0.76 for Feed No. 2. The solvent stripper (solvent recovery column) was operated
TABLE 7 Composition of Heavy Aromatics Feeds for ED Study
Component (wt%) Feed No. 1 Feed No. 2

Nonaromatics 12.51 24.03
Benzene 0.31 0.40
Toluene 2.66 1.52
C8-aromatics 63.82 59.91
C9⫹-aromatics 20.71 14.17
TABLE 8 Composition of Product Streams from the ED Unit for Heavy Aromatic
Feeds
Feed No. 1 Feed No. 2

Components Extract Extract
(wt%) Raffinate Extract Recovery Raffinate Extract Recovery
Nonaromatics 85.10 0.11 0.75 87.75 1.09 3.34
Benzene 1.95 0.00 0.00 1.51 0.00 0.00
Toluene 3.02 2.59 83.29 2.33 1.31 63.38
C8-aromatics 8.07 73.16 98.06 8.51 78.95 96.91
C9⫹-aromatics 2.15 23.81 98.34 0.05 19.03 98.76
with stripping gas under the proper level of vacuum to minimize the stripper tem-
perature. The analyses of the production streams are presented in Table 8.
Shown in Table 8, under a solvent-to-feed ratio of 3.0, the overall aromatic
recovery and purity have achieved the commercial requirements. The overall aro-
matic recovery for Feed No. 1 was 97.7 wt%, and for Feed No. 2, it was 95.7
wt%, and the overall aromatic purity for Feed No. 1 was 99.89 wt%, and for Feed
No. 2, it was 98.91 wt%. It is also observed that under similar operating conditions,
the process performance from Feed No. 1 is indeed better than that of Feed No.
2, probably due to higher aromatic content in Feed No. 1 (87.5 versus 76 wt%).
Revamping Existing LLE Processes Using the ED Method for BTX

Recovery
The ED method can be most effectively applied to revamping an existing LLE

facility for recovering BTX aromatics from reformate or pyrolysis gasoline. This
approach has been recently reported by Gentry and Kumar [16]. In a typical LLE
process where the solvent has higher density than the feed, the feed is fed into
the lower section of the LLE column and flows countercurrently against the sol-
vent. The solvent is introduced to the top of the column and flows downward
through the column to preferentially extract the more polar components in the feed
into the bottoms. The bottoms stream is then fed to a solvent recovery column to
recover the purified more polar components in the overhead and the lean solvent
as the bottoms to be recycled to the LLE column.
BTX aromatics are recovered using LLE with sulfolane as the extractive solvent.
A typical schematic diagram of this type of process is shown in Fig. 13. Reformate
containing BTX aromatics and the extractive solvent are fed into the LLE column
according to the manner described in previous paragraph. The solvent extracts the
aromatics and some nonaromatics into the bottoms, which is fed to the extractive
stripping column. This column strips the nonaromatics from the solvent and aromatics,
for recycle to the LLE column. The bottoms from the extractive stripping column
contain the aromatics and solvent are separated in a solvent recovery column. Lean
solvent from the solvent recovery column is recycled back to the LLE column. The
raffinate stream from the top of LLE column contains some solvent, which is recovered
in a water-wash column. The water is returned to the system in a closed-loop recycle.
FIG. 13 Schematic diagram of LLE process using sulfolane solvent.
A fundamental aspect of this process is that the solvent exhibits a selectivity fa-
voring lower-boiling components more than the high-boiling components. The solvent
selectivity favors the hydrocarbon species according to the following sequence: aro-
matics ⬎ naphthenes/olefins ⬎ paraffins. Lighter nonaromatic impurities are more
likely to be coextracted due to their solvent affinity in LLE column, but they should
be the easiest to remove in the ED column due to their lower boiling point.
Adding just one ED column to the existing LLE process system can not only
substantially increase the process throughput but also improve the performance in
terms of product quality and purity. The following are some examples.
Case A: Purifying By-product Benzene
The xylene isomerization and toluene disproportionation units within the aromatic
complex produce benzene as a by-product, but the quality of benzene is low and
requires reprocessing in the LLE unit to upgrade its purity. Figure 14 shows a new
approach using a hybrid of the LLE process with ED that bypasses part of the
feed around the original extraction section.
FIG. 14 A hybrid of LLE and ED process purifying by-product benzene.
In the hybrid scheme, the by-product (benzene-rich feedstock) is fed to the

stand-alone ED column, where the maximum aromatics limit in the feed charge
is not a concern. The original feed to the extraction section is not affected by this
new ED operation. The rich solvent from both LLE and ED operations are com-
bined into the existing solvent-recovery column. The typical solvent-recovery col-
umn can usually manage the higher capacity or can be redesigned to do so. If
desired, the raffinate from the two can be segregated for optimum disposition; the
ED raffinate rich in cyclohexane may be recycled to the reformer unit, whereas
the LLE raffinate rich in paraffins could be blended into the feedstock for a naphtha
cracker. The conventional LLE process can be retrofitted to use this hybrid process,
without requiring extensive modifications, investment, or shutdown time. The pri-
mary changes are modifying the solvent system to be compatible with both LLE
and ED operations and to make the appropriate tie-ins to the ED column.
Case B: Optimize the BTX Product Distribution
Among the BTX aromatics, toluene has historically contributed the least upgrade
over its alternative value in motor fuel (e.g., the petrochemical value of toluene
FIG. 15 A hybrid of LLE and ED process for selective purge of toluene.
is only marginally above its fuel blending value); thus, it is not profitable to extract
toluene. In a conventional LLE unit for BTX aromatics recovery, toluene is inevita-
bly extracted along with benzene and xylenes.
Figure 15 shows a LLE and ED hybrid scheme where toluene is selectively
purged from a BTX mixture to shift the product mix toward benzene and xylenes
and to avoid some operating cost for toluene. As shown in Fig. 15, the reformate
splitter is retrofitted to include a side cut of the C 7 and C 8 components, which is
fed to an ED column operated in parallel with the existing LLE unit. Operation
of the ED column is made to intentionally purge the majority of the toluene along
with the nonaromatics to the column overhead. Then, the toluene-lean ED column
bottoms are combined with the benzene-rich solvent mixture from the extractive
stripper bottoms as feed to the solvent-recovery column. A number of benefits from
this operation can be realized: (1) overall processing costs are reduced because the
stream contains less toluene; (2) xylenes recovered should have higher purity be-
cause the majority of the C 8 –C 9 nonaromatics are purged with toluene in the ED
column; (3) substantial increase in overall process capacity by adding only one
ED column to the existing LLE system.
Case C: Capacity Increases
Adding a new ED column to an existing LLE unit (as shown in Fig. 13) can double
the capacity of the unit. As demonstrated in Fig. 16, the new ED column takes
FIG. 16 A hybrid of LLE and ED for substantial increase of throughput.
the fresh feed while the main liquid–liquid extractor takes the feed from the ED
column overhead raffinate stream. Solvent is divided between the ED column and
the raffinate extractor. The original extractive stripper column is converted into a
solvent-recovery column operating in parallel with the existing solvent-recovery
column. Using a single new ED column to retrofit the existing LLE unit can create
significant increase in throughput and improvement in product quality with mini-
mized capital costs.
Styrene Recovery from Pyrolysis Gasoline
One of the most difficult separations, using the ED method, is the purification of
styrene from the close-boiling C 8 aromatic isomers. The method is based on the
slightly higher polarity in styrene than the other C 8 aromatics, due to the double
bond in the side chain of the styrene molecule. Recently, a proprietary ED process
was developed for the commercial application for recovering styrene directly from
pyrolysis gasoline [17].
In developing this process, a number of extractive solvent candidates were
screened in the laboratory for selectivity, solubility, and other important properties,
such as thermal stability, toxicity, corrosivity, boiling point, freezing point, and
so forth. The selected solvent underwent an extensive pilot-plant test program to
determine its performance in the ED process, and, consequently, to optimize the
TABLE 9 Composition of Feed and Products of the ED Pilot

Plant for Styrene Recovery
Feed Overhead Bottom

Component (wt%) (wt%) (wt%)
Dicyclopentadiene 0.26 0.40 ⬍1 ppm
Benzene 0.22 0.23 ⬍1 ppm
Toluene 35.81 43.68 ⬍1 ppm
Vinylnorbornenes 3.73 4.25 ⬍1 ppm
Ethyl Benzene 12.03 13.47 ⬍1 ppm
p-Xylene 2.97 3.30 ⬍1 ppm
m-Xylene 7.45 8.80 ⬍1 ppm
Cumene 395 ppm 431 ppm ⬍1 ppm
o-Xylene 4.52 5.79 ⬍1 ppm
Styrene 23.82 10.31 1.11
Allylbenzene 390 ppm 269 ppm 23 ppm
Nonaromatics 9.08 9.72 ⬍1 ppm
2,5-Dimethylthiophene 172 ppm 195 ppm ⬍1 ppm
Solvent 0 0.37 98.88
key process variables to support the computer process simulation for scale-up and
commercial design.
The pilot-plant tests were conducted in a 7.6-cm-diameter ED column packed
with 7.3 m of knitted wire-mesh packing (Goodloe Style #773). The C 8 cut of
pyrolysis gasoline with the composition shown in Table 9 was fed at a location
4.3 m from the column bottom and the lean solvent was introduced at a location
6.4 m from the column bottom. A schematic diagram of the pilot plant can be
represented by Fig. 12. The column was operated under reduced pressure to mini-
mize the column operating temperature, and a proprietary inhibitor was added in
trace amounts to the feed to prevent styrene polymerization in the column. The
key variables, such as S/F, the reflux ratio, and the kettle temperature, were prop-
erly adjusted to yield styrene with 99.9 wt% purity (on a solvent-free basis) in the
column bottoms. The composition of the column overhead and the bottom products
are also given in Table 9. In this operation, a cosolvent was used as the key to
improve the styrene purity from 95 to 99.9 wt%, to reduce the column temperature
by 35°C, and to decrease the solvent circulation by 20%. The bottom product (the
rich solvent) was routed to the solvent stripper column, where styrene was distilled
overhead, and the lean solvent exited from the bottom of the column for recycle
to the ED column.
The separation strategy for recovering styrene from pyrolysis gasoline is to
remove the majority of the light and heavy components in pyrolysis gasoline by
conventional distillation and to use ED to remove the remaining close-boiling
components. Figure 17 shows a possible scheme for processing pyrolysis gaso-
line, which includes styrene recovery by ED. The main benefits for recovering
styrene from pyrolysis gasoline generated from a naphtha cracking complex are
as follows:
FIG. 17 Schematic diagram for pyrolysis gasoline processing including styrene recovery.
1. The styrene component is upgraded from motor fuel value to petrochemical

value.
2. The xylenes can be upgraded from motor fuel value to the feedstock value to
xylene isomer unit.
3. The overall hydrogen consumption to convert styrene to ethylbenzene is re-
duced.
4. The catalyst fouling and operating costs in the selective hydrotreater are re-
duced.
5. The potential debottleneck of the hydrotreating area can be avoided; it other-
wise would be required for naphtha cracking expansion.
The economics of styrene recovery from pyrolysis gasoline depend to a great

extent on the quantity of styrene available in this stream. Units produce at 10,000
to 15,000 metric tons per year of styrene in pyrolysis gasoline would be the candi-
date for this technology. Table 10 shows that the economics for styrene recovery
with a pretax return on investment (ROI) of 41% can be achieved, based on a
25,000-metric tons per year plant capacity.
Cyclohexane Recovery from Natural Gas Liquid or Naphtha
Cyclohexane exists naturally in naphtha and natural gas liquid (NGL) streams and
is an important raw material for the nylon industry. As shown in Table 11, it is
impossible to recover high-purity cyclohexane from these streams by conventional
distillation, because of the close-boiling C 7 iso-paraffins in the streams. Because
TABLE 10 Economics for Styrene Recovery from Pyrolysis

Gasoline
Typical U.S. Gulf Coast capital cost $ 20 million

Styrene value in pyrolysis gasoline $ 180 per metric ton
Styrene product sales value $ 550 per metric ton
Processing cost $ 40 per metric ton
Gross margin $ 8.3 million per year
Pretax return on investment 41%
Note: Basis: 25,000 metric tons per year styrene capacity from a world-scale
naphtha cracker. Values on styrene product, feedstock, processing cost, and
capital investment were calculated based on the 1997 published information.
cyclohexane and the close-boiling components in the feed mixture have only a very
small difference in polarity and are relatively insoluble in the selective solvents, it
also takes a very difficult ED process to do the separation. Because no effective
single ED solvent has been found, a mixed solvent was developed commercially
to recover high-purity cyclohexane directly from an NGL fraction containing 85%
cyclohexane [18].
The proprietary mixed solvent (the MIST solvent) was developed through ex-
tensive test in the laboratory and the evaluation in a 150-mm-diameter ED pilot
plant using a refinery NGL stream, which has an average composition shown in
Table 11. In fact, the cosolvent in MIST solvent played a major role in the success
of this process [18]. As demonstrated in Fig. 18, The overall cyclohexane recovery
changed from 100 to 56 wt% as the cosolvent concentration decreased from 30
to 10 wt% under a constant kettle temperature of the ED column. Meanwhile, the
recovery of 2,4-dimethylpentane in the raffinate stream (ED column overhead)
increased from 87 to 96.3 wt% over the same composition range of the MIST
solvent. The higher 2,4-dimethylpentane in the raffinate stream, the higher cyclo-
hexane purity in the extract (product) stream.
Table 12 summarizes the results for 80% and 90% cyclohexane recoveries at
various cosolvent concentrations. At an 80% cyclohexane recovery, MIST solvent
TABLE 11 Average Composition and Boiling Point of the

Feedstock for Pilot-Plant Testing
Boiling point
Component Weight% (°C)
Cyclohexane 89.1 80.7
2,2-Dimethylpentane 1.3 79.1
2,2,3-Trimethylbutane 0.8 80.8
Dimethylcyclopentane 1.0 90.6
n-Heptane 0.1 98.3
FIG. 18 Effect of cosolvent in MIST solvent on product purity and recovery.
containing 10% cosolvent appears to give the greatest cyclohexane purity. At 90%
cyclohexane recovery, MIST solvent having 25% cosolvent had similar perfor-
mance to that with 10% cosolvent. Finally, the MIST solvent with 25% cosolvent
showed better performance than the one with 10% cosolvent. Based on the success-
ful pilot-plant testing on the MIST solvent, a commercial plant for purifying 100
metric tons per day cyclohexane was designed, constructed and started up in 1991.
TABLE 12 Effect of Cosolvent Concentration on Cyclohexane Recovery and Purity
2,4-
Cyclohexane Cyclohexane Dimethylpentane
Cosolvent (wt%) Recovery (wt%) Purity (wt%) Recovery (wt%)
25 80 98.9 89.8
20 80 99.0 92.0
10 80 99.1 93.0
30 90 99.2 87.2
25 90 99.2 90.0
10 90 99.2 90.3
25 94 99.1 86.8
10 94 99.1 80.0
Polyolefins Produced by Single-Site Catalyst 231
References
1. A. P. Colburn and E. M. Schoenborn, Trans. AIChE, 43, 42 (1945).

2. G. T. Atkins and C. M. Boyer, Chem. Eng. Prog., 45, 553 (1949).
3. J. M. Chambers, Chem. Eng. Prog., 47, 555 (1951).
4. K. H. Hackmuth, Chem. Eng. Prog., 48, 617 (1952).
5. R. M. Butler and J. A. Bichard, U. S. Patent 3,114,783 (1963).
6. R. E. Brown and F. M. Lee, ‘‘Effect of Packing on Distillation Columns with High
Liquid to Vapor Ratios,’’ AIChE Annual Meeting, Miami Beach, FL, 1992.
7. R. Billet, ‘‘Packed Column Analysis and Design,’’ Department for Thermal Separa-
tion Processes, Ruhr-University Bochum, 1989, p. 11.
8. Cannon Instrument Co., ‘‘Pro-Pak Protruded Metal Distillation Packing,’’ Bulletin
23, Cannon Instrument Co., State College, PA.
9. R. Billet, ‘‘Packed Column Analysis and Design. Department for Thermal Separation
Processes,’’ Ruhr-University Bochum, 1989, p. 41.
10. D. P. Kurtz, et al., Chem. Eng. Prog., 87,(2), 43 (1991).
11. C. C. Herron, Jr., B. K. Kruelskie, and J. R. Fair, AIChE J., 34,(8), 1267 (1988).
12. B. A. Todd and F. M. Lee, ‘‘Two Liquid Phases in Extractive Distillation for Aromatic
Recovery,’’ AIChE Summer National Meeting, Seattle, WA, 1992.
13. M. Van Winkle, Distillation, McGraw-Hill, New York, 1967, p. 464.
14. J. C. Gentry and F. M Lee, ‘‘New Extractive Distillation Process for Aromatics Recov-
ery,’’ AIChE Spring National Meeting, Houston, TX, 1995.
15. G. Emmrich, ‘‘Morphlane: Operational Experience and Results Obtained with New
Plants,’’ NPRA Spring Meeting, San Francisco, 1995.
16. J. C. Gentry and C. S. Kumar, Hydrocarbon Process, 69, (March 1998).
17. F. M. Lee and J. C. Gentry, Hydrocarbon Eng., 3(6), 62 (1998).
18. R. E. Brown and F. M. Lee, Hydrocarbon Process, 83 (May 1991).
FU-MING LEE
Structure, Properties, and Applications

of Polyolefins Produced by Single-Site
Catalyst Technology
Introduction
Polyethylene is composed of only carbon and hydrogen (with some exceptions),

which can be combined in number of various ways to make many different polyeth-
ylenes. These can generally be grouped into six types:
232 Polyolefins Produced by Single-Site Catalyst
• LDPE, low-density polyethylene

• EVA, ethylene vinyl acetate copolymers
• HDPE, high-density polyethylene
• LLDPE, linear low-density polyethylene
• ULDPE, ultralow-density polyethylene (also known as Very low-density poly-
ethylene, VLDPE)
• Single-site polyethylenes (e.g., substantially linear homogeneous polyethylene)
Polyethylene technology encompasses a range of crystallinity and melting

points. Figure 1 illustrates the approximate range of densities, crystallinities, and
melting points available within each major type of polyethylene. Specialty ethylene
copolymers such as acid copolymers and ionomers are not included. The total
polyethylene consumption is expected to exceed 100 billion pounds by the year
2000. Applications include films, extrusion coatings, injection-molded and blow-
molded parts, fibers, adhesives, wire and cable coatings, large parts such as storage
tanks made by rotational molding process, foams, and so forth.
The most recent advance in polyethylene technology is the development and
commercialization of polyethylenes produced by single-site-catalyst technology.
Two major classes of single-site catalyst (SSC) technology developed for the poly-
merization of ethylene and α-olefins are the metallocene catalyst (MTC) and the
constrained-geometry catalyst (CGC) systems. The use of these catalyst technolo-
gies has allowed a very rapid development of olefin copolymers with a wide range
of structures and related properties. This technology has initiated a major revo-
lution for the polyolefin industry [1–4]. Several families of MTC- and SSC-
technology-based polyolefin copolymers have been commercialized in the 1990s.
These include polyolefin elastomers (e.g., ENGAGE from DuPont Dow Elasto-
mers, LLC), polyolefin plastomers (e.g., AFFINITY from The Dow Chemical
Company; EXACT from Exxon Chemical Company), EPDM (NORDEL IP
from DuPont Dow Elastomers, LLC), enhanced polyethylene (ELITE from The
Dow Chemical Company); gas-phase LLDPE (EXCEED from Exxon Chemical
Company); slurry LLDPE (mPACT from Phillips Petroleum Company), and
FIG. 1 The approximate range of density, crystallinity, and melting point available within each major
type of polyethylene.
polypropylenes (ACHIEVE from Exxon Chemical Company). In addition to

these commercial activities, several other single-site-catalyst-related technologies
that allow the copolymerization of α-olefins with polar comonomers are also under
industrial and academic development [5,6].
This article will focus on the solid-state structure, rheology, properties, and
typical applications of homogeneous polyolefin copolymers made by copolymer-
ization of ethylene and α-olefins (e.g., 1-butene, 1-hexene, 1-octene) using SSC
technology. Unlike conventional linear low-density polyethylenes (LLDPE) made
by copolymerization of ethylene and α-olefins with Ziegler–Natta (Z-N) catalysts,
ethylene–α-olefin copolymers produced by SSC technologies have narrow compo-
sition distributions (narrow molecular-weight and comonomer distributions).
Hence, they are called homogeneous copolymers and they behave much more like
ideal polymers. The polymerization kinetics and the resulting polymer and copoly-
mer structures can be modeled. This significantly advances the fundamental under-
standing of the structure–property relationships. The major advantage of single-
site catalysts is its versatility in building well-defined molecular structures. This
capability allows the polymer and material scientists to design new polymers using
a molecular architecture approach and to develop new products with exceptional
speed.
Preparation of Ethylene–α-Olefin Copolymers

by SSC Technology
Two major families of high-efficiency SSC are commercially used for the pre-
paration of polyethylene copolymers. These are a bis-cyclopentadienyl (Bis-Cp)
single-site metallocene catalyst (also known as a Kaminsky catalyst) and a half-
sandwich, constrained-geometry mono-cyclopentadienyl single-site catalyst
(known as constrained-geometry catalyst, CGC, under the trademark of INSITE
by The Dow Chemical Company). These two catalyst systems are illustrated in
Fig. 2. The Zr in the Zr-based MTC used by many polymer producers has an
FIG. 2 Structure of the Bis-Cp metallocene catalyst and the constrained geometry catalyst.
oxidation state of ⫹4 and the Ti in the Ti-based CGC system has an oxidation
state of ⫹2.
Single-site-catalyst technology polyolefin copolymers can be produced by
high pressure, solution, gas-phase, and slurry polymerization processes. Typical
process conditions for making polyolefin copolymers in these processes are as
follows:
1. High-Pressure Process: Two types of commercial reactor, stirred autoclave

and a tube reactor, are used for the polymerization of ethylene and ethylene–
α-olefin copolymers at high pressure. Ethylene and an α-olefin comonomer
are usually compressed to at least 10,000 psi when fed into the reactor. The
polymerization temperature usually exceeds 100°C.
2. Solution Process: Stirred reactors are usually used for the polymerization
of ethylene and ethylene–α-olefin copolymers in a solution phase. In most
cases, C6 –C8 hydrocarbons are used as the solvent. The reactors are oper-
ated under about 500 psi pressure and the polymerization is carried out at
⬎60°C.
3. Gas-Phase Process: In the gas-phase process, ethylene and α-olefin como-
nomers (1-butene and/or 1-hexene) are polymerized in the solid state in a
fluidized-bed reactor into a powder form. The polymer powder is then con-
verted into pellet form by an extrusion process. The reactor pressure is usually
set at ⬎300 psi and the polymerization process is generally carried out at
⬍90°C.
4. Slurry Process: In the slurry process, polymers are made in stirred or loop
reactors with an organic liquid carrier (C 4 –C6 hydrocarbons). The polymeriza-
tion process temperature is generally carried out at ⬍90°C at a reactor pressure
of ⬍300 psi. Products made in this process are in powder form and are con-
verted into pellets using extrusion processes.
Molecular Structure of Polyethylene Copolymers

Made by Single-Site-Catalyst Technology
Molecular-Weight Distribution
Ethylene–α-olefin copolymers prepared by single-site-catalyst technologies ex-

hibit a narrow molecular-weight distribution (MWD). MWD, or polydispersity, is
the ratio Mw /Mn, where Mw is the weight-average molecular weight and Mn is the
number-average molecular weight. Copolymers prepared by a conventional
Zeigler–Natta catalyst have a MWD usually larger than 3, whereas the MWD of
homogeneous polyolefins made by SSC technology is usually less than 2.5. Figure
3 compares gel permeation chromatography (GPC) traces of a conventional, het-
erogeneous ethylene–octene copolymer versus a homogeneous copolymer. Poly-
mers with a narrow MWD in general have increased toughness and less ‘‘solvent
extractables.’’ On the other hand, the narrow MWD of a linear homogeneous co-
FIG. 3 GPC MWD comparison of two ethylene–octene copolymers having a 0.920-g/cm3 density.
polymer also results in poor melt processability (low melt strength, high extruder
back-pressure, high-energy consumption during extrusion, etc.).
Crystallinity
The comonomer content in the copolymer has a profound effect on the properties
of the polymer, including crystallinity, thermal, and mechanical properties. In the
case of ethylene–α-olefin copolymers, the crystallinity is measured and specified
using density. The density of the amorphous phase (ρa) and crystalline phase (ρc)
of ethylene–α-olefin copolymers at room temperature is about 0.853 g/cm3 and
1.000 g/cm3, respectively. Weight percent crystallinity can be obtained from the
measured density (ρ) as follows:
Wt% cryst. ⫽
冢
ρc ρ ⫺ ρa
ρ ρc ⫺ ρa 冣 (1)
The effect of comonomer content on the density of homogeneous ethylene–octene

and ethylene–butene copolymers, made using a CGC catalyst, is illustrated in
Fig. 4. The comonomer content was measured using nuclear magnetic resonance
(NMR). Higher mole% butene is required to achieve the same density compared
to octene, especially at lower densities.
Comonomer Distribution
Because of the significant effect of the α-olefin comonomer on the properties of

the polymer, it is critical to understand and to measure the comonomer distribution
FIG. 4 Densities of homogeneous ethylene–octene and ethylene–butene copolymers as a function

of mole% comonomer.
among the polymer molecules (intermolecular distribution) and along the backbone
(intramolecular distribution). Intermolecular comonomer distributions can be mea-
sured by the temperature rising elution fractionation (TREF) technique [7]. In this
procedure, a heated solution of the polymer is placed in a column, packed with
very small stainless-steel shot, and slowly cooled to room temperature. The temper-
ature is then increased while solvent flows through the column to a detector that
records the amount of polymer in the solvent at any given temperature. As illus-
trated in Fig. 5, the intermolecular comonomer distribution for a homogeneous
ethylene–octene copolymer prepared by the CGC technology is much narrower
than that of a conventional LLDPE, which is a mixture of polymer molecules
having different levels of an α-olefin comonomer incorporated in the polymer
backbone.
The narrow TREF curve for the homogeneous copolymer signifies that the
number of comonomer units per unit chain length between the copolymer mole-
cules is very similar. However, although the intermolecular comonomer distribu-
tion for the homogeneous polymer is very narrow, this does not mean that the
intramolecular comonomer distribution is uniform. The narrow intermolecular
comonomer distribution for the homogeneous polymer arises from the single-site
nature of the MTC and CGC. The uniformity of the intramolecular comonomer
distribution, however, is dictated by the reactivity ratio of the monomer and the
comonomer. Intramolecular comonomer distribution in homogeneous copolymers
made by SSC technology can also have an effect on the solid-state structure and
properties of the polymer (e.g., thermal properties, optics, etc.).
To address the issue of the effect of the intramolecular comonomer distribution
on polymer properties of a homogeneous polymer, structural characteristics for
FIG. 5 Intermolecular comonomer distribution of ethylene–octene copolymers measured by TREF.

(From Ref. 10.)
CGC ethylene–octene copolymers were modeled using the Monte Carlo simulation
[8]. Figure 6 illustrates the intramolecular comonomer distribution for three CGC
copolymers, from 0.87 g/cm3 to 0.92 g/cm3 density, in terms of ethylene block
length between the hexyl branches within a polymer molecule. As illustrated in
Fig. 6, the intramolecular comonomer distribution for the higher-density polymer
(0.92 g/cm3), in terms of ethylene block-length distribution between the short
branches that are formed from the α-olefin comonomers, is much broader than
that of the lower-density copolymers. This is due to the fact that the lower-density
FIG. 6 Model prediction for intramolecular comonomer distribution of three CGC ethylene–octene
copolymers: ethylene block-length distribution.
copolymers have more comonomer units along the polymer backbone. This results
in a shorter ethylene block length between the short branches, and the distribution
is also narrower.
Long-Chain Branching
Homogeneous ethylene homopolymers and ethylene–α-olefin copolymers first

made by CGC technology have one more unique molecular structural feature not
found in the original MTC technology polymers. This unique molecular structural
feature is long-chain branching (LCB). Homopolymers and copolymers made by
the CGC technology at certain process conditions contain a controlled amount
of long-chain branching. These polymers are referred to as substantially linear
homogeneous polyethylenes. To summarize this, the molecular structure of three
ethylene–α-olefin copolymers (conventional LLDPE made by a Z-N catalyst, ho-
mogeneous copolymers made by MTC, and substantially linear homogeneous co-
polymers made by CGC) are schematically illustrated in Fig. 7. One possible mech-
anism of LCB formation via CGC technology is as follows. Thermal termination
is one of the most effective ways to control molecular weight during the polymer-
ization process. In the thermal termination process, polymeric molecules with a
vinyl chain end are formed due to a ‘‘β-hydride elimination’’ mechanism that is
taking place in the thermal termination step (Fig. 8). Depending on the last mono-
mer or comonomer insertion, the unsaturation could be vinyl, vinylidene, or trans
as shown in Fig. 8. The polymer with a vinyl chain end becomes one of the re-
actants (in addition to ethylene and α-olefin) that reacts with the catalyst site and
forms long-chain branching.
A polymer with LCBs made by the CGC technology has many unique rheologi-
cal properties [9,10]. A few of the most significant features for the CGC-technology
polymer are its melt fracture resistance and the control of shear-thinning behavior,
as illustrated in Figs. 9 and 10 respectively. In Fig. 10, I2 is the melt index (MI)
of the polymer (flow rate in grams per 10 min at 2.16 kg weight, at 190°C) and
FIG. 7 Molecular structure comparison of three different ethylene–α-olefin copolymers. (EXACT is

a trademark of Exxon Chemical Company. AFFINITY is a trademark of The Dow Chemical
Company.)
FIG. 8 Reactor sources of unsaturation in polyethylene during polymerization of ethylene and α-

olefin comonomers. (From Ref. 10.)
I10 is the flow rate in grams per 10 min at 10 kg weight, at 190°C. The I10 /I2 ratio
is a measure of shear-thinning behavior of the polymer melt.
Solid-State Structure and Morphology

of SSC-Technology Ethylene Homopolymers
and Ethylene–α-Olefin Copolymers
The ethylene homopolymer and ethylene–α-olefin copolymers are semicrystalline

polymers. Three major factors that affect the crystal morphology and crystallinity
of ethylene polymers in the solid state are (1) the amount and size of α-olefin in
the polymer, (2) the molecular weight of the polymer, and (3) the crystallization
FIG. 9 Extrudates of CGC polymer and LLDPE at 3.66 ⫻ 106 dyn/cm2 shear stress. (Irgafos is a
trademark of Ciba-Geigy Corporation.)
FIG. 10 Rheology of CGC polymers measured at 190°C: effect of LCB on shear-thinning behavior
of three 1 MI polymers with various amount of LCB. LCB/10,000°C was estimated using
a kinetic model.
conditions (crystallization temperature at isothermal condition and/or cooling rate

at nonisothermal crystallization conditions) [11]. A recent review article on poly-
mer crystals was written by Phillips [12]. The most generally accepted crystal
morphology for ethylene polymers is lamellae formed from a folded-chain confor-
mation [13–15].
For very low-density SSC-technology ethylene–α-olefin copolymers (which
contain a high percentage of comonomer), the crystal morphology can be very
different from the conventional lamella model. For example, let us consider the
morphological model of a 60/40 wt% ethylene–octene copolymer made by CGC
technology. At this level of comonomer content, the polymer exhibits about 10%
crystallinity, as measured by differential scanning calorimetry (DSC) and a density
of approximately 0.87 g/cm3. The intramolecular comonomer sequence distribu-
tion of the hexyl branches from the octene comonomer, calculated from the reac-
tive-ratio kinetic model (Fig. 6), illustrates that more than 90% of the octene units
are less than 50 ethylene units apart. The regular ethylene block length between
the octene units is, therefore, much less than the minimum length to form one
folded unit to form the thinnest possible lamella (which is about 30 Å thick). For
a chain with this molecular structure, it is expected that the polymer has to crystal-
lize in a crystalline form different from the conventional folded-chain lamella
model.
Figure 11 is a transmission electron micrograph of the crystal morphology of
a higher-density (0.920 g/cm3) ethylene–octene copolymer made by CGC technol-
ogy. At this density and octene level, the copolymer clearly shows a lamellar mor-
phology. Figure 12 is a transmission electron micrograph of a very low-density
ethylene–octene copolymer (0.87 g/cm3). It clearly shows that the major crystalline
structure of this very low-density, low-crystallinity copolymer is ‘‘spotlike’’
fringed micelle crystals. Polymers having higher crystallinities with the lamella-
FIG. 11 Transmission electron micrograph of a 0.920-g/cm3 ethylene–octene copolymer made by

CGC technology.
FIG. 12 Transmission electron micrograph of a 0.87-g/cm3 ethylene–octene copolymer made by CGC

technology.
FIG. 13 Classification of SSC ethylene–α-olefin copolymer based on crystal morphology. (From

Ref. 16.)
type crystal morphology are expected to have higher moduli and undergo yielding
when deformed. Polymers having low crystallinities with the fringed micelle crys-
tals, however, are expected to be more like elastomers and do not have well-defined
yielding behavior. With these two different types of crystal structure, the SSC-
technology homogeneous ethylene–α-olefin copolymers can, therefore, be classi-
fied into four major domains [16], as illustrated in Fig. 13.
Thermal and Dynamic Mechanical Properties

Melting Behavior of SSC Polymers
Differential scanning calorimetry is one of the most popular methods for studying
the thermal properties (melting and crystallization) of semicrystalline polymers.
Structural information can be uncovered by a careful interpretation of DSC thermo-
grams generated at different conditions.
Due to the narrow intermolecular comonomer distribution, SSC copolymers
usually have a much narrower melting peak than their heterogeneous counterparts
produced by multiple-site Z-N catalysts. Figure 14 shows the DSC melting curve
of two ethylene–octene copolymers, both at similar density: one made by a conven-
tional multiple-site Z-N catalyst and one by SSC technology. The heterogeneous
LLDPE copolymer always has a peak melting point at around 120–130°C over a
broad density range (⬃0.89–0.95 g/cm3). This is because the conventional hetero-
geneous LLDPE copolymer is a reactor blend of molecules ranging from the un-
FIG. 14 DSC melting curve of SSC and LLDPE ethylene–octene copolymers at about 0.903 g/cm3
density. Samples were cooled and heated at 10°C/min.
crystallizable and poorly crystallizable type to the HDPE type containing only of
α-olefin [17]. These HDPE-type linear chains can, therefore, crystallize to a rather
large size crystal that has a melting point in that temperature range. The shape of
the melting peaks of all the homogenous copolymers still represents a single peak
or a single peak with a shoulder, very different from that of the heterogeneous
LLDPEs, as illustrated in Fig. 15. The peak melting point of the homogeneous
copolymer, however, drops accordingly as the density/crystallinity of the polymer
is lowered, as seen in Fig. 15. This characteristic has a very significant commercial
value for heat-seal and oriented-shrink-film food-packaging applications.
A plot of the melting points of LLDPE/VLDPE, LDPE, SSC ethylene–octene,
and EVA resins as a function of density is shown in Fig. 16. All the samples were
cooled and heated at 10°C/min using a Perkin-Elmer DSC-7. LDPE resins have
slightly lower melting peak temperature compared to SSC ethylene–octene copoly-
mers made using CGC technology at a given density. The density of EVA resins
increases as the vinyl acetate content increases, even though the degree of crys-
tallinity decreases. This is due to the bulky nature of the vinyl acetate group in-
creasing the amorphous phase density. Hence, the density of EVA resins cannot
be compared with the density of ethylene–α-olefin copolymer resins.
A plot of melting points of LDPE, LLDPE/VLDPE, and SSC ethylene–octene
and EVA resins as a function of resin crystallinity is shown in Fig. 17. Prior to
1990, EVAs were the only cost-effective polyethylenes widely available for pack-
aging applications requiring low-temperature sealing, low-temperature shrinkage,
and toughness properties. This is due to their lower crystallinity (typically less than
about 40%) and lower melting point (typically less than about 100°C). Beginning in
FIG. 15 DSC melting curve of SSC and LLDPE ethylene–octene copolymers at various densities.
Samples were cooled and heated at 10°C/min.
FIG. 16 Peak melting temperatures of heterogeneous and homogeneous ethylene–octene copolymers,

LDPE, and EVA resins versus polymer density.
FIG. 17 Peak melting temperatures of heterogeneous and homogeneous ethylene–octene copolymers,

LDPE, and EVA resins versus polymer crystallinity by DSC.
early 1990, polyolefin plastomers (POPs) and polyolefin elastomers (POEs), made
using a single-site catalyst, have become available over a wide range of crystallin-
ity and melting points. When plotted against resin crystallinity, the melting points
of EVA resins lie very close to the curve for the SSC ethylene–octene resins (Fig.
17). Hence, SSC resins can potentially be used in various film applications where
EVAs are being used. Two applications of SSC resins, sealants, and oriented shrink
films where EVAs have been traditionally used will be discussed in detail later.
Many detailed studies of the thermal properties of SSC technology, homoge-
neous ethylene–α-olefin copolymers, have been performed by many different insti-
tutes [11,16,18]. The first publication showing the effect of increasing comonomer
content on the melting points of homogeneous copolymers was U.S. Patent
3,645,992 by Elston of DuPont, Canada [19].
The DSC melting curve of a polyolefin elastomer (POE) at 0.87 g/cm3 density
and one melt index is shown in Fig. 18. The glass transition temperature of the
POE resin was about ⫺54°C. The POE exhibited a very broad single melting peak
with a shoulder and a peak melting temperature of 59°C. The melting begins at
temperatures as low as about ⫺40°C. A substantial amount of crystallinity is mol-
ten by room temperature. The broad melting range of the POE can be attributed
primarily to the intramolecular comonomer distribution. For example, the longer
ethylene runs may form a larger lamella crystal with a higher melting point and
the shorter one may form a small lamella crystal or even a fringe micelle crystal
with a lower melting temperature.
FIG. 18 DSC melting curve of ethylene–octene polyolefin elastomer at 0.87 g/cm3, made using CGC
technology.
Dynamic Mechanical Properties
Dynamic mechanical properties of the homogeneous copolymers as a function of

density are illustrated in Figs. 19 and 20. The storage modulus decreases with
increasing temperature due to a decrease in crystallinity. The storage modulus de-
creases sharply near the melting point. The γ-transition peak of all four copoly-
mers and the homopolymer appear at about ⫺120°C in the plot of tan δ versus
temperature. In some literature the γ peak was designated as the true glass transition
temperature (Tg) of polyethylene. The β-transition peak for the polyolefin elastomer
(0.870 g/cm3) appears at about ⫺40°C; for the polyolefin plastomer (0.898 g/cm3),
it is about ⫺25°C, and for the 0.920-g/cm3 copolymer, it is about ⫺20°C. The
0.954-g/cm3 polymer has a broad β peak, also at around ⫺20°C. In most cases,
the β-transition temperature can be related to the low-temperature performance
of ethylene-based polymers and copolymers. For example, below the β-transition
temperature, the polymer usually becomes brittle. Therefore, most polyethylene
users usually report the β-transition temperature as the practical glass transition
temperature. Also, the glass transition temperature measured using DSC matches
well with that of the β-transition temperature. For example, as shown in Fig. 18,
the DSC Tg of the 0.87-g/cm3 elastomer is about ⫺54°C. The β-transition tempera-
ture of the 0.87-g/cm3 elastomer is about ⫺40°C. The β-transition temperature
would be higher than the DSC Tg due to the high frequency (10 rad/s) used in the
measurement. For the 0.87-g/cm3 elastomer, the α-transition is almost merged with
the β-transition. For higher-density SSC polyethylene, distinct α-transitions can
also observed. The mechanical properties and deformation behavior of these homo-
geneous polymers will be discussed further in the next section.
FIG. 19 Storage modulus of homogeneous ethylene–octene copolymers and a homopolymer as a

function of temperature at 10 rad/s.
FIG. 20 Tan δ of homogeneous ethylene–octene copolymers and a homopolymer as a function of

temperature at 10 rad/s.
Deformation Behavior and Mechanical Properties

of Homogeneous Ethylene–␣-Olefin Copolymers
Made with SSC Technology
Tensile Properties
The stress–strain curves of homogeneous ethylene–octene copolymers and a ho-

mopolymer, made using CGC technology, are shown in Fig. 21. The polymers
were heated well above the melting point and cooled at 1°C/min. The yield region
of copolymers is also enlarged in Fig. 21. The density (crystallinity) of polymer
profoundly affected the response to deformation, as evident by the broad spectrum
of tensile properties. At high densities, the deformation had characteristics common
to many semicrystalline thermoplastics with localized yielding and cold drawing
[16]. For copolymers having medium densities (0.902, 0.91, and 0.918 g/cm3),
significant strain hardening was observed. For copolymers having low densities
(less than 0.885 g/cm3), the moduli were low and the deformation was essentially
uniform (homogeneous) and elastomeric.
Differences in yield behavior of the four homogeneous polyethylenes at differ-
ent densities are shown in the photographs in Fig. 22. These photographs were
taken at 150% engineering strain. These polymers exhibited deformation behavior
ranging from necking at room temperature (density greater than about 0.910 g/
cm3) to uniform deformation (density less than about 0.910 g/cm3). The effect of
increasing comonomer content on the tensile deformation behavior and the correla-
tion between the structural classification and the large-scale deformation behavior
have been studied and discussed in detail in many publications [16,20–24] and,
therefore, will not be further discussed in this article.
FIG. 21 Engineering stress–strain properties of homogeneous ethylene–octene copolymers and a

homopolymer, measured at a strain rate of 0.04 s⫺1. (From Ref. 16.)
FIG. 22 Photographs of profiles of deformation behavior of Type I to IV homogeneous ethylene–

octene copolymers, taken at 150% engineering strain. (From Ref. 16.)
Modulus and yield strength are important properties for ethylene homopoly-
mers and copolymers for many commercial applications, such as packaging film,
injection molded containers, and so forth. The slope of the stress–strain curve at
very low strain (less than or equal to 2% strain) is measured as the modulus of
the polymer. Secant modulus at 1% or 2% strain and Young’s modulus are the
ones most commonly used.
Moduli of the polyethylenes in the solid state are strongly controlled by poly-
mer crystallinity, crystallite size distribution, and fabrication conditions, which
results in orientation. Even with this complexity, there are some ‘‘rules of thumb’’
which can be applied to the modulus. For example, it is generally true that the
initial modulus increases with density (crystallinity) of the polymer. There is also
a direct relationship between initial modulus and crystallite size. It has been shown
[24] that two polyethylenes of the same degree of crystallinity can have very differ-
ent moduli (up to 100% difference), which is related to a difference in crystallite
size.
The moduli of a series of homogeneous ethylene–octene copolymers made by
CGC technology, several homogeneous ethylene–butene copolymers made by
MTC technology, and several conventional LLDPEs made by a Z-N catalyst over a
range of polymer densities and comonomer content were measured for comparison
purposes [25]. These samples were prepared by compression molding at similar
heating and cooling conditions to impart the same heat history on each of the
samples. The data are summarized in Fig. 23. It seems that if the polymer samples
are prepared under similarly controlled conditions, the Young’s modulus of these
polymers is simply a function of the polymer density. However, it should be noted
that it is very difficult to produce any ethylene copolymer having a density below
about 0.885 g/cm3 using Z-N catalysts. Therefore, data for Z-N heterogeneous
FIG. 23 Young’s modulus versus density of ethylene copolymers determined on compression-molded

plaques.
LLDPE at below 0.885 g/cm3 are not available for comparison purposes. Based
on common knowledge of semicrystalline polymers, the very low-density hetero-
geneous polymer made by Z-N catalysts, if one can make it, may have a higher
modulus than the homogeneous copolymer at similar densities. This is because
the heterogeneous polymer, no matter how low the density is, will always have
some polymer chains that have a very low level of comonomer incorporated. These
polymer chains will crystallize to form larger-sized crystals, which may result in
higher modulus than the homogeneous polymer at equivalent density.
Elastic Properties of Polyolefin Elastomers
Polyolefin elastomers (POEs), very low-density (crystallinity) homogeneous ethyl-

ene–α-olefin copolymers, have a fringed micelle crystal morphology and exhibit a
very different deformation behavior as compared to the higher-density copolymers
having lamella crystal structures. POEs are now commercially available from Du-
Pont Dow Elastomers, LLC (ENGAGE). The small fringed micelle crystals dis-
persed in the soft, amorphous matrix act as tie-points to anchor the amorphous
chains during deformation and, therefore, result in an elastic recovery upon release
of stress. The load/unload property under a tensile deformation mode for a repre-
sentative octene-based POE (ENGAGE EG-8100, 0.870 g/cm3, 1 MI) is illustrated
in Fig. 24.
The elastic recovery (permanent set) of various polyethylenes is illustrated in
Fig. 25. The slow-cooled (15°C/min) 30-mil-thick compression-molded samples
were pulled to desired elongation at 10 in./min (gauge length ⫽ 2 in.). The sample
was held at the desired elongation for 30 s. The crosshead was brought back to
the initial grip separation at 10 in./min and held for 1 min. The sample was pulled
FIG. 24 Load/unload behavior of a representative octene-based polyolefin elastomer (ENGAGE EG-

8100, 0.870 g/cm3, 1 MI). Strain rate, 2.25 min⫺1; specimens were compression molded and
cooled at 15°C/min; test was run at room temperature.
again at 10 in./min until the load rises above zero. Percent permanent set is the
percent elongation at which the load rises above zero. The permanent set of homo-
geneous polyethylenes increased with increasing density. At densities below 0.885
g/cm3, the percent set is low (less than about 20%) at elongations less than 100%.
However, the unrecovered strain became much higher beyond the 100% strain.
FIG. 25 Permanent set of various polyethylenes as a function of elongation.

This phenomenon can hypothetically be explained by a slip-link theory in which

the fringed micelle crystals are treated as slippage links. Beyond 100% strain,
these crystals started to slip, which resulted in permanent deformation. A detailed
discussion of the slip-link model and the use of this model to predict the overall
elastic properties of POE has recently been published [22]. New applications for
this class of elastic materials were developed commercially for wire and cable
insulation, shoe soles, elastic fiber and films, foams, and so forth.
Tie-Molecules in Ethylene–␣-Olefin Copolymers

Made by SSC Technology
Consideration of the crystalline domains has long dominated research to explain

the properties of semicrystalline polymers such as linear low-density polyethylene
(LLDPE). Although crystalline domains control low-strain properties of semicrys-
talline polymers such as modulus and yield stress, it has clearly been established
by many researchers that large-strain properties such as stretchability, impact, tear,
failure processes, and so forth are also controlled by the amorphous region, particu-
larly by tie-molecules, the amorphous chains that bridge adjacent lamellae [26–
33]. However, development of appropriate structure–property relationships in
semicrystalline polymers has been perceived to be hindered by the inability to
analytically measure relative tie-chain concentration. In the past, relative tie-chain
concentration has been semiquantitatively characterized using techniques such as
measurement of the brittle fracture strength [27], infrared dichroism after deforma-
tion, and chlorination of films [26]. The relative tie-molecule concentration has
also been estimated from chain dimensions and the semicrystalline morphology
(topology) of the polymers [28–33].
Tie-molecules in the semicrystalline polymer are critical for enhancing me-
chanical properties such as environmental stress crack resistance (ESCR), impact,
tear, and tensile strength. A schematic diagram of the tie-molecule structure in an
ethylene–α-olefin semicrystalline copolymer with a lamellar morphology is illus-
trated in Fig. 26. A main cause for rejection of a polyethylene chain from a crystal
is the presence of imperfections along the chain backbone, which are usually
branch points formed by the α-olefin comonomer. Without these branch points
(e.g., HDPE), the major part of the polymer chain can possibly be incorporated
into the same lamella crystal and, thus, few tie-molecules can be formed. This will
result in a polymer with very low mechanical strength.
Probabilities for forming tie-molecules in a homogeneous ethylene–α-olefin co-
polymer made by SSC technology versus a heterogeneous copolymer were estimated
[34]. Unlike the heterogeneous ethylene copolymer made by conventional Z-N cata-
lyst technology, the SSC technology polymer has a homogeneous distribution of the
α-olefin among the polymer chains. This allows all the polymer chains to crystallize
similarly, which results in a narrow crystallite size distribution. The effect of density
(crystallinity) on relative tie-chain formation probability and concentration is mod-
eled [35] and the results are illustrated in Fig. 27. The probability of tie-chain forma-
tion alone does not reflect the actual tie-chain concentration in semicrystalline poly-
FIG. 26 Schematic diagram of tie-molecule structure in an ethylene–α-olefin copolymer.
mers. The relative tie-chain concentration would also depend on the concentration
of ‘‘junction points,’’ which would approximately depend on the volume fraction
of the crystallinity. The relative tie-chain concentration was obtained from the prod-
uct of tie-chain probability and the volume fraction of the crystallinity.
Figure 27 illustrates the optimum density range and the molecular weight effect
on tie-molecule formation. The Huang–Brown model used to calculate probability
of tie-chain formation does not take into account the effect of the type of α-olefin
comonomer. Intrinsic Elmendorf tear strengths on compression-molded 10-mil-
thick films of various ethylene–α-olefin copolymers were measured [36] and the
data are illustrated in Fig. 28. Figure 28 shows that higher α-olefin copolymers
(octene and hexene) have much better intrinsic tear strength than butene and pen-
FIG. 27 Relative tie-molecule concentration in a SSC-technology ethylene–octene copolymer at vari-

ous molecular weights.
FIG. 28 Intrinsic tear strength of various SSC-technology ethylene–α-olefin copolymers.
tene copolymers, with octene being the highest of all. The optimum tear strength
for all polymers studied is found to be in the density range between 0.89 and 0.92
g/cm3. These experimental results are in good agreement with the tie-chain model.
Applications
In previous sections, three key distinctions have been noted between ethylene–
α-olefin copolymers produced with single-site catalysts and ethylene–α-olefin
copolymers produced with Ziegler–Natta catalysts: (1) an ability to incorporate
higher levels of the α-olefin to achieve low polymer density or crystallinity, (2) a
uniform comonomer distribution giving a lower melting point at a given density,
and (3) a narrow MWD with a Mw /Mn of about 2. The ability to incorporate higher
levels of comonomer has made possible new product families (e.g., POP and POE).
For example, POEs with densities less than 0.885 g/cm3 are available from SSC,
whereas traditional Z-N ethylene–α-olefin copolymers typically are not available
below about 0.89 g/cm3 density. The narrow molecular-weight and comonomer
distributions contribute to several unique properties, including controllable melting
points, reduced extractables, reduced blocking, excellent optics, and excellent me-
chanical properties.
The unique characteristics of the homogeneous ethylene–α-olefin copolymers
described make them useful for packaging applications. For example, the ability
to control melting and crystallization behavior, the excellent optics, and excellent
mechanical strength make POPs an ideal candidate to compete with the traditional
high-performance sealants such as EVA copolymers containing 9–18% vinyl ace-
tate and ionomers. Indeed, one important commercial application for plastomers
is use as a high-performance sealant in multilayer coextruded or laminated films.
Table 1 shows several examples of key properties of plastomers produced with
SSC and the resulting packaging benefits.
TABLE 1 Benefits of Plastomers in Flexible Packaging

Polymer properties Packaging benefits
Toughness of a linear polyethylene Protection of goods, gauge reduction
Low sealing temperatures Faster packaging line speeds
Low extractables Better taste and odor characteristics
Excellent optics Package appeal
High oxygen transmission Breathable films
Elasticity High recovery and flexibility
Hydrocarbon composition Polyolefin compatibility, recycle friendly
Thermal stability Processing flexibility
Moisture insensitivity Bulk handling, good moisture barrier
Food-Packaging Film Applications
The primary distinguishing feature of food packaging is the need to prevent con-
tamination of the food and to maintain or extend the shelf-life. The package acts
as a barrier to the environment. Barrier properties will vary depending on the spe-
cific type of food being packaged. The barrier of a flexible package can be compro-
mised when (1) an hermetic seal of the package is not obtained during packaging,
(2) the seal of the package is not maintained during the packaging, distribution,
and sales of the product, or (3) the package itself fails due to inadequate puncture,
tear, impact, or abrasion resistance. Seal performance, shrinkage, and abuse resis-
tance are some of the critical performance requirements for many, if not all, of
the food packaging applications to be described.
High-Performance Sealants
Polyethylenes are widely used as sealants in various packaging applications. Many

high-performance films are multilayer structures, where the individual layers per-
form a specific function(s). High-performance sealants often must meet a number
of performance requirements, placing constraints on the polymer design. Beyond
parameters like heat-seal-initiation temperature (HSIT), caulkability, seal through
contamination, and hot-tack range, consideration is given to parameters like pro-
cessability during extrusion, machinability (stiffness, coefficient of friction, perme-
ability, appearance, cost, and/or FDA compliance. Types of polyethylenes used
as high-performance sealants include EVA, ULDPE, ethylene acrylic acid (EAA)
copolymers, ionomers, and, recently, polyolefin plastomers.
One of the key attributes of a high-performance sealant is the low melting
point, which facilitates the key performance requirement of a low seal-initiation
temperature. When plotted against resin crystallinity (Fig. 17), the melting points
of EVA resins lie very close to the curve for plastomers produced via SSC technol-
ogy. Hence, plastomers can potentially be used in various films applications where
low-melting-point polymers such as EVAs and ionomers are currently in use (e.g.,
sealants, oriented shrink films, etc.). Other key attributes of a high-performance
sealant are the hot-tack strength, hot-tack window, and heat-seal strength.
Hot-tack strength is a measure of the force required to separate a semimolten,

just-made seal. This test is designed to predict the performance on vertical form,
fill, and seal (VFFS) equipment, in which the strength of the seal after it has just
been made may be the rate-limiting step in this automated process. High hot-tack
strength reduces the likelihood that the food product will break through the seal
when being dropped into the forming package. The ultimate hot-tack strength is
the highest hot-tack strength achieved over a full range of sealing temperatures.
Hot-tack strengths of ethylene–octene plastomers and EVA resins are compared
in Fig. 29. EVA polymers exhibit much lower hot-tack strength compared to plasto-
mers. This is due to the very high degree of long-chain branching present in EVA
copolymers, which significantly lowers diffusion rates across the molten interface.
In the case of EVA resins, an increase in melt index actually increases the hot-
tack strength due to higher diffusion rates [37].
Heat-seal strengths of ethylene–octene plastomers and EVA resins are com-
pared in Fig. 30. Interestingly, at the same melting point, EVA resins exhibit some-
what higher heat-seal initiation temperatures compared to plastomer resins (at melt
index of approximately 1 or less). For example, although the melting point of
0.896-g/cm3 plastomer is about 94°C and the melting point of ELVAX 3165 (18%
VA EVA) is about 86°C, the 0.896-g/cm3 plastomer exhibited lower seal-initiation
temperature. This may due to the high degree of LCB significantly lowering diffu-
sion rates in EVA resins. The ethylene–octene plastomer resins exhibit slightly
higher seal plateau strengths compared to EVA resins. Polyolefins plastomers with
their low, sharp melting points are thus well suited for high-performance sealants
because the ultimate seal and hot-tack strengths of the polymer are achieved at
low temperatures [38–41].
One of the applications of high-performance sealants is the box inner liners
FIG. 29 Hot-tack strength of ethylene–octene plastomers made using CGC technology and EVA
resins as a function of seal bar temperature. Nylon–EAA–sealant (1/1/1.5 mil)-blown coex-
trusion film was used.
FIG. 30 Heat-seal strength of ethylene–octene plastomers made using CGC technology and EVA
resins as a function of seal bar temperature. Nylon–EAA–sealant (1/1/1.5 mil)-blown coex-
trusion film was used.
for dry foods such as cake mix, cereal, and crackers. Whereas a high-oxygen barrier
is critical to preserve the freshness of meat and cheese, a high-moisture barrier is
essential for preserving the freshness of dry products. A typical plastic film struc-
ture for cereal and cake-mix inner liners is a coextrusion of HDPE with a sealant.
The sealants typically used for these applications are ionomers or EVAs containing
high levels of vinyl acetate (VA) (i.e., ⱖ18% VA).
Again, because a strong, hermetic seal is critical for maintaining the barrier of
the package, POPs are another option for replacing ionomers or EVA copolymers
(18% VA). A comparison of the other critical sealant performance requirements for
a polyolefin plastomer (POP 2), an ionomer (Zn ionomer), and an EVA copolymer
(18% VA) are discussed below and summarized in Table 2. POP 2 and EVA copoly-
mers (18% VA) have comparable seal-initiation temperatures (69°C and 72°C, re-
spectively). They are followed by the Zn ionomer, with a seal-initiation temperature
of 84°C. Table 2 shows that POP 2 provides the highest ultimate hot-tack strength
of the three products, followed by the Zn ionomer and the EVA copolymer. Note
that the 18% VA copolymer provides very low ultimate hot-tack strength due to
very high levels of long-chain branching retarding diffusion across the interface and
is generally not suitable for the packaging of heavy products, such as cake mixes.
Oriented Shrink Films
Oriented shrink films can be differentiated from conventional hot-blown shrink

films by their fabrication processes. The conventional blown shrink-film method
involves extrusion of the molten polymer through an annular die at a certain draw-
down ratio and a certain blowup ratio and then cooling the bubble via ambient or
chilled air. Orientation of the film takes place in a completely molten state and is
TABLE 2 High-Performance Sealants for Box Inner Liners

EVA
Resin POP (18% VA) Zn Ionomer 1
Melt index (dg/min) 1.6 0.8 5.5
Density (g/cm3) 0.8965 Not available Not available
2.0-Mil monolayer blown-film properties
Puncture (ft-lb./in.3) 270 222 104
Tear Resistance (g) 300 118 190
Haze (%) 1.3 1.5 2.9
Odor intensity rating 1.2 Not available 2.7
Water vapor transmission rate 6.2 Not available
(g mil/100 in.2 day atm) 2.0
1.5-Mil HDPE/0.5-mil sealant, blown
coextrusion
Heat-seal initiation (°C) 69 72 84
Ultimate hot-tack strength (N/in.) 7.5 3.4 4.4
primarily in the machine direction, due to the drawdown ratio, and secondarily in
the cross direction, as a result of the blowup ratio. In contrast, the oriented shrink-
film process can be described generically by the following steps:
Extrusion–quenching–reheating–baxially stretching–cooling
The reheating step involves temperatures just above the glass transition tempera-
ture in the case of amorphous polymers, or below the peak melting temperature
in the case of semicrystalline polymers.
There are two basic methods to produce biaxially oriented films. The first
method is the tenter frame process and the second method is often referred to as
the ‘‘double- bubble’’ or ‘‘trapped-bubble’’ process. More in-depth descriptions
of these processes can be found elsewhere [42,43]. Orientation by these processes
takes place in a semimolten state (i.e., at a temperature below the melting point
of the semicrystalline polyolefin). As a result, a significantly higher degree of orien-
tation is obtained compared to hot-blown shrink films. These orientation processes
produce high-tensile, high-modulus films with high shrink and shrink tension, as
well as excellent clarity [42,43]. Biaxially oriented films made via the ‘‘double-
bubble’’ or ‘‘trapped-bubble’’ process are used to produce packages for very large,
subprimal cuts of meat after slaughter. The packages are often referred to as barrier
bags. The subprimal cuts of meat are inserted into a barrier bag that is generally
sealed at one end, the air evacuated, and then the bag heat sealed. The package is
then heated, usually via hot water, to obtain shrinkage of the film around the meat
[44]. Typical barrier bag structures range from three to five layers and minimally
contain an abuse/shrink layer, an oxygen barrier layer such as a poly(vinylidene
chloride) (PVDC) or ethylene vinyl alcohol copolymer (EVOH), and a sealant
layer. In addition, adhesive layers may be used to tie the structure together.
The use of LLDPEs and ULDPEs alone or as blends with EVA copolymers
in both the abuse and sealant layers have been taught in the patent literature [44,45].
The broad comonomer distributions and melting ranges of LLDPEs and ULDPEs
create a sufficiently broad orientation window for the double-bubble process. Fur-
FIG. 31 Hot-water shrinkage at 90°C of films oriented on a T.M. Long stretcher under isothermal
conditions at a 4.5 ⫻ 4.5 draw ratio at 5 in./s.
thermore, the excellent toughness of these linear polymers provides the high level
of abuse resistance needed to prevent punctures from the bones in subprimal meats
and to sustain impact abuse during the distribution process. ULDPE resins offer
improvements in shrinkage over higher-density LLDPE resins, due to their reduced
crystallinity. Further improvements in shrinkage can be obtained using POPs. POPs
can offer low-temperature shrinkage improvements over ULDPEs at the same den-
sity because of their lower melting points. Figure 31 illustrates the improved
shrinkage at 90°C for POPs at a density below about 0.908 g/cm3 [46]. In addition,
it is assumed that the improved sealability and abuse-resistance properties for POPs
in conventional blown films also translate to improvements in oriented shrink films.
As mentioned earlier, blends of EVA with ULDPE or LLDPE have been taught
for use in barrier bag structures. A particular disadvantage of these blends is the
poor optics and reduced abuse resistance. As shown in Table 3, the POP/LLDPE
blend provides significantly better optics and potentially better toughness in an ori-
ented shrink film than the EVA/LLDPE blend. Both the POP and EVA have compa-
TABLE 3 Optics of Oriented Films
EVA (12% VA)/

LLDPE POP*/LLDPE †
Blend ratio 30%/70% 30%/70%
Haze (%) 7.6 0.5
Shrinkage at 90°C (%) 16 16.5
Note: Films oriented on T.M. Long stretcher under isothermal conditions at

a 4.5 ⫻ 4.5 draw rate at 5 in./s.
* POP is an ethylene–octene copolymer having a melt index of 0.9 and den-
sity of 0.898 g/cm3.
† LLDPE is an ethylene–octene copolymer having a melt index of 1.0 dg/
min and density of 0.920 g/cm3.
rable melting points and crystallinity. The poor optics of the EVA/LLDPE blend
are believed to be due to the partial immiscibility of these two polymers [47].
Other important applications of homogeneous polyethylenes made using SSC
technology include fresh-cut produce packaging [48–50], high-performance films
[51–54], batch inclusion bags [55], cling layer in stretch films [56,57], extrusion
coating [58,59], and impact modification of polypropylenes [60–65].
Conclusion and Summary
Development and implementation of SSC technology have greatly expanded the

product range of polyolefins. These homogeneous polymers have narrow molecu-
lar-weight and composition distributions, resulting in enhanced mechanical, opti-
cal, and heat-seal properties. Because of the simple and predictable molecular
structure of this class of polyolefin copolymers, building a model to predict proper-
ties for these polymers became feasible. This allows the materials scientists to
design products by a molecular-architecture approach, using property and perfor-
mance requirements as guidelines. With the advancement of the SSC technology
for the production of polyolefin copolymers with well-defined molecular structures,
the authors expect the polyolefin industry can take great advantage of this technol-
ogy to design unique polymers and fulfill their customer needs in the future.
Homogeneous polyolefins provide excellent utility in numerous packaging appli-
cations, ranging from retail meat packages to industrial stretch films. These resins
may be fabricated into packaging films or containers via blown- and cast-film meth-
ods, biaxial oriented film processes, extrusion coating, lamination, and injection
molding. In packaging applications, the resins based on CGC technology have suc-
cessfully replaced and/or upgraded EVA, ionomer, LDPE, LLDPE, and ULDPE.
Acknowledgments
The authors of this article would like to express their sincere appreciation to Profes-
sor Eric Baer, Professor Anne Hiltner of Case Western Reserve University, and
Pradeep Jain, Kalyan Sehanobish of The Dow Chemical Company. They provided
many useful data in this article.
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STEVE CHUM

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Encyclopedia of chemical processing and design.

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Contributors to Volume 69 iii

Conversion to SI Units vii

Bringing Costs up to Date ix

Circulating Fluidized Bed Reactors: Basic Concepts and

Effect of Pressure and Temperature in Bubbling Fluidized Beds

Fundamentals of Process Safety and Risk Management

Introduction to the Selective Catalytic Reduction Technology

Nanophase Materials in Chemical Process

Process Safety and Risk Management Regulations: Impact on

Recent Advances in Biomaterials

Recent Development of Extractive Distillation: A Distillation

Structure, Properties, and Applications of Polyolefins Produced by

To convert from To Multiply by

acre square meter (m 2 ) 4.046 ⫻ 10 3

To convert from To Multiply by

light year meter (m) 9.46 ⫻ 10 15

Nelson Cost Indexes (Oil and Gas J.), quarterly

Year CE Index M&S Index Year CE Index M&S Index

TABLE 2 Nelson-Farrar Inflation Petroleum Refinery Construction Indexes since 1946

1994 1995 1996

FIG. 1 Basic design of circulating fluidized beds.

TABLE 1 Some Fluidized and Circulating Fluidized Bed Reactor Processes

Product Process Developer

FIG. 4 Various fluidization regimes with increasing superficial gas velocity.

Minimum and Smooth Fluidization

where the Archimedes number, Ar, is defined as

and Re p is the particle Reynolds number having the expression

By solving for Re p, mf, Eq. (6) can be rewritten as

where the particle Reynolds number at minimum fluidization is a simple function

TABLE 2 K1 and K2 Values for Eq. (7)

Source: Adapted from Ref. 7.

u mb 2300ρ 0.13 0.52

This expression is based on observations that the minimum bubble velocity is

d′p ⫽ 2.7d p (12)

For Group A or B powders in large-diameter beds, where the maximum bubble

where 2 ⬍ Ar ⬍ 1 ⫻ 108 or, in terms of dimensionless numbers,

Re mt ⫽ 1.24 Ar 0.45 (15)

As the velocity continues to increase in a fast-fluidized bed, the axial transition

Pressure Balance in a CFB

In designing a circulating fluidized bed (CFB), special attention needs to be given

[(P 4 ⫺ P 3 )] fluid bed ⫹ [(P 5 ⫺ P 4 )] freeboard