.4) r ro /Z) it.

r4 it _I Ai
4
. C I,- 04., 4.

fLATFORMING PROCESS TECHNOLOGY BOOK

This book was printed in October 1987. The sections in this

manual that contain substantive revisions over previous
books are listed below.

REVISED SECTIONS REVISION NUMBER

Catalyst Chemistry 1
Process Variables 2

Process Evaluation
(Water Chloride) 2

Procedures - Startup 3

Regeneration 3
 %

,,
 UOP Inc.
Des Plainrs, Illinois
United States of America

UOP PLATFORMING PROCESS

IIVITRODUCTION

This material is UOP Inc 's technical information of a conficlontial nature for use only by personnel
within your organization requiring the information. T he material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc

PLATFORMS-11
NC
 COURSE SCHEDULE

Chemistry
Hydrocarbon Chemistry
Reaction Rates/Heats of Reaction
Equilibrium & Selectivity Considerations
Hydrocarbon Conversion Profiles
Catalyst Chemistry/Pressure Effects

Process Variables
Catalyst Activity Determination
Effects of Process Variables on C5 + Yield
Effects of Process Variables on Catalyst Deactivation
Calculation of Heat of Reaction

Process Flow
Variations of Commercial Flow Schemes
Selected Control Schemes

Water-Chloride Control
Typical Water/Chloride Injection Rates
Methods of Proper Water/Chloride Control
On-Stream Catalyst Sampling

Bimetallic Platforming Catalyst Poisons

Maximum Allowable Concentrations
Possible Sources
Process Symptoms
Possible Mechanical Consequences
Methods of Detection
Suggested Operational Response

Analytical Methods
Typical Sampling Schedule
Required Sample Size
Shipping Considerations
Outlines of Selected Laboratory Methods
 Catalyst Handling
Catalyst Loading Considerations
Unloading Spent (Carbonized) Catalysts

Procedures
Startup
Shutdown
Emergency
Operation of Recycle Gas Drier
On-Stream Catalyst Sampling

Regeneration
Procedure
Sulfate Removal
Regeneration Piping Locations
Chemical Specifications and Properties
Calculations
Sampling Schedule

Mechanical
Corrosion/Materials of Construction
Inspection Considerations
Compressor Washing Procedure
Acidizing Procedure
General 30 Day Shutdown
Mechanical Evaluation Test

Energy Conservation
Process Changes
Mechanical Improvements

Safety
Entering a Contaminated Atmosphere
Chemical Hazards

Continuous Platforming
Need For Continuous Catalyst Regeneration
Process Description

A4
 117013

HISTORY OF UOP

I. Formed in 19 14 as the National Hydrocarbon Company to

commercialize the patents of Jesse A. Dubbs and his son
Carbon Petroleum (C.P.) Dubbs.

A. Strong backing by J. Ogden Armour, Chicago meat packer.

B. Changed name to Universal Oil Products Company in

1915.

C. Financial direction: Hiram J. Halle

Technical Direction: Gustav Egloff (Gasoline Gus)

D. 1919 demonstration of the continuous Dubbs cracking

process for representatives of 14 refineries.

E. Moved headquarters to Chicago, research to Riverside-

McCook.

II. In 193 1 UOP was sold to a group of its largest licensees

including Standard of California, Shell Oil Company, Standard
of Indiana, Standard of New Jersey, and Texaco.

A. Dr. Egloff had secured the services of Professor

Vladimir Ipatieff, a Russian catalysis expert, and Dr.
Hans Tropsch, an eminent German hydrocarbon
authority.

B. Development of polymerization catalysts, alkylation,

isomerization, fluidized catalytic cracking; , some in Joint
effort with various oil companies during World War H.

III. In 1944 the oil companies divested themselves of UOP, placing

UOP in trust with the American Chemical Society named as
beneficiary.

A. Developed a successful "small" FGA- unit design for

Smaller,i ndependent refiners in 1947.

t3. Commercialized the Plat forming process in 1949.

C. Moved offices to Des Plaines, Illinois, in 1952. Research

Center completed in 1955.

I V. To broaden its investment program, the American Chemical

Society sold UOP to the public in 1959 with provisions in t he
i ncorporation to assure independent refiners of a continued
flow of technology.

A-7
 (17013

Recent years have seen continued strong emphasis on new

process and catalyst development. Some of the more notable
developments are:

Merox
Molex
Udex
Sulfolane
Olex
Butamer
Penex
Isomax (Unibon) - IZCU, HUG, LPG, etc.
Detergent Alkylation
Alkar
ii yd eat
Tatoray

V. Acquisition of 100% of UUP stock by Signal Holding Company.

Some adjustment of corporate operations, but other wise,
business as usual under the name of UUP Process Division.
 UOP ORGANIZATION CHART

I LIOP RN;.

ppocESS
D‘InsioN

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RNAMCI SwenuelAusa lawman TicR summit IMARKSTUla PLANNING
I
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Rom pRociEss DISTRICT
OPCRATIOKS SuSINESS
aRouPs *LS»Cis DEVELOpilitiff laiSPCCnces
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PLATPoRsusea
 117013

I NTRODUCTION

The Plat forming Process

The catalytic reforming process has been a mainstay in most

refineries throughout the world for many years. The original
function of this process was to upgrade low octane number
Straight-run naphthas to higher octane motor fuel blending com-
ponents by catalytically promoting specific groups of chemical
reactions. Naphtha boiling range products from other processes
(thermal cracking, coking, etc.) were soon being included in the
charge to catalytic reforming units for octane improvement. The
reforming application was logically and rather quicklby expanded to
include the production of specific aromatic hydrocarbons. High
purity benzene, toluene, and mixed xylenes were made available to
the chemicals industry from petroleum fractions by the combination
of reforming, aromatics extraction, and fractionation. Hydrogen,
t he "by-product" from the aromatic producing reactions, was
found to be useful in supporting t he operation of ,reformer feed
preparation units as well as other hydrotreating units. The light
hydrocarbon gases, by-products of t he cracking reactions, were
generally added to refinery fuel gas systems. Butanes, other
cracking by-products, were commonly used in adjusting vapor
pressures of gasoline pools. Thus, most refiners and many
petrochemicals manufacturers have found the catalytic reforming
process an increasingly valuable tool.

OOP's catalytic reforming process, the Plat forming process, has

continually been improved to meet the changing needs of the
industry. Combined efforts in t he areas of catalyst and engi-
neering development have increased the flexibility of the
Plat forming process to meet the current and anticipated future
needs of the industry. Today more than ri50 HOP Plat forming units
are on stream with a capacity of over 5 million BP1) of feedstock.

A significant step in catalyst development was made in the late

1960's. This was the commercialization of bimetallic Plat forming
catalysts. UOP has commercialized four series of hi metallic cata-
-

lysts: t he Platinum/Rhenium R-16, R-18, and R-19 series, the

R-20 series, the R-30 series, and the R-50 extruded series. These
catalysts have been proven to give better activity, stability, and
selectivity than the all platinum catalysts. In many cases, they
have allowed refiners to extend their Plat forming operations to
higher charge rates and higher product octane levels than would
have otherwise been practical. Because of the increased
sensit ivity of these catalysts to feedstock contaminants and
operational upsets, the refiner must now pay closer attention to
t he daily operation to realize their full benefits. More precautions
need to be taken to ensure clean, continuous, upset free
operation. Ever, with these added requirements, refiners are
realizing better Plat former operations than ever before.

A-11

uop Inc
 117013

I n 1971, a new Plat former started up which revolutionized the

process. It was the first Continuous Catalytic Regenerated Plat-
former. Now extremely high severities arc obtainable without
frequent shutdowns due to catalyst deactivation. At the present
time, there are over SO such units on stream representing over 1.1
million BPD with many more in the design and construction stages.
New unit sales are almost exclusively of the CCR design.

The Process Technology Handbook

The purpose of t his handbook is to provide refining process

engineers and unit supervisors with the necessary information for
successful operation of UOP bimetallic Platforming catalysts. This
handbook does NOT provide detailed operating instructions to be
applied to any individual unit.

It is important to remember that UOP-issued procedures are

general in nature. It is the responsibility of the refinery engineer
to develop procedures specific to his unit from the general
procedures presented in this manual. Operating personnel should
be supplied with well detailed, specific procedures before they
attempt catalyst loading, startup, shutdown, or regeneration.
Also, well detailed emergency and safety procedures (complying
with all acceptable refinery practices and federal, state, and local
codes) should be available to all operations personnel.
 CHEMICAL ABBREVIATIONS AND SYMBOLS
A aromatic
A6 6 carbon number aromatic (benzene)
A7 7 carbon number aromatic (toluene)
"etc.
Al203 alumina

B or BZ benzene
BTX benzene, toluene, xylene

C1 1 carbon number hydrocarbon (methane)

C2 2 carbon number hydrocarbon (ethane, ethylene)
" etc.
CH cyclohexane
CH6 6 carbon number cyclohexane (cyclohexane)
CH7 7 carbon number cyclohexane (methylcyclohexane)
" etc.
CI,C1 - chlorine, chloride
CP cyclopentane
CP6 6 carbon number cyclopentane (methycyctopentane)
CP7 7 carbon number cyclopentane (dimethylcyclopentane or
ethyl cyclopentane)
" etc.
Cr chromium

EDC ethylenedichioride

F, F - flourine, flouride
Fe iron

H2 molecular hydrogen

MCP methylcyclopentane
Mn manganese
Mo molybdenum

N naphthene (nitrogen)
N6 6 carbon number naphthene
N7 7 carbon number naphthene
" etc.
Na sodium
Na2CO3 sodium carbonate (soda ash)
NaOH sodium hydroxide (caustic)
Ni nickel

0 olefin (oxygen)

P paraffin
P1 1 carbon number paraffin (methane)
P2 2 carbon number paraffin (ethane)
P3 3 carbon number paraffin (propane)
" etc.
Pb lead
POC propylene dichloride
PONA paraffin-olefln•naphthene•aromatic
Pt platinum

Re rhenium

S sulfur

T toluene
ICE trichloroethane
TEL tetraethyl lead
TML tetramethyl lead

X xylene

aromatic ring compound

saturated 6 carbon number ring

compound (a cyclohexane)

saturated 5 carbon number ring

compound (a cyclopentane)

a radical or side chain (for example

R —

CH2CH3 an ethyl radical)

A•16
 GENERAL PLATFORMER TERMS
A — angstrom, 10 - Mmeter
ABD — average bulk density
activity — the temperature requirement needed by a catalyst to produce a
given octane Platformate at fixed operating conditions and feed•
stock quality
acid site — a position or function of the catalyst needed to promote certain of
the desired reactions; generally provided by flouride or chloride
ASTM — American Society for Testing and Materials
attenuation — modification or tempering of the metal function of the catalyst

BPD — barrels per day

BPP — barrels per pound
BR — boiling range

caustic — sodium hydroxide

CCR — continuous catalyst regeneration
chg — charge (feed)
CS — carbon steel

DC4 — debutanizer
delta P (QP) — pressure change
delta T ( QT) — temperature change (normally across a reactor)

FOR — end of run

EP — end point (of a distillation)

F-1 octane — Research octane

F-2 octane — Motor octane
FBR — full boiling range (about 190-400°F or 88.204 °C)

GC — gas chromatography
GHSV — gas hourly space velocity
GLC — gas/liquid chromatography
G/O ratio — gas/oil ratio (total moles of recycle gas divided by moles of fresh
naphtha feed)
gph — gallons per hour

H2/HC ratio — hydrogen/hydrocarbon ratio (moles of recycle hydrogen divided by

moles of fresh naphtha feed)
HC — hydrocarbon
HPS — high pressure separator
HR,AH — heat of reaction

A-17
 IBP — initial boiling point

lean naphtha — a naphtha high in paraffin content, low in naphthene content

LHSV — liquid hourly space velocity (volume of hourly naphtha feed divided
by catalyst volume)
LOI — loss on ignition: a laboratory test, see UOP Method 275
LPS — low pressure separator
LV% — liquid volume percent

m or M — prefix for thousand

mm or MM — prefix for million
metal site a position or function of the catalyst needed to promote certain of
the desired reactions; provided by the Platinum and second metal,
if any
micro octane — an octane determination made with small sample size
MON — motor octane number
MONC — motor octane number clear (unleaded)
MW — molecular weight

PONA — paraffin, olefin, naphthene. aromatic breakdown of a hydrocarbon

stream
ppb — parts per billion
ppm — parts per million
precursor — something which leads to a second object; i.e. a coke precursor In
the naphtha is a compound which directly leads to coke formation
on the catalyst
Platinum agglomer-
ation — the clustering or grouping of Platinum molecules on the catalyst
surface

Rich naphtha — a naphtha high in naphthene content, low in paraffin content

RON — research octane number
RONC — research octane number clear (unleaded)
RVP — Reid vapor pressure
rx — reactor

scallop — part of radial reactor internals (see page G-13)

scf — standard cubic feet
scfb — standard cubic feet per barrel
scfh — standard cubic feet per hour
sch — schedule (measure of metal thickness)
seal catalyst — catalyst added to the top of a radial flow reactor to prevent vapor
bypassing (see page G•10)
Selectivity — the quality of a catalyst enabling it to produce high yields of a
specific product; generally a highly selective Platforming catalyst
is one which gives high C5 + Platformate yields
severity — an overall measure (qualitative) of the difficulty of a Platforming
operation

A•18
SG — specific gravity
shield — part of radial reactor internals (see page G-11)
skirt — same as shield
slump catalyst — extra catalyst added to the top of a radial flow reactor to com-
pensate for bed settling during operation (see page G-10)
soda ash — sodium carbonate
SOR — start of run
stability — the quality of a catalyst enabling it to run for long periods of time
with almost constant yields and temperature requirement

WABT — weighted average bed temperature (the sum of the average reactor
temperatures multiplied by the fraction of catalyst in each reactor)
WAIT — weighted average inlet temperatures (the sum of the reactor inlet
temperatures multiplied by the fraction of catalyst in the reactor)
wt, wt.% — weight, weight percent
 UOP P + I DIAGRAM ABBREVIATIONS
AR Analysis Recorder
ARC Analysis Recording Controller
DR Specific Gravity Recorder
FA Flow Alarm
FE Orifice Flange Assembly
FFRC Flow (ratio) Recording Controller
Fl Flow Indicator
FIC Flow Indicator Controller
FIF Flow Indicator Float Type
FQI Flow Meter Displacement Type
FR Flow Recorder
FRA Flow Recording Alarm
FRC Flow Recording Controller
FRCF Flow Recording Controller Float Type
FRCQI Flow Recording Controller Integrator
FROI Flow Recorder Integrator
FRQIA Flow Recorder Integrator Alarm
HC Hand Control
II Current Indicator
LA Level Alarm
LC Level Controller
LG-E1 Gage Glass Boiler Type — Visible Length Shown
LG R - Gage Glass Reflex Type —Visible Length Shown
LG-RLT Gage Glass Reflex Type — Visible Length Shown — Low Temperature
LG-T Gage Glass Through View Type Visible Length Shown
—

LG-TK Gage Glass Through View Type — Visible Length Shown — KEL-F
LG - TLT Gage Glass Through View Type — Visible Length Shown — Low Tem-
perature
LI Level Indicator
LIA Level Indicating Alarm
LIC Level Indicating Controller
LR Level Recorder
LRA Level Recording Alarm
LRC Level Recording Controller
PA Pressure Alarm
PC Pressure Controller
PDC Pressure Differential Controller
PDI Pressure Differential Indicator
PDIC Pressure Differential Indicating Controller
PDR Pressure Differential Recorder
PORA Pressure Differential Recording Alarm
PDRC Pressure Differential Recording Controller
PORCA Pressure Differential Recording Controller Alarm
PI Pressure Indicator
PIA Pressure Indicating Alarm
PiC Pressure Indicating Controller
PR Pressure Recorder
PRA Pressure Recording Alarm
PRC Pressure Recording Controller

A-20
Si Speed Indicator
SR Speed Recorder
TA Temperature Alarm
TC Temperature Controller
TDR Temperature Differential Recorder
TDRA Temperature Differential Recording Alarm
TDRC Temperature Differential Recording Controller
TI Temperature Indicator
TIC Temperature Indicating Controller
TIX Temperature Indicator Skin
TR Temperature Recorder
TRA Temperature Recording Alarm
TRC Temperature Recording Controller
TRX Temperature Recorder Skin
TW Thermowell
ZI Valve Position Indicator

WHEN INSTRUMENTS ARE DESIGNATED WITH AN ALARM

H Indicates High
L Indicates Low
 ENGLISH METRIC CONVERSIONS AND ABBREVIATIONS
Multiplied
English Unit Abbrev. By Metric Unit Abbrev.

length inch in. 25.4 millimeter mm

foot It. 304 8 millimeter mm

area square toot ft2 09290 square meter m2

volume cubic foot ft 3 .02832 cubic meter m3

standard cubic' SCF .02826 standard cubic STD m 3
feet of gas meters of gas
gallon gal .003785 cubic meter m3
barrel bbl .1590 cubic meter m3

degrees Fahrenheit °F = 5/91°F•32) degrees Centigrade Oc

temperature

pressure pound per square inch psi 6.895 kiloPascal kPa

inch of mercury at 32 ° F in Hg .1333 kiloPascal kPa
inch of water at 4 ° C in H 2O .2491 kiloPascal kPa
pound per square inch psi .07030 kilograms per kg/cm 2
square centimeter

mass pound mass lb or .4536 kilogram kg

lbm

energy British Thermal Btu 1.055 kiloJoule kJ

Unit

power horsepower hp .746 kilowatt kw

British Thermal Btu/hr .2931 watt
Units per hour
°
' UOP calculates standard cubic feet of gas at 60 F and 14 696 psia_ UOP proposes lo calculate standard cubic molars of gas at 15 C and
1 01.325 kPa.
 UOP Inc.
Plainns. Illirtctic
United States of America

UOP PLATFORMING PROCESS

HYDROCARBON
CHEMISTRY

This material is UOP Inc.'s technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc

PLATFORMING 1
 117013

I NTRODUCTION

The following is a discussion of both naphtha and catalyst

chemistry involved in the Platforming process. The subjects of
naphtha chemistry and catalyst chemistry have been segregated as
much as possible to make the discussion easy to follow. However,
the two subjects are necessarily and inherently interrelated and
some overlap of subject matter in the ensuing sections is
unavoidable. The subject material has been presented with the
assumption that the reader is familiar with basic organic chemistry
and the concept of thermodynamic equilibria. The organization of
topics is outlined below:

I. Platforming Hydrocarbon Chemistry

A. Composition of Feed and Product

h. Plat forming Reaction s

C. Relative React ion Rates

D. Heats of Reaction

E. Equilibrium Considerations

F. Effects of Pressure and Temperature on Reaction

Selectivity

G. Reactor Hydrocarbon Conversion Profiles

II. Platforming Catalyst Chemistry

A. Dual Function Catalyst Chemistry

tt tects of Pressure on Catalyst Design

C. PlatfOrming Catalysts
 117013

I. PLATFORMING HYDROCARBON CHEMISTRY

A. Composition of Platformer Feed and Product

Feed naphtha to a Platforming unit typically contains C6 through

C11 paraffins, naphthenes, and aromatics. 1 he purpose of the
Platforming process is to produce aromatics from naphthenes and
paraffins, either for use as a motor fuel (because of high octane
ratings) or as a source of specific aromatic compounds. In motor
fuel applications the feed naphtha generally contains the whole
range of C6 through C11 hydrocarbons, essentially maximizing the
amount of gasoline produced from the crude run. In aromatics
applications, t he feed naphtha generally contains a inure select
range of hydrocarbons (C6; C6-C7; C6-C8; or C7-C8) which
serves as the source of the desired aromatic products. For either
application, the basic naphtha chemistry is identical. However,
aromatics processing, in most cases, emphasizes C6 and C7 hydro-
carbon reactions. These are slower and more difficult to promote.

Naphthas from various crude sources vary greatly in their "ease of

reforming". This "ease of reforming" is primarily determined by
the amount of the various hydrocarbon types (paraffins, naph-
t henes, aromatics) contained in the naphtha. Aromatic hydrocar-
bons pass t hrough the Platformer essentially unchanged. Most
naphthenes react rapidly and efficiently to aromatics. This is the
basic reaction of Platforming. Paraffins are the most difficult
compounds to convert. In most low severity applications, there is
only a small amount of paraffin conversion to aromatics. In high
severity applications, paraffin conversion is slow and inefficient
and constitutes the real challenge to the process and the catalyst.

Figure 1 shows the hydrocarbon conversion that must take place in

a typical Plat forming operation on a "lean" naphtha (high paraffin,
low naphthene content) and on a "rich" naphtha (low tiara? fin,
higher naphthene content). For the richer feed, less paraf fin
conversion will be necessary, making t he operation much easier
and more efficient.
 117013

FIGURE 1

HYDROCARBON TYPES VOLUME

CONVERSION IN PLATFORMING
CONVERSION OF LEAN AND RICH NAPHTHAS TO MODERATE OCTANE
PLATFORMATES AT CONSTANT OPERATING CONDITIONS

LEAN RICH
PLATFORMATE PLATFORMATE
NAPHTHA NAPHTHA

LOSS
L O SS

P
P
P
N —N
FROM P
FROM P
N A FROM N
N A FROM N
A }FROM A A • FROM A

LEGEND
P = PARAFFINS LOSS: DUE TO BOTH CRACKING
N = NAPHTHENES AND SHRINKAGE
A ir AROMATICS

Figure 1 shows the overall hydrocarbon conversions that occur in a

Plat forming operation. The remainder of this hydrocarbon
conversion section will detail the types of i ndividual reactions,
relative reaction rates, heat of reaction, equilibrium constraints,
and pressure and temperature effects involved in these overall
hydrocarbon conversions.

B-7

uopprbc.
 117013

B. Platforming Reactions

The following reactions take place in the Platforming process to an

extent dependent on the severity of the operation, the quality of
t he feed.

1. Dehydrogenation of Naphthenes:

FIGURE 2

NAPHTH EN E DEHYDROGENATION

+ 3H 2

NOTE

DENOTES SATURATED RINGS (NAPHTHENES)

DENOTES A DEHYDROGENATED RING (AROMATIC)

DENOTE RADICALS OR SIDE CHAINS

R R' R" ATTACHED TO THE RING, FOR EXAMPLE
CH. CH3' AN ETHYL RADICAL
z
 117013

The final step in the formation of an aromatic from a naphthene

( either a cyclohexane or a cyclopentane) is the dehydrogenation of
a cyclohexane; see Figure 2. The reaction of a cyclohexane to the
corresponding aromatic is extremely rapid and essentially
quantitative. Naphthenes are obviously the most desirable feed
components because the dehydrogenation reaction is easy to pro-
mote and produces by-product hydrogen as well as the aromatic
hydrocarbons. This reaction is very endothermic. It is promoted
by a metal catalyst function, and is favored by high reaction
temperature and low pressure.

The discussion of catalyst acid and metal functions is contained in

the Catalyst Chemistry section. It is now important to only note
which reactions are catalyzed by the acid function and which ones
are catalyzed by the metal function.

2. Isomerization of paraffins and naphthenes:

FIGURE 3

NAPHTHENE ISOMERIZATION

II 0
 117013

a. The isomerization of a cyclopentane to a cyclohexane, shown in

Figure 3, must occur as the first step in converting the
cyclopentane to an aromatic. This isomerization involves ring
rearrangement and the probability for ring opening to form a
paraffin is quite high. Therefore, this reaction of alkylclo-
pentanes to cyclohexanes is not quantitative. The reaction is
strongly dependent on the processing conditions.

FIGURE 4

PARAFFIN ISOMERIZATION

C
R-C-C-C-C R-C-C-C

trOP , 0 , 11

b. Paraffin isomerization, shown in Figure Li, occurs readily in

commercial Plat forming operations but at typical operating
temperatures, the thermodynamic equilibrium is only slightly in
favor of the more desirable (higher octane) branched isomers.
I n motor fuel applications, this reaction does make a contribu-
tion to octane i mprovement of t he naphtha.

Isomerization reactions result from carbonium ion intermediate

reactions. The reactions are promoted by an acidic catalyst
function, and are not dependent on operating pressure.
 117013

3. Dehydrocyclization of paraffins:

FIGURE 5

PARAFFIN DEHYDROCYCLIZATION

+H
2

R-C-C-C-C 11

+ H2
.101..“8"

Dehydrocyclization of paraffins, shown in Figure 5, is the most

difficult Platforming reaction to promote. It consists of a very
difficult molecular rearranqemoot from a paraffin to a natilithene.
I n the case of light paraffins, equilibrium considerations limit this
reaction. This equilibrium effect is quantified in another section.

The paraffin cyclization step becomes easier as the molecular

weight of the paraffin increases because of increased statistical
probability for the formation of the naphthene. Somewhat coun-
teracting this effect is the increased probability of the heavier
paraffins to hydrocrack. Dehydrocyclization is favored by low
pressure and high temperatures. Vieth metal and acid catalyst
functions are needed to promote this reaction.
 117013

4. Hydrocracking:

FIGURE 6

HYDROCRACKING

C HC
R-C-C-C + H2 --as- RH C-C-C

.20P •71, .2

Because of the strained ring isomerization and ring formation

reactions that the feed alkylcyclopentanes and paraffins must
undergo, and because the catalyst needs to have an acid function,
the possibility for acid-promoted hydrocracking, depicted in
Figure 6, is strong. Paraffin hydrocracking is relatively rapid and
is favored by high pressure and high temperature. The disap-
pearance of paraffins from the gasoline boiling range via hydro-
cracking does concentrate aromatics in the product and hence
contributes to octane improvement. the reaction does, however,
consume hydrogen and results in lower Platformate yield.

5. Demethylation:

FIGURE 7

DEMETHY LATION

R-C-C-C-C + H R-C-C-CH + CH 4
2

AND

R-C RH
+ H
2 Cji + CH 4

Li- 1 2
 117013

Demethylation reactions, shown in Figure 7, generally occur only

in very severe Platforrning operations ( high temperature and high
pressure). Under certain conditions, they may occur during the
i nitial startup of a unit following catalyst replacement or regenera-
tion. The reaction is metal catalyzed and is favored by high
temperature and pressure. It can be inhibited by attenuation of
t he metal catalyst function by addition of sulfur or a second metal
( as in some bimetallic catalysts).

6. Dealkylation of aromatics:

FIGURE 8
AROMATIC DEALKYLATION

rr
+ H2 +R

von ,Olti 14

The dealkylation of an aromatic, shown in Figure 8, is similar to

aromatic demethylation, differing only in the size of the fragment
removed from the ring. If the alkyl side chain is large enough, this
reaction can be visualized as acid catalyzed carbonium ion cracking
of the side chain. The dealkylation reaction is also favored by high
temperature and high pressure.

Because of the wide range of paraffins and naphthenes included in

the Platformer feed, and because the reaction rates vary con-
siderable with the carbon number of the reactant, these reactions
occur in series and in parallel to each other forming the rather
complicated overall reaction scheme indicated in Figure 9.
 117013

TABLE 1
RELATIVE REACTION RATES
C 6 AND C 7 HYDROCARBONS

HYDROCARBON TYPE PARA FAN ALKYLCYCLOPENTANES ALKYLCYCLONEXANES

CARBON NO. C. C7 C6 C7 C6 C7

a
REACTION CLASS RELATIVE REACTION RATE

ISOMERIZATION
PARAFFIN 10 13
NAPHTHENE 10 13
DEHYDROCYCLIZATION 1.0 4.0
HYDROCRACKING 3.0 4.0
DECYCLIZATION
( RING OPENING) 5 3
DEHYDROGENATION 100 120

■ - DATA DETERMINED FROM INITIAL RATES FOR PURE COMPONENTS AND

MIXTURES OF PURE COMPONENTS. ALL RATES RELATIVE TO RATE OF
DEHYDROCYCLIZATION OF NORMAL HEXANE.

The primary reactions for the C6 and C7 paraffins proceed at

significantly different rates. The rate of dehydrocyclization for
hexane is only one-third that of hydrocracking so the fraction of
t he normal hexane converted to benzene is relatively low. Normal
heptane hydrocracks at about the same rate as normal hexane so
the faster rate of dehydrocyclization ( about four times that of
hexane), leads to significantly greater fractional conversion to
aromatics for normal heptane in comparison to hexane. Both
paraffins are isomerized very rapidly to the various possible
isomers.

Reactions of the naphthenes show marked differences between the

alkylcyclopentanes and alk ylcyclohexaneS. Both cyclohexanes
dehydrogenate very rapidly and completely to aromatics. The
cyclopentanes react at much slower rates and undergo both
isomerization to the corresponding cyclohexanes and decyclization
to paraffins.

The ratio of the rate of isomerization to the total rate of reaction

(isomerization plus decyclization) is an indication of t he expected
selectivity to aromatics for the alkylcyclopentanes. 1 his ratio is
0.67 for the methylcyclopentane and 0.81 for the dirnethylcyclo-
pentane. The ease of isomerization increases with carbon number
and the C 8 + alkylcyclopentanes have relatively high selectivities to
aromatics.

B-15

UOP Inc
 117013

E. Equilibrium Considerations

Most modern fixed - bed motor fuel Platformers operate at conditions

such that the degree of conversion of the major components in the
feed is not limited by equilibrium. However, BTX naphtha feeds
contain high concentrations of light hydrocarbons, and for these
feeds, the level of conversion is affected by equilibrium. The
least reactive and most strongly influenced by thermodynamic
factors are the six carbon number hydrocarbons. The effect of
temperature and hydrogen partial pressure on equilibrium conver-
sion will be examined for this system. A similar analysis would
apply for seven and eight carbon number hydrocarbon systems,
but the degree of thermodynamic limitation would be much lower.

The t echnique used to calculate equilibrium ratios for t he various

reactions is illustrated by the following example. Consider t he
reaction of normal hexane undergoing dehydrocyclization to form
methylcyclopentane.

nC6 2`.. 1 MCP + 11 2

k2

where k1 and k2 are the forward and reverse reaction constants,

respectively.

At equilibrium, the following equation is valid

K k1 = ( P ■ACP)(P112)
P
k2 (P
nC )
6

where K is the equilibrium constant and P is the partial pressure

I)
of the component. The larger the value of K. the more favorable
the reaction.

The equilibrium ratio for this reaction t hen becomes

PMCP

P
nC P
EI
6 2

Values of K can be calculated from t he thermodynamic properties

of the reactants and products and then the extent of equilibrium
li mitation established.
 117013

The isomerization of methylcyclopentane to cyclohexane does not

i nvolve hydrogen as a product or reactant, therefore the
equilibrium ratio is a function of temperature only. The effect of
temperature on the equilibrium ratio of cyclohexane to methyl-
cyclopentane is illustrated in Figure 11. The equilibrium ratio is
quite tow over the normal Platforminq temperature region and
decreases slightly as temperature is increased. This low
equilibrium ratio inhibits conversion of methylcyclopentane to
cyclohexane because the cyclohexane concentration must be
reduced to very low levels before t he forward methylcyclopentane
reaction can proceed. The complexity of the ring isomerization
reaction and the unfavorable thermodynamics combine to reduce
the selectivity of methylcyclopentane to benzene substantially
below 100%.

FIGURE 11
CYCLOMEXANE
METHYLCYCLOPENTANE
EQUILIBRIUM
0.14
0
1
17. 0.12
4

2 0.10
a.
Ca A 0.08

Ci 0.06

0.04
400 450 500 550 800
(752) (932) (1112)
TEMPERATURE, °C (°F) , t •t
 ▪ •
117013

F. Effects of Pressure and Temperature on Reaction Selectivity

As an extension of the pure component equilibrium pilot plant

studies, the effects of pressure and temperature on the selectivity
to aromatics for normal hexane, methylcyclopentane, and normal
heptane were investigated in detail. These hydrocarbons have low
selectivities, and thus optimization of operating conditions to
maximize the selectivity is the key to improved yields of aromatics.

The effect of operating conditions on normal hexane selectivity to

benzene is illustrated in Figure 1 3. Here the selectivity to benzene
is defined as the mole ratio of hexane converted to benzene divided
by the total moles of hexane converted (conversion was based on
disappearance of total hexane so that iso hexanes in the product
-

were treated as unconverted normal hexane). This is, in essence,

the extent to which the dehydrocyclization of hexane is occurring.
As shown in Figure 13, normal hexane selectivity to benzene in-
creases with temperature at each pressure. this is due to
equilibrium shifting in favor of dehydrocyclization with increasing
temperature. Selectivity i mprovement with decreasing pressure is
due to the combined effects of improved equilibrium ratio and a
suppression of the rate of hydrocracking.

FIGURE 13

SELECTIVITY OF NORMAL HEXANE

TO BENZENE

Z
kil uj .40
5 kg / cm2 (71 psig)___
Z cg

ca > .30 9 kg / cm2 (128 psig)-

O Z
0

14 k / cm2 (200 psig)

e— J .20
?O

LAI cc .10
IIJ
N
a
2 0 NU, ,17f1

0 450 500 550

X (842) (932) (1022)
Lai
I REACTOR TEMPERATURE,°C (°F)

uop Inc
 •
117013

Figure 15 summarizes the results obtained when normal heptane

was processed at various conditions. Heptane selectivity to
toluene follows a pattern similar to that found for normal hexane to
benzene. Again, the improvement in selectivity as temperature is
increased and pressure decreased is due to the combined effects of
i mproved equilibrium ratio and a suppression of the rate of
hydrocracking. For example, at a reactor temperature of 540°C
(1000°F), reducing plant pressure from 21 kg/cm 2 (300 psiy) to 14
ky/cm 2 (200 psiy) increased heptane selectivity to toluene by 30%,
while a further reduction to 7 kg/cm 2 (100 psiy) pressure provided
a selectivity 60% greater than that at 21 kg/cm 2 (300 psig)
pressure. Heptane selectivity to toluene is two to three times
higher than hexane selectivity to benzene at identical operating
conditions.

FIGURE 15
SELECTIVITY OF NORMAL HEPTANE
TO TOLUENE

W.80
7 kg I cm 2 1100 psig) —
> .60
> Q 14 kg/cm± 42000 prig)
0
• u 21 kg/cm 2 130(---
) psig)
w .40
w
ca

cc
I .20
• "

aL ch

Lki 0
X -1
500 550
O 450
2 (842) (932) (1022)
REACTOR TEMPERATURE, "C (°F)

The preceding pure component work indicates that the processing

conditions utilized can greatly affect the selectivity to aromatics
for the C6-C7 paraffins. Specifically, more aromatics are produced
at low pressure, high temperature conditions. Note, however,
t hat the catalyst stability becomes a constraint as moves are made
toward conditions favoring increased aromatics production.
 117013

1.0, and 0.5 moles per 100 moles of feed through reactors 1 through
4. Paraffin disappearance on an absolute molar level is comparable
to cyclopentane conversion (4.0, 4.0, 7.0, and 6.5 moles per 100
moles of feed) but on the basis of percent converted per mole of
specific hydrocarbon feed, the paraffin conversion is much lower.

Table 3 quantifies the conversion of each hydrocarbon type based

on the amount of that hydrocarbon in the Plat former feed.

TABLE 3
PARAFFIN AND NAPHTHENE
CONVERSION PER REACTOR

TOTAL
REACTOR NO. 1 2 3 4 CONVERSION

CONVERSION OF FEED
HYDROCARBON TYPE,
PERCENT

CYCLOHEXANES 95 3 0" 1" 99

CYCLOPENTANES 39 35 9 4 87

PARAFFINS 7 7 13 12 39

'CONCENTRATION TOO LOW TO ACCURATELY MEASURE •

Figure 16 and Table 3 demonstrate the rapid quantitative conver-

sion of cyclohexanes, the slower conversion of cyclopentanes, and
t he very slow paraffin conversion. Note that isomerization is not
i ncluded in paraffin conversion.
 117013

Figure 17 demonstrates the effect of cyclopentane carbon number

upon the rate of conversion. In reactor 1 there is generally either
no change at all, or actually an increase, in absolute amount of
methylcyclopentane. Such an increase would result from cyclo-
hexane isomerization and is generally observed in low severity
units. Figure 17 shows the more rapid conversion of the heavier
cyclopentanes; C 9 and heavier cyclopentanes are essentially
completely converted in the first two reactors. C8, C7, and C6
cyclopentanes react progressively slower.

FIGURE 17

CYCLOPENTANE CONVERSION
REACTOR PROFILE

3
MOLES PER 100 MOLES OF FEED

111111i
Rim CP
6

1
1 CPS

11114
7-CPS
CP9

CP10 j
I 01 0.25 0.5 i.
FRACTION OF TOTAL CATALYST
 117013

G. Reactor Profiles: Commercial Platforminq Data

Having considered the relative rates of the various Platforming

reactions, equilibrium constraints, and heats of reaction, [lie
overall Platforming process can now be examined. Consider a
modern, low pressure, motor fuel operation from the aspects of
hydrocarbon concentration, product quality, and temperature
profiles as the reactants pass through the reactor system.

The following data were obtained from a commercial, four reactor

Platformer. Feed, product and inter - reactor samples were taken
in such a manner as to follow hydrocarbon conversion and product
quality through the reactors. The profiles from this unit vividly
demonstrate the practical aspects of the hydrocarbon chemistry
discussed above.

FIGURE 16
HYDROCARBON TYPES CONVERSION
REACTOR PROFILE
2 2

A
MOLES PER 100 MOLES OF FEED

—ger

30

10
CP
CH
0_1 0.25 0.5 1

, FRACTION OF TOTAL CATALYST

Figure 16 shows hydrocarbon types yield, expressed as moles of

the particular hydrocarbon type per 100 moles of feed, across the
reactor system. The lines at 0.1, 0.25, 0.50, and 1 .0 fraction of
total catalyst indicate individual reactor boundaries and points of
sampling. Note that in this particular operation, aromatic forma-
tion is 22, 10, 5.5, and 5.5 moles per 100 moles of feed respectively
in reactors 1, 2, 3, and 14. Because of their rapid reaction rate, 95
percent of the feed cyclohexanes disappear in the first reactor.
Slower to react, the cyclopentanes disappear at rates of 4.5,

13-2
 117(113

At a reactor temperature of 5 140 ° C (1000 ° F), decreasing the plant

pressure from 14 kg/cm 2 (200 psig) to 9 kg/cm 2 (130 psig)
increases the selectivity of normal hexane to benzene by 33%, while
a further decrease to 5 kg/cm 2 170 psig) yields a 70% improvement
over the selectivity at 1 1 4 kg/cm l (200 psig). Benzene yields from
hexane precursors will be greatly enhanced by operating at high
temperature and low pressures. At these conditions, however,
the rate of coke formation is very high, and catalyst stability
becomes a primary concern.

The effect of process conditions on the methylcyclopentane selec -

tivity to benzene is illustrated in Figure 114. Methylcyclopentane
shows the same trend of i mproved selectivity with increased
temperature and reduced pressure as noted for normal hexane. At
comparable , conditions, however, the methylcyclopentane selec -
tivity is two to three times as large as the hexane selectivity. The
best selectivity (about 70%) was obtained at 7 kg/crn 2 (100 psig)
pressure and 5140°C (1000°F) reactor temperature. Increasing the
pressure to one that many fixed bed B I X Plat formers operate at
today, 21 kci/cm 2 (300 psig) lowered the selectivity to about 504.
Thus a 40% improvement in methylcyclopentane selectivity to
benzene is obtained by operating at the lower pressure.

FIGURE 14
SELECTIVITY OF
METHYLCYCLOPENTANE TO
BENZENE
W
Z uji
uj 1.. .70 7 kg / cm - (100 psig) —

ITJ
ef t-
,
• r 0

fo! (ret:viAlgo
W
o .60
14 kg / cm (200 psig) _
W
.so 21 kg / cm2 (300
P-
o cz
W

I" .40
ti) faa

0
2 2
.30
400 450 500 550
(752) (842) (932) (1022)
REACTOR TEMPERATURE, °C (°F)

B-22
 117013

The dehydrogenation of cyclohexane to form benzene is the most

rapid and simplest of the Platforming reactions. The effects of
temperature and hydrogen partial pressure on the equilibrium ratio
for this reaction are illustrated in Figure 11. 1 he formation of
benzene is highly favored over the entire range of typical Plat-
forming operating conditions. Thus, this reaction is essentially
irreversible and thermodynamic factors have little effect on
selectivity.

FIGURE 12
CYCLOHEXANE - BENZENE
EQUILIBRIUM
103

15 20
5 10
Ill) (142) 1213) (295)
2
HYDROGEN PARTIAL PRESSURE, kg / cm (psig)

ii 1 t,
•

117013

Figure 10 shows the effect of temperature and hydrogen partial

pressure on the equilibrium ratio for the conversion of normal
hexane to methylcyclopentane. It can hi. seen that, in general, the
equilibrium ratio is low, but it does improve rapidly as temperature
is increased and hydrogen partial pressure is decreased. It should
be noted that the level of MCP in the reactor must be reduced below
the equilibrium value before there will he any net conversion of
hexane to cyclic materials. Since the rate of hydrocracking is
inhibited by lower hydrogen pressures, the selectivity of the
hexane to aromatics is greatly enhanced by low pressure, high
temperature operations.

FIGURE 10

NORMAL - HEXANE /
METHYLCYCLOPENTANE
EQUILIBRIUM
1.2

1.0
CI
▪ U 0.8
cea.e

▪11u
2
O.
0.6
-400 ° C (752 ° F)

▪
ca

5
E
.
0.4

0.2
. .Ai 600 °C (1112 °F) -
W 500 °C (932 °F)
0 5 10 15 20 kg / cm
(71) (1421 (213) (285) ( Psig)
HYDROGEN PARTIAL PRESSURE ono .0 , 11 irf
 117013

Figure 18 shows the paraffin content of the reactant stream ( moles

of paraffin per 100 moles of feed) across the reactor system. I t is
interesting to note that in the first two reactors there is an
i ncrease in the absolute amounts of C6 and C7 paraffins present.
This is due to cracking of the heavy paraffins (note the rapid
disappearance of C9 through C11 paraffins) and possibly to
decyclization of C 6 and C7 cyclopentanes back to corresponding
paraffins. The more rapid conversion of the heavier paraffins
results from increased ease of ring formation, dehydrocyclization,
and increased rate of hydrocracking.

FIGURE 18
PARAFFIN CONVERSION
REACTOR PROFILE
MOLES PER 100 MOLES OF FEED

Pg

P 10
P11

01 0_25 05 1.0
FRACTION OF TOTAL CATALYST

l3-27

uop
 117013

Figure 19 shows the increasing isomerization in the C6 through C H

paraffin fraction across the reactors. These iso/normal ratios
approach but do not quite reach equilibrium values. This
isomerization plays a role in octane upgrading of the remaining
paraffin fraction.

FIGURE 19
PARAFFIN ISOMERIZATION
REACTOR PROFILE

os
4
0

r
it
-
i■
3

2
0 2 _....
O
1

0 0.1 0.25 05 1.0

FRACTION OF TOTAL CATALYST
 117013

One of the more interesting aspects of these results is demon-

strated in Figure 20. This figure shows aromatic content by carbon
number (again in moles of aromatic per 100 moles of feed) across
the reactors). The absolute amount of an individual aromatic
formed, of course, depends on the amount of precursors in the
feed. However, the rates at which the aromatics form are
indicative of the kinetics of the aromatic forming reactions. C 1 0
and C 11 aromatics are all formed in reactors 1 and 2; there is no
net formation of these aromatics in the last two reactors. Figure 18
does indicate conversion of C10 and C11 paraffins in reactors 3 and
4 and it is felt that some of the converted paraffins are
dehydrocyclizing, but that an offsetting amount of dealkylation to
lighter aromatics is occurring.

FIGURE 20
AROMATIC FORMATION
REACTOR PROFILE
20

Ac
MOLES PER 100 MOLES OF FEED

16 Ag-
As
A7-
12 W
FWEL 111
MOW A9

8
VA
Aio
WA.
A 10

211111W44
Mg
4

All
/II A
ll
0 01 0.25 05 10

FRACTION OF TOTAL CATALYST . 0P ,

M11 I
 117013

C 7 through C 9 aromatics continue to be produced throughout the

reactor system. Inspection of the previous figures show that very
little C7-Cg aromatic production in reactors 3 and '4 can he
attributed to naphthene conversion, because most of these
naphthene precursors are converted in reactors 1 and 2. This
aromatic production must then be attributed to paraffin dehydro-
cyclization and dealkylation of heavier aromatics. Finally, very
little net benzene production occurs in reactor 3 and none occurs in
reactor Li. This is the result of rapid cyclohexane conversion in
reactors 1 and 2, slower methylcyclopentane conversion in
reactors 2 and 3, and minimal hexane conversion. Hexane
conversion at these moderate severity conditions was low, as
expected. More severe processing conditions are employed in
modern BTX Platforming designs to force higher conversions of
hexane to benzene.

Figure 21 shows octane increase across the reactors. Predictably,

the octane rating increases more rapidly in the first reactors, a
result of the extensive naphthene conversion. Octane upciracling in
the last reactors results from the sluwer isumerization,
hydrocracking, and dehydrocyclization.

FIGURE 21
C5+ RESEARCH OCTANE RATING
REACTOR PROFILE
100
MICRO RESEARCH CLEAR OCTANE

90

SO

70

60

0.1 0.25 0.5 1.0

FRACTION OF TOTAL CATALYST '11

l3-30
•

117013

Finally, Figure 22 shows the reactor temperature profiles. The

inlet and outlet temperatures can be measured commercially; the
shape of the profile was determined by a Plat forming kinetic model.

FIGURE 22
TEMPERATURE
REACTOR PROFILE
I NLET

U.
-20
• (-36)

▪ 40
E4
1

tiJ
CC
-80
(-108)
ce
W
E -80
(-144)

01 0.25 0.5 1.0

FRACTION OF TOTAL CATALYST Wo V ,

 UOP Inc.
Des Plaines. Illinois
United States of America

UOP PLATFORMING PROCESS

CATALYST
CHEMISTRY

This material is UOP Inc 's technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not he reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc.

PLATFORMINC
 117013

II. PLATFORMING CA TALYST CIIEMISTRY

A. Dual Function Platforming Catalyst Chemistry

Examination of the reactions listed in Figure 9 shows that some of

them are acid-catalyzed while others are promoted by a metallic
hydrogenation - dehydrogenation catalyst function. A Platforming
catalyst, therefore, belongs to the general class of dual functional
catalysts.

The classical picture of such a catalyst involves t wo separate and

distinct sites with the reacting molecule migrating from one site to
another. Current thinking leans toward a modified picture in
which a single site or single complex is responsible for the entire
reaction sequence. This concept will perhaps become clearer when
we look at the details of the reaction mechanisms. It should he
pointed Out that presently it is only a concept and is not supported
by unequivocal evidence. It is known that the method of catalyst
preparation effects t he activity to at least the same extent as the
absolute level of catalytic species, indicating that a specific
arrangement of them is critical. In addition, since the rates of the
reactions over a modern Plat forming catalyst are high, then
presumably there are no mass transfer limitations. One would
expect mass transfer between separate sites to be limiting.

The concept of a single complex site does not effect the inherent
dual functional nature of a Platforming catalyst. The surface must
still possess both acidic and metallic characters. The acidic
character is mainly responsible for the formation of carbonium ions
by either extraction of hydride ions or addition of protons to
double bonds. Carbonium ions are, in turn, the intermediates in
such reactions as isomerization and hydrocracking. The metal
function is responsible for the extraction of hydrogen from
hydrocarbons, the splitting of hydrogen molecules and subsequent
addition of hydrogen atoms to unsaturated species. Combinations
of these two functions into a single complex site allows these
reactions to occur simultaneously.

The means are available to increase metal and/or acid activity of

catalysts. The primary tasks in the development of a Platforming
catalyst are to achieve the proper balance between the acid and
metal functions and to adjust this balance and the absolute activity
levels to fit the reaction conditions. More commonly, of course,
the reaction conditions are changed to accommodate the charac-
teristics of a given catalyst.
 117013

The selection of a catalyst and a set of operating conditions will

depend on the relative emphasis that is to be put on activity,
yield, stability, or some particular combination of all factors. This
makes the picture complex. However, UOP Platforming catalyst
development has proceeded such that a great deal of flexibility is
available to the refiner in the selection of a specific catalyst for
specific applications.

Catalyst acidity has undergone a great deal of optimization over the

years. The use of silica-alumina supports has long since been
abandoned and, more recently, we have moved away from the use
of fluoride. Fluoride provides too high an acidity level fur many
applications, and it is also not subject to adjustment in situ.

The present chloride system provides a titeans for precise control

while the plant is in operation. Water-chloride ratios play a
critical role, not only in maintaining the proper chloride (and
therefore acidity) level, but also in providing for uniform
distribution of chloride throughout the reactor train. The
i mportant point is that the system permits lowering the acidity to
levels that are close to the minimum required for the crucial
aromatics-forming reactions. The acidity cannot be reduced much
further without af fecting the rate of t he desired reactions.

For special purposes, the acidity of a Platforming catalyst can be

i ncreased. The best example of this is the R-15 LPG Platforming
system, where the target is the production of maximum propane
and butane. This was accomplished by adding another acidic
component to a Plat forming catalyst. The added acidity is believed
to be largely Bronsted ( protonic) in nature, as compared to the
Lewis t ype acidity on an ordinary Platforming catalyst. Figure 23
illustrates the effect of such increased acidity on product
distribution in the case of a relatively mild processing of a
mid-continent naphtha.
 FIGURE 23
STANDARD PLATFORMING
CATALYST VERSUS R-15
COMPARATIVE YIELD STRUCTURES
IMO R-15 LPG STANDARD CATALYST

- 85
YIELD, WT - % OF CHARGE

20

% OF CHARGE
18 MIDCONTINENT NAPHTHA - 80
PRODUCT 95 RONC
12 75

a - 70

- 65 ci

+ C2 C3 + C4 C5 +
H2
 117013

It is important to note that the effect of increased acidity becomes

significant only at higher pressures. Figure 2 14 illustrates the
effect of pressure on the performance of an k-15 catalyst. At 7
kg/cm 2 (100 psiy), R - 1 5 behaves very nearly like a standard
Platforming catalyst.

FIGURE 24
EFFECT OF PRESSURE ON YIELD
STRUCTURE OF R-15 CATALYST
42 kg/cm 2 1000psig) 7 kg/cm 2 (100 psig) 771
90
24

YIELDS, WT - % OF CHARGE
YIELDS, WT - % OF CHARGE

80
20 HONG
70
2
99.9
16 7 kg/cm
42 kg/cm 2 104.2 80
12
50
8
40
4
30
s\
C2 C3 C4 C5 +
 1 17013

B. Effects of Pressure on Catalyst Design

At this point, it is appropriate to discuss the roll of pressure on

t he design of a Flat forming catalyst. Figure 25 dramatically
illustrates the relationship between pressure and yield of light
hydrocarbons for a given Plat forming system.

FIGURE 25

EFFECT OF PRESSURE
ON YIELD STRUCTURE
100
HYDROGEN
PRODUCT YIELD, WT -

90
+ C2 C3 +

Jr

80

C5 + PLATFOR MATE

70

0 10 20 30 40
(143) (285) (428) (570)

PRESSURE kg/crn 2 (psig) LOP .0713 2 ,

The source of the light hydrocarbons is the cracking of paraffins.

The yield of aromatics from paraf fins declines by more than 30A as
t he pressure is increased from 14 to 35 kg/cm ( 2110 to 500 psig).
2

Figure 26 shows that this is specifically the result of the

substantial increase in hydrocracking.
 117013

FIGURE 26
EFFECT OF PRESSURE ON
PARAFFIN CONVERSION
4

HYDROCRACKED
MOLE % OF FEED PARAFFINS

TO AROMATICS
35
.. 42
/
I

■
i

.........
30 //
'"
,
..
.0,04
\
25 -,1---.
,

'di REMAINING I N PLATFORMATE

20

15
10 15 20
(285)
25
J
In
(42R)
lc an
(570)
PRESSURE, kg/cm2 ipsigi

The relationship between pressure and acidity can be summarized

as follows: at higher pressures, the acid function is not li miting,
and the addition of excess acidity will therefore tend to promote
hydrocracking rather than aromatization reactions. At lower
pressures, on the other hand, all dehydrogenation and aromatiza-
tion reactions occur rather readily, the metal function is riot
li miting and acidity can become a controlling factor. In this case,
added acidity brings the catalyst more nearly into balance, and,
hence, does not promote any additional hydrocrackiny.
 117013

C. UOP Platforminq Catalysts

The type of information presented above on the relationship

between pressure and yield encouraged UOP to focus attention on
low pressure Platforming some time ago. The yield advantages in
that region are obvious, but the problem is catalyst stability and,
specifically, the stability of the metal component. The arguments
supporting this are a corollary of the reasoning used previously to
explain the effects of acidity. At higher pressures, the activity of
the metal function is limiting and stability is less of a problem. As
the pressure is reduced, acidity becomes the controlling factor and
the catalysts become overbalanced on the side of excess metal
activity. This leads to excessive dehydrogenation, the formation
of coke precursors and catalyst instability. For a number of
years, therefore, UOP Platforming research has been directed
towards the control of excess metal activity in low pressure
Platforming or, on a practical basis, towards i mproving catalyst
stability under such conditions.

Success in developing more stable Platforming catalysts came by

adding a second metal component to the catalyst to control the total
metal function. The R-16 series catalysts employ rhenium as the
added metal, and these catalysts represent a tremendous improve-
ment in catalyst activity and stability. The R-20 series catalysts
followed shortly, and demonstrated, (or the first time, improved
initial selectivity over all-platinum catalysts. The R-20 catalysts
also show greatly improved stability characteristics when compared
to all-platinum, although they are not as stable as R-16 series
catalysts. R-30 series catalysts proved to be a further refinement
of the high yield R-20 series catalysts. R-30 catalysts show initial
selectivity identical to that of R-20 series catalyst, but also show
the benefits of improved activity and stability over R-16 and R-20
catalysts at low pressure processing conditions.
 117013

Figure 27 compares an all-platinum catalyst (R-11) and three

representative bimetallic catalysts at high severity, low pressure
operating conditions. The absolute magnitude of the selectivity
advantage for the R-20 and R-30 series catalysts and the stability
advantage of all the bimetallic catalysts will vary with feed
properties, unit design, and processing conditions. In some
instances, one of the above variables (e.g., unit operating
pressure, temperature li mitation, feedstock sulfur content) will
preclude the use of one or all of the bimetallic catalyst series. To
benefit from the advantages of bimetallic catalysts will therefore
often require physical changes to an existing unit. UOP bimetallic
Platforming catalysts have found extensive use in units originally
designed for all-platinum catalysts.

PERFORMANCE SUMMARY OF
CURRENT COMMERCIAL UOP
PLATFORMING CATALYSTS
+8

+6
R-22 n-7 0

■
.... .,
R-60, R-62
w +4 - n•50
R• 16G

c." +2
ALL PT
BASE
+60
REACTION TEMPERATURE, 'C

+50
ALL PT R-22
+40

+30 - 11•504R-70 - --

R-d0, 62
+20
+10
BASE
a 711 40 60 80 100 120 140 160 18
CATALYST LIFE, DAYS ON STREAM
 117013

It should be pointed out that these bimetallic catalysts, because of

their more precisely controlled metal and acid functions, are much
more sensitive to feedstock sulfur and water levels. Many of the
problems associated with bimetallic Platforming operations,
especially in older units, can be traced to excessive amounts of
sulfur and water in the unit. These contaminant problems are
discussed in detail elsewhere.

A comparison of different UOP catalysts is made in Table 4, which

lists the major properties of Platforming catalysts R-5 through
R-50.

TABLE 4
UOP PLATFORMING CATALYSTS

SOCK
NOMINAL LOADED
DIAMETER DENSITY PLATINUM RHENIUM CHLORIDE
CATALYST mm k g/m 3 WT 4o WY% WT% STATE

R•9 1.6 505 0.375 — 0.9-1.0 R

R-16F 1.6 505 0.2 0.2 0.9-1.0 RIS
R-16G 1.6 505 0.375 0.375 0.9-1.0 RIS
R-16H 1.6 505 0.375 0.20 0.9-1.0 BIS
R-18 1.6 561 0.375 0.375 1.1-1.2 RIS
R-20 1.6 505 0.375 — 0.9-1.0 R
R-22 1.6 505 0.375 — 0.9-1.0 R
R-50 1.6 x 3.2 (EX) 833 (0) 0.25 0.25 0.9-1.0 R/S
R-51 1.6 x 3.2 (EX) 673 (D) 0.25 0.25 1.05-1.15 !VS
R-60 1.6 721 0.30 0.80 1.0.1.1 nis
R-62 1.6 721 0.22 0.44 1.0-1.1 RIS
R-70 1.6 721 0.375 — 1.0.1.1 R

I
NOTES: EX = EXTRUDATE R - II, II - 11, R - 16H, R -22 and R -32 aro also
D = DENSE LOADED BY MACHINE available as 1/6" (Ramat*catalyst Those
,

- 16H (L).
= REDUCED AND SULF1DED cater/1e are deelgdaled with (1.), i... R
R = REDUCED

The information presented in this section has been taken from

other recent DOI' Technical Papers. Recent commercial data has
been included, the catalyst discussion includes rurreni IMP
thought on catalyst applicability, and the information has been
edited and presented with refinery operations personnel in mind.
The Platforming groups of the U01) Corporate Research Department
and the Process Division Process Development Department are
responsible for most of the theories and data included in this
presentation. Their cooperation with the Technical Service
Department in assembling this section is greatly appreciated.
 UOP Inc.
Des rhinos. Illinois
United States of America

UOP PLATFORMING PROCESS

PROCESS
VARIABLES

This material is UOP Inc.'s technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not he reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc

1
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 1170136015
Rev. 2

PROCESS VARIABLES

The purpose of this section is to discuss the major Platforming

operating variables, their relation to unit performance and the
estimation of shifts in performance due to operational changes.

The operating variables which are the most pertinent are shown in
Table 1. For practical purposes, these variahles are sufficient to
define a Platforming operation.

MAJOR PLATFORMING VARIABLES

INDEPENDENT VARIABLES DEPENDENT VARIABLES

• CATALYST TYPE • CATALYST ACTIVITY

• REACTOR TEMPERATURE
• SPACE VELOCITY
• REACTOR PRESSURE
• H2/HC RATIO
• CHARGE STOCK PROPERTIES
• FEED ADDITIVES
• RX. EFFLUENT YIELDS
• PRODUCT QUALITY
• CATALYST STABIILITY
‘10. 10,C.11

Although there are interrelationships bet ween the variables (for

instance the reactor temperature, reactor pressure, and reactor
effluent yield relationships discussed in Section R), this section
treats each independent variable separately where possible.

Note to the Reader:

It is necessary to define two (2) modes of Platformer operation and

the terms which will be used to distinguish between them:

Type of Mode
Platforming Operation Descriptor

Fixed Bed SEMI-REGEN

Continuous Catalyst
Regeneration CCR

1
 117013F,015
Rev. 2

The discussion which follows will be applicable to both "modes" in

general. However, where a distinction is to he made between the
t wo modes, especially in the calculation procedures, the reader
should decide which mode applies to his case and look under the
appropriate heading.

I. Discussion of the Major Platforminq Independent Variables

It is of interest at this point to discuss briefly and qualitatively the

effects of the major process variables on Platformer operation.

A. Catalyst Type

Catalyst selection has most likely been tailored to the refiner's

individual processing requirements. The 1_1 0P Plat forming catalyst
( one of those from Table 4, Section R) has been chosen to meet the
refiner's yield, activity, and stability needs. As such basic
catalyst formulation, chloride level, platinum level, and in the case
of bimetallic catalysts, activator level are not discussed in this
section.

There are some basic differences between individual catalysts

which will be taken into account in the calculations described
below. For instance, catalyst type will affect the temperature
required to meet a particular product quality.

B. Reactor Temperature

The temperature at which the Plat forming reactor catalyst beds are
held is the major control parameter the refiner uses to meet
product quality requirements. Platforming catalysts are capable of
operation over a wide range of temperature with little adverse
affect on product yield and catalyst stability. However, very high
temperatures, above 543°C ( 1010°F), may cause thermal reactions
which will decrease Platformate yield and catalyst stability.

Reactor temperature can be defined in t wo fashions, either

weighted average inlet temperature (WAIT or weighted average
bed temperature ( WAB T ). These can be calculated as follows:

The summation of the

WAIT Wt. fr action lied

catalyst multiplied by inlet
in bed temperature

The summation of the

WABT Wt. fraction Average of the

catalyst multiplied by hed inlet and outlet
in bed temperatures

- 2 -
 1 171J13&015
Rev. 2

Although both the WAIT and the WART are of practical use,
neither exactly defines the true average catalyst temperature.
Also, in the discussion to follow, the WAIT will be used
exclusively. The WART will only have to fall within bounds as a
criterion for certain calculations.

C. Space Velocity

Space velocity is a measure of the amount of naphtha which is

processed over a given amount of catalyst over a set length of time.
When the hourly volume charge rate of naphtha and the volume of
catalyst are used, the term is liquid hourly space velocity (LIISV).
When weights are used, the term is weight hourly space velocity
( WHSV). Either is applicable in following a Platformer operation
when a set catalyst density and volume is involved. LHSV, hr -1 ,
is commonly used since most refiners define their charge rate on a
volume basis, and hourly rates yield conveniently sized numbers.

Space velocity has a major effect on product quality (example:

octane number). The higher the space velocity the lower the
product quality or the less the amount of reaction allowed.
I ncreased reactor temperatures will offset this effect. Within
normal Plat former design parameters, space velocity has little
effect on product yields and catalyst stability (on a barrel per
pound basis). At very low space velocities, thermal reactions can
occur to a sufficient degree to decrease Platformate yields. While
there is no known upper limit on space velocity, reactor tempera-
tures have to be increased in order to maintain the product quality
and above a certain point, this can again cause unfavorable
thermal reactions which will lower selectivity.

0. Reactor Pressure

Because of its inherent effect on reaction rates, hydrogen partial

pressure is the basic variable, but for ease of use, the information
which follows has been adjusted so the total reactor pressure can
he used and the hydrogen purity is not needed.

Reactor pressure is most accurately defined as the average

catalyst pressure. Since 50% of the catalyst is usually in the last
reactor, a close approximation is the last reactor inlet pressure.
Separator pressure, as an operating parameter, is of limited value
since the pressure drop from unit to unit can be considerably
different and even within the same unit, the pressure drop will
vary considerably with charge rate, recycle gas rate, recycle gas
gravity, etc.

The reactor pressure affects the Platformer yields, reactor

temperature requirement, and catalyst stability. Reactor pressure
has no theoretical limitations, although practical design limitations
have an effect. Reactor pressures as high as 49 kg/cm 2 (700 psig)
and as low as 6.3 kg/cm 2 (90 psig) have been run commercially.

-3
 117013&015
Rev. 2

Decreasing the reactor pressure will increase the hydrogen and

Platformate yield, decrease the temperature requirement to make
the product quality, and shorten the catalyst cycle (increase
catalyst coking rate).

E. Hydrogen/Hydrocarbon Ratio

Hydrogen/hydrocarbon (H2/HC) ratio is defined as the moles of

recycle hydrogen per mole of naphtha charged to the unit.

Recycle hydrogen is necessary in the Platformer operation for

purposes of catalyst stability. It has the effect of sweeping the
reaction product and condensable materials from the catalyst and
supplying the catalyst with readily available hydrogen.

An increase in H 2 /HC ratio will move the naphtha through the

reactor at a faster rate and supply a greater heat sink for the endo-
thermic heat of reaction. The end result is increased stability with
little effect on the product quality or yields.

For CCR applications only, TOTAL H2HC is defined as H2HC mol

ratio I n the combined feed to the reactor plus 70 percent of the net
hydrogen produced on a mol H2 in net gas to mol of feed basis.

F. Charge Stock Properties

The charge stock properties which are pertinent to this discussion

of Plat forming variables are as follows:

Laboratory
Property Method

Source of Stock

I nitial boiling point (IBP)

Mid boiling point (SO) ASTM D-86 Distillation
End boiling point (EP

Paraffin Content (P)

Naphthene Content (N) HOP 777 PONA
Aromatic Content (A)

Feedstocks such as FCC naphtha, hydrocracker naphtha and

raffinates have a higher ratio of C5 and C6 naphthenes than do
most straight run naphthas. Stocks such as coker naphthas tend
to have more polycyclic material for a given boiling range. This
makes these stocks more difficult to reform. For this reason, only
straight run naphthas should be compared when using the calcula-
tion procedures described later on.

-4
 117013&015
Rev. 2

Charge stocks with low IBP will generally contain a significant

amount of C5 material. Since the pentanes are relatively low in
octane, this will cause a dilution of the C 5 plus Platformate octane.
Typically, feed naphthas are C 6 plus.

Stocks with low EP's have C6 and C7 hydrocarbons concentrated.

These are the most difficult species to reform. High EP stocks
cause higher catalyst coking rates. They also contribute signifi-
cantly to high Plat formate endpoint.

Generally, the calculation procedures described later are based on

correlations of pilot plant and past commercial data. As such, the
UOP Method 273 PONA analysis provided the naphthene and
aromatic data used for the correlating parameters. Currently, a
more precise analysis, the UOP Method 777, is viewed by UOP as
giving the best representation of P/N/A content.

Suffice it to say that the reader will obtain reasonable results when
using the following charts with either the UOP Method 777 or UOP
Method 273 PONA data. The important thing to hear in mind is (as
stated in the Chemistry Section) the leaner the stock is the more
difficult it is to reform. The converse is also true.

G. Feed Additives

It is assumed that chloride and water additions to the feed are

sufficient to maintain the chloride balance on t he dual-function
UOP Platforming catalyst. Chloride control will be discussed in
detail in the Water Chloride Section.

Catalyst poisons and feed contamination will also he covered in the

Catalyst Poisons Section.

II. Discussion of Platforming Dependent Variables

I n this portion of the Process Variables section, the effects of the

Plat forming independent variables on the major dependent
variables will he discussed. More importantly, methods for
estimating t he effects of operating changes on one or more of the
dependent variables will he illustrated.

A. Catalyst Activity

Catalyst activity is a term used to describe the temperature at

which a particular catalyst must he operated to produce a given
product quality. In this discussion, the catalyst temperature will
he defined exclusively as the WAIT or weighted average inlet
temperature. Product quality as it applies to motor fuel operations
will he defined as the RONC or research octane number clear.
 117013E015
Rev. 2

The WAIT requirement to meet a given RONC is obviously affected

by many things. At the outset of a run with fresh catalyst, one
would expect that the WAIT required would only he effected by
the feed character, RONC desired, catalyst type and between the
semi-regen and CCR modes, the average reactor pressure. Things
are only this simple one time. As a semi-regen unit runs along, the
catalyst deactivates due to gradual coke laydown. In either the
semi-regen or CCR mode, an operation upset could occur which
will effect the water-chloride balance and the apparent catalyst
activity will change. The list goes on and on.

There is a simple calculation procedure for estimating the start-of-

run WAIT requirement. This SOR WAIT is the temperature at
which a fresh catalyst loading would operate i n order to produce a
certain RONC from a feed characterized by a certain N and A
content and charged at a given LI{SV. There are at least three ( 3)
i mportant ways at which this estimate can be put to use:

i. Semi-regen or CCR Platformer startup WAIT target

ii. Semi-regen "Delta WAIT" ( actual WA I T minus predicted

SOR WAIT) for tracking catalyst deactivation on a
normalized basis.

iii. CCR Platformer "Delta WAIT" for tracking catalyst quality

with respect to regeneration cycles.

The first use, (i), is fairly straightforward. The calculation

enables the process engineer or supervisor to estimate the WAIT
required to meet product requirements following a fresh catalyst
loading and, in many cases, following a semi-regen unit catalyst
regeneration.

Numbers (ii) and (iii) require some explanation, but the reader
will note that the concept is simple. The basic idea is to determine
a number (Delta WAIT) which puts the catalyst temperature
requirement on a consistent basis for comparing day-to-day
operation. This would not be necessary, of course, if the semi-
regen or CCR Plat former ran at the same conditions (Feed N and A,
RONC, LI ISV) all the time. This is seldom t he case.
-

What "Delta WAIT" does then is normalize reactor temperature data

with respect to Platformer feed N and A, RONC and LI-ISV. It is
defined as the difference between the WAIT the Platforrner is
operating at, given the three parameters above, and the fresh
catalyst WAIT requirement for the same parameters. It is the
activity difference between the real catalyst and a hypothetical
"perfect" catalyst.

- 6 -
 117013&015
Rev. 2

Tabulation or graphical plotting of "Delta WAIT" is a natural

followup. In maintaining a plot, the process engineer can track
semi regen activity decline with catalyst life (usually barrels per
-

pound of catalyst) due to coke laydown. Perhaps near the end of

run, a prediction of when the catalyst will need regeneration can
be made. In the CCR application, the engineer can monitor the
effects of operating changes made to remedy a catalyst activity
problem due to, for instance, a feed sulfur upset. In this case,
" Delta WAIT" can be plotted versus regeneration cycles. It
probably would take a few catalyst regeneration cycles for the CCR
activity to get back to "normal", so on a clay-to-day basis, the
engineer can track the improvement in activity. For both the semi-
regen and CCR modes, disruptions in and recovery of the water-
chloride balance can be tracked using the "Delta WAIT" calculation
and plot.

The SOR WAIT requirement calculation will now he explained. The

calculations for both semi-regen and CCR applications will be
shown in a side-by-side example calculation to follow. The figures
used are not meant to cover all variables which can affect the
apparent fresh catalyst activity. Predictions of the SOR WAIT
requirements from the figures should, however, he within plus or
minus 3°C (5°F) of the actual requirement.

Below is an outline of how the calculation proceeds, with reference

to the appropriate Tables and Figures for semi-regen and CCR
applications:

Semi-regen CCR
Step Mode Mode

1. List - RONC 95
- N and A '1'13
d
a; .3 - Actual Unit Operating Data-
- N + 3.5A
21
' 3 s. 3 33.:*
- LI--ISV
- Catalyst Type 2- 62.

2. Estimate SOR WAIT

at 1.0 LIISV Figure 1 5/3.."— C Figure 2

3. Estimate Correction
for actual LIISV Figure 3 0-
0 Figure 3

4. Estimate Correction for

Actual Catalyst Type Table 2 -1c4 Table 3

5. Add the results of 2,3,4

to give SOR WAIT aqt15•6,

111A T
•te, a Al
4)14
i I
((An e2 e...rneA ote.1
-
14 ea.., 4 4 . 4...c,40 .( W

rya° •4 Atiti &at eert-4-4"..

IAA C 4"-14,„
.e. e." A.(
'7/1:ace_ 040 us-14.) racre,
k
- 7 -
 117013E015
Rev. 2

The following numerical examples are presented in order to give

the refiner a guide for calculating the SOR WAIT requirement.

SEMI-REGEN CCR
APPLICATION APPLICATION

1. Process Conditions 1. Process Conditions

Catalyst R-16 Catalyst R-32

RONC 95 RONC 95
LHSV, hrl 1.5 LHSV, hrl 1.9
Feed N, LV-% 20 Feed N, LV-% 15
A, LV %
- 10 A, LV-% 8

N + 3.5A = 20 + 35 = 55 LV-% N + 3.5A = 15 + 28 = 43 LV-%

2. From Figure 1 2. From Fig ure 2

SOR WAIT = 944°F SOR WAIT = 922°F

at 1.0 LHSV at 1.0 LHSV

3. From Figure 3 3. From Figure 3

Correction = +18°F Correction = +28°F

1.0 to 1.5 LHSV 1.0 to 1.9 LHSV

4. From Table 2 4. From Table 3

Catalyst Correction Catalyst Correction

for R-16 = - 5°F For R-32 = 0°F

5. SOR WAIT requirement 5. SOR WAIT requirement

SOR WAIT = 944 + 18 5 - SOR WAIT = 922 + 28 + 0

= 957 ° F = 950°F

Suppose now that the semi-regen unit for the day in question was
running an actual WAI r of 970°F. The engineer would tabulate and
plot for this day the following "Delta WAIT":

Delta WAIT = 970 - 957 = 13°F

I n other words, the catalyst has lost a total of 13°F activity from
fresh catalyst. Day to day calculations would allow the engineer
- -

to assess the catalyst deactivation on a normalized basis and

determine whether it is along the lines that would be expected.

8
 117013&015
Rev. 2

The temperature-octane response for a Platformer, for either the

CCR or semi-regen modes of operation, is shown in Figure 4. This
chart can be used to estimate the changes in the WAI r required to
switch daily operations from one RONC to another.

B. Catalyst Selectivity

Selectivity is defined as the tendency of a given Platforming

catalyst and the operation of that catalyst to produce the most
desired material. In most Plat former operations, the most desired
material is Platformate or more specifically the yield of C5 plus
liquid. Also, for the purpose of this section and those to follow,
product quality will continue to be defined as RONC, the octane
number.

The selectivity of a Plat forming catalyst and operation is

dependent upon several variables. At this point, only the effects
of Platformer feedstock characteristics (N and A content), product
quality (RONC), and reactor average pressure on selectivity to C5
plus liquid will be discussed. As previously, methods for esti-
mating the effect on C5 plus yield of operating charges will be
illustrated. Although there are significant differences in the
degrees of yield response for semi-regen and CCR Platformers,
both types of operation will be discussed in side-by-side fashion.

A preliminary glance at the selectivity curves presented for each

mode of operation allows the following general conclusions to he
made.

1. C5 plus yield increases with a decrease in average reactor

pressure. Furthermore, comparing the pressure effect at two
octane levels and constant N+2A shows the higher the octane,
the larger the increase in yield.

2. C5 plus yield decreases as octane is raised at constant reactor

pressure and feed N+2A.

3. C 5 plusyield generally increases with an increase in feed

naphtha N+2A at constant pressure and RONC. The effect
becomes less pronounced as feed changes occur at high N+2A
value.

It is important to realize that in the following procedure absolute

yields are not calculated. The estimate gives the shift in yield in
going from a base condition (the current Platformer operation, for
instance) to a new case.
 1170136015
Rev. 2

A sample calculation of the C 5 plus yield change estimate is given

below for both semi-regen and CCR modes.

SEMI-REGEN CCR
APPLICATION APPLICATION

1. Base Case 1. Base Case

Case A Case A

RONC 93 95 IZONC 96 100

N/A, LV-% 40/10 34/10 N/A, LV-% 34/10 40/10
N+2A, LV % - 60 54 N+2A, LV-% 54 60
Avg. Rx. Avg. Rx.
Press, psig 450 330 Press, psig 150 120

2. Averages: 2. Averages

RONC 94 RONC 98
N+2A 57 N+2A 57

3. RONC Effect, Figure 5 3. RONC Effect, Figure 8

A. C5+ yield decrease A. C5+ yield decrease

= - .83 L V VRONC
- = - .82 LV %/RONC
-

B. Yield Delta = ( - .83)(2) B. Yield Delta = (-.82) (4)

= -1.66 LV-% = -3.28 LV-%

4. N+2A Effect, Figure 6 4. 1\14-2A Effect, Figure 9

A. C5+ yield increase A. C5+ yield increase

= .25 LV %/N+2A - = .25 LV-%/N+2A

B. Yield Delta = (.25) (-6) B. Yield Delta = (.25)(6)

= -1.50 LV-% = 1.50 LV-%

5. Pressure Effect, Figure 7 5. Pressure Effect, Figure 10

A. C5+ yield increase A. C 5 + yield increase

= 1.4 LV-%/100 psi = 1.74 LV-%/100 psi

B. Yield Delta B. Yield Delta

= (1.4)(120)/(100) = (1.74)(30)/(100)
=1.68 LV % - = .52 LV-%

6. Overall Yield Change 6. Overall Yield Change

Net Yield = (-1.66)4(-1.50) Net Yield = (-3.28)+(.25)

Delta +(1.68) Delta +(.52)

= -1.48 LV-% Total = -2.51 LV-% Total

- 10 -
 1171113&015
Rev. 2

C. Catalyst Stability

Catalyst stability is a measure of the coke-fori dency_of a

given catalyst. For semi-regen Platformers, stability is measured
as deactivation rate, as the coke laydown will certainly require
that the WAIT be increased to maintain product quality. C 5 plus
yield decline with time is also an indirect measure of activity
decline because increasing WAIT usually results in more production
of light hydrocarbons. For CCR Platformers, apparent catalyst
activity usualiy remains the same under normal operating condi-
tions. However, the coke-forming tendency of the CCR's catalyst
will significantly affect the continuous regenerator's operation. As
more or less coke is formed, changes in the Plat former and regen-
erator operations will be required to ensure that coke burned is
equal to and NEVER less than coke formed.

I n the following discussion, calculation procedures for estimating

the effects of process variables on the coke-forming tendency of
t he catalyst will be illustrated. It becomes necessary, however, to
treat the two different modes of operation, semi-regen and CCR,
separately. This is because, as inferred above, the concepts of
catalyst stability for the two modes are significantly different.
The following distinctions will be made:

Mode of Catalyst Stability

Operation Measure Significance

Semi-Regen Relative Catalyst Performance

Deactivation Rate Loss

CCR Relative Coke production with

Coking Factor respect to coke burn-
ing capacity

The rate at which a given catalyst forms coke is set by the process
variables listed below. The appropriate figures for both semi-
regen and CCR modes are also given and the reader may wish to
examine the differences between the two sets.

SEMI REGEN
- CCR
Relative Relative
Process Variables Deactivation Rate Coking Factor

RONC Figure 11 Figure 16

Feed Naphtha N+A Figure 12 Figure 17
Feed Naphtha End Point Figure 13 Figure 18
Avg. Rx. Pressure Figure 14 Figure 19
Hydrogen/Hydrocarbon Ratio Figure 15 Figure 20

These curves are based on a combinination of pilot plant and

commercial data. The data are normalized to eliminate inter-
relationships bet ween variables as much as possible. The figures,
 117013&015
Rev. 2

therefore, give the relative deactivation and coking factors in

terms of single variables (e.g., Figure 11, Relative Deactivation
Rate versus C5 plus RONC).

The following numerical examples will illustrate how the respective

stability measures for semi-regen and CCR modes of operation are
estimated.

1. Relative Deactivation Rate - Semi-Regen Applications

This semi-regen example demonstrates how to estimate the relative

deactivation rate between the base case and case "A".

a. Case Base A

RONC 93 95
N+A, LV-$ 50 44
Feed EP °F 360 385
Avg. Rx Pressure, psig 450 330
H2/HC 7 5.2

b. From Figure 11: Case A/Rase =2.37/1.67

=1.42
From Figure 12: Case A/Base =.955/.83
=1.15
From Figure 13: Case A/Base =1.22/.94
=1.30
From Figure'1 14: Case A/Base =1.3/.85
=1.53
From Figure 15: Case A/Base =1.55/.99 =1.57

c. The overall relative deactivation rate is the product of the f ive

individual relative deactivation rates.

(1.42)(1.15)(1.30)(1.51)(1.57) = 5.10

Thus, case "A" will deactivate 5.10 times faster than the base
case. If the base case had shown at 30°F deactivation in WAIT
requirement over 100 BPP catalyst life, then case "A" would show
a 30 ° F WAIT deactivation over only 19.6 BPP catalyst life.

2. Relative Coking Factor - CCR Applications

This CCR example demonstrates how to estimate the relative coking

factor and the change in coke production bet weed the base case
and case "A".

I n using the procedure, one point cannot he overemphasized: To

derive the greatest possible accuracy in estimation of a new carbon
laydown rate, the process variables (including feedstock) should
be held constant for one complete turnover of the reactor catalyst
before actual carbon laydown can be compared to the estimated
value. Likewise, when calculating the "base" carbon laydown
rate, the reactor should be turned over one full time at constant

- 12 -
 117013E015
Rev. 2

processing conditions before the base coking level can be estab-

lished. Since many refiners do not always run with constant
feedstock for one full catalyst cycle at a time, this estimation
method should he used only to show a direction and a rough
approximation of expected carbon laydown rates.

The refiner should also realize that any significant periods of Plat-
forming operation without catalyst circulation will increase the
amount of carbon on the spent catalyst above the level calculated
by the estimating procedure.

When used with the proper caution regarding process variable

changes, this estimated coking procedure should allow the refiner
to better anticipate regenerator coke loadings as his processing
needs vary.

a. Base Case: The unit is operating at the following conditions:

Charge: 20,000 BPD

38 N + A, LV-%
350°F EP

Severity: 125 psiq

1 00 RONC on C5 + Plat formate
*5 H2/HC mol ratio total

CCR: 450 lbs/hr

Spent carbon level: 3.8 wt-% (X=0.038 wt. fraction)

17.78 lbs/hr
(0.038) (450) =
Carbon laydown =X (CCR) =
1 -X ( 0.962)

b. Case A: Operating conditions are then changed to the following

and held constant for at least one catalyst turnover in the
reactors.

Charge: 18,500111'1)
36 N + A, LV-%
350°F EP

Severity: 125 psic;

98 RONC on C5 + Platformate
*E1.5 t12/11C mol ratio total

*Total H2HC mol ratio equals H2HC mol ratio to the reactor plus 70
percent of the net gas hydrogen produced, on a mol ratio net gas to
mol ratio feed basis.

- 13 -
 117013&015
Rev. 2

c. Calculate the effect of these changes on coking rate:

( RCF = Relative Coking Factor)

( N = New conditions)
( B Base
= conditions)

New carbon = (Base ( BPDN) (RCFN) (RCFN) (RCFN) (RCFN) (RCFN)

laydown laydown) (BPL)B) (RCFB-1 (RCFB) (RCFB) (RCFB) (RCFB)

RONC N+A EP Press. H2HC

(Fig 16) (Fig 17) ( Fig 18) ( Fig 19) ( Fig 20)

= (17.78) (18,500) (0.61) (1.11) (0.76) (1.0) (0.63)

(2 ) 1176T Tr:TC) 777161 11:0) uTTiT
4
12.37 lbs/hr carbon

d. If the CCR is maintained at 450 lbs/hr, then the spent catalyst

carbon level can be predicted by

or X Carbon Laydown
CCR Carbon Laydown

12.37
450 + 12.37

0.027 wt. fraction carbon

or about 2.7 wt--$ carbon on spent catalyst

D. Endothermic Heat of Reaction

The final portion of this section will address an estimating

procedure for the endothermic heat of reaction for a given Plat-
former operation. The procedure is applicable to both semi-regen
and CCR modes of operation.

The endothermic heat of reaction, when regularly calculated for a

fairly constant charge stock PONA and Plat formate octane number,
may he used as an indication of catalyst deactivation. The
decreasing heat of reaction shows the decreasing aromatics forming
ability of the catalyst. These curves do not correct heat of
reaction for charge stock composition or product octane number
because of the complexity of these relationships. If these values
vary, the heat of reaction will also vary.

The total delta T over the catalyst is directly related to the total
heat of reaction. While the heat of reaction is not a function of the
H2/HC mole ratio, the total delta T is, due to the "diluent effect"
of the recycle gas. Li-6V does not materially affect of the heat of
reaction.

- 14 -
 11711136015
Rev. 2

Using Figures 21A and 21B or Figures 22A and 22)3, the heat of
reaction may he determined when the following are known:

Recycle gas purity (mole percent hydrogen)

H2/HC mole ratio
Total delta T
Charge stock molelcular weight.

The heat of reaction value as calculated from these graphs indi-

cates the aromatization ability more accurately than total delta T.

The following sample problem demonstrates the use of the figures in

calculating the heat of reaction.

1. Total delta T (all Plat forming reactors) 1 145°F

Hydrogen/Hydrocarbon Ratio 6
Recycle Gas Hydrogen Purity 75%
Charge Stock Molecular Weight (MW) 110

2. From Figure 21A

Total heat of reaction (11R) = 153(145/100) =222

( Btu/lb of naphtha)

3. From Figure 2113

MW correction =
+8(145/100) +12

4. The correct heat of reaction:

Corrected Heat of Reaction 222 + 12

234 iltu/lb of naphtha

 1170136015
Rev. 2

TABLE 2

SEMI-REGEN APPLICA TIONS

CATALYST CORRECTIONS
FIGURE 1 - SOR WAIT REQUIREMENT

Catalyst Correction
°F °C

R-5, R-7, R-8 +10 +6

R-9, 10, 11, 12, 14 -
R-16 Series -5 -3
R-18 -15 -8
R-20 Series
R-30 Series -20 -11
R-50 Series -25 -14
R-60 Series -25 -14
R-70 Series -25 -14

*Note: Figure 1 is based on activity of all Platinum catalysts

and R-20 series.

TABLE 3

CCR APPLICATIONS
CATALYST CORRECTIONS
FIGURE 2 - SOR WAIT REQUIREMENT

Catalyst Correction

R-30 Series None*

R-20 Series +11°C (+20°F)

*Note: Figure 2 is based on the activity of R-30 series

catalysts.
 117 13 0 1 5
Rev. 2

FIGURE 1

SOR WAIT REQUIREMENT AT 1.0 LHSV

SEMI •-• REGEN

1000
, --, BASIS:
r/411 MT

v'' ill - 530 1. R SERIES OR

,

980
♦ IF•
r iv/

ALL PLATINUM
RONC-
4.1

520 CATALYSTS
,,
I4

960 `'46-7,.104
1

1T- 1 1

2 200.600 PSIG

/
r

510

1 Z(1.1. 11111
AVERAGE REACTOR
fa 1

/I/ /itlitl
1/
i
WAIT REQUIREMENT

fit!

940 PRESSURE
1111-1
►

`
- 500
1;11
1, ► 1

100 3. STANDARD WATER

I
I
920 AND CHLORIDE
;r.f

!
490 LEVELS

-.1■414wimummi libb.
1_;

900
Jiil
4. 100 165 'C (210 330 -TI

(rrif
480
:

95 _—
►
1

ii1

.1‘1111irNIZNII
1

AS1M 501". POINT

1111111.
. itI
f
J/

lim
ON CHARGE
880
I
- 470
90 5. I WAIT - WABTI
LESS THAN 15°C
860 460 125"F)
85
840 450
1111111111 80 _
440
820
30 50 70 90 110
HYDROTREATED NAPHTHA N + 3.5A CONTENT, LV%
 117013&015
Rev. 2

FIGURE 2

SOR WAIT REQUIREMENT AT 1.0 LHSV

°F
CCR APPLICATIONS
°
970 C
BASIS:
1. R-30 SERIES
950 510 CATALYST

930 -- 500 2. B.S TO 12 kg/cm 2

(125 to 175 psigl
910 - 490 AVERAGE REACTOR
PRESSURE
- 480
890 3. STANDARD WATER
- 470 AND CHLORIDE
• 870 LEVELS
- 460
850 4. 100-165"C(210-3313°F1
C - 450 AST M 50% POINT
ON CHARGE
830
- 440 S. 'WAIT — WART)
810 LESS THAN 20'C
- 430 (35-11
790
30 50 70 90 110 UO•°3011 14

HYDROTREATED NAPHTHA N + 3.5A CON PENT, LV%

 FIGURE 3

WAIT REQUIREMENT
CORRECTION FOR LHSV
°F °C
- 35
60
- 30
50
- 25
WAIT CORRECTION

40
- 20
30
- 15
20
-- 10

10
- 5

-10 - -5

.75 1
 1170 13F,0 15
Rev. 2

FIGURE 4

TEMPERATURE OCTANE RESPONSE

8

4
7

WAIT °C/RONC
WAIT °F/RONC

3
5

4
2

3
75 80 85 90 95 100 u0P 15413 4

C5 + PLATFORMATE RONC
 117013&015
Rev. 2

FIGURE 5

EFFECT OF F-1 CLEAR OCTANE

NUMBER ON C5 + LV% YIELD
GOOD FOR
1. FULL BOILING RANGE STRAIGHT RUN NAPHTHA
2. 21 kg / cm 2 (300 psig) AVERAGE REACTOR PRESSURE

5.0
MMEMMOIMMEMMEMINIMMEMMEMMINI
4.0 MEMMEMERMINIMINIMMEMMEMMEMM
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 117013E015
Rev. 2

FIGURE 7

EFFECT OF REACTOR
PRESSURE ON C 5 + LV% YIELD
GOOD FOR
1. FULL BOILING RANGE STRAIGHT RUN NAPHTHA
2. AVERAGE REACTOR PRESSURE 8.5 TO 42.0 kg / cm 2
(125 TO 600 psig)

4.0
IIIIIIIIIIIIIIIIIIIIIIII1
1111111111111111111111111
InoImilmommoIErna INFA
3.5
MMEMMIIMINIMMINIM IIIMMETMEM
MOMMIIMMO MM. MOW 30
MI MOM
MI WM IMO MMOMM 1.4. 40

N + 2A, LV°/o
E 3.0 mmEMMIWAvA
MOMMOMMEMMOMMOMMINWAINV 50
MINIMMOMMEMOMMTIMITAFA
90.4
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cc
2.5 1111111111.1111 Lb Ad 70

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9

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0
80 85 90 95 100 105
C 5 RONC
UOP 19IR

- 23 -
 117013F.015
Rev. 2

FIGURE 8
EFFECT OF F-1 CLEAR OCTANE
NUMBER ON C5+ LV% YIELD
GOOD FOR
1. FULL BOILING RANGE STRAIGHT RUN NAPHTHA

2. 8.5 kg/cm2 (125 psig) AVERAGE REACTOR PRESSURE

3. R - 30 SERIES CATALYSTS
5
111111111111111111111111111111111111M11111111111
11111111111111111111111M11111111111M1111111111
IN F-1 CLEAR OCTANE NUMBER

4
1 11 11111 1111111111 1111111111 1111111111
3 II 30

11 0 40
1

N + 2A LW/0
2 11111111111111111111111 111111111111111111r 0:4
p ll' 1
50
60

1 11111 1 0 °
1111111 011 I 1111 /1 ,00:00/0 70

,.,,,,,,0,0 /
80

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1
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- 2ri -
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3 NI 3SV3U3NI
 1 17013&015
Rev. 2

FIGURE 10

EFFECT OF REACTOR
PRESSURE ON C5 4- LV% YIELD
GOOD FOR
1. FULL BOILING RANGE STRAIGHT RUN NAPHTHA
2_ AVERAGE REACTOR PRESSURE 8.5 TO 42.0 kg / cm 2
1125 TO 600 psig I

4.0
INIMMEMINIMMIONEMMEMMMOMMEE
OMMEMEMMEMMEMMEMINIMMEMME
MOMMINIMMOMMIIIMMOMMIMM
MOMMIMMIMINME 11111MOMMOMM
3.5
MEMEMMOMmmommE MIMMEMMEM
MEMMIMMIIMMONIMMOMMOMMINI
MMINIMMINMEMEmmommlIMMEMINIMI 30
MMOMOMMEMMAMMIMMEMMOMMVJ
MEMEEMMOMM MO NOMMEEMPAIr 40
MIIIMMEMMEMM Mm immilIMIWAWAI
+ LV% YIELD PER 7 kg / cm 2

3.0
MMEMMEMMEMMMOMMIMMWARINV 50
OMMINIMMOMMIMMEMEMON TO4
MINIMMEMMOMMEMOMINIVA IMF
60
1100 PSI) DECREASE INPRESSURE

MMOMONOMMIMMME mrAm Ar i 70

2.5 mommommommomm rAmilwA.,AN

mummomommorAmpuirr
ImmummolK e imploi
80

rannunpuip,ria.,F A,' .al•A

90

IEIIIMIIIIIIIIIIIP AMMO ...MirasoI

2.0
•0111111111111• WAIIIIIWAInalr, r ANt/
...
IIIIMMIIIMMAMINIIrAwr.m11 ,411 A iso AM
IIMIII ■ il•ip Apo .drAprr
MIIIIIMIMIP:COM
tn

1.5

MOO Am, 0 p._41; mom

dOMMMOVAMITIVWVIMMO
111111111P.IN1110 4 , Ar.d.,,, MEN
INCREASE

ii

1.0 niglIgkOodtirdtP5 011111

r
P rirli
Mi 0"
_Amilip ArAd A•A
—0 de
l°
dildili IN
nd.o......... E. • .
P,I AIP .411 .4 AMMIIINEUMMOM
..no
PP
0.5
illPfa ipp .:IP
_,g111111Ell
P-
mummum
0.1 0 .0.:PA•mml•mommummipl•
doolotalomMMINNOMOMMIMINOM
0 1:11111111111111111111111
80 85 90 95 100 105
C5 RONC
110P 1 546 5
 I17013&015
Rev. 2

Figure 11

RELATIVE DEACTIVATION RATE

HYOROTREATE0 STRAIGHT RUN NAPHTHA
18
17
16
15
14
• 13
12
o 11
10
9

O a

3 6
• 5
4
3

1
0
78 80 82 84 88 88 90 92 94 96 98 100 102 104 106

C5+ RONC

def e t i„•

r Y f► t .. ha 1 1)

if eL t(fele.
E

- 27-
 1170136015
Rev. 2

FIGURE 12

RELATIVE DEACTIVATION
RATE
HYDROTREATED STRAIGHT
RUN NAPHTHA

1.6

1.5

1.4
I
1.3
RELATIVE DEACTIVATION RATE

1.2

1.1

1.0

0.9

0.8

0.7

0.6

0.5
30 40 50 60 70
UOP 1539 9
N + A RV %)

o 4
I .
) fl 4 ,4 / A

- 28 -
 117013&015
Rev. 2

FIGURE 13
RELATIVE DEACTIVATION
RATE
HYDROTREATED STRAIGHT
RUN NAPHTHA
1.6

1.5

14
RELATIVE DEACTIVATION RATE

13

1.2

1.1

1.0

0.9

0.8

0.7

0.6

0.5
149 160 171 182 193 204
(300) (320) (340) (360) (380) (400)
ASTM ErC ("F)
 117013&015
Rev. 2

FIGURE 14

RELATIVE DEACTIVATION
RATE
HYDROTREATED STRAIGHT
RUN NAPHTHA
2.6

2.4

2.2

2.0
RELATIVE DEACTIVATION RATE

1.8

1.6

1.4

1.2

1.0 •

0.8

0.6

0.4

0.2

0
7.0 14.0 21.0 28.1 35.1 42.1
(100) (200) (300) (400) (500) 1600)

AVERAGE REACTOR PRESSURE, kg / cm 2 (psig)

1,r P
.
- Z 0 t -0 ei

- 30 -
 117013&015
Rev. 2

FIGURE 15

RELATIVE DEACTIVATION
RATE
HYDROTREATED STRAIGHT
RUN NAPHTHA
2.5

2.4

2.3

2.2

2.1 -O. • •■■•••■••••••

2.0
RELATIVE DEACTIVATION RATE

1.9

1.8

1.7

1.6

1.5

1.4

1.3

1.2

1.1

1.0

0.9

0.8

0.7
4.0 5.0 6.0 7.0 8.0
H 2 / HC MOLE RATIO
J y- 19 t 1, /a ru
--1 , UOP 1S48
f•-#

S, 0 iv 'I.0 f/ )./ r. I.
IC I e-
- 31 -
 117013&015
Rev.

FIGURE 16

EFFECT OF C5+ RONC ON

RELATIVE COKING FACTOR
HYDROTREATED STRAIGHT RUN NAPHTHA

2.4

2.0
RELATIVE COKING FACTOR

1.6

1.2

0.8

0.4

0.0
96 98 100 102 104
C5 -4- RONC
UOP 391 9
 FIGURE 17

EFFECT OF N + A ON RELATIVE
COKING FACTOR
HYDROTREATED STRAIGHT RUN NAPHTHA

1.6

1.4
RELATIVE COKING RATE

1.2

1.0

0.8

0.6
30 40 50
N -4- A, LW/0
•
117013&015
Rev. 2

FIGURE 18

EFFECT OF CHARGE ENDPOINT

ON RELATIVE COKING FACTOR
HYDROTREATED STRAIGHT RUN NAPHTHA

1.4

O 1.2

2
O

0.8

0.6 1
BASIS: IBP 82°C (180'F)

0.4 I

149 160 171 182 193 204

(300) (320) (340) (360) (380) (400)
ASTM EP °C (T)
U0 P 39111
 117013&015
Rev. 2

RGURE 19
EFFECT OF AVERAGE REACTOR
PRESSURE ON RELATIVE COKING FACTOR
HYDROTREATED STRAIGHT RUN NAPHTHA

0 0

75 MO 125 150 173 200 223

(5.27) (7.1113) 11.79) (10.55) (12.30) (14.06) (15.82)
2
AVERAGE REACTOR PRESSURE, psis (kgiem )

inor i2or
roy. 15:54
 117013&015
Rev. 2

FIGURE 20
EFFECT OF H2/HC RATIO ON
RELATIVE COKING FACTOR
HYDROTREATED STRAIGHT RUN NAPHTHA

4.4 •

4.0

3.6

cc
• 3.2

Le
O
Ni

L4

2.0

1.5

1.2

ILI

IA
1.0 1.5 2.0 2.5 30 40 4.5 5.0
HYDROGEN HYDROCARBON
mol• ratio
H2HC RATIO = COMBINED FEED H2HC RATIO + O.T•H2 NET GAS MOL RATIO
(H2 NET GAS MOL RATIO IS BASED ON FRESH FEED)
u0P t2410-2

-36-
 117013E015
Rev. 2

FIGURE 21A
TOTAL HEAT OF REACTION
FROM TOTAL DELTA T

N1111
ENGLISH UNITS
260

240
1, IL
IIq
H 2 / HC
• 220

r-

GQ 200

u
w cc 160
OC kai

Of 160
W I
X a-
(
z
140
00
H
120

co
100
-

11 0
60 70 80 90 100
MOLE % HYDROGEN IN RECYCLE GAS
,f1. r 1

FIGURE 218
MOLECULAR WEIGHT CORRECTION
TO HEAT OF REACTION
ENGLISH UNITS

+ 40
PARAMETER

g I -4
+20 HR / 100 °F QT

g!!
C0•
100
0 113,
B . 150
200
10 -20
260
100 120 140
CHARGE MOLECULAR WEIGHT

- 37 -
 117013F.015
Rev. 2

FIGURE 22A
TOTAL HEAT or REACTION
FROM TOTAL DELTA T
METRIC UNITS
1100

1000

I-

!go
z 0
0
800
•8

• W
8. 700
1-

ax
IU

_1 Q.
2I
600
4
W
0 ha,
▪ 0
• SOO

.st

400

300 -
81170 80 40 ¶00
MOLE "; HYDROGEN IN RECYCLE GAS

FIGURE 22R
MOLECULAR WEIGHT CORRECTION
TO HEAT OF REACTION
METRIC UNITS
100

160
1-
4E
X 120 PARAME 1F11
HR 100 C.2‘,3
Z
O 6.4. in
• o
CI71
1.14 „ 40
° 0
0 v. o 0
V 400
-", w. - 40 800
a
600
-80
1000

100 170 140

CHARGE MOLECULAR WEIGHT

- 8 -
 UOP Inc.
Des Plaines, Illinois
United States cA America

UOP PLATFORMING PROCESS

PROCESS FLOW

This material is UOP Inc 's technical information of a confidential nature for use only by personnel
within your organization requiring the information. The material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc and
except as authorized under agreements with UOP Inc

I
PLATFORMSINII
 117013

PROCESS FLOW SCHEMES

I NTRODUCTION

The reactions that take place in the UOP Plat forming Process are
mostly endothermic (require heat input), and must occur at
elevated temperatures in a hydrogen atmosphere to obtain optimum
catalyst life and product yields. If the conditions are unfavorable,
product yields and/or catalyst life will be poor. Unit designs vary
depending upon processing conditions, optimum capital invest-
ment, desired yield structure and operating costs (based on infor-
mation projected at the time of the unit's design).

The basic components of Platforming are shown in Figure 1: a

naphtha feedstock, hydrogen (for the hydrogen atmosphere), a
heat source (for the elevated temperature and endothermic heat of
reaction), a reaction vessel and some sort of product separation
device. To make this basic configuration workable and economical,
a number of changes need to be made to Figure 1, and the result is
a typical commercial flow scheme shown in Figure 2. The changes
made are: (1) provide cooling and separation of reactor products
to allow hydrogen to be separated, and recycled by a compressor;
( 2) combined feed-reactor effluent heat exchange is provided to
reclaim heat from the reaction products; (3) the heat input and
reaction chambers are separated to provide optimum usage of the
catalyst with respect to reaction temperature; and (4) product
stabilization is provided to remove light cracked products from the
gasoline or aromatic concentrate product.

FIGURE 1
BASIC PLATFORMING PROCESS
REQUIREMENTS

HEAT
HYDROGEN
AND
OTHER GASES

HYDROGEN
LEGEND
NAPHTHA
RV = REACTION VESSEL
PS = PRODUCT SEPARATOR

PLATFORMATE

D-3

uop
 117013

FIGURE 2

CONVENTIONAL PLATFORMING

CH 114 IH

COMBINED
FEW-REACTOR
CHARGE EFFLUENT
EXCHANGER

RECYCLE
EFFLUENT
LEGEND COMPRESSOR
CONDENSER
CH = CHARGE HEATER
I H = INTERHEATER
R = REACTOR
SEPARATOR
NET
SEPARATOR
GAS SEPARATOR LIQUID
TO FRACTIONATION

Reactor Section Variations

Some variations were utilized at various stages of the development

of the Plat forming process. One common variation is to use reactor
effluent to reboil either the hydrotreater stripper, the Platformer
stabilizer or both (See Figure 3). The reactor effluent-stripper
reboiler system was dropped when it became necessary to have the
charge to the Platforming unit completely stripped before charging
it to bimetallic Plat forming catalyst. 1 his could not he accom -
plished without a fired reboiler on the stripper. 1 he reactor
-
effluent -
stabilizer reboiler has been de emphasized because (1) a
fired reboiler and a single pass combined feed exchanger are more
efficient than the mixed scheme, and (2) there is considerably
more reactor section pressure drop which has become a major
concern on new lower-presure
 117013

FIGURE 3
REACTOR EFFLUENT REBOILING

LAST
REACTOR DPIC

COLUMN
REBOILER COLUMN
TO
CHARGE
HEATER
TRC

FRC
COMBINED
FEED
41P0 I

TO SEPARATOR

A more recent variation in process Flow is the dual separator

system (see Figure 4). As new Plattorming catalyst developments
allow lower and lower operating pressures, the recycle gas gravity
tended to rise as the pressure was decreased, due to lower flash
pressure at the reactor products separator. This increased the
load on the recycle compressor (more gas to compress for the same
11 2 /IIC ratio), and on the heating and cooling equipment (more mass
flow to heat and cool). It also increased the duty on the fractiona-
tion system since there was more hydrogen with respect to the
amount of light ends in the separator liquid, which required
additional reflux and reboiling. Recontacting the recycle gas and
the separator liquid at the pressure of the recycle compressor
discharge and then cooling and reseparating gives a single stage of
absorption, which reduces the amount of heavier material in the
recycle gas. !he possible drawbacks are that additional energy is
required for the recycle compressor (more presure drop), and an
additional pump and cooler are needed. As energy, product, and
interest ( on investment) values have changed, the break-even
point for a dual separator system has varied as well. At present,
energy and investment considerations generally limit dual
separator systems to units with the compressor suction pressure
below 14 kg/cm 2 (200 psig) and above 8.8 kgicm 2 (125 psig).
Other variations of the dual separator system have been used in
special instances. One of these contacts only net gas with the low
pressure separator liquid, another contacts only recycle gas with
the low pressure separator liquid.

I) ',

UOP Inc
 117013

FIGURE 4

DUAL SEPARATOR SYSTEM

RECYCLE
GAS

• ■tio NET
■•■ +I
SEPARATOR
GAS
RPC

LPS HPS

REACTOR EFFLUENT
FROM COMBINED
FEED EXCHANGER TO
STABILIZATION
FACILITIES

LEGEND
HPS HIGH PRESSURE SEPARATOR
LPS —IOW PRESSURE IOR INTERMEDIATE) SEPARATOR
RC RECYCLE COMPRESSOR
RPC= REACTOR PRODUCTS CONDENSER

A major change in the flow scheme was the introduction of

continuous catalyst regeneration, or CCR as it is often called. The
hydrocarbon side of the process flow was not changed significantly
( see Figure 5); the process flow still passes through the reactors
in the same manner, although some or all of the reactors are now
stacked one on top of another. Figure 5 shows the internals of a
typical stacked reactor set up for CCR. As shown in Figures 7, 8,
and 9, the hydrocarbon flow is radial, as in a conventional radial
flow reactor. Fiyure 10 shows the catalyst flow path. The
catalyst is removed in a number of frequent small batch operations,
is regenerated in a separate vessel, and is put hack into the
reactors. The result is that the catalyst performs, continuously,
as though it is near start-of-run condition. This means that
operating temperatures are lower, and more importantly, yields
are near start-of-run yields at all times. The use of a CC H section
also allows continuous operation in which normal cycle lengths
would be too short to be practical without massive expenditures
for equipment, catalyst, and energy.

LOOP Inc
 FIGURE 5
PLATFORMING WITH CONTINUOUS
CATALYST REGENERATION
N•M•MMM.M)k ...s.

T
/ N
COMBINED
FEED-REACTOR
EFFLUENT
CH 1--
r- \ r 1 1

EXCHANGER

CHARGE
r
RECYCLE SR
COMPRESSOR 0 EFFLUENT
CONDENSER

LEGEND
CH - CHARGE HEATER
NET 1 = I NTERHEATER
SEPARATOR
SEPARATOR SR = STACKED REACTORS
LIQUID
GAS

D?
 FIGURE II
CCR PLATFORMER
REACTOR DESIGN

REACTOR 2
FEED

RUNWAY
REACTOR I
EFFLUENT

CATALYST
TRANSFER
PIPES

REACTOR 2

I
CATALYST
ENACTOR WALL

CENTER
PIPE
TER BARRET
OA SCALLOP

CONES FOR CATALYST

-FLOW CASTRIBUTION

REACTOR 2
EFFLUENT
 FIGURE 7
CCR PLATFORMER
HYDROCARBON FLOW
I NTO REACTOR

D•9
 FIGURE $

CCR PLATFORMER
HYDROCARBON FLOW
THROUGH CATALYST

D•10
 FIGURE
CCR PLATFORMER
HYDROCARBON FLOW
OUT OF REACTOR

n 11
 FIGURE 10
CCR PLATFORMER
CATALYST FLOW

0.12
 1171113

Figure 11 shows a simplified flow diagram of the CCl2 section.

After nitrogen purging, the catalyst is transferred from the last
reactor to the regeneration tower. In the regeneration tower,
carbon is burned off and the catalyst is oxidized. The catalyst is
nitrogen purged and transferred to a reduction zone at the top of
the first reactor. This simple cycle completes the regeneration.
The entire procedure is monitored and controlled by a logic system
which prohibits the mixing of oxygen and hydrogen (or hydrocar-
-
bons) through a series of lock out and purge procedures and
analyzers. Variations are available to allow catalyst transfers to
and from an additional reactor or an additional stacked reactor unit
or to allow regeneration of catalyst from a separate conventional
Plat forming unit.

FIGURE 11

_
PLATFORMING CATALYST
REGENERATION SECTION
DISENGAGING
REDUCTION HOPPER — DUST o
ZONE —N COLLECTOR-'

REGENERATION LIFT GAS

TOW ER— N BLOWER
PLATFORMING
REACTORS—vo — Y:4

CATALYST
. — FLOW
LIE, LINES
CON I ROL
HOPPER

i
CATALYST
SURGE
COLLECTO
HOPPER
LOCH
LOCK HOPPER

,
/ HOPPER NO. 2 -s.
LIFT
NO. I LIFT
ENGAGER
NO. 7—E;IGAGER
NO. 2

NITROGEN
LIFT GAS — HYDROGEN
LIFT GAS
 117013

Other Variations

The preceding discussions were concerned with the reaction

section. There are a number of pre and post reaction fractionation
schemes, ranging from no prefractionation and basic Platformate
stabilization (Figure 12) to feed splitting and Plat formate
debutanizing and splitting (Figure 13). Figure 14 lists other
variations which may enter into the flow scheme.

FIGURE 12

FEED AND PRODUCT HANDLING

BASIC FLOW SCHEME
HYDROGEN RICH
GAS - GAS
NAPHTHA

PLATFORMER
REACTOR
SECTION

PLATFORMATE
 117013

FIGURE 13

FEED AND PRODUCT HANDLING

COMPLEX PROCESS FLOW SCHEME

Cs - HYDROGEN H S+ HYDROGEN LIGHT

RICH GAS
2
RICH GAS PLAT FOR MATE
C3
• •

HYDRO- ST SP PLATFORMER O SP
NAPHTHA ...lir TREATER
REACTOR
REACTOR
SECTION
SECTION

CCR

LEGEND
HEAVY
P = PREFRACTIONATOR PLAT FOR MATE 4
ST = STRIPPER
SP - SPLITTER
D = DEBUTANIZER
CCR .• CONTINUOUS CATALYST
REGENERATION

FIGURE 14
OTHER PROCESS FLOW OPTIONS

• NUMBER OF REACTORS (3, 4 OR 5)

• PARALLEL REACTORS
• PARALLEL REACTOR SECTIONS (COMMON PRE / POST REACTOR SECTIONS)
• LOW PRESSURE-DROP PLATFORMER RECYCLE GAS CIRCUIT
• OFF-GAS COMPRESSION FOR OTHER USERS
• OFF-GAS TREATING CONSISTING OF
— ABSORBER IS)
— ADSORBER (S)
— CHILLERS
— REFRIGERATION FOR HYDROGEN PURIFICATION AND / OR
PRODUCT RETENTION
• LIGHT ENDS FRACTIONATION TO PRODUCE
iC 4
C 4's
C3
C2-
SEPARATELY ''L

• RERUNNING PLATFORMATE FOR ENDPOINT OR COLOR CONTROL

• PLATFORMATE TREATING FOR DOWNSTREAM PETROCHEMICAL PROCESSING

UCIP Inc
 117013

Control Systems

Most of the control schemes used in a Plattorming unit are easy to

understand. Most are either straight XRC loops or XRC reset by
YRC loops, where X and Y are generally . 1 (temperature), (pres-
sure), F (flow), or L (level).

one system which is sometimes difficult to understand is the shut-

down system for heater firing. Figure 15 shows the general design
of the most recently adopted system. I n general, the heater firing
is stopped automatically if: (1) recycle gas flow (in a reactor
circuit) or reboiler circulation flow (in a reboiler) is lost on two
separate orifice meters; or if (2) pilot gas pressure drops below a
safe level. In addition, if atomizing steam is lost, fuel oil firing
will be stopped. If low process flow or low atomizing steam
pressure shuts down the firing, the pilots will remain on, but if low
pilot gas pressure occurs, the pilot gas supply will also be
isolated. All of the solenoid valves used must be manually reset to
avoid problems which could be encountered if they were to be
reset by the panel operator.

FIGURE 15
HEATER SHUTDOWN SYSTEM
r
FUEL GAS TO BURNERS
FUEL GAS
PIAL
PILOT GAS TO PILOTS

HEATER
FUEL OIL TO RURNERS
r- - 1
ATOMIZING STEAM
0
RETURN +•■■••1 TO BURNERS
11---
1
9I r• ■••
1

FUEL OIL
SUPPLY

ATOMIZING
STEAM

LOW FLOW SHUTDOWN

PROCESS STREAM ♦-.1 R

1)-16
 117013

Another complex control system is often the Platforming reactor

section pressure control system. If the control is not a straight or
split range system PRC (pressure recorder controller), the system
is usually one of these shown in Figures lb through 18. In Figure
16 there is a booster compressor between the Plat former and hydro-
treater with a PRC on the Platformer separator and a PRC on the
hydrotreater. The sequence of events is as follows: (1) as pres-
sure on the hydrotreater rises, the hydrotreater PRC opens valve
3 to control the pressure; (2) as pressure on the hydrotreater
falls, its PRC will close valve 3 and when valve 3 is fully closed
will attempt to close valve 2; (3) as the Platformer pressure rises,
its PRC will attempt to close valve 2, and if the pressure still
rises, will open valve 1. The signals from each PRC to valve 2 are
compared by a low signal selector, which chooses the lowest signal
to actuate valve 2. The purpose of this arrangement is to keep the
booster compressor compression ratio at or below the normal ratio.
As it operates, the system will let the hydrotreater pressure fall
off if there is not enough gas to supply its requirements, while
holding the Platformer pressure steady. Excess gas will he vented
from the hydrotreater if the compressor capacity is greater than
the gas production, or from the Plat former (or the Plat former and
hydrotreater) if the compressor capacity is less than the
production.

FIGURE 16

PRESSURE CONTROL
SCHEME I

SPLIT SPLIT RANGE

RANGE

BOOST ER PRC
PRC COMPRESSOR

LOW SIGNAL
SELECTOR

LEGEND
S SEPARATOR
H = HYDROTR EATER
 117013

Figure 17 shows the same type of system for a dual separator

Platformer. In cases where no flow is expected from valve 1, the
line comes from the low pressure separator. If flow is normal for
valve 1, the line comes from the high pressure separator. The
reason is that it is desirable to vent from the low pressure
separator in the case of an upset (loss of recycle compressor,
pressure surge, etc.), but if a constant stream is to be vented,
less C5 plus material will he vented in the gas from the high
pressure separator than in the gas from the low pressure
separ ator.

FIGURE 17
PRESSURE CONTROL
SCHEME II

SPLIT RANGE ilo• FUEL GAS

RECYCLE ROOSTER
PRC
COMPRESSOR COMPRESSOR

* 101 TO HYDROTREATER

L_. — FROM HYDROTREATER

PRC

H PS
O \-- LOW SIGNAL
SELECTOR
'40' RECYCLE
LEGEND GAS

LP'S... LOW PRESSURE SEPARATOR xrcru 2

HPS HIGH PRESSURE SEPARATOR

 117013

Figure 18 shows a system similar to the one shown in Figure 16,

but for a multi-stage booster compressor. Each stage is protected
from an excessive compression ratio, just as in the system shown in
Figure 16.

FIGURE 18
PRESSURE CONTROL
SCHEME III

BOOSTER COMPRESSOR SPLIT

SPLIT RANGE
RANGE )
PRC
PRC
STAGE 2 ,PRCEi ( 11
STAGE 1 .1
H -4) 4•—*
1

SPLIT —LOW SIGNAL

RANGE SELECTOR
LOW
\--

SIGNAL
.7 SEPARATOR
(FOR THREE OR MORE STAGES,
LEGEND DUPLICATE AS REQUIRED)
S - SEPARATOR
H-HYDROTREATER
 117013

One other unusual control loop may he encountered on reboiler

control systems (see Figure 19). This utilizes a PDRC (pressure
differential recording controller) to control reboiler heater firing
instead of a TRC (temperature recorder controller). The reason
for using a PDRC is that in some cases there is a very small
temperature increase across the reboiler. In this case, an absolute
temperature setting would not give good control. The PDRC is
utilized to control the amount of vaporization occuring in the
reboiler, rather than the temperature. This system will work
regardless of the temperature rise across the heater, but it is not
often used, unless it is necessary, due to the higher cost of the
installation compared to a TIC.

FIGURE 19
REBOILER FIRING CONTROL

PDRC
TR

REBOILER
PUMP

LEGEND
FUEL
PRODUCT C = COLUMN
RH - REBOILER HEATER
 ABSORBER SYSTEM
NET GAS

PRC

30
4 NET SEPARATOR GAS
LRC
DEBUTAN1ZER GAS

r-1 FR
LEGEND
A = ADSORBER

FRESH FEED FEED TO NHT

UOP 673-13

D-21
uoP Irv,
 RECONTACT DRUM
- -- 1
PRC
I
I
I

I
I
NET GAS FROM I
COMPRESSORS
I1
FR
E) 1
_I
PUMPED -

SEPARATOR
LIQUID LC
I
1
NET
I GAS
1

LIQUID TO
DEBUTANIZER
U04' 673- 34
.77

CHILLED RECONTACT/ABSORBER
TO
PULL OAS
r-

FR

TO FRACTIONATION

REFRIGERATOR
UNIT

FROM 30 LC
BOOSTER
COMPRESSORS

2.) 14
HYDROGEN TO
NATITHA USERS
HYDROTREATER
1 t ( ;,

SEPARATOR
LJOIND

LEGEND
• ABSORBER
=
F = FLASH DRUM
= SEPARATOR
 THE MECHANICAL
ASPECTS OF
PLATFORMING

I. CORROSION

II. INSPECTION
III. SPECIAL MAINTENANCE PROCEDURES FOR EQUIPMENT
PROTECTION AND CLEANING

IV. MECHANICAL EVALUATION TEST PROCEDURE

I. CORROSION
Corrosion is not a serious problem in most Platforming units. However, it is im-
portant to continually check for the unsuspected elements which might cause corrosion
and shutdowns. There are recent developments in the philosophy of maintenance, equip-
ment inspection, and corrosion prevention, and these are discussed in detail.

The original Platforming units were put into operation over 25 years ago, charging
untreated naphtha. The sulfur levels in the charge to some of these units required that
recycle gas scrubbers (Girbotol scrubbers) he utilized to remove hydrogen sulfide from the
recycle gas. The recycle gas in these units was saturated with water and also contained
sulfur and nitrogen compounds, all of which promoted fouling and corrosion. The
metallurgy was upgraded to combat the corrosion, and this helped a great deal. The in-
creased demand for higher octane gasolines led to the development and use of better
catalysts, but the new catalysts required a "cleaner" feedstock to perform as desired. The
answer was feed hydrotreating. Hydrotreating not only removed essentially all of the sulfur
and nitrogen in the charge, but also the arsenic, lead, copper, sodium and other metallic
contaminants. In addition, the hydrotreater product strippers were designed to minimize
the water content in the charge. Since most of the contaminants were now being removed
from the charge, the bulk of the remaining corrosion problems were elminated.

The remaining area which is still subject to corrosion in "wet" units is the
Stabilizer overhead system. This area (both the column and the overhead receiver) is sub-
ject to hydrochloric acid corrosion, usually in the bottom half of the overhead receiver and
in the top few trays of the stabilizer. One method used to combat corrosion in this area is
to inject water into the overhead vapor line, and add ammonia (if necessary) to control the
drawoff water at 6 to 7 pH.

Table 1 shows the materials commonly specified for various services in Plat-
forming units. If a particular unit is different, a review of the unit should be made before or-
dering replacement equipment to make sure that the original specifications are still valid.
 Table 1

Materials of Construction

ASTM
Material Specifications

Heater Tubes
Conventional 2 1/4 Cr-1 Mo A-335 Gr P22
A-199 Gr T22
A-213 Gr T22
Low Pressure Drop 9 Cr-1 Mo A-335 Gr P9
A-199 Gr T9
A-213 Gr T9

Reactors
Hot Wall 1 1/4 Cr- 1/2 Mo A-337 Gr 11

Cold Wall C 1/2 Mo

- A 204 Gr A/B/C
-

Internals (hot and 18.8, Type 316 A-240 TP 316

cold wall) Type 321 TP 321
Type 347 TP 347

Combined Feed-Reactor
Effluent Exchangers

Above 450T (850° F) 11/4 Cr-1/2 Mo A-387 Gr 11

A-199 Gr T11
A-213 Gr T11
1 Cr-1/2 Mo A-387 Gr 12
A-213 Gr 12

290-450T (550-850°F) C-1/2 Mo A-204 Gr NEM

A-209 Gr T1
Mn-1/2 Mo A-302 Gr B

Below 290T (550°F) Killed Carbon Steel A-515 Gr 55-70

A-516 Gr 55-70
A-179

Expansion bellows in Inconel 600

single pass Incoloy 800
exchangers Inconel 825
RA 330

Reactor Circuit Piping 1 1/4 Cr-1/2 Mo A-335 Gr P11

Mesh Blankets Monel

Trays (caps and trim) 11.13 Cr A-240 TP 410

J4
 SOURCES OF HCL
SEPARATOR GAS

NET GAS TO FUEL GAS

( HCL)

NET GAS
TO HYDROGEN
USERS IHCL)

RECYCLE
GAS

SEPARATOR

SOURCES OF HCL
STABILIZER OVERHEAD SYSTEM

go. OFF GAS

TO FUEL
( HCL ►

0 NET OVERHEAD
LIQUID (HCL)

J-4a
 FUEL GAS CORROSION

WET
HYDROGEN H2 S
AMMINE FUEL GAS
FROM TO USERS
OTHER SOURCES AMMONIA
• HCL
• IRON SULFIDE
NET GAS TO • IRON CHLORIDE
FUEL GAS • AMMONIA SALTS
( HCL) • WATER

STAB. OFF GAS

( HCL) FUEL GAS
MIX DRUM

FUEL GAS CORROSION

PROBLEMS:

• PILOT CORROSION
• BURNER CORROSION
• REFRACTORY CORROSION
• SALT PLUGGING OF SHUT OFF VALVES,
CONTROL VALVES,
PILOTS,
BURNERS

SOLUTIONS:

• WATER OR DILUTE CAUSTIC WASH OF FUEL GAS

• STEAMING (WET) OR WASHING OF FUEL GAS HEADERS
• FREQUENT INSPECTION b CLEANING „•

J ab
NET GAS TO HYDROGEN USERS

OFF GAS
ONCE THRU WET, H2S
NET GAS
( HCL) HDS RX
0.1
SECTION oc

WATER •Z=,
WASH SEPARATOR

• NORMALLY NO CORROSION PROBLEMS

NET GAS TO HYDROGEN USERS

RECYCLE GAS HDS ** NET GAS CORROSION
MAKEUP PROBLEMS
WATER ( HCL)
WASH

HDS RX
SECTION

NET GAS SEPARATOR

MAKEUP
WICL) RECYCLE GAS 10•■••

* NORMALLY NO CORROSION PROBLEMS

* * SOLUTIONS:
• RELOCATE NET GAS MAKEUP ADDITION POINT
• WATER WASH NET GAS

J -4c
 HYDROGEN (FUEL GAS)
CORROSION POSSIBILITIES
NET GAS
Ow HYDROGEN USERS
(HCL)
— NORMALLY NO CORROSION PROBLEMS
BOOSTER
COMPRESSOR(S)

NET GAS
HYDROGEN
( HCL) USERS
BOOSTER
COMPRESSORS)

POSSIBLE CORROSION POSSIBLE CORROSION

HYDROGEN FROM ALTERNATE HYDROGEN

OTHER SOURCES FROM OTHER SOURCES

SOLUTIONS: WATER WASH NET GAS

HYDROGEN (FUEL GAS)

CORROSION POSSIBILITIES

NET GAS sir GAS TO

( HCL) FUEL ( HCL)

HYDROGEN FUEL GAS

HEADER HEADER I POSSIBLE
POSSIBLE
CORROSION CORROSION

J-4d
 NET STABILIZER
OVERHEAD LIQUID
NET OVERHEAD LIQUID
( HCL)
► TO LPG RECOVERY
(POSSIBLE CORROSION)

SOLUTIONS

• PROVIDE CORROSION PROTECTION IN THE

OVERHEAD SYSTEMS OF THE LPG
RECOVERY SECTION
• WATER OR DILUTE CAUSTIC WASH THE NET UQUID

DEPOSITION OF AMMONIA SALTS

NET GAS
CONDENSER

TRIM
COOLER RECYCLE
PLATFORMER COMPRESSOR
REACTOR
EFFLUENT
SEPARATOR
RECYCLE GAS
SOLUTIONS:
WASHING OF EQUIPMENT PRIOR TO
REGENERATION OR BEFORE OPENING
EQUIPMENT FOR UNIT TURN AROUND AM SALT DEPOSITS

J.4
 DEPOSITION OF AMMONIA SALTS
STABILIZER OVERHEAD SYSTEM

.• OFF GAS

b. NET OVERHEAD
LIQUID
SOLUTIONS
• WASHING OF EQUIPMENT BEFORE
OPENING FOR UNIT TURN AROUND
?4Q.1.4, SALT DEPOSITS
• ON STREAM WATER WASH

ON STREAM WATER WASH /, =•

• ■••• OVH
SYSTEM
OF STABILIZERS 4 REFLUX

T
O RECYCLE +
NET GAS

(SEPARATOR

40•-•• FROM
REBOILER

WATER
WASH
MPS SALT
DEPOSITS PLATFORMATE 4 TO
REBOILER
• WASH WATER INJECTED IN SMALL AMOUNTS TO AVOID
COLUMN UPSETS. WATCH COLUMN tP ITOP/BOTTOMI
• WASH WATER WITHDRAWN AT OVERHEAD RECEIVER OR
TAKEN OUT IN NET LIQUID
COLUMN OVERHEAD CORROSION
PROTECTION SYSTEM
WATER
TANK

----
::-_,3
•••- AMMONIA
I NJECTION

s OFF GAS

/ \
NET
OVERHEAD
LIQUID 1 00' WATER DRAW
 II. INSPECTION

Although there are many factors which contribute to long operational runs and
plant safety, preventive maintenance is probably the most important one. A proper and
thorough plant Inspection not only results In extended run lengths and maximum safety,
but also greatly reduces the probability of unscheduled shutdowns. An unanticipated
emergency shutdown can be extremely costly, particularly if accompanied by a loss of
property and prolonged Interruption to continued operations.

To avoid these emergencies. UOP recommends periodic preplanned inspections

of the Platforming unit, together with a periodic re-education of operating personnel to en-
Sure that they are kept continually aware of the potential hazards of misoperation.

A good, well recorded inspection enables the refiner to determine equipment

corrosion rates and, subsequently, to develop life expectancy information,

A well planned inspection program pays off in many other ways as well:

1. It helps maintain employee morale through the knowledge that management

is giving them added protection.

2. It is a major line of defense against fires and explosions.

3. It provides a way to anticipate material requirements for maintenance and

repair, thereby enabling the refiner to keep his warehouse inventory at a proper level.

4. It permits stocking major renewal equipment not usually stocked, and which
normally may require a long delivery time, so that they will be on hand for prompt in-
stallation when needed.

5. It provides information (through inspection records) for economic studies with

respect to the use of more expensive but longer lasting materials.

6. It permits intelligent preplanning for turnarounds, thereby reducing downtime

and turnaround costs.

Many refineries run various types of charge to their Platformers, and many ti mes
the charge is of an unknown quality in regard to content of corrosives. Many types of
chemicals used today for well treatment are retained in the crude, and where these
chemicals become corrosive, if they do, is not known until It Is too late. Chemicals used in
cleaning units while on stream can also become corrosive under certain conditions.

During a turnaround, normal planning usually does not include sufficient time for
preparation and inspection of piping systems. Normally, after all other equipment has
been opened, cleaned, and inspected, the inspector then finds time to start checking the
piping system, usually by ultrasonic instruments.

The proper inspection of all piping during a turnaround can be carried out only if a
full inspection crew and sufficient maintenance personnel are available. To overcome the
need for large manned groups during a turnaround, it is recommended that a thorough
piping inspection be made prior to the turnaround.

J-5
 Some time prior to a scheduled turnaround, a thorough thickness check should
be made of all process piping in the unit (within temperature limitations). This will require
less personnel, both inspectors and maintenance people, than performing the inspection
during the shutdown. A program of making holes in insulation and moving ladders can be
done by only two men on a normal working day basis. Also, ladders are more readily
available and can be placed where required, and scaffolding can be erected without in-
terferring with other work which normally takes place during a turnaround.
A far larger number of check points can be made when the inspectors and main-
tenance personnel have only piping to check. During an on-stream piping Inspection, many
other important conditions can be noted, and in many cases, rectified prior to the turna-
round.

1. Thin piping can be scheduled for replacement and most of the fabrication can
be completed before the shutdown.

2. Leaking flanges and valves can be identified and scheduled for repairs.

3. Inoperative valves can be scheduled for replacement or reworking.

4. Repair or replacement of poor insulation can be completed either immediately

or can be scheduled for the turnaround. Since scaffolding may be required to check some
piping, the scaffolding can be used to complete repairs of the insulation at the same time.

Consideration of the advantages of an on-stream piping inspection is strongly

recommended. Even if only one important line is scheduled for replacement during the
turnaround, the time saved will more than pay for the time and expense of the inspectors.
In general, there is little corrosion on Platforming units, but a number of areas should be
checked anyway.

The hot alloy piping on Platforming units with hydrotreated feedstocks has been
almost corrosion-free. In a few instances, carbon steel has been installed by mistake in
place of alloy. In each case the carbon steel failed from hydrogen attack in about twelve
months, even though the carbon steel showed no metal loss.

The cold piping downstream of the reactor products condensers and the bottom
of the products separator is vulnerable to hydrochloric acid attack in wet plants. The drains
at the low points of these lines should be watched.

The compressor suction piping should be checked for scale accumulation In

some cases, it has been found necessary to acidize these suction lines to alleviate com-
pressor problems.

In wet units, there is generally corrosion in the stabilizer overhead area (the top of
the column and the overhead receiver) from wet acid (HCI) attack. In dry plants HCI
corrosion has not been encountered, and stabilizer section piping corrosion has been
essentially nil.

J6
 A. Heaters

There is a large number of items to be inspected in the heaters during a shut-

down. The more important points are covered below.

1. Firebox Casings: The condition of the firebox casings is very important.

Any openings between panels should be closed. This will prevent failure of the brick or
refractory which in turn would allow moisture and air into the heater. If the panel Joints are
not packed properly, moisture will enter the heater. The heater environment is such that
the moisture becomes acidic, thus causing deterioration of the refractory and corrosion of
the panels and refractory anchors.

2. Refractory: If the refractory is in good condition, it prevents considerable

heat loss. Expansion will cause hair-line cracks, and this is expected, but where large
cracks are present and loose or soft refractory exists. the refractory should be repaired or
replaced.

3. Burners: Burners should be removed and cleaned, and bad burner tips
must be replaced. The burner blocks and ports must be in good condition. Burners should
be kept in alignment to prevent flame impingement on the tubes.

4. Tubes: Experience has shown that the corrosion rate is practically nil on
Platforming heater tubes processing hydrotreated feedstock; however, thickness
measurements should be taken on the tubes during each turnaround to check the rate of
metal loss. Normally, the tubes are checked at each end and at the center on the fire side
using an ultrasonic tester (this is a reliable method for checking heater tube wall
thickness).
The external tube surface should be checked closely to determine whether
vanadium and/or sulfur attack has occurred. If the tubes are covered with oxide or ash, this
should be removed before the tubes are examined. Fine pitting is often an indication of a
fuel oil having a high sulfur or vanadium level.

5. Miscellaneous: The following should be checked:

a. Stack casing, refractory and damper.
b. Tube hangers for vanadium attack.
c. Hanger bolts for proper support of tubes.

B. Reactors

There are two types of reactor vessels employed in Platforming service; cold-wall
and hot-wall. Although hot-wall vessels are usually preferred by our licensees, satisfactory
service may be obtained from cold-wall reactors.

1. Cold-Wall Reactors: The life of the concrete lining in cold-wall reactors is

indefinite. If the concrete is properly installed, only a failure of the alloy fining should have
an effect on the serviceability or life of the concrete. A temperature-indicating paint is a
wise investment because it indicates Immediately when something has gone wrong with
the internal lining. Prompt action and minor repairs often avoid major repairs or
replacement of the linings.

J-7
 In downflow reactors having internal liners, the reactor pressure drop should
not be allowed to exceed design — usually 3.5 kg/cm 2 (50 psi) to prevent liner ruptures.
When a liner ruptures, an unscheduled shutdown with possible extensive repairs is man-
datory.

Type 405 alloy steel lining has been used very successfully in Platformer
reactors where the charge stock is hydrotreated. Corrosion of Type 405 alloy lining has
been encountered in units operating on non-hydrotreated feedstocks. This material has
been replaced with Type 321 or 347 and no further corrosion has occurred to the alloy
lining.

2. Hot-Wall Reactors: There is normally no corrosion problem with hot-wall

reactors. in cases where corrosion has taken place, Type 405 alloy strip lining was applied
over the corroded area only.

The bottom heads in the hot - wall reactors may be lined with refractory or fire
brick. This lining is installed to serve as a filler and not as an insulator. It must be installed
in a good manner to prevent catalyst movement into the refractory and coke buildup in it.
There have been cases where poorly installed refractory allowed coke to buildup in the
refractory and force the center pipe out of the socket joint, after which the catalyst
migrated from the reactor.

C. Reactor Section Separator(s)

No serious corrosion is normally found in these vessels. Scale and chloride

deposits accumulate in the bottom of the vessels, so they should be opened and washed
out at each shutdown before regeneration. The mesh blanket or demister pad should be
cleaned as well. The mesh blanket must be installed tightly to insure as dry and as clean a
recycle gas as possible.

D. Combined Feed-Reactor Effluent Exchangers

Combined feed exchangers in Platforming service where the feed is hydro-

treated normally have no serious fouling problems. Scale buildup is very slow, forming on
both sides of the bundles.

One of the biggest maintenance problems on Platformers Is hydrostatic testing

of these exchangers each inspection. The tube bundles should be hydrostatically tested
on the basis of the operating differential pressure between shell side and tube side. On
2
this basis the pressure required would be around 20-30 kg/cm (300.400 psi) and not 140
2
kg/cm (2000 psi) or more.

In some cases, refineries are experiencing exchanger leakage between the tube
sheet and the shell. The cause may be a combination of any of the following factors.:

1. Yielding of bolts due to uneven temperature of thick tube sheets and

flanges, or unequal torquing of the bolts.

2. Temperature differential on each side of the tube sheet causing leaking

flanges.

3. I mproper design of piping geometry .

J8
 E. Reactor Products Condensers

Air coolers are normally trouble-free on the process side. Atmospheric fouling is
sometimes experienced on the external fins. Washing with water or blowing with air has
been effective in cleaning them.

Water coolers are fabricated from mild steel if noncorrosive cooling water is
used. With brackish or salt water as a cooling medium, Admiralty brass is often used. The
process conditions on the product side are normally noncorrosive. Corrosion is possible in
wet units having stagnant traps between the tube bundle transverse baffles. This con-
dition Is avoided when drain "V" slots are provided in the baffles. Many refiners have had
unfortunate failures due to ammonium chloride attack (stress cracking) on Admiralty tube
bundles. Cracks normally occur in the U-bends but can occur anywhere on the tubes. Reac-
tor products condensers constructed of Admiralty brass tubes should be water-flushed
free of chlorides prior to hydrostatic testing with water or before opening to atmosphere.
Ammonium chloride is hygroscopic and atmospheric humidity is enough to produce a very
corrosive condition.

During regeneration, the lower than normal flow rates to air coolers sometimes
result in distribution problems. The basic water circulation used to neutralize HCI during
regeneration may not distribute evenly to all air condenser bundles, and the result is high
corrosion rates in localized areas. In order to eliminate the corrosion problem UOP recom-
mends that the basic water circulation rate be equal to the design hydrocarbon charge
rate, and that the outside bundles of the condenser be blinded off during regeneration (see
Figure 1). It may also be advantageous to turn off the fans, if there is a water trim cooler, to
prevent condensation in the air cooler; since the cooling requirement during regeneration
is only about 30 to 50 percent of the design duty, use of the trim cooler is usually satisfac-
tory.

F. Monet Trim Valves

Early Platforming units were equipped with valves having 12% chrome stainless
tri ms. Reports from these plants indicated stress corrosion and cracking of stainless
plugs and seats in the low temperature section of the plant from the condenser through
the separator and compressors. This was attributed to moisture and chlorides, present in
the charge stock or added for process reasons.

At ambient temperature, the low pH solution which resulted proved to be

somewhat corrosive to low chrome or carbon steel and very destructive to the high chrome
alloys. Replacement of the valves in this zone of the plant with Monel-trimmed valves has
eliminated this trouble.

Since most of today's Platforming units normally operate at much lower recycle
gas moisture levels, 12% chrome valve trims can be reconsidered and used. Even if the
Platformer reactor section is considered dry, the stabilizer overhead may be wet and
corrosive if outside material is fed to this column, as has been done in some instances to
maximize LPG recovery from other unit gases. If this is the case, proper consideration
should be given to the choice of metallurgy in the stabilizer overhead system.

J 9
 G. Condensate and Chloride Injection Points

Corrosion of the injection nozzle and the area of the pipe around the point of in-
jection can be expected to occur when both condensate and chloride are injected together
in the same nozzle. Corrosion has occurred on some units when these materials were in-
jected separately because the nozzles were too close to each other. To eliminate this
problem and a possible fire hazard if connections fail, the chloride is injected into the com-
bined feed at the combined feed-reactor effluent exchanger inlet and the condensate is in-
jected into the hot stream at the outlet of the exchanger.

H. Recycle Gas Compressors

The recycle compressor is the most valuable piece of equipment in a Platforming

unit. When the compressor is properly cleaned, inspected and maintained, It will be
trouble - free for an extended length of time. At all shutdowns, the compressor should be
kept under a nitrogen blanket. Prior to opening the compressor and exposing its internals
to moisture, it should be washed free of acidic deposits. Washing is carried out with a 2%
soda ash solution. Higher carbonate concentrations should not be used because of the
need to avoid damage to any aluminum labyrinths in the compressors. If cleaning
procedures are not adhered to, stress cracking (intergranular corrosion) can be an-
ticipated. The procedures for washing centrifugal and reciprocating compressors are in-
cluded at the end of this section. On centrifugal compressors, traces of chloride deposits
are sometimes still found between the impeller blades when the impellers are removed. A
high pressure Jet of warm water is the best method for a final cleaning.

I. Inspection Schedule

A thorough inspection can save valuable operating time and avoid costly
mechanical failures. Accumulated experience with many Platforming units has allowed
UOP to develop optimum inspection intervals for the equipment.

Table 2 indicates the intervals recommended between complete inspections of

the principal items of equipment in a Platforming unit. Inspections at these intervals will
help ensure the well being of the mechanical aspects of the Platforming unit.
-

J 10
 Table 2

Platforming Unit
Inspection Intervals

Maximum Intervals Between

Inspections, Months
Equipment "Wet Units" "Dry Units"
Heaters 18 30
'Reactors 24 30
Combined Feed Exchangers 18 36
Reactor Products Condensers 18 36
Reactor Products Separator 18 30
Stabilizer Column 18 30
Stabilizer Receiver 18 30
Stabilizer Exchanger and Coolers 18 30
Prefractionator Column 18
Prefractionator Receiver 18
Prefractionator Exchanger and Coolers 18

' From a process standpoint reactors should be inspected for cleanliness every third regeneration or every two years

FIGURE 1

AIR FIN CONDENSER ISOLATION

FOR REGENERATION
REACTOR EFFLUENT
FROM COMBINED FEED
REACTOR EFFLUENT EXCHANGER

1
a
4

Irk
1
_
Tina' IIIIII REGENOERRATION

1
TO TRIM COOLER

J 11
 III. SPECIAL MAINTENANCE PROCEDURES FOR EQUIPMENT
PROTECTION AND CLEANING
A. Compressor Washing

During operation, a fine gray powder-like deposit may collect 011 the internals of
Platforming recycle gas compressors. This material (mostly ammonium chloride salts) is
soluble in hot water. It is non-corrosive when dry, but when exposed to the air it absorbs
moisture readily and becomes corrosive not only to iron and carbon steel but also to all
stainless chrome steels, especially if they have been hardened. For protection of the com-
pressor internals, steps must be taken to avoid contact with air when this deposit is
present. Several precautions will assist in this matter.

For centrifugal compressors, a thorough washing of the compressor internals is

recommended before the machine is opened. Such washing is carried out with a 2% soda
ash solution to which a small amount of non-sudsing detergent has been added. Higher
carbonate concentrations are unsatisfactory because of the need to avoid damage to any
aluminum labyrinths in the compressor. After several such washes have been carried out,
the internals are flushed with clean water, dried and treated with a corrosion inhibitor. The
following details a satisfactory procedure for carrying out this operation:

1. Shutdown; nitrogen purge and maintain a nitrogen blanket on the com-

pressor until ready to proceed with the following steps.

2. Provide sufficient 2% soda ash solution with 0.1 to 0.3% non-sudsing

detergent, such as Calgon, tripotassium phosphate, etc., for at least five washings,
estimated at 150.300 liters (40.80 U.S. gallons) for each washing, at a temperature of
°
25-35
3
C (80-100°F). A pump for circulation of the washing solution should be available. A 3-5
m /hr (10-20 gpm) pump is a convenient size.

3. Break the suction and discharge piping and blind off the compressor.
Make reversing connections to the inlet and outlet drains under the case so that the
solution can be pumped through from either end.

4. Pump the solution slowly into the suction drain connection with the seal
oil circulating system operating as per the manufacturer's instructions, and with the rotor
turning over at approximately 60 to 250 rpm run by an air motor, a small auxiliary motor, or
by a rope wraped around the coupling. In order not to take any chance of accelerating to a
high speed with liquid in the case, do not use the main driver to turn the rotor over. Wash
for approximately ten minutes each time, observing the color and pH of the solution.

5. Drain and replace the wash solution with fresh solution; continue the
washings until there is no change in the solution. Maintain the temperature of the solution
with a steam hose, if necessary.

6. Flush out with clean hot water at 65°C (150°F) for ten minutes; drain and
repeat twice. Remove the drain plugs to the intermediate stages in order to drain all water.
Note: If any discoloration of the drain water occurs, proceed wtih an additional soda ash
treatment.

7. If the compressor does not have individual stage drains, steam it until all
of the case is up to 95''G (20(7'F), and blow with nitrogen or dry air to remove water from
case.

J-13
 8. Provide about 200 liters (50 U.S. gallons) of Platformate with four liters
(one U.S. gallon) of Unicor thoroughly mixed. (For an alternate inhibitor, Gulf Agent 178 or
Kontol 77 may be used.) With the stage drains closed, introduce Platformate through the
suction drain with the rotor turning over slowly. Wash thoroughly for at least 30 minutes
and drain.

9. Remove all blinds and prepare for startup with nitrogen purges, or if an in-
spection is desired, proceed to dismantle the machine and remove the rotor in accordance
with the manufacturer's recommendations.

For non-lubricated reciprocating compressors, the procedure is somewhat dif-

ferent. First, the valves should be freed of salts as soon as they are removed from the
machine. This is done easily by washing the valves in a bucket of hot water which will
dissolve the corrosive powder. The valves can be tested for leakage with water during this
procedure. Do not allow prolonged soaking in water, since acidic compounds will buildup
in the water which can also damage the parts. When the valves are removed from the hot
water, they will dry very quickly and are then ready for reinstallation. If the valves are to be
stored for some time, it is advisable to apply a coating of light oil to the valve faces to
prevent possible rusting. This oil should be removed before the valve is reinstalled.

In order to inspect the piston and rings, it is necessary to remove the outboard
head of the cylinder, remove the rod from the crosshead, and pull the piston out far enough
to view the rings. The dust should be wiped from the internal surfaces with a lint-free cloth
when possible.

If the piston is entirely removed, the exposed cylinder bore and valve seating sur-
faces should be covered with a li ght coat of oil to avoid contact with air and thus prevent
corrosion of the honed and polished surface of the bore. All of this oil should be removed
before the piston is reinstalled. The bore can be plugged with a pump cup or other similar
plug to assist in isolating it from the atmosphere. A steam hose can be used to remove
powder and scale from the cylinder gas passages but before doing this, the valve ports
must be blocked to avoid getting steam or water on the highly finished cylinder bore sur-
face. Extreme care must be taken if such cleaning is attempted.

If the rings are stuck, a small amount of additional clearance can be obtained by
removing the rings and sanding the sides of the rings lightly on a flat surface. If carbon
piston blocks are used and these are stuck together, washing with hot water may serve to
free them and permit removal from the rod. When a compressor is assembled before the
rest of the plant is ready for operation, it should be blanketed with gas to avoid contact
with air. Close the block valves and pressure the compressor to about 0.3 kglcm 2 (5 psig)
with nitrogen after purging out all air in the system.

Platforming reciprocating compressors are normally installed in outdoor

locations. Therefore, the proper weight and quality of lubricating oil in the crankcase must
be used during the various seasons of the year and oil should be changed with the
seasons, particularly in cold climates. Use the manufacturer's recommended type of oil for
the anticipated temperature.

J 14
 B. Acidizing Heater Tubes'

Essentially, acidizing consists of seven mutally interdependent operations, not

one of which can be left out without jeopardizing the success of the entire procedure.
Since conditions, equipment, and facilities vary from refinery to refinery, it is necessary to
keep instructions such as these general in nature; however, there are certain basic
requirements that remain the same and do not change.

1. Preparation, assembling supplies, and setting up equipment: tanks, a cir-

culating pump, lines, instruments, water, steam, air, soda ash, and inhibited hydrochloric
acid containing a detergent and an emulsifier are all required. See Figure 2 for a suggested
equipment layout.

2. Circulation of the acidizing solution at high velocity by a large pump. The

combination of a large pump and strong acid not only removes the scale from the tube wall
but also keeps the resultant sludge in suspension until It can settle out in the receiving
sump of the acid circulating tank.

3. Large quantities of hydrogen sulfide gas generated during the acidizing

should be vented into the refinery flare or into some sort of sour gas disposal system. Note
that hydrogen sulfide (H2 S) is an extremely poisonous gas, and special precautions
should be observed.

4. Measure the acid concentration and temperature at regular time intervals

so that an acid concentration curve can be plotted and control of the operation can be
maintained (see Figure 3).

5. Water wash the tubes before and after neutralizing with soda ash and
detergent to remove all traces of acid and neutralizer.

6. Dry the tubes using a low fire in the heater; blow first with steam and then
with compressed air so that no moisture is left in the tubes.

7. Remove the acidizing equipment and supplies and clean the area.

General Instructions

1. Calculate the volume of the system (heater tubes, connecting

piping, and acid circulating tank sump) and then determine the amount of concentrated
inhibited hydrochloric acid required to give a 20 wt. % circulating solution.

2. Transfer cool clean fresh water into the acid addition tank, and
slowly add acid to make up the desired concentration.

3. Fill the system with warm (25°C/80°F) fresh water and circulate it to
check the system for leaks and to check the operation of the valves and the pump.

4. Drain the circulated fresh water.

NoI to be used on Austenttle stemless steels

J.15
 5. Start to slowly circulate the 20 wt. % acid solution through the
system drawing from the acid addition tank and discharging into the acid circulating tank.
Check the operation of the ejector to be sure that the H 2 S is being removed from the acid
circulating tank.

6. When the gas production decreases, increase the circulation rate

and slowly raise the temperature to 70r (160°F) or to the maximum limit recommended by
the acid or inhibitor supplier. Do not exceed this temperature because the inhibitor will
breakdown and become ineffective.

7. When the gas production again decreases, reverse t he flow through

the heater. The reversal of flow is necessary in order to clean areas that may have been
blanketed by gas, or by channeling or eddying effects set up by a single flow pattern.

8. Check the acid concentration in the solution at regular time in-

tervals and plot the time concentration graph. Five cm 3 of potassium citrate added to a
10 cm 3 sample of the dark green acid solution will generally complex the iron ions forming
a white slurry which will titrate to a very sharp endpoint.

9. When the acid concentration curve has stabilized for one or two
hours, or when t he concentration has fallen below 1 wt.%, circulation should be stopped
and the spent acid and sludge in the bottom of the acid circulating tank sump should be
drawn off.

10. Fresh 20 wt.%, acid from the acid tank should again be charged to
the system and circulation should be resumed. When mixing is complete, as a result of cir-
culation, the temperature should again be brought up to 70`t (160°F) or the maximum tem-
perature as recommended.

11. Again, at regular time intervals, the acid concentration should be

determined and a curve plotted.

12. When the acid concentration curve has, after several flow reversals,
stabilized at not lower than 5 -6 wt.% concentration for an hour or two, the acidizing can be
considered complete.

13. Drain the spent acid from the system and begin a vigorous water
flushing using clean fresh water and adding just enough steam at the inlet connection to
keep the water warm (40-50°C/100-120°F). Reverse the flow of the flushing stream several
ti mes.

14. After half an hour of water flushing, begin circulating a 2 wt.% soda
ash solution containing 0.1 wt.% detergent, previously prepared in the soda ash neu-
tralizing tank. Continue circulating, with several reversals of flow, for half an hour to neu-
tralize any acid t hat may be in the heater tubes and to remove any of the filming inhibitor.

15. Close the circulating valves and once again vigorously flush the
tubes with clean fresh water.

16. After another half hour of water flushing, shut off the water and
blow out the tubes first with steam and then with compressed air .
 17. When all water possible has been blown out of the heater tubes at a
low point drain, light a few of the burners and slowly begin to heat up the tubes. Heat
slowly to approximately 200-250 (400-500°F) firebox temperature and continue to blow
compressed air through the tubes. When no more water vapor is seen emerging from the
outlet, shut off the fires and let the heater cool down.

18. Wash down the working area to remove all traces of spent acid,
soda, or sludge. When the acidizing operation is finished, all equipment should be flushed
with water before being dismantled for removal; all acids should be sent to safe storage,
and all sludges should be properly discarded.

Notes and Precautions

It is assumed that the usual precautions of handling hydrochloric acid

are known and will be observed. However, special consideration must be paid to the
disposal of the hydrogen sulfide that is evolved in the acidizing operation so that per-
sonnel will not be exposed to it. Therefore, make certain that proper preparations are made
to allow safe disposal of the hydrogen sulfide.

Too low an acid concentration, and inadequate circulating velocity will

result in incomplete scale removal; thus, plugging of the reactor catalyst beds may result
shortly alter the plant goes into operation.

Equipment and Supplies

1. Acid

The concentrated hydrochloric acid should contain an inhibitor (it must

not contain arsenic), a detergent, and an emulsifier.

2. Pump
A high capacity pump of approximately 50 m 3lhr (250 gpm), in good
working order, built or modified to handle acid solutions is required.

3. Piping
Sound pipe in good condition, not scrap or rejects, with new gaskets in
all flanges and sharp, clean threads in all screwed connections.

4. Acid Addition Tank

A tank of approximately 2 cubic meters (500 gallons) capacity, large

enough to hold four or five carboys of concentrated acid and the necessary diluting water.
The tank must be made of sound material, not scrap.

5. Soda Ash Neutralizing Tank

A tank of approximately 2 cubic meters (500 gallons) capacity, large
enough to dissolve the soda ash and detergent, and act as a sump for the pump during the
neutralizing circulation.

J 17
 6. Acid Circulating Tank
A large tank of at least 10 cubic meters (2500 gallons) containing:

a. A vapor disengaging space behind a perforated baffle, so that

the H 2 S can readily release itself from the circulating acid solution and escape through
the venting system;

b. A weir to divide the tank into a settling basin, to trap the pieces
of scale and sludge carried by the circulating acid solution, and a sump for the pump suc-
tion. The tank must be made of sound material, not scrap, and must be capable of
withstanding a slight vacuum.

C. General 30-Day Plattorming Process Unit Shutdown

1. HIgh•Pressure Reactor Systems

The safest procedure for protection of catalyst in the Platformer and for
other high-pressure equipment in the system will be to keep these systems under a slight
nitrogen pressure. The procedure recommended following the shutdown will be to
evacuate and purge with nitrogen, then blanket with nitrogen at about 0.7 kglcm 2 (10 psig)
and blind the system.

2. Towers and Vessels

It will be adequate to merely drain all hydrocarbons in various fractionators,
receivers, surge drums, etc., and apply a gas blanket to be maintained during the entire
shutdown. Where appropriate, it is recommended that the system be allowed to float under
fuel drum pressure.

3. Utilities
a. Cooling Water
It will be adequate to simply shutdown the cooling water circulation
system during warm weather and start one circulating pump during freezing weather.

The cooling water in compressor cases should be drained if these

systems have not been protected against freeze-up.

b. Steam
Minimum steam requirements must be maintained for insurance pur-
poses and fire protection, and also to operate turbine-driven pumps.

All steam turbines should of course be drained and all steam header
dead ends should be checked for possible freeze ups. Make sure that all steam traps con-
-

tinue to operate during this period.

c. Fuel Gas
Fuel gas will be used to gas blanket all of the fractionators in the unit.
All process heaters will have the fuel gas blinded off at the burners or at the main header.

J-18
 d. Power
The normal power supply may need to be maintained depending on the
utility pumps In the unit and emergency requirements. Lighting requirements, etc., will
have to be satisfied.

e. Instrument Air
Having dry instrument air on all idle instruments will be of a major factor
in protecting against corrosion.

f. Plant Air
There may be no need for plant air as a standby utility. If for any reason
during the shutdown, plant air is required, It can be started at that time. We therefore
recommend that the plant air system be shut down.

g. Hot Oil System

This consideration is mentioned because of the freeze point of the hot
oil being used. Unless precautions are taken, it might set up in the exchangers where it is
used.

h. Sewer Systems
In all cases as the various units are shut down, the remaining drips and
drains from the various vessels will be drained to the sewer. Careful attention should be
given to flush the sewer with fresh water and make certain all hydrocarbons have been
swept out after the units are down.

4. Pumps
No special corrosion considerations are necessary, except for small
chemical pumps, such as the chloride injection pumps. It would be better not to drain
these pumps, but take precautions that moisture does not get into them. Block them at the
discharge and keep the suctions open so that they cannot be damaged by expansion. All
other pumps should have suction and discharge valves blocked and the drains opened.
Reciprocating pumps should have the rods lightly lubricated to prevent corrosion.

Cooling water to pump glands and base coolers should be blocked in and
the water drained.

5. Turbines
No special precautions are required tor me t uroineb,exi- epi
that all condensate has been carefully drained. Turbines and pumps can remain coupled
up and once every few days or so they can be turned by hand with lubricators in service.

6. Compressors
When compressors in the Platforming unit are of the non lubricated type,
they will require special consideration it the plant is to be down for as long as thirty days.
The suction and discharge block valves should be closed to prevent nitrogen blanketing
gas from leaking out of the reactor systems, but nitrogen must be kept in the compressor
cases to avoid corrosion due t o the ammonium chloride on the compressor valves. Simply
pressuring the compressors and blocking them would not be adequate, because over a
thirty day period the compressor cases would breathe, allowing moisture to enter and

J.19
 corrosion would be the result. It is therefore recommended that a nitrogen blanket from
cylinders controlled by a small regulator be installed to continuously bleed nitrogen
through a small pipe manifold in all compressor cases. The quantity of nitrogen should be
such that just a few inches of water pressure be maintained. Keeping the pressure at a
minimum will conserve nitrogen lost due to leakage.

A very light coat of oll should be applied to the exposed part of the com-
pressor rods, taking special care not to get oil on the carbon packing. After this, do NOT
turn the compressors over or the packing will of course wipe the oil off.

All cooling water in the closed circulating system should be drained if it is

not protected against freezing with glycol.

When compressors are of the centrifugal type, the manufacturer's recom-

mendations should be followed. In general the lube/seal oil system should be circulated
periodically and the compressor maintained under a nitrogen blanket.

7. Valves and Cocks

During the shutdown all plugged cocks should be greased while finally
closing them. No special consideration need be given to gate or globe valves.

8. Relief System
Since the system will be full of fuel gas the flare system should remain in
service and the flare kept lit.

9. Coolers and Exchangers

As explained in the cooling water system it is best to keep the cooling water
flowing through coolers to keep the water from freezing during cold weather. No other con-
sideration is required. Regarding exchangers, no special consideration is necessary ex-
cept to protect hot oil exchangers from setting up. Do NOT attempt to wash ammonium
chloride from the Platformer exchangers at this time. This can only be done properly by
pulling the bundles and immediately starting the unit up after washing.

10. Heaters
The best protection for heaters against corrosion and spalling of internal
heater box insulation is to keep a very small fire going at all times, such as with pilot lights.
The stack damper should be wide open during the entire shutdown period.

11. Tank Farm

Keep water drained wherever necessary, and if any tanks are gas blanketed,
keep the gas blanketing system in service.

12. Manpower Requirement

A skeleton force must be maintained for adequate plant protection. This will
require at least one man per shift, and as many maintenance personnel as necessary to
keep the unit, gas blanketing systems, etc., under constant surveillance.

J-20
 FIGURE 2
ACIDIZING SYSTEM PIPING
EJECTOR
SAMPLE POINTS-

H 2 S TO
FLARE OR
SAFE DISPOSAL
sPI
STEAM HIGH POINT
VENTA\ TI
PI

STEAM
AIR

I. U
LIP SPENT ACID TO
DISPOSAL

WATER
CIRCULATION HEATER COILS
PUMP
-
A r ACID CIRCULATION TAMP(
– ACID ADDITION TANK
SODA ASH NEUTRALIZING TANK

FIGURE 3

TYPICAL ACID
CONCENTRATION CURVES
20
ae I i I I
1ST ACIDIZING CYCLE 2ND ACIDIZING CYCLE
it
•
•
•
••
▪ 10
z
%
CURVE A
• 5
0
CURVE B
0
U 0
4 0 1 2 3 4
r.-4..,
5 8 0 1 2 3 4 S
TIME IHOURSI

J 21
 IV. MECHANICAL EVALUATION TEST PROCEDURE

While the majority of UOP Platforming unit performance tests are conducted in
order to satisfy contractual agreements between UOP and the customer, the potential
significance of a mechanical evaluation is much greater. From the information generated
and collected during an evaluation test, the refiner has the means to assess the potential
of his unit, to plan for future debottlenecking and to optimize refinery operations.

The following description includes data necessary for contractual tests plus in-
formation required for evaluating hydraulic systems, heaters, exchangers, pumps, com-
pressors, etc. A large amount of the information would be gathered in any case (flows, tem-
peratures, pressures, samples, etc.), and much of the rest can be obtained on a one-time
basis.

However, the test information may not be of much value unless the following
criteria are met:

1. The unit must weight balance. The weight balance must be consistently be-
t ween 98 and 102 wt.%, and preferably between 99 and 101 wt.%.

2. All operations must be steady, including quality of charge stock, product

specifications, exchanger outlet temperatures, etc.

3. Sufficient sample containers and laboratory analytical time must be available,

including containers for sample shipment to UOP.

4. Sufficient technical manpower must be available to gather data and take sam-
ples, in addition to those normally available for operating the unit.

5. Instrument technicians will be required before and during the performance

test in order to calibrate the instrumentation daily during the test.

The following list indicates the amount and type of information required:

1. Flows: All process flows into and out of the unit, and also intermediate
streams such as recycle gas and reflux, utility flows such as steam, BFW, instrument and
plant air, cooling water, fuel oil and gas, power consumption .

2. Temperatures: All process temperatures, including those not usually

measured, but provided for by thermowells, heater and exchanger temperatures, storage
tank temperatures.

3. Pressures: All process pressures, including single gauge hydraulic surveys

on reactor systems and columns, pump and compressor suction and discharge pressures.

4. Levels: Particularly storage tank levels for feed and products, chemical con-
sumption (chloride, alcohol, Unicor, BFW chemicals, etc.), process levels in columns,
drums, receivers, compressor seal oil and/or cylinder oil losses, etc.

J 23
 5. Samples: Samples of feed and products, intermediate streams such as reflux,
recycle gas, fuel gas and oil, flue gas, sour water, catalyst.

Why is all this data required? There are many reasons, but those used most
frequently are to enable the refiner to debottleneck the unit or to predict how much
material he can put through it without a revamp, or for the UOP Engineering Department to
review in order to evaluate actual performance. It is suggested that the data be ac-
cumulated at one time (during the performance run for contract demonstration), and that
evaluation of the equipment be made later. It is important, however, to have all the
necessary information available. To this end, the following lists and data sheets are given
to use as guides in collecting data.

General
Ambient air conditions: temperature
relative humidity
barometric pressure
wind velocity and direction
(show on rough plot plan)

General description of unit — includes process flow diagram.

Unit system used (e.g. USA, Imperial, Metric) and definition of any uncommon
units (e.g. kPa) and Standard Conditions (0 °C, 760 mm; 60 °F, 14.7 psla, etc.)

Guarantee

Data as required for Guarantee Agreement.

Complete weight balance, including meter correction factors.

Exchangers
Flow through exchangers on both sides (gas and liquid), composition and mass
flow.

Temperature in and out on both sides, also between shells, bundles.

Pressures in and out on both sides, if possible.

If air coolers; air temperature out, air velocity out, motor amps, note any belt slip-
page, variable pitch positions, louver positions, etc_

In preparing data, submit overall heat transfer coefficient, specifics on ex-

changers.

J-24
Heaters

Process flows (volume and mass, avg. mol wt., composition, etc.)

Process pressures in and out

Process temperatures in and out

Flue gas composition

Fuel gas composition

Fuel oil composition (Specific Gravity, distillation, vis, metals, sulfur)

Steam pressure for oil atomization

Temperatures at bridgewall, any intermediate convection points, stack, tube

skins, firebox skins, fuel oil, preheat air

Temperature of BFW coils in and out, superheated steam pressure and temp.

Steam generation rate, pressure, temperature

BFW pressure, rate, temperature

Fuel oll rate, temperature

Fuel gas rate, pressure, temperature

Draft, each cell

Basic data on process coils (size, number, mall., layout sketch, etc.)

Basic data on steam generating coils (size, number, man., layout sketch, etc.)

Burner data (rating, design release, etc.)

Need sufficient data to calculate heat flux from process side, heat flux from fire
side, calculate steam balance, calculate total heat release, calculate heater
efficiency.

Chemical Consumption

PDC or other organic chloride

H 20 or alcohol

BFW chemicals

Unicor

Other
Hydraulic Survey and Process Separations

Single gauge pressure survey of every point available on reactor circuit.

All control valve positions (including fuel, BFW, etc.)

Pump and compressor motor amps

Pump suction, discharge pressure, flow rates, composition, temperatures, with

mfgrs. curve data for comparison

Compressor suction, discharge pressures, flow rates, composition, tem-

peratures, with mfgrs. curve data for comparison

Single gauge pressure survey of fractionation systems, with sufficient data to

calculate internal reflux, no. of theoretical trays, etc.

Samples of LPS liquid and vapor and HPS liquid and vapor for phase separation
data
Utility consumption/production data:
Steam (all pressures)
Air (Plant and Inst.)
N2
Cooling water
BFW
Utility water
Steam condensate
Process condensate

Samples (typical)

Unit charge

LP sep. liquid

LP sep. gas

HP sep. gas

HP sep. liquid

DC4 ovhd. gas

DC, ovhd. liquid (even if only reflux) repeat for other columns as required

DC. bottoms

Catalyst - fresh
CCR Platformer, on stream catalyst sample(s) if possible.
-

Catalyst - spent

J-26
 Flue gas for each cell, if divided

Fuel gas

Fuel oil

Comments:

It is not necessary to obtain all the data at one time. It is acceptable to run various
segments of the survey at different times, and one possible period would be during the
line-out period prior to the guarantee test period. Data collections for heater and air-lin ex-
changers, in particular, are lengthly processes, and may be done any time when the unit is
stable, provided all the required process data is available.

If the data are collected, it obviously is necessary to have a good weight balance
(100 + 2%) for the information to be meaningful. For most pieces of information, if the
unit is lined out, spot data will be sufficient, rather than long-term averaged data. It might
be possible, taking this into consideration, to obtain the spot data in sections spread out
during the guarantee test (one exception is column performance).

In presenting the data, some order should be kept. Probably the best method is to
keep sections by type of information, i.e., one section on the guarantee test results, one on
heaters, one on exchangers, one on hydraulics, etc. Attached are some typical summary
sheets for this purpose.

J-27
COLUMN SUMMARY page
date
Item No • by
.
Service
Type of operation-
No. of trays: Reflux ratio:
Type of trays:

Net
Off Reb. Ovhd.
Feed Reflux Gas Btms. Out Liquid Other

Mass Flow
Temperature
Pressure
Composition,
H2
N2
H 2S
H 20
C
C2
C3
iC ,

nC i
ICs
nC s
C+
Avg. Mol. Wt.
Gravity
Distillation
IBP
5
10
20
30
40
50
60
70
80
90
95
EP
(Sketch system showing flows, P, T, Q on separate page)
Weight balance , Heat balance
Deviations from UOP Specifications:

J-29
 COMPRESSOR SUMMARY page
date
Item No.: by
Service:
Type:
Manufacturer
No., Size and Style (Mfgrs. Designation):

Pressure Temperature

Suction
Discharge

Other Information:
Flow (SIP)
Flow (Suction/Discharge cond.)
Sp. Gr.
Avg. Mot. Wt .

Comp. Ratio
Discharge Head
Pct. Loaded
Speed
Seal Oil Loss to Process
Seal Oil Differential

Driver type,
Motor: Mfgr. No., Size, Rating, Efficiency and Style ( Mfgrs. Designa-on)

Power
Speed
Power Factor

Turbine Driver: Mfgr. No., Size, Rating and Style (Mfgrs. Designation)

Speed
Steam Supply
Steam Exhaust
Steam Flow

Speed changer: Mfgr. No., Rating, Gear Ratio, rated gear power loss, style ( Mfgrs.
Designation)

Supply copy of Mfgrs. compressor curve and driver, and plot operating point.
Deviations from UOP Specs.:

I /I
CONTROL VALVE SUMMARY page
date
Item No.: by
Service:
Description of Valve Design CV:
Mfgr. and catalog no.:
Positioner?

Actual Design

Percent open (Valve position)

Flow rate:
Upstream pressure,
Downstream pressure,
Flowing temperature, °

Deviations from UOP Specifications:

AIR FIN COOLER SURVEY page
dale
Item No : by
Service:
Type .
Manufacturer
No. of Bundles No of Passes
No. of Tubes per Pass Fansibundle
Tube size ID x Gauge x Length
Piping Geometry: Type'
Overall heat transfer coefficient

Pressure Temperature
Inlet
Outlet

Air in
out
No. fans on Pitch control
Louver position

Air Process
Mass flow
O (calc.)
Composition
H2
H 2S
N2
C ,
C2
C3
1C 4

nC 4
1C 5
nCs
C6+
H2O
Avg. Mol. Wt.
Relative humidify

Gravity
Distillation
IBP
10
30
50
70
90
EP
Deviations from UOP Specifications:

*Include sketch of piping geometry if different from UOP standard practice types.

J-32
 FIGURE 4
MANIFOLD PIPING REQUIREMENTS
FOR AIR COOLED ITEMS

=-
TYPE A
WATER
•••- ro —1 — ro— •••■

HYDROCARBON 4

TUBE
BUNDLES

TYPE B

WATER

14
HYDROCARBON ft SI
TUBE FL] I ] 1' H
1
i ELI Eli
1 1 1 1
BUNDLES 1 1

TYPE C

4
r-17
TUBE
BUNDLES
r

TYPE D

MANIFOLDING TO BE DETERMINED
BY CONTRACTOR

TYPE E

1 1 1 1
4 1 1 1 1
rUBE
[ 1 11 1 11 1 11 1 1 11 1 1[ 1 11 1 1
I
BUNDLES
I I I I I I I
4 WO' tO7J I

J-33
FLOW METER SUMMARY page
date
Item No. by
Service:
Type of fluid: Normal Units of Flow
Type of meter:

Meter reading,
Pressure,
Temperature
Sp. Gr. • •
Meter factor
Corrected flow rate
Mass flow rate
Avg. mol. wt.
Molar flow rate

Sketch Piping Layout, showing distances in nominal pipe 10's

J.31
 HEAT EXCHANGER SURVEY page
date
Item No.: by
Service:
Type:
Manufacturer:
No. of Bundles
No. of Passes/Bundle Tubes per pass
Tube size ID x Gauge x Length
Heat exchange surface aiealbundle
Piping Geometry: (Sketch if necessary):
Length of service -
Design Heat Transfer Coefficient:

Stream Pressure Temperature

Shell Side Inlet A
Outlet

Tube Side Inlet B

Outlet

Q (calc.) Shell side

0 (calc.) tube side

Composition, Stream A
N :

H7S
H2
C
C2
C3
iC
nC4
IC s

+
H2O
Mass flow
Avg. Mol. Wt.

Gravity
Distillation
IBP
10
30
50
70
90
EP

Deviations from UOP Specifications:

J-35
HEATER SURVEY Page
date
Item No. by
Service:
Type:
Manufacturer:
No. Passes:
& Tubes per Pass:
Tube size ID x Wall x Length
Geometry (Process):
Geometry (Flue Gas):

Stream Pressure Temperatures

Radiant Inlet A
Outlet

Convection I Inlet
Outlet

Convection II Inlet
Outlet

Convection III Inlet

Outlet

Fuel Gas

Fuel Oil

Flue Gas Under Convection I

Flue Gas Under Convection II

Flue Gas Under Convection III I

Flue Gas Under Stack Damper

Flue Gas Above Floor

J•36
 REACTOR SECTION PRESSURE SURVEY page
(delete unused equipment) date
by

Pressure Temperature
Feed pump discharge
Feed CV Inlet
Outlet

Recycle Gas Dryer Inlet

Outlet

Combined Feed Exchanger Inlet

Intershell A
B
C
D
E
F
Outlet

Water Injection Pump Discharge

Chemical Injection Pump Discharge

Charge Heater Inlet

Outlet

No. 1 RX Inlet
Outlet

No. 1 Interheater Inlet

Outlet

No. 2 RX Inlet
Outlet

J-39
 REACTOR SECTION PRESSURE SURVEY page 2
date
by

Pressure Temperature

No. 2 Interheater Inlet

Outlet

No. 3 RX Inlet
Outlet

No. 3 Interheater Inlet

Outlet

No. 4 RX Inlet
Outlet

No. 4 Interheater Inlet

Outlet

No. 5 RX Inlet
Outlet
1
Combined Feed Exchanger Inlet
Intershell G
H
1
J
K
L
Outlet

Fractionator Feed Exchanger Inlet

Intershell A
B
C
Outlet

J.40
 HEATER SURVEY date by page
G, H,
Stream A 8 C P E F I, J
Mass Flow,
Composition
H2
N
02
CO
CO2
H 2S
SO2
C,
C2
C3
I C.
nC4
ICs
nCs
Cs-205°C (400°F)
205 °C (400 OF) +
Avg. Mol. Wt.
Gravity
Viscosity
Total Sulfur
Metals
(talc.) absorbed
o (calc.) released
Heater gross e(liciency
Excess air, %
Tube skin temps:

Burner pressure % of rating

Provide sketch showing piping and controls for process piping

Deviations from UOP Specifications:

J3/
 REACTOR SECTION PRESSURE SURVEY page 2
date
by

Pressure I emperalure

No. 2 Interhealer Inlet

Outlet

No. 3 RX Inlet
Outlet

No 3 Interheater Inlet
Outlet

No. 4 RX Inlet
Outlet

No. 4 Interheater Inlet

Outlet

No. 5 AX Inlet
Outlet

Combined Feed Exchanger Inlet

Intershell G
H

J
K
L
Outlet

Fractionator Feed Exchanger Inlet

Intershell A
B
C
Outlet

J-40
 REACTOR SECTION PRESSURE SURVEY page 3
date
by

Pressure Temperature

Reactor Effluent Finfan Inlet

Outlet

Reactor Effluent Condenser Inlet

Intershell A
B
C

E
F
Outlet

Reactor Effluent Trim Cooler Inlet

Interstage A
B
Outlet

Low Pressure Separator

LPG Pump Suction

Discharge

LPS Liquid CV Inlet

Discharge

LPS off gas CV Inlet

Discharge

LPS gas to booster compressor

Recycle compressor A Suction
Discharge

Recycle compressor B Suction

Discharge

J 41
 REACTOR SECTION PRESSURE SURVEY page 4
date
by

Pressure Temperature

HPS cooler Inlet

Interstagp A

Outlet

High Pressure Separator

HPS Pump Suction

Discharge

HPS Liquid CV Inlet

Discharge

HPS off gas CV Inlet

Discharge

HPS gas to booster compressor

Booster Compressor Discharge

Spiliback to CV
From CV

Recycle gas from HPS

Makeup gas CV Inlet

Discharge

RX quench CV Inlet
Discharge
to Reactor

Supply sketch of the system showing flow sot eme and all equipment.

J•42
 UOP Inc.
Des Plaines, Illinois
United States of America

UOP PLATFORMING PROCESS

PROCESS
EVALUATION

This material is UOP Inc.'s technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc.

PLATFORIfili
ING
WATER/CHLORIDE CONTROL

A. PILOT PLANT DATA

B. CATALYST CHLORIDE DETERMINATION

C. COMMERCIAL EVALUATION
 FIGURE 1
PILOT PLANT DATA

YIELD-OCTANE STUDY OF R-50

WITH HIGH CATALYST CHLORIDE LEVEL
1 MAP 200
190 .)
100

a
UM
1 000 \ 1 170
• %II...
icier/AC.4V
ilellA 160
• e
1%

900 a ove...A.A 150 ).

•ah.,._
MM. 140
82
■
so
78
• i
78
74
72 ■
i Oil

70
68
66
93 RONC--• 100 RONC —...
1 uuu _
NI
990 1.1 I
530
.6 NO
A...A
A■PAI"N"..""--
970 520
960 I 'I k
l-s• /SYMBOL R•50 CATALYST CHiOR IDE
10 ■ 1.01 Yft•% (vo. FREI 510
1.40 Yet•% (Vol. FREE)

-
•

MO ---
wialma. w/" LEAH
7 I
ED 0 2S AND
A 100 RO W

I 500
X0.0 05 10 1.5 2.0 2.5 3.0 3.'
(0.175) (0.351) (0.526) (0.701) (0.876) (1.052) 0 227)
CATALYST UFE, BPP
PUG) UC1, 1 244C- It
 FIGURE 2
PILOT PLANT DATA

300 psIg ACCELERATED

STABILITY TEST FOR R-50 CATALYST
WITH A HIGH FEED CHLORIDE LEVEL
LIRI

180 I
1 000 • ir- -
N•91-4-• „, 160
•
WO N...T .. • .. ... ....
140 9
120
.1
74
72
•

MOP II. ■
1
1. im,
ra
ft%

70 filt
w

-
■

68 I
er/1

-..-

68 I
N,
64
1020
540
1010 V
/
1000 II
II • 530
990 °
II e .
IP•ae.
so
w. Vi
980 "' 520
. Mr .•
-

leirl ..emo SYMBOL CATALYST FIE0 Cl

970 II R SO
- 1.0 Yttloprim dr •e
•
960 'e LEAN FEED • 11100
-5° ILO
R0RC Wt1"1" —
' 510
950 • •
/
I I I
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
(0.175) (0.351) (0.526) (0.701) (0.876) 1 052
( . ) (UM
CATALYST LIFE., OPP
(MUM
UOP I NSG.if
 LOW CHLORIDE AST TEST

1.2
1.10
I -III
1.17 —
1.1• —
1.11 —
1.14
1.13
1.12 —
1.11 —
1.1
Og riel
1.00 —
1.07
1.0•
1.00
1.04
1.0a —
1.02 —
1.01
1
0 4.

CAT urry. ow*

CAT ulrt. DPP

0 2 4 •
C.^7 Li re. SPP
 ADJUSTED BLOCK TEMP, °F ADJUSTED C5• YIELD, LV% H2 YIELD, SCFB
...
0 ....
U3 0 4rj U3 0 U3 0 C. 0
ii3
...) Ai LA m -JP CO 0 0 --.• •■.1 •..I — 4 0
c1. 0 0 0 0 0 a a 00 Kb al a 0 0
0

0 1
.. . ...... —... ••• - _. _ 7
. ' .
• t •i a . .....' ...i.. . • •• a .— •• 7
•• •
■ • •-•-• •
.• . •: - • •• •-•••• -1 r. ........ - .... .......-• ... ••..... —... ... ••• ••■••••••• •••• ••... • •• • rao ••••••••••• 1••

• • •• ... ., , ...., t•
!

O
•
ill
i .. : .11
•

.
.

• •t
..
•
.

. . .. ...
••'1

• • I !1'
•
, . • 'i
.. • . • t !•• '
• •
e • I I, • •
•• . 1 . ".. ' .4.•
. .....
• •
• • l• 7 .. . ..... Ir .. 4-••• •••• • me.- •• . •• •
_ •• -
• •••
• , .11•••
, ...• •• • I ■I,

-
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7 '
e 1.4.1. 4 • .•
'
•
1- H

1 i• • 6 ...
• • • •••• •• .

.• • 1' •t • • • • •' • •-• •

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... . . . .. .
. . . .., .. ; -• o• • .
• .. . . . • . -
'
le- • •• • :
-. . . . ..
•. . . • ••
.... -
7,
• •• . • ..

. p. .•. • • • • •! •• • •.
-• .• •
. ••
. . . .. . . . ••
••• • . • ..... • ..... • -•••• ■ • • • . ...............,, .... -
. .... .
a • • •

$ •• ' • •• •• •
:FER_Er4c

I
t wATEIZ-

• ••••• • • • ! •.

•• : •• • •a . • • • •!i•
:

.. . . .-
7 7 •
••••••••...... ••••11••••.• .. ••• . •••••• -...... . .... • ••••••• • •!••••• • •7••• •••
- r air
t

a • • •• •• • is 4
.•:

' • ..• • • ••- .4. • a 1 I 1..i

(

i
...-.
1

I 40 6 a• • • • •
•! • • !'

•a , •* P II. , 4 • • • 4 P• -• •. •. . • • !
• • • .. ' •• •- • • • • . 7 • ' I -

..........•-• ...... ................ --la L... ••••••••• .6... • ■■•••• -. •••••• ••■■•••• ••••• •••••••••••••■ — -
, •••• •-• •••••••• .
- • • . .... •: ' . •• -'• !1
•
!• .•• • • 10 .1.• ••• • • 16 : •111 Ail • 11••• • • • • • t• i•
• •• . . 7 , - .... ' ! i.
• ..• . t ...
..
. - . .'
. -... •••.
. "
..• .. • ..,.
• a_ . . .
,•
H;414d

D . . •• . • •-• - . .
. . •
. .. • • •• • •1-• • •, .... •• !. t !' • ! •!• • ' i I ' '' ! " 1"' '. ?I
. . ■ - 1!-+
.
.•••••••••••• •-••••• 4......1 •4., , 4•1
, 1 ,. •
•i 4 • • • • 1.• ,. • r.• . . t II t t, t •
... . .-
- ''' ".I' ' ' " "'' ''' 1! '' '
• , i 7 I
• •. .
 ft 90° v) A

b/ a 0
S 6Z := J. / /.

FIGURE 5
UOP PLATFORMING PROCESS
WATER—CHLORIDE EQUILIBRIUM CURVE
( 950 *F AVG. CATALYST TEMP.)

R-50 & R-60 SERIES

/ -R-16 & R-20

_ TE MP. CORRECTION =- 0.18% CL 1100°F

0.7
-0.32% CL 1100°C
0 6 I I I I , I f--'
-
0: 5 10 15 20 25 30 35 40
/3
H2 O / NCI MOLE RATIO IN COMBINED FEED TO REACTORS
UOP 1248C-10

o
T
.
1A)T /. . 4= )
J (!
1( 4. (

) /44 rt 0‘
S 0/6 0 0( e t/ *

- 4,s v (0 0 t)1,1 ) 0 - T)

r11 I: AP A T3

If r. r e 4 1) (
12 1- ■ 0 1,A1
. ( I,I .' -I e
 MUMS
HYDROGEN CHLORIDE
D,
• . ,

1now
1 1
11111iNall„ • IIi •It
/

Nutta lvt/ ir ma
04 ill
,
,••
„ • 1
101

/
r #

;'• #
o o

illiftfiwi/grami
FINa Iii Amp
o :•
I
to
1 • /
••
win INIFI o

ite 200 23 0 X0 150 400 450 500 150 100

(3-51 ( 71 r141 an as4 1351 (421
sanuurrow plutasu PIE. WIMP

noun 7
EQUILIBRIUM RECYCLE
GAS HCL CONTENT

100 SOO 1000 1200 1400 law

(187) (1421 (1711 (2141 (201 f2141
NWT II ATON ElAW
kits irinOtn. 31
SHORT CUT WATER/CHLORIDE CALCULATION

* COMBINED FEED
WATER/CHLORIDE RATIO, R = 1.8 *WPPM WATER IN FEED
WPPM CHLORIDE IN FEED

NOTE: WPPM WATER IN THE FEED = (INJECTED WATER)

+ (WATER IN FEED FROM STRIPPER; CA. 1 WPPM)
 FIGURE 2

CHLORIDE INJECTION RATE I

/I
5 vat ppm MO (R-50 catalysts)
0.$

0.6

0.5

1 I 1
1 r 1 I I I r 4
1100 IMO 900 920 940 990 990

lEiGHT AVERAGE f3ED 113JPERATURE

 •

FIGURE 4

.4
WATER AND CHLORIDE RATIO VERIFICATION
(

mol

4 =MI

O r ' T i l t
1.41 2 2.11
0.4 1.2
CHLORIDE RATIO. tom and ppavi/feed Irt ppm

C
 117015
Rev. 2

BIMETALLIC PLATFORMING CATALYST POISONS

The purpose of this section is to discuss bimetallic Platforming

catalyst poisons with respect to:

Maximum allowable contaminant level

Possible sources of contamination

Process symptoms

Consequent mechanical problems

Methods of detection

Suggested operational response

Above the recommended maximum levels of feed stock contami-

nants, catalyst performance will be measurably and negatively
affected and steps should be immediately taken to solve the
problem. In the cases of sulfur and nitrogen, UOP strongly
recommends operation at as low a level as possible, not at the
maximum allowable levels. Such minimization of known poisons
will help assure maximum selectivity and stability of a Plat forming
operation.

The listings of possible sources of contamination, typical process

symptoms, and possible mechanical consequences have been com-
piled from operations experience of hundreds of Platforming
units. We are interested in receiving refinery feedback on these
subjects so that we may add to our understanding and awareness
of current operational difficulties. This also provides for sharing
of effective solutions to process and mechanical problems among
refiners.

The suggested operational responses to the presence of poisons

are those responses that, in general, minimize catalyst and equip-
ment damage. It often occurs that other considerations such as
product octane level, production quotas, shutdown schedules,
etc., are in conflict with the suggested operational response. If
this does occur, the refiner must weigh the alternatives of
additional catalyst or mechanical damage versus violation of these
other factors.

A. Sulfur

1. Maximum allowable concentration in the naphtha feed is 0.5

weight ppm. Operation at 0.1 to 0.2 weight ppm in the feed is
normally possible with minimal added expense and will provide
added assurance of realizing maximum catalyst stability and
selectivity.

1
 117015
Rev. 2

Neither a lamp sulfur method nor a doctor test are adequate

for this purpose.

b. Sniffer tube H2S determinations to quantify H2S levels in

the recycle and stabilizer gases.

6. Suggested operational response:

Catalyst damage will be minimized by maintaining reactor tempera-

tures as low as possible. (There is no need to go below 482°C
(900°F) or 471°C (880°F).) In no case should reactor tempera-
t dre be increased to compensate for decreasing RONC if sulfur is
present in the recycle gas.

Every attempt should be made to eliminate sulfur from the feed.

Once low sulfur naphtha feed has been restored, the sulfur will
gradually desorb from the catalyst. When the recycle gas H2S
content has decreased to 1-2 ppm, normal operation may be
resumed. Slightly increased chloride addition (perhaps double
normal addition rate) during the time in which sulfur is present in
the recycle gas will improve the rate of sulfur desorption from the
catalyst.

B. Nitrogen

1. Maxi mus allowable concentration:

The maximum allowable concentration of nitrogen in the naphtha

feed is 0.5 weight ppm. Every attempt should be made to
absolutely minimize the nitrogen content of the naphtha. A real
level of 0.5 weight ppm nitrogen in the feed to a 10,000 BPD
Plat forming unit will result in the deposition of 823 kilogram (1814
pounds) per year of ammonium chloride deposits in the recycle
gas circuit and stabilizer column overhead.

2. Possible sources:

a. I nadequate naphtha hydrotreating: Most virgin straight

run naphthas contain very little nitrogen. Consequently,
hydrotreaters processing such naphtha can be designed at
lower pressures than would be required if the naphtha
contained higher nitrogen levels. The difference in design
pressure is normally 14 to 28 kg/cm 2 (200 to 400 psi) and
cannot be compensated for after the unit is designed.
Therefore, it is necessary to avoid processing higher
nitrogen content naphthas in hydrotreaters originally
designed for lower nitrogen naphtha. The hydrogf.n partial
pressure is not sufficient to accomplish complete nitrogen
removal.

b. I nclusion of cracked naphthas in the Platforming unit

charge: Most cracked naphthas will have a high nitrogen
content.
3
 117015
Rev. 2

6. Suggested operational response:

During the period that nitrogen is entering the Platforming unit,

an attempt should be made to maintain proper catalyst chloride
level. Of course, the first priority should be to isolate the source
of nitrogen and eliminate it from the Platforming unit feed. If
accurate feed nitrogen analyses are available, an added amount of
chloride equal in moles to the nitrogen contamination can be added
to Platforming unit charge to help maintain the proper chloride
level on catalyst. This extra chloride addition should be limited
to 5 weight ppm of naphtha charge. It must be remembered that
operation for more than a few days with such feed contamination
is almost certain to produce serious mechanical problems. Also,
during the period of nitrogen contamination, do not raise temper-
ature to maintain octane, since increased coking may result from
"pushing" an operation with unbalanced catalyst acid/metal
functions.

C. Metals

1. Maximum allowable concentrations:

Because of the quantitative and irreversible effects of Platforming

catalyst metal contamination, there should be no detectable levels
of metals in the Platforming unit charge.

2. Possible sources:

a. Some virgin naphthas do contain measurable levels

( ppb) of arsenic.

b. Lead can be introduced by either reprocessing of off-

spec leaded gasoline or contamination of Platforming unit feed
tanks with leaded gasoline.

c. Corrosion of products:

Corrosion of plant hardware can result in migration of the

corrosion products into the reactors. Iron is the most
common such corrosion contaminant; molybdenum, chrome,
and copper are other possibilities. Especially in the case of
iron, these corrosion contaminants are better tolerated by
Platforming catalysts than are organic metals. These corro-
sion products often enter the first Platforming reactor as
sulfide scale from the charge heater, combined feed ex-
changer and hydrotreater. The scale will accumulate in the
first Platforming reactor and may cause flow distribution
problems. Catalyst regeneration provides an opportunity for
liberation of sulfur from scale and may hinder proper oxida-
tion and reduction of the catalyst.

5
 117015
Rev. 2

6. Suggested operational response:

Periodic checks for metal content should be made of the naphtha

hydrotreater charge. Any periods of significant metal content in
the hydrotreater feed should be documented in an attempt to
quantify the total weight of metals going to the hydrotreater.
Normally, UOP hydrotreating catalyst can still function effec-
tively up to a total metals loading of 2 to 3 weight percent. If the
hydrotreating catalyst has been exposed to sufficient metals to
approach this 2 to 3 weight percent level, strong consideration
should be given to replacing the hydrotreating catalyst. Like-
wise, if -any detectable metals level is found in the hydrotreated
naphtha (an increased hydrotreater temperature does not elimi-
nate the problem), a hydrotreater catalyst change is necessary.
Any metals that do enter the Platforming unit will irreversibly
damage the catalyst, but quick detection and subsequent metal
contaminant removal on the refiner's part can often limit the
damage to only the first Platforming reactor.

D. High Feed End Point

A Platforming unit is designed to produce aromatic hydrocarbons.

This aromatic production apparently cannot occur without some
very small amount of single ring aromatic condensation into multi-
ring polycyclic aromatics. These polycyclic aromatic hydrocar-
bons are direct coke precursors. Once they are formed, they are
strongly held to the catalyst surface and will further convert to
what is typically referred to as coke on the catalyst. The rate of
natural formation of coke on the catalyst is fortunately very slow
at typical Platforming operating conditions. As discussed in the
Process Variable Section, coke formation does increase signifi-
cantly as Platforming unit pressure and hydrogen circulation are
decreased and/or temperature (octane) is increased. These are
all changes that would favor further aromatic condensation to
coke. One other operating variable that was shown to have a
significant effect on catalyst deactivation (coke formation) was
naphtha feed end point. As the feed end point approaches 204°C
(400°F), increased levels of naturally occurring polycylic
aromatics are carried with the naphtha. The absolute amount
will probably vary significantly with crude type and with fraction-
ation efficiency since these compounds are still present in ppm
ranges even at 204 ° C (400°F) naphtha end point. Since they are
direct coke precursors, these compounds can be considered as a
catalyst poison. Once deposited on the catalyst, they can only be
removed by regeneration.

7
 117015
Rev. 2

1. Maximum allowable concentration:

204°C (400°F) is a critical temperature regime for the naphtha

cut point. Above this end point (based on an ASTM D-86 distilla-
tion), the concentration of polycyclic aromatics in the feed
naphtha will increase rapidly. UOP does not recommend operation
above this end point.

2. Possible sources:

If the Platforming unit feed is coming from multiple refinery

sdurces . (e.g., straight run naphtha, hydrocrakate, coker
naphtha), each stream should individually be analyzed for
compliance with the 204°C (400°F) end point limitation. Blending
of a high end point stream with a low end point stream will 'mask"
the high boiling fraction of the heavy stream. The polycyclic
aromatics will still be present, but will not be indicated or
detected by t he ASTM D - 86 end point.

3. Process symptoms:

The effect of more rapid coke deposition will be more rapid

overall catalyst deactivation, with decreasing catalyst activity
and selectivity.

It. Mechanical problems:

There are no mechanical consequences other than more frequent

catalyst regeneration.

5. Methods of detection:

Measure the ASTM D-86 end point of each feed stream to the Plat-
forming unit or hydrotreating unit.

6. Suggested operational response:

Analyze each feed stream for ASTM D - 86 end point once per shift
and adjust the fractionation to maintain each streams end point
below 204°C (400°F). Maintain sufficient reflux to minimize
'sloppy' end points on all appropriate columns.

E. Water

A Platforming unit performs best when the feed to the unit is

essentially dry and the water:chloride balance is maintained via
injection systems. The optimum performance of the catalyst is a
function of several variables. One of which, the catalyst chloride
level, is set by the reactor conditions and the water/chloride

8
 117015
Rev. 2

d. Separator level control and foaming problems during

regeneration can provide carryover of sodium hydroxide or
sodium carbonate through the recycle gas circuit to the
reactors.

e. Water treating compounds containing zinc, copper,

phosphorus, etc., have at times been mistakenly added to
Platforming unit charge.

f. Some cracked naphtha can contain silicon, added as an

antifoaming agent elsewhere in the refinery.

3. Process symptoms:

Most metals are poisons to the platinum function of the catalyst.

I n general, metal poisoning occurs chromatographically through-
out the reactors, completely loading up the first reactor's
catalyst before breaking through to the following reactor. The
first reactor, therefore, assumes the burden of metal poison
damage.

The observable effects will be less severe loss of delta T in the

affected reactor(s), loss of overall catalyst activity and selec-
tivity. In the case of silicon, severe overcracking may result In
any reactor significantly contaminated with this compound.

4. Possible mechanical problems:

Metallic scale migration into the Platforming reactors may cause

flow distribution problems if the scale accumulation is great
enough. These problems include fines accumulation in the
catalyst bed, scale accumulation on the scallops, scale accumula-
tion i n the scallops, and plugging of trash baskets in downflow
type reactors.

5. Method of detection: for small concentrations in the naphtha

feed

Arsenic in Petroleum Naphthas: UOP 296

Trace of Concentrations of Lead

i n Gasoline or Naphtha: UOP 350

Copper in Gasoline and Naphtha: UOP 144

For analysis of a catalyst sample for possible metal contamination:

I mpurities in Alumina Base

Catalysts by Spectrography: UOP 303

6 _
 117015
Rev. 2

They must, therefore, be hydrotreated at high pressure in

preparation for inclusion to Platforming unit feed. A stream
of cracked naphtha, even though small relative to total Plat-
forming unit charge, should not be included to Platforming
unit charge if only low pressure hydrotreating is available.

c. I mproper use of inhibitors: Use of filming and neutral-

izing amines as corrosion inhibitors throughout the refinery
can sometimes lead to inadvertent naphtha nitrogen contamina-
tion. Areas of caution are crude system overhead, hydro-
treater stripper overhead, and hydrotreater reactor effluent
in addition to any other refinery units processing a naphtha
which will be sent to the Platforming unit. Carefully mon-
itored ammonia and increased water injection is often a less
expensive and less dangerous solution than inhibitor injec-
tion. Where inhibitor usage is absolutely necessary, strictly
adhere to the recommended dosage.

3. Process symptoms: Nitrogen is an acid function poison.

Organic nitrogen that enters the Platforming unit will be con-
verted to ammonia. This ammonia will react with chloride on the
catalyst to form volatile ammonium chloride. The overall effect is
to reduce catalyst chloride level producing the following
symptoms:

a. loss of catalyst activity;

b. i ncreased hydrogen production;
c. increased hydrogen purity;
d. increased reactor delta T 's.

4. Possible mechanical problems: Ammonium chloride deposits

will accumulate in the Platforming unit products condenser,
separator, recycle compressor suction lines, and stabilizer
column. This can result in decreased cooling capacity in the
products condenser, possible compressor damage (especially
during regeneration when high water levels move the deposits
onto the compressor wheels or valves), and erratic stabilizer
operation.

Moreover, extreme care must be taken when ammonium chloride

contaminated equipment is to be opened or inspected. Such
equipment must first be thoroughly washed to remove the
ammonium chloride deposits. Otherwise, the hydroscopic deposit
will adsorb atmospheric moisture and cause serious corrosion
problems.

5. Methods of detection: analyze naphtha feed

Kjeldahl Nitrogen Method: UOP 384

Chemiluolnescence: ASTM D-4629

4
 117015
Rev. 2

2. Possible Sources:

a. Inadequate naphtha hydrotreating: this can result from

low activity hydrotreating catalyst or from simply running at
too low of a hydrotreating reactor temperature.

b. Sulfur recombination reactions: combinations of high

hydrotreater temperature and low hydrotreater pressure can
promote recombination of hydrogen sulfide with trace
quantities of olefins. Such problems can normally be solved
by lowering the hydrotreater temperature.

c. Hydrotreater stripper upsets: these may result in

Incomplete stripping of H2S.

3. Process symptoms:

Sulfur contamination in the Platforming unit results in attenuation

of platinum activity. This in general means that the
hydrocracking (acid catalyzed) reactions will increase relative to
the dehydrogenation and dehydrocyclization (metal catalyzed)
reactions. Resulting observable effects include:

a. Decreased hydrogen production;

b. Decreased recycle gas hydrogen purity;

c. Increased hydrocracking (higher C 3 and C4 yield);

d. Reduced delta T I s;

e. Lower C5 plus yield;

f. Lower catalyst activity in more severe cases;

g- I ncreased catalyst coking rate (decreased stability).

4. Possible mechanical problems:

a. Increased iron sulfide formation throughout the unit;

b. Extra regeneration steps will probably be required in

order to completely remove the sulfur from the catalyst.

S. Methods of detection:

a. Feed naphtha sulfur analyses:

Nickel Reduction Method: UOP 357

Microcoulometric Method: UOP 727
Tracor Atlas: ASTM D-4045

2
COMMERCIAL EVALUATION
"COLLECT AS MUCH DATA AS POSSIBLE PERTAINING TO
H20/CL BALANCE"

1. H2O/CL INJECTION RATES

2. H2O AND CL IN RECYCLE GAS
3. CHLORIDE IN STABILIQER GAS
4. UNIT MASS BALANCE
5. LIGHT GAS YIELDS
6. RECYCLE GAS DENSITY
7. REACTOR DELTA TEMPERATURES
8. TEMPERATURE - OCTANE RESPONSE
9. CALCUALTED/MEASURED CATALYST CHLORIDE
 FIGURE 3

CHLORIDE INJECTION RATE

5 wt ppm 1420 (R-60 970 cotorysts)
1 . 1

0.7

0.3 i 1 r r 1 1 T II I I T T

840 $60 ROO 900 220 WO No

WEIGHT AVERAGE RED TEMPERATURE

 FIGURE 1

CHLORIDE INJECTION RATE

5 wt ppm 1120 (R-16, 20, & 30 cotelysb)

0.4
540 BOO MO 900 $20 140

MUT AVERAGE BED 11:161RATURE

 FIGURE •
WATER

111It EN
i411120

l
II
I •
, • 1 I •
1,1 I I I
11

rill
' I

ig
f4:11 110 LO • I

41 ri
I it I
I P
III I I ,A
,
I I
tsq 100 II 1 I
I
,
•
,
•
,
I rm •
/ /MI
'

f, , , ,

IN
134 N
11i I N • • •
•:
LO
1
T f1
4 I ,•
•
•I
#
•
,
I f ISM, 8 ,/ i
4
I
i
II/ If / ' / '
70 I i ill A ! 4 1
1
RI

50 100 130 200 250 300 330 400 450 500 550 SOO
P) 171 (14 ) (21 ) rzs) PSI
saupaRaTon •Kessums. POW
WargyLli
4.101.
,
101g.

FIGURE
EQUILIBRIUM RECYCLE
GAS MOISTURE CONTENT

41

1000 1200 1400 1500

I
(170I (21 4) R•41
NIT SaPAPIATON abs
sum Ouvri/v011
 CALCULATION OF CATALYST
CHLORIDE LEVEL
NECESSARY DATA
Er a WT. ppm CHLORIDE INTO THE FRESH FEED
Yr si WM ppm WATER IN FRESH FEED (1)
MWp a MOLECULAR WEIGHT OF FRESH FEED
AR a MOLE ppm HCL IN RECYCLE GAS (2)
YR s MOLE ppm WATER IN RECYCLE OAS (3)
O ai OM RATIO (MOLES RECYCLE GAS I MOLE FRESH FEED)

(1) THE VALUE NORMALLY USED IS THE WT. ppm WATER INJECTED INTO THE
FRESH FEED PLUS AN ADDITIONAL 0.5 TO 1.0 WM ppm ASSUMED TO BE IN
THE FRESH CHARGE.

(2) THE HCL CONTENT OF THE RECYCLE GAS CAN BE ESTIMATED FROM
FIGURES 6 & 7.

(3) THE WATER CONTENT OF THE RECYCLE GAS CAN BE ESTIMATED USING THE
VALUE OF Ypr TIMES THE MULTIPUER OBTAINED FROM FIGURES 8 &
Si
EQUOUBRIUM RECYCLE OAS MOISTURE CONTENT.

CALCULATION

WATER / CHLORIDE MOLE RATIO IN COMBINED FEED (FRESH CHARGE PLUS

RECYCLE GASI

MVO
R fa Y G + iYr
*RR +(Xp MWF
) I
 ADJUSTED BLOCK TEMP, 'F ADJUSTED C5* YIELD, LV% H2 YIELD, SCFB
••••

w o In 43
m0 S 0 .4 -4
0
0
Or'
1.3 0 -J
0 O Co o 0 0 0
m
 117015
Rev. 2

injection rates. If an unknown source of water enters the

system, the long term effects can be a shorter catalyst life and a
decrease in yield and activity.

1. Maximum allowable concentraction:

A recycle gas water content of 30 ppm indicates excessive water,

dissolved oxygen, or combined oxygen in the feed to the Plat-
forming unit. Moisture levels at or above this level may lead to
excessive hydrocracking and coke laydown. Additionally, the
chloride will be stripped from the catalyst upsetting the catalyst
balance.-

1. Possible sources:

a. Inadequate hydrotreating of feed may allow unconverted

oxygen compounds to enter the Platforming unit.

b. Further, any properly hydrotreated feed that is not

completely stripped will allow water and other catalyst
poisons to enter the Platforming unit.

c. Other possible sources are leaks in upstream steam or

water exchangers.

3. Process Symptoms:

Water tends to act as an acid function, in that it evolves chloride

from the catalyst to form HCI in the recycle gas. in the short
term, this high level of HCI accentuates the acid function, most
notably hydrocracking. Therefore, the short term observable
effects include:

a. Decreased hydrogen production

b. Decreased recycle gas hydrogen purity
c. Higher C3 and C4 yields
d. Reduced delta
e. Lower C5 plus yield
f. I ncreased catalyst coking rate
g. I ncreased recycle gas HCI levels

If feedstock with a high water content is charged to a unit over a

long period of ti me, the catalyst will become chloride deficient.
The extent of this deficiency will determine whether the catalyst
damage is reversible within the remaining catalyst life.

4. Possible mechanical problems:

The excessively high HCI in the net gas from the Plat forming unit
may be corrosive to downstream users.

9
 117015
Rev. 2

5. Methods of detection:

a. Suggested on-stream moisture analyzers

Du Pont 560 Recycle Gas
Panametrics 3000 Feed/Recycle Gas
Mitsubishi Water Analyzer CA-03 Feed

b. HCI in recycle gas by Praeger Tube.

6. Suggested operational response:

Catalyst-damage will be minimized by maintaining reactor tempera-

tures as loW as possible. (There is no need to go below 482°C
(900°F).] Failure to lower temperatures could result in a
substantially shorter catalyst life.

Locate the source of the water contaminant and either remove It

outright, or make the appropriate process adjustments to the feed
pretreating units. When the recycle gas water has decreased to
less than 30 ppm, re-establish normal operating temperatures.

10
 UOP Inc.
Des Plaines, Illinois
United States of America

UOP PLATFORMING PROCESS

ANALYTICAL

This material is UOP Inc 's technical information of a confidential nature for use only by personnel
within your organization requiring the information The material shall not be reproduced in any
manner or distributed for any purpose whatsoever except by written permission of UOP Inc. and
except as authorized under agreements with UOP Inc
 117013

ANALYTICAL METHODS

The UOP Plat forming° Process depends heavily upon various

analytical methods for control and protection of the process, the
catalyst, and the equipment. Since there is an almost bewildering
number of analytical methods available to laboratory personnel,
some guidance is necessary in order to obtain laboratory results
which will be meaningful to the operator and his supervisor.
Attached as separate sections are a typical laboratory schedule for
a Platforming unit and outlines of some of the more common
procedures.

A few notes are in order on some of the procedures and these

follow.

PONA

All of UOP's current correlations utilizing P/N/A (paraffins/naph-

thenes/aromatics) breakdown are based on UOP Method 273.

I n the event that the material is high in endpoint, the UOP Method
777 is most preferred. Any time the PONA is questionable, the
UOP 777 PONA should be run as a check. This method's P/N/A
data will also give reasonable results when used with the UOP
correlations.

Sulfur

The Raney nickel (nickel reduction) method for sulfur (UOP 357)
is the one which is recommended for Platformer charge sulfur
analysis. A new method which also is acceptable is UOP 727 (micro-
coulometric sulfur). The Lamp Sulfur method (ASTM U - 1266) is
not acceptable because it does not allow accuracy at the lower
levels required.

Chloride

UOP Method 395 is recommended for chloride analysis in Platformer

charge. UOP Method 588 is an extension of UOP Method 395 for use
in high sulfur naphthas.

Composition (C5 - 1

UUP Method 690 is recommended for naphthas and Platformates.

UOP Method 539 should be used for LPG and gas/vapor samples.

11 25 and HCI

Through a great range of exprience using various "sniffer" tubes,

we have found the Drager Multi Tester to be the easiest "sniffer"
apparatus to use and read. Since both 1125 and 'ICI analysis of the
separator and fractionator gas streams are for unit control

F-3
uop I ne.
 117013

purposes, it makes sense to do the samples at the unit, if that is

possible. The various "sniffer" tube devices are all applicable at
the unit and give rapid results (much quicker than a laboratory
test.)

Aromatics

There are a number of methods for determining aromatics in the

Platformate; however, UOP 273 does not work for streams with
large aromatics concentrations (i.e., Platformate). UOP 394 gives
benzene, toluene, total xylenes and Cy + aromatics. UOP 581
gives the isomer distribution of the C8 aromatics; UOP 744 gives A 9
and A10 isomers. UOP 741 gives paraffins and naphthenes by
carbon number, and UOP 690 gives paraffin naphthene isomers
through C 8 .

Catalyst Analyses

Many refinery laboratories have neither the time nor the budget to
run catalyst analyses. UOP's laboratory will run samples for a
refiner at the refiner's request.

Samples for UOP Analyses

Samples which are sent to UOP for analysis sometimes go astray,

either in shipping or within UOP. In order to minimize delays
caused by lost, misplaced, or unidentified samples, please observe
the following "ground rules".

1. Identify each sample with refiner, location, unit, sample, and

date. Make certain that the sample tag is well secured to the
sample and remains legible, even if it is wet with water or
hydrocarbn.

2. When shipping samples, mail or phone shipping information (air

way bill, flight number, bill of lading, etc.) to UOP.

3. Send a copy of the request for analysis with the samples; send
the original to:

Mr. R. W. Bennett
UOP Process Division
20 UOP Plaza
Des Plaines, Illinois 60016

Ship samples to:

Central Receiving
UOP, Inc.
Ten UOP Plaza
Des Plaines, Illinois 60016
 117013

5. For large or "rush" samples being sent to UOP by air, indicate

the shipping instructions as:

Ship to UOP, Inc.

Chicago, Illinois
Hold at O'Hare Airport
Call 391-3043 upon arrival

6. I nternational samples with no invoices are often received.

These samples have to be turned over to a customs broker whose
minimum charge is about $30.00. What is needed with each sample
is a commercial invoice (sometimes referred to as a pro-forma
invoice). There are no standard forms. Requirements vary
depending on country of origin. The basics required on the
statement/invoice are:

1. Quantity of sample.
2. Complete identification/description of sample.
3. Statement of value of sample for customs purposes only.

Shipments should be accompanied by t wo copies of the commercial

i nvoice plus a packing list in duplicate. Normally, the invoice
shows price as "No Charge" and "Value for Customs Purposes
Only" as the actual value. One additional copy of the invoice and
packing list should be airmailed to:

UOP Process Division, Attention: Traffic Department.

20 UOP Plaza
Mt. Prospect and Algonquin Roads
Des Plaines, Illinois 60016

It is important that samples from overseas be properly described,

valued, marked, and accompanied by proper papers to avoid delay
in U.S. Customs.

The amount of sample required for various analyses is indicated on

the next page, entitled "Minimum Sample SizeTM. Sending the amount
shown will ensure sufficient sample for analysis. For special or
unusual analyses, contact UOP Service Department fur the amount
of sample required.
 117013

MINIMUM SAMPLE SIZE

Analyses Preferred Minimum

( cm 3 )

Platformer Fed

API 100
Distillation 210( 1)
Gross PONA by UOP 273 5 0 (2)
Detailed Hydrocarbon Types by UOP 273 200( 2)
PONA by UOP 777 50
Sulfur, Microcoulometric 10
Nickel Reduction IOU
Nitrogen, Kjeldahl SUM
Micr OCOLI lometric 10
Chloride 100
Arsenic 400
Lead 100

Platformate

API 100
Distillation 210( 1 )
Hydrocarbon types by GC 150( 2 )
G5 - by GLC 50
BTX by GLC 50( 2)

RON, Clear Micro 300 per octane type

Leaded
MON, Clear Standard 1000/per octane type
Leaded

Catalyst

All common analyses 50

Notes: (1) May also be used for API Gravity.

(2) based on depentanized sample; allow at least 10%
overage to depentanize.
 117013

UOP PLATFORM' NG PROCESS

TYPICAL LABORATORY TEST SCHEDULE

Sampling
Method Frequency
Platformer Charge
(Stripper Bottoms)

Specific Gravity D 287 3/D

Distillation D 86 3/D
Color D 156 3/D
Sulfur UOP 357 1/D
Chloride UOP 395 1/W
Nitrogen UOP 384 1/W
Composition (PONA) UOP 273 1/W
UOP 777 Occas
Composition (C5 - ) UOP 690 Occas
Arsenic UOP 296 1/M
Lead UOP 350 1/M
Octane, Research D 2699 Occas

LP Separator Gas

Specific Gravity UOP 114 1/0

Composition UOP 539 1/W

HP Separator Gas

Specific Gravity UOP 1 114 3/D

Composition UOP 539 1/D
ti2S Dr3ger Tube 1/D
HCI Dr5ger Tube 1/D

Stabilizer Gas

Specific Gravity UOP 11 14 1/I)

Composit ion UOP 539 1/W
H2S Dryer Tube 1/D
HCI DrAger Tube 3/D

Stabilizer Overhead Liquid

Bollaway UOP 155 3/D

Composition UOP 539 1/W
 117013

Sampling
Method Frequency

Stabilizer Bottoms
(Platformate)

Gravity D 287 3/D

Distillation D 86 3/D
Reid Vapor Pressure D 323 3/D
Octane, Research D 2699 1/D
Color D 156 3/0
Composition (C5-) UOP 690 1/W
Composition (BTX) UOP 396 or Occas
(A8, Isomers) UOP 581 or
(A9, A 10 Isomers) UOP 7144 or
(P + A By C-Number) UOP 741 or
( P, N Isomers thru C8) UOP 690

Regeneration Recycle Gas

(Every Cat Regen)

CO), 02 By Orsat UOP 172

H2S Dr5ger Tube
SO2 Dr5ger Tube
HCI Drier Tube

Regeneration Circulating
Liquid (Every Cat Regen)

Chloride Content D 291

Iron Content D 1068
Gravity, Baume
Hydrometer MISC 1
pH (pH Meter) MISC 8
pH ( Litmus Paper) MISC 4

* Refer to Plat forming Catalyst Regeneration Procedure

CCR Plat former Samples

Spent Catalyst

Carbon (oven
dried sample) UOP 703 3/W
Chloride UOP 291 3/W

Regenerated Catalyst

Carbon UOP 703 3/W

Chloride UOP 291 3/W
Surface Area, Pore Vol.,
Pore Dia. UUP 425 Occas
 117013

Sampling
Method Frequency

On Stream Catalyst
Samples (Non—CCR)

Carbon (oven
dried sample) UOP 703 Occas
Chloride UOP 291 Occas
Sulfur UOP 439 Occas
Surface Area,
Pore Volume,
Pore Diameter UOP 425 Occas
 117013

UOP PLATFORMI NG PROCESS

OUTLINES OF SELECTED ANALYTICAL METHODS

Subject Index

Test Description Method

A8 Isomer Breakdown by GC UOP 581

API Gravity ASTM D 287
Aromatics by GC UOP 394
Arsenic in Hydrocarbons UOP 296
Arsenic in Hydrocarbons and Catalysts UOP 387

Boilaway UOP 155

Bromine Number ASTM D 1159
UOP 304

Carbon on Catalyst UOP 703

Chloride in Hydrocarbons UOP 395
UOP 588
Chlorine in Gases UOP 317
Chlorine in Catalysts UOP 291
Color of Hydrocarbons ASTM D 156
Copper in Gasoline & Naphthas UOP 144
Copper in Refinery Waters UOP 314

Distillation ASTN11.) 86
Doctor Test UOP 41

Emission Spectometry UOP 30.3

Fluoride in Catalyst UOP 290

Fluoride in Hydrocarbons (as chloride) UOP 395
Fractional Distillation UOP 79

Gas Chromatography (GC)

Aromatics UOP 394
Gases (C5_) UOP 539
C8 Aromatic Isomer Breakdown UOP 581
C a _ Saturates by Carbon Number UOP 690
Saturates by Carbon Number UOP 741
PONA UOI'777
Gravity, Specific
Schilling COP 114
API ASTM D 287
Gum, Steam Jet UOP 277

H2S (Hydrogen Sulfide)

futwiler UOP 9
H 2 S, Mercaptans & Carbonyl Sulfides UOP 212
Doctor UOP 41
Hydrocarbon Types (PONA) HOP 273
 117013

Test Description Method

Iron in Waters UOP 314

Karl Fisher Water UOP 213

Lamp Sulfur ASTM D 1266

Lead in Gasoline UOP 350
Loss on Ignition ( L01) UOP 275

Mercaptans UOP 212

Doctor Test UOP 41
Metals by Emission Spectometry UOP 303

Nickel Reduction Sulfur UOP 357

Nitrogen in Hydrocarbons UOP 384

Octane Rating
Research ASTM U 2699
Motor ASTM D 2700
Or sat UOP 172

pH, Iron and Copper in Waters UOP 314

PONA DUI' 273
UOP 777

Reid Vapor Pressure (RVP) ASTM D 323

Research Octane Rating ASTM 0 2699

Sampling Methods UOP 516

Schilling Gravity UOP 114
Specific Gravity
API ASTM D 287
Schilling UOF' 114
Sulfur
Nickel Reduction UOF' 357
In Catalyst UOP 439
Micro coulometric
- UOP 727
Lamp AS 1 M L.) 1266
Surface Area, Pore Volume, Pore Diameter UOP 425

True Boiling Point (TBP) Distillation UOP 79

Vapor Pressure, Reid ASTM D 323

Water in Gases UOP 213

Weathering Test UOP 155
 117013

UOP PLATFORMING PROCESS

OUTLINES OF SELECTED ANALYTICAL METHODS

Numerical Index

Test Method Description

1.1 0P 9 H 2 S (Tutweiler)
UUP 41 Doctor Test
UOP 79 Laboratory Fractionation, Ti3P
ASTM D 86 ASTM Distillation
UOP 114 Schilling Gas Gravity
UOP 144 Copper in Gasolines
UOP 155 Weathering Test (Boalaway)
ASTM D 156 Saybolt Color
UOP 172 Orsat
UOP 212 H 2 S, Mercap tans and Carbonyl Sulfides
UOP 213 Karl Fischer Water
UOP 273 PONA
UOP 275 Loss on Ignition at 900 ° C
UOP 277 Steam Jet Gum
AS TM D 287 API Gravity
UOP 290 Fluoride in Catalysts
UOP 291 Chloride in Catalysts
UOP 296 Arsenic in Naphtha
UOP 303 Emission Spectrometry on Catalysts
UUP 314 pH, Iron, Copper in Water
UOP 317 Chlorine in Hydrogen
ASTM U 323 Reid Vapor Pressure
UOP 350 Lead in Gasoline
UUP 357 Raney Nickel Sulfur
UOP 384 Nitrogen in Hydrocarbons
UOP 387 Arsenic in Catalysts and Hydrocarbons
UOP 394 Aromatics by CC
UOP 395 Chloride in Distillates
UOP 1425 Surface Area, Pore Volume,
Pore Diameter of Catalysts
UOP 439 Sulfur in Catalysts
UOP 516 Sampling of Liquids
UOP 539 Gas Analysis (GC)
UOP 581 C B Aromatic Isomer (GC)
UOP 588 Chloride in Distillates
UUP 690 Saturates thru C8 (GC)
UOP 703 Carbon on Catalysts (Leco)
UOP 727 Sulfur in Distillates (micro-coulometric)
UOP 741 Saturates thru C11 ( GC)
UOP 777 PONA (GC)
ASTM I) 1159 Bromine Number
ASTM 0 1266 Lamp Sulfur
ASTM D 2699 Research Octane
 HYDROGEN SULFIDE IN GASES
BY THE TUTWILER METHOD
UOP METHOD 9.59
Scope
This method is for the determination of hydrogen sulfide in gas mixtures. Mer-
captan sulfur, if present, is determined as hydrogen sulfide. The accuracy of this method
Is not sufficient to obtain reliable results below 5 grains of H 2 S per 100 cu. ft.•

Outline of Method

The sample is admitted to a Tutwiler buret, displacing a starch solution. A known

volume of starch solution is retained in the buret and a standard iodine solution is ad-
mitted and measured from the buret until the starch solution assumes a faint permanent
blue color. The concentration of hydrogen sulfide is calculated from the volume of iodine
used and its known normality.

Precautions

It Is recommended that gases to be analyzed for hydrogen sulfide content be

sampled directly from the plant stream into the buret. If the sample is to be transported, it
should be done In a dry glass or stainless steel container.

Do not confuse the blue color of the iodine-starch complex with the opalescent
milky appearance resulting from the separation of free sulfur.

Precision

Duplicate results by the same operator should be considered suspect if they dif-
fer by more than the following amounts, depending on the iodine solution used:

Iodine Solution A: 10 grains'

Iodine Solution 0: 20 grains•
Iodine Solution C: 5 grains•

• Note: To convert to weight ppm:

grain/100 SCF x 542.1

= ppm (wt)
MW gas

F-15
 DOCTOR TEST
FOR PETROLEUM DISTILLATES
UOP METHOD 41.74
Scope
This is a qualitative test for the presence of hydrogen sulfide and mercaptans in
gasoline, jet fuel, kerosine and similar petroleum products.

Outline of Method

The sample is shaken with a sodium plumbite solution in a test tube. if hydrogen
sulfide is present the following reaction occurs:

NazPbO2 + H 2S + 2NaOH

The lead sulfide is black and readily visible. If this reaction does not appear,
sulfur is added to the test tube and the mixture shaken again. If mercaptans are present, on
shaking they undergo a series of reactions, coloring the hydrocarbon layer first orange,
then red and brown, and finally a black precipitate of lead sulfide appears. The overall reac•
tion may be written:

NazPbO2 + 2RSH —•-(RS) 2 Pb + 2NaOH

(AS) 2 Pb + S—► RSSR + PbS

Report
(a) Hydrogen sulfide present.

If hydrogen sulfide is detected. report it.

(b) Sample sour.

If a brown or black precipitate forms, the sample contains a relatively high con-
centration of mercaptans and is reported "sour".

(c) Sample borderline or sweet.

If the mercaptan content of the sample is low, observe the sulfur layer and judge
as follows:

Discoloration of Floating Sulfur Report

Definitely discolored "sour"
Barely discolored borderline
Not discolored "sweet"

Precaution
Use only sufficient sulfur to form a thin film floating on the interface between the
sample and the doctor solution.

F-16
 FRACTIONATION OF PETROLEUM
DISTILLATES AND CRUDE OILS
UOP METHOD 79.68T
Scope
This method describes laboratory fractionation equipment and procedures used
in obtaining true boiling point data for petroleum distillates and crude oils. Procedures are
also given for obtaining specific boiling range fractions for further analysis.

Outline of Method
A known volume of a petroleum distillate or a crude oil sample is fractionated in a
high efficiency laboratory column. The distillation may consist of: (1) the precision frac-
tionation of normally liquid hydrocarbons to collect fractions for further identification: (2)
the quantitative separation of normally gaseous hydrocarbons, such as C3 and/or C.
hydrocarbons from Cs and heavier gasoline or crude oil fractions, and/or (3) the deter-
mination of true boiling point (TBP) distillation curves at atmospheric and reduced
pressures.

F-17
 DISTILLATION OF PETROLEUM PRODUCTS
ASTM D-86
Scope

This method covers the distillation of motor gasolines, aviation gasolines,

aviation turbine fuels, special boiling point spirits, naphthas, white spirit, kerosines, gas
oils, distillate fuel oils, and similar petroleum products, a 100-m1 sample is distilled under
prescribed conditions and systematic observations of thermometer readings and volumes
of condensate are made.

Definitions:

1: Initial boiling point (1.8.P.) thermometer reading at Instant first drop of

—

condensate falls from the lower end of the condenser tube.

2: End point (E.P.) — maximum thermometer reading obtained during the test.

3: Dry point — thermometer reading observed at instant last drop of liquid

evaporates from lowest point in flask. Any drops or film of liquid on side of
flask or on thermometer are disregarded.

4: Decomposition point — thermometer reading that coincides with first in-

dication of thermal decomposition of the liquid in the flask; as evidenced by
fumes and erratic thermometer readings which usually show a decided
decrease after any attempt to adjust the heat.

5: Percent recovery — maximum percent recovered.

6: Percent total recovery — combined percent recovery and residue in the

flask.

7: Percent loss — 100 minus percent total recovery.

8: Percent residue — percent total recovery minus percent recovery.

9: Percent evaporated — sum of percent recovered and percent loss.

F•18
 SPECIFIC GRAVITY OF GAS BY
SCHILLING EFFUSION METHOD
UOP METHOD 114-59
Scope

This method describes the procedure for the determination of the specific gravity
of hydrocarbon and other gases whose specific gravities do not exceed 1.3 with respect to
r
air.

This method is based on the kinetic theory of gases, i.e. the speed with which a
gas will pass through a small opening must be proportional to the average speed of the
molecules. Since the molecular speed of a gas is inversely proportional to the square root
of its specific gravity, the rate of effusion is inversely proportional to the same quantity.

The respective effusion times for the sample and air to pass through the same
orifice under identical conditions are measured. Since effusion time is directly propor-
tional to the same square root of specific gravity and the specified gravity of air Is 1.0 by
definition, the specific gravity of the gas sample may be calculated readily. The loss of
energy through friction in the orifice is assumed negligible.

Precision

Values obtained by this method for the specific gravity of gases below 1.3 are
repeatable to within ± 1%.

F•19
 I
COPPER IN GASOLINE AND NAPHTHA
UOP METHOD 144-70
Scope
This Is a method for determining small concentration of copper present in a
hydrocarbon•soluabie form in gasoline, kerosine and similar distillates. It is particularly
useful on products that have been copper sweetened and its lower limit of detection is
0.002 mg of copper per liter of oil sample.

An aqueous extract containing the copper is prepared. To this is added a solution

of sodium diethyldithiocarbamate. This reagent forms a yellow•colored complex with cop•
per. The colored complex is extracted almost quantitatively with chloroform. Estimation of
the copper present is made by measuring the intensity of the yellow color spec-
trophotometrically or visually.

Precautions
This method is for the detection of extremely small concentrations of copper.
Therefore, keep all glassware scrupulously clean in order to avoid contamination. The best
results are obtained when the glassware is reversed only for these analyses.

Precision

Based on the arithmetic mean range for 7 pairs of duplicates, the estimated stan•
dard deviation is 0.0005 at the 0.0040 mg Cu/I concentration. Duplicate results by the same
operator should not be considered suspect unless th ;y differ by more than 0.002 at the
0.004 mg Cu/I concentration.

F.20
 WEATHERING TEST FOR GASES
UOP METHOD 155.59
Scope
This is a rapid procedure for the estimation of iso- and normal butane in liquefied
butane samples. Propane does not interfere with the analysis and is determined if present
In concentrations not exceeding 25%. Pentanes and olefins will Interfere in the analysis, if
present. The test is sufficiently accurate for routine control of plant operations, the ap-
paratus is inexpensive and the technique involved requires little experience.

A 94 -ml sample of liquefied butanes is drawn into a precooled centrifuge tube. It

is then weathered in air to the 90 -ml mark. The centrifuge tube and contents are then
transferred to a water bath maintained at 60.70F, Temperature readings are recorded when
the liquid level has dropped to the 50- and 15- ml graduation marks of the centrifuge tube.
From these temperatures and a weathering test curve, the approximate concentrations of
propane, isobutane and normal butane are determined.

Precision

Duplicate results by the same operator should be considered suspect if they dif-
fer by more than the following amounts:

Maximum
Hydrocarbon Deviation, *A
Propane ± 2.5
i- butane ± 1.5
n-butane ± 10

F-21
 SAYBOLT COLOR OF PETROLEUM PRODUCTS
(SAYBOLT CHROMOMETER METHOD)
ASTM D-156
Scope
This method covers the determination of the color of refined oils Such as undyed
motor and aviation gasoline, jet fuels, naphthas and kerosine. A sample of the liquid is ad-
ded to a tubular column through which a light source is seen. The color Is compared with
specified glass standards: The height of the liquid sample is decreased by levels until the
color of the sample is lighter than that of the standard. The color number above this level is
reported. The range of number is + 30 (lightest) to 1 8 (darkest color). Color standards
-

correspond to sample depth and color number.

Precision
Duplicate results by the same operator should be considered suspect if they dif-
fer by more than 1 color unit.

Results submitted by one laboratory should be considered suspect If it differs

from that of another laboratory by 2 color units.

F-22
 FLUE GAS ANALYSIS (ORSAT)
UOP METHOD 172-59
Scope

This is a method for the quantitative determination of carbon dioxide, oxygen and
carbon monoxide in flue gases.

Outline of Method
Systematically, the gas sample is admitted Into a series of pipets, each con-
taining a reagent for the removal of an individual component. After contact with each
reagent, the gas is returned to the buret. The difference in residual volume indicates the
amount of component absorbed. In this manner, percentages of carbon dioxide, oxygen
and carbon monoxide are determined.

Precision

Duplicate results by the same operator should be considered suspect if they dif-
fer by more than the following amounts:

Carbon dioxide + 0.2%

Oxygen + 0.3%
Carbon monoxide ± 0.3%

F-23
 HYDROGEN SULFIDE, MERCAPTAN SULFUR
AND CARBONYL SULFIDE IN HYDROCARBON
GASES BY POTENTIOMETRIC TITRATION
UOP METHOD 212.72
Scope
This method Is for determining hydrogen sulfide, mercaptan sulfur and carbonyl
sulfide in gaseous hydrocarbons and in liquefied petroleum gas (LPG) of ordinary proper-
ties. Also covered is the determination of mercaptan in non-ordinary LPG which may con-
tain a wide range of hydrocarbon types from ethane to such gasoline boiling range
hydrocarbons as pentane and hexane. The hydrogen sulfide concentration range which
can be determined is from 0.3 to several thousand wt•ppm. The method is also applicable
to LPG samples containing as little as 1.0 ppm mercaptan sulfur.

The sample, taken either from a sample bomb or directly from a refinery stream,
is scrubbed first through a potassium hydroxide solution and then through a
monoethanolamine solution. A potentiometric titration of the absorbed hydrogen sulfide
and mercaptan sulfur follows. The monoethanolamine solution, which contains the ab-
sorbed carbonyl sufide, is titrated potentiometrically with alcoholic silver nitrate in an
acidic titration solvent. The concentration of each item sought is estimated' from the
titration curve.

Precision

Samples containing hydrogen sulfide, mercaptan and carbonyl sulfide sulfur

An estimated standard deviation is not reported since insufficient data are

available at present to permit this calculation with at least 4 degrees of freedom.

Samples containing mercaptan sulfur only and appreciable concentrations or

pentane and higher boiling materials

The estimated standard deviation (esd) based on indicated replicates is shown

below. Duplicate results by the same operator should not be considered suspect unless
they differ by more than the amounts shown in the "allowable difference" column (95%
probability).

Mercaptan esd, Allowable

Type of No. of level, wt• wt•ppm difference,
Sample Pairs ppm, S S wt-ppm S
LPG containing
appreciable concen-
trations of pentane 5 6.0 0.28 1.1.
and higher boiling
materials

F-24
 MOISTURE IN GASES FISCHER REAGENT
UOP METHOD 213.59
Scope

This is a method for the determination of small quantities of water in normally

gaseous hydrocarbons and gives best results when the samples are free of hydrogen
sulfide or methyl mercaptan. The apparent water content is erroneously high when the
concentration of hydrogen sulfide or equivalent sulfur compound exceeds 10 grains per
100 cu ft. This is due to the reaction of the sulfur compound, or other reducing agents, with
the iodine contained in the Fischer reagent.

The method can be applied to the determination of dissolved water in liquefied

hydrocarbon gases or to the determination of water vapor in a homogeneous mixture of
water and hydrocarbon vapors.

Outline of Method

This is a modification of the volumetric method for determining water originally

proposed by Karl Fischer. It is based on the following reaction.

H2O + 12 + SO2 + SO3

The method depends upon the fact that iodine does not oxidize sulfur dioxide ex-
cept in the presence of water. On reaction with water the dark brown Karl Fischer reagent
(brown color due to the presence of free iodine) becomes light yellow. A small excess of
the reagent will change the color back to brown. This is taken as the end point of the reac-
tion.

Precision

Duplicate determination should agree within ± 5% of the mean on a sweet gas.

In the presence of sulfur compounds the results are not reliable.
 HYDROCARBON TYPES IN PETROLEUM
FRACTIONS BOILING BELOW 400°F
UOP METHOD 273.64
Scope

This method is for the determination of paraffinic, olefinic, naphthenic and

aromatic hydrocarbon types in gasolines, and fractions therefrom. The endpoint of these
stocks (by ASTM Method D 86) should not exceed 400 °F.

Specific aromatics and naphthenes, including methylcyclopentane and

cyclohexane, may also be determined If desired.

The sample is depentanized and the Cs - minus fraction is analyzed for total paraf-
finic and total olefinic hydrocarbons. The depentanized sample is subjected to
Fluorescent Indicator Adsorption (FIA) analysis to determine olefins, aromatics and total
saturates. A breakdown of the total saturates to determine the proportions of paraffins and
naphthenes is accomplished by processing a depentanized sample through silica gel to
Isolate a total saturates portion and analyzing this by means of a density-refractivity in-
tercept relationship. More detailed determinations of specific aromatics and naphthenes.
Including methylcyclopentane and cyclohexane, are obtained by fractionations of the
depentanized sample and total saturates portion, followed by analysis of the individual
fractions.

Repeatability

Duplicate results should be considered suspect if they differ from the mean by
more than the following amounts:

Aromatics 1%
Olef ins 1%
Paraffins 2%
Naphthenes 2%

Data for the standard deviation for the FIA part of the procedure are not available.

The standard deviation for the paraffin-naphthene split, as calculated from 14

duplicate analyses, was 0.64% for the paraffins and 0.64% for the naphthenes.

F•25
 LOSS ON IGNITION OF CATALYSTS AT 900°C
UOP METHOD 275.64
Scope

This is a method for determining the loss on ignition of fresh or used catalysts or
catalyst bases of the various commercial shapes and sizes, when an ignition temperature
of 900°C is specified. It is also applicable to other sample types, such as catalyst fines.

A representative weighted sample is heated at 900 °C to constant weight and the

loss in weight calculated as percent loss on ignition.

Precision

Duplicate determinations should not differ by more than 0.2% absolute for
values below 3.0%, or more than 0.3% to 10.0%.

Based on 10 pairs at the 2% loss on ignition level, the standard deviation

calculated from the mean range was 0.072%.

Time for Analysis

Elapsed time per test is about 21/4 hours (5.0 hours when fines are being
analyzed).

F-27
 1
EXISTENT GUM IN DIOLEFIN-CONTAINING
GASOLINES AND NAPHTHAS BY THE
STEAM JET METHOD
UOP METHOD 277.73
Scope
Some gasolines and naphthas contain appreciable concentrations of diolefins or
other materials which are sensitive to oxidation. Examples are: (1) pyrolysis naphtha
(ethylene coproduct gasoline), (2) certain catalytically cracked gasolines, and (3) certain
thermally cracked gasolines. This method is used to determine the existent gum in these
types of materials. An inert gas, steam in this case, is used in the evaporation step in order
to prevent gum from forming in the test beaker during the evaporation. It has been ob-
served that the ASTM air-jet Method D 381, when used on oxidation-sensitive samples,
tends to give falsely high gum values because of gum formation during the evaporation.

Outline of Method

The steam jet method is similar to ASTM Method D 381 for "Existent Gum in
Fuels by Jet Evaporation". The sample in a tared beaker is placed in a heated metal block
apparatus maintained at 330 °F and evaporated to dryness by a jet of steam which has been
superheated to 350°F. The residue is weighed and reported as milligrams of gum per 100 ml
of sample.

Precautions

The types of gasolines and naphthas for which this method is intended must be
sampled and handled carefully in order to prevent oxidation. For best results it is recom-
mended that: (1) the sample containers be purged with inert gas such as nitrogen, carbon
dioxide, or sweet refinery gas prior to taking the samples. (2) any storage between time of
sampling and analysis be in the dark (preferably refrigerated storage). (3) the time lapse
between smapling and analysis be as short as possible.

Precision
Duplicate results by the same operator should not be considered suspect unless
they differ by more than approximately 25% of the result.

F• 28
 API GRAVITY OF CRUDE PETROLEUM
AND PETROLEUM PRODUCTS
(HYDROMETER METHOD)
ASTM D-287
Scope
Using a glass hydrometer the API gravity of crude petroleum and petroleum
products which have Reid Vapor Pressures under 26 lbs. can be determined. Gravities are
determined at 60°F, or converted to 60°F, by means of standard tables. Conversion tables
are not applicable to nonhydrocarbons or essentially pure hydrocarbons such as the
aromatics. Of interest: the ID of the sample cylinder must be at least 25mm greater than
the OD of the hydrometer. The height of the cylinder shall be such that the sample height
is 25mm more than the submerged portion of the hydrometer.

Precision
Repeatability: Duplicates should not differ by more than 0.2 degrees API.

Reproducibility: Results should not differ by more than 0.5 degrees API when
done by different labs.

The above judgements are valid providing API gravities were obtained at a tem-
. perature not differing from 60°F by more than 18°F.
 FLUORIDE IN CATALYSTS
UOP METHOD 290-64
Scope

This method is applicable to the determination of fluoride in catalysts containing

from 0.03 to 8% fluoride. Higher levels can be included by making appropriate reductions
in sample sizes and/or aliquot volumes.

The method consists of steam distilling fluorine as hydrofluorosilicic acid from a

sulfuric acid solution and then titrating the distillate with thorium nitrate in the presence
of alizarin red S indicator in a buffered solution.

Repeatability

In the range of 1.1 to 8% fluoride, duplicate determinations should agree within

0.15% fluoride; in the lower range, the agreement should be within 0.03% fluoride.

Based on 20 sets of duplicate determinations, the standard deviation is 0.082 for

the high range. Based on 9 sets of duplicate determinations, the standard deviation is
0.015 for the low range.

Time for Analysis

Elapsed time per test is 4 hours.

F•30
 TOTAL CHLORINE IN PLATFORMING
CATALYSTS BY DIGESTION AND
POTENTIOMETRIC TITRATION
UOP METHOD 291-65
Scope

This is a procedure for the determination of total chlorine and bromine in Plat-
forming catalysts.

The catalyst is leached with hot dilute sulfuric acid. Chloroplatinic acid, if
present, Is reduced. The chloride is titrated potentiometrically with silver nitrate solution.

Precision
Duplicate determinations on catalyst samples should not differ by more than
0.02% for the 0.02 to 1 wt•% chloride levels.

Time for Analysis

The total elapsed time for an analysis is between 3 and 20 hours depending on
the time required for the catalyst to dissolve or to be leached; fresh catalyst dissolves in 3
hours while used catalyst requires between 6 and 20 hours.

F-31
 I
ARSENIC IN PETROLEUM NAPHTHAS
UOP METHOD 296.58
Scope
This is a method for determining total arsenic in petroleum naphthas. The limit of
detection is approximately 0.5y (1y . = - 0.001 mg). For a 500 g naphtha sample, this
corresponds to a limit of detection of one part per billion (1 ppb).

The arsenic is extracted from the naphtha in 2 steps, using 5% sodium

hypochiorite solution and 70% sulfuric acid, respectively. The combined extracts are
digested with nitric acid and hydrogen peroxide to destroy organic matter. The resulting
sulfuric acid solution containing the arsenic is diluted and transferred to an arsine
generator. Zinc is added and the arsine produced is first passed through a lead acetate
tube to remove hydrogen sulfide and sulfur dioxide. The arsine then comes in contact with
a strip of paper which has been Impregnated with mercuric bromide. The length of the
orange-brown coloration produced on the strip is compared with standards which have
been run under identical conditions.

Precautions

Samples must not be stored in the light In clear bottles prior to analysis since ar-
senic may be lost. Wrap sample bottles in dark paper or otherwise protect from light.

Precision
The quantitative estimation of the amount of arsenic will be most precise in the
range of 5 to 10 micrograms. In this range the accuracy and repeatability should be ± 10%.

F-32
 I MPURITIES IN ALUMINA-BASE
CATALYSTS BY SPECTROGRAPHY
UOP METHOD 303.63
Scope

This method is designed for the determination of 22 trace elements in fresh and
used alumina-base catalyst. Fe, Si, Mg, Ca and As are determined quantitatively. Cu, Pb,
Ga, Mn, Zn, Ni, Mo, Cr, V, Ti, Na, Sn, P, Sb, Co, Zr and Ba are determined semi-
quantitatively, but they may be determined quantitatively with proper standardization. The
sensitivity is as follows for a large 3.4 — m grating spectrograph: Cu, Ga, Mn, Mo, CO-
0.001%; Fe, Si, Ca, Mg, Pb, V, Ti, Zr — 0.002%; Ni, Cr, Sn-0.003%, As-0.004%; Sb-0.01%;
Zn-0.03%; Ba•0.05%; Na, P-0.1%.

Catalyst samples are mixed with spectrographic grade graphite in a ratio of 1 part
sample to 2 parts graphite. A weighed portion of the mixture is burned to completion using
a 8-amp do arc. Aluminum is used as the internal standard. A microphotometer is used to
measure the densitites of selected iron, silicon, magnesium, calcium and aluminum lines.
Concentrations of these metals are then determined from calibration curves prepared from
spectra of synthetic standard mixtures. The remaining elements are determined by visual
comparison of the sample spectra to the spectra of standard powders whose com•
positions bracket the elemental concentrations in the catalyst.

Precision

Duplicate determinations should not differ from the mean by more than 0.002%
at the 0.010% level and below based on 5 replicate samples.

The estimated standard deviation (esd) was calculated to be:

Element Level, % esd

Fe 0.010 0.0014
Mg 0.010 0.0010
Ca 0.003 0.0002
Si 0.004 0.0009

F.33
 ANALYSIS OF REFINERY WATERS FOR
pH, IRON, AND COPPER
UOP METHOD 314.68T
Scope
This method is designed for measuring the extent of corrosion caused by refinery
waters. Copper and iron are determined at a level of 0.1 ppm and higher. The metals may be
present as simple dissolved ions, as complex ions with cyanide or other complexing
agents, or as part of the suspended solids that often are present. Ammonia, hydrogen
Sulfide, hydrogen cyanide and organic matter do not interfere.

The pH of the water Is determined because it usually correlates with the extent of
corrosion.

The water sample, including any suspended solids, is concentrated in the presen-
ce of sulfuric acid until sulfur trioxide fumes appear and then treated successively with
nitric acid and aqua regla.

Iron is determined calorimetrically. The lower limit of detection is 0.1 ppm iron.

Copper is determined colorimetrically. The lower limit of detection Is 0.1 ppm

copper in the water sample.

The pH of the original water sample is determined with a pH meter using a glass-
calomel electrode system. Samples drawn for determination of pH at the refinery should
be taken in glass bottles, leaving little or no air space above the liquid, and should be stop-
pered immediately with rubber or neoprene. The pH should be measured as soon thereaf-
ter as possible as it is often subject to fairly rapid change with ti me. Draw samples to be
sent out of the refinery in polyethylene bottles to avoid breakage.

Precision

Insufficient data available to calculate an esd with at least 3.7 degrees of

freedom.

Time for Analysis

The elapsed time is about 8 hours per sample.

F-34
 CHLORINE IN HYDROGEN GAS BY
A COLORIMETRIC PROCEDURE
UOP METHOD 317.66T
Scope

This method can be used for the determination of chlorine in compressed

hydrogen gas or for the determination of hydrogen chloride in other gas systems, such as
refinery recycle gases. The method as applied to compressed hydrogen does not
distinguish between chlorine and hydrogen chloride and the results are expressed in
terms of mol ppm of chlorine. For recycle gas analysis, the chlorine is in the form of
hydrogen chloride and is expressed as such. Two to six cubic feet of sample is sufficient
to detect a chlorine or hydrogen chloride content equal to or greater than 1 mol ppm.
Chlorine content in the range of 0.1 to 1.0 mol ppm can be determined by the use of a
proportionately larger sample.

A. For Compressed Hydrogen

The gas sample is scrubbed with a dilute hydrogen peroxide solution to collect
the chlorine and convert it to ionic chloride. The solution from the scrubber is made basic,
heated to destroy excess peroxide and concentrated to a smaller volume. The resulting
Concentrate is acidified and the chloride content determined by a colorimetric method.
This is based on the liberation of thiocyanate ions from mercuric thiocyanate by chloride
ion and measurement of the colored ferric thiocyanate complex:

— 2C1• + Hg (SCN)2 + 2FE + + + —0. HgC1 2 + 2 (Fe(SCN)) + +

B. For Recycle Gases

The gas sample is scrubbed with water and the scrubber is acidified and boiled to
remove hydrogen sulfide. An aliquot is then used to determine chloride by the colorimetric
method described above.

Precision

An estimated standard deviation is not reported since insufficient data are

available at present to permit this calculation with at least 4 degrees of freedom.

Based on a limited amount of data it is believed that duplicate results should not
differ from the mean by more than 10% for the 0.1 to 1 mol•ppm range.

Time for Analysis

The elapsed time required for one analysis is about 2 hours.

 I
VAPOR PRESSURE OF PETROLEUM
PRODUCTS (REID METHOD)
ASTM D-323
Scope

This method determines the absolute vapor pressure of volatile crude oil and
volatile nonviscous petroleum products, except LPG. The gasoline chamber of the testing
apparatus is filled with a chilled sample and connected to the air chamber section which
should be at 100°F. The container Is then Immersed in a constant-tem mature bath and
shaken periodically until equilibrium Is reached. A manometer attached at the end of the
cylinder-like apparatus is read and corrected It the air chamber temperature is initially at
Something other than 100°F.

Precision
Repeatability: duplicate results by the same operators should be considered
suspect if they differ by more than the following:

Range Repeatability
0- 5 psi 0.1
5-16 psi 0.2
16 - 26 psi 0.3

Reproducibility: results by two laboratories should be considered suspect if they

differ by more than the following:

Range Repeatability
0- 5 psi 0.35
5.16 psi 0.3
16 - 26 psi 0.4

F-3t5
 TRACE CONCENTRATIONS OF LEAD IN
GASOLINE OR PETROLEUM NAPHTHAS
UOP METHOD 350-72T
Scope
This is a rapid method for determining trace concentrations (10 to 400 ppb) of
lead in gasolines and petroleum naphthas.

The sample is brominated and the lead present is extracted with a dilute nitric
acid solution. The total lead present is measured colorimetrically after conversion to lead
dithizonate.

Precision

Insufficient data are available to calculate an estimated standard deviation with

at least 3.7 degrees of freedom. Based on experience, duplicate determinations will
probably not differ by more than 20 wt-ppb in the 0-100 wt-ppb range.

Time for Analysis

The average elapsed time for one analysis is 0.83 hr.

F-37
 TRACES OF SULFUR IN
PETROLEUM DISTILLATES BY THE
NICKEL REDUCTION METHOD
UOP METHOD 357.64
Scope

This method is for the determination of low concentrations of sulfur, ranging

from 0.1 to 200 ppm. in distillate stocks. It may be applied to non-olefinic materials, such
as straight run naphthas, hydrogen treated stocks, reformates and aromatic hydrocarbons.
It is li mited to samples containing not more than 2% olefins, Oxidized sulfur forms, such
as sulfonic acids, are not determined quantitatively: therefore, this method must be ap-
plied with discretion to the analysis of stocks which have been treated with sulfuric acid.

The sample is reacted with activated Raney nickel to convert organically-bound

sulfur to nickel sulfide. Acid is then added to liberate the sulfur as hydrogen sulfide. The
hydrogen sulfide is absorbed in a sodium hydroxide-acetone solution and titrated with
standard mercuric acetate, using dithizone as the indicator.

Precision

Duplicate results should be considered suspect if they differ from the mean by
more than the following amounts:

Allowable Deviation
Level of from Mean,
S, ppm ppm, S

1 0.2
10 0.4
50
250 3

The estimated standard deviation (esd) based on the indicated replicates is as

f ollows:

Number of Replicates Level, ppm eds

5 1 0.02
5 10 0.05
4 50 0.71
4 100 2.6

F-111
 NITROGEN IN PETROLEUM DISTILLATES AND
HEAVY OILS BY ACID EXTRACTION OR DIRECT
KJELDAHL PROCEDURE
UOP METHOD 384-64
Scope

This acid extraction method is specifically intended for the determination of

combined nitrogen in petroleum distillates and heavy oils in concentrations ranging from
0.2 to 20 ppm. Non-extractable samples, and samples containing nitrogen concentrations
ranging from 20 ppm to several percent, can be handled by a direct Kjeldahl analysis.

The types of nitrogen compounds which can be determined are those which
usually are determined by a macro Kjeldahl procedure and include amines, amides,
-

pyridines, pyrroles and quinolines. The method does not apply to organic nitro - compounds
nor to those containing a -N = N- linkage.

Precision

Duplicate determinations run in the same laboratory by the same operator on the
same equipment should not differ from the mean by more than the percent relative in the
table below:

Total Percent,
Nitrogen, ppm Relative

0.5 20
5 11
45 5
500 2

The estimated standard deviation was calculated to be 0.35 at the 16-ppm level,
based on 5 replicate samples; 1.38 at the 54-ppm level, based on 6 replicates.

Time for Analysis

Four hours are required for one analysis.

F-39
 ARSENIC IN PETROLEUM STOCKS AND
CATALYSTS BY SPECTROPHOTOMETRY
UOP METHOD 387.62
Scope

This is a method for determining arsenic In petroleum stocks which contain a

minimum of 5 parts per billion (ppb) of arsenic. It also provides a rapid, accurate method
for determining arsenic in various types of catalysts.

Arsenic Is extracted from the liquid petroleum stock by boiling with a sulfuric
acid-hydrogen peroxide mixture and Is then converted to arsine. The evolved arsine is reac•
ted with a solution of silver diethyldithlocarbarnate in pyridine and the red coloration
produced by this reaction is measured spectrophotometrically.

Precision

Sample Type
Liquid Petroleum Stocks Repeatability
5 20 ppb As
- ± 10%
Over 20 ppb As ± 5%
Catalysts + 3%
 AROMATICS IN HYDROCARBONS
BY GAS CHROMATOGRAPHY
UOP METHOD 394.71
Scope

This is a method for determining benzene, toluene, and total Ce aromatics in

stabilized liquid hydrocarbons. Total C9 and heavier aromatics are resolved and deter-
mined as a composite In samples containing hydrocarbons with 11 or fewer carbon atoms
per molecule. The lower limit of detection for a single component is 0.1 volume per cent.

Outline of Method

A 2-column chromatographic system connected to a thermal conductivity detec-

tor is used. A reproducible volume of sample is Injected into the column containing a polar
liquid phase. The non-aromatics, composed of 11 carbon atoms or fewer per molecule, are
vented to the atmosphere as they elute. The column Is backflushed immediately, before
the elution of benzene, and the aromatic portion is directed into the second column con-
taining a non polar li quid phase. The aromatic components elute in the order of their
-

boiling points.

I mmediately after the Ce aromatics have eluted, the flow through the non-polar
column is reversed to backflush the Co and heavier aromatics from the column through the
detector. Quantitative results are obtained from the measured areas of the recorded
aromatic peaks by utilizing factors obtained from the analysis of a blend of known
aromatic content.

Precision
Based on 5 pairs of analyses the estimated standard deviation (esd) In Table 3
was calculated for the components listed at the 10 liquid volume-percent level.

Table 3

Allowable
esd, Difference,
Component LV-% LV•%
Benzene 0.08 0.3
Toluene 0.07 0.3

CB Aromatics 0.14 0.6

F-41
 TOTAL CHLORIDES IN LOW-SULFUR
DISTILLATES BY SODIUM BIPHENYL
REDUCTION WITH COLORIMETRIC FINISH
UOP METHOD 395-66 (Procedure A and B)
Scope
This method is for the rapid determination of low concentrations of chloride In
li quid hydrocarbons low in sulfur. This method can be used only on H I S-free samples con-
taining less than 100 ppm total sulfur. Otherwise, erratic chloride results are obtained and
UOP Method 588 should be used instead.

Both organic and inorganic chlorides, as well as bromides and iodides, will be
determined by this method. Since bromides and iodides are rarely, if ever, present in
petroleum samples, the method treats all halogens as chlorides.

This method cannot be used on samples, such as styrene, that are polymerized
by sodium biphenyl.

Precision

For low sulfur distillates:

Based on a limited number of samples, duplicate determinations should not dif-

fer from the mean by more than 0.2 ppm in the range of 0.5 to 5.0 ppm.

Based on 10 determinations on laboratory prepared samples, the estimated stan-

dard deviation (esd) is 0.12 ppm C1 in the 1.0•ppm range.

For high purity aromatics:

Based on a limited number of samples, duplicate determinations should not dif-

fer from the mean by more than 10% In the range of 0.1 to 2.0 ppm.

Based on 5 determinations on laboratory prepared samples, the estimated stan-

dard deviation (esd) is 0.02 ppm C1.

F-42
 SURFACE AREA, PORE VOLUME AND
PORE DIAMETER OF POROUS SUBSTANCES
BY NITROGEN ADSORPTION
UOP METHOD 425-63
Scope

This method is for the determination of surface areas of porous substances by a

t wo-point system, using the basic Brunauer-Emmett-Teller (B.E.T.) theory of multilayer ad-
sorption, and pore volumes of the substances, using the capillary condensation theory.
Surface areas greater than 10 m 2/g may be determined, as well as the volume of pores up to
a diameter of 600 Angstroms. Pore diameter is calculated from surface area and pore
volume.

The surface area of a substance is determined by measuring the volume of

nitrogen gas adsorbed at liquid nitrogen temperature and relative pressures of 60/760 and
160/760, and applying the B.E.T. theory.

The pore volume is determined by measuring the amount of gaseous nitrogen

condensed in the pores at liquid nitrogen temperature and a relative pressure of 7351760. It
can be shown by use of the Kelvin equation for capillary condensation and the proper
correction for multilayer adsorption that this volume is that required to fill all pores of
diameter less than 600 Angstroms.

Precision

Surface Area

Duplicate determination should not differ by more than 8% from the mean.

Based on 2 sets of 5 replicate determinations, the standard deviation at the 500-

600 m 2/g level was 12.

Based on 2 sets of 5 replicate determinations, the standard deviation at the 100-

200 m2/9 level was 2.

Pore Volume

Duplicate determinations should not differ by more than 0.04 m11g.

Based on 4 sets of 5 replicate determinations, the standard deviation in the range

of 0.30 to 0.90 m1/g was 0.013.

F-43
 Pore Diameter

Duplicate determinations should not differ by more than 5% from the mean.

Based on 2 sets of 5 replicate determinations, the standard deviation at the 50-60

Angstrom level was 1.0.

Based on 2 sets of 5 replicate determinations, the standard deviation at the 90-

130 Angstrom level was 15.

Time for Test

The elapsed time for 1 sample is 9 hours.

The elapsed time for 6 samples is 10.5 hours.

F-44
 SULFUR IN CATALYSTS BY HIGH
TEMPERATURE FURNACE METHOD
UOP METHOD 439-75
Scope
This method Is a modification of ASTM Method D1552 to permit the deter-
mination of total sulfur In various catalysts. Halogens and nitrogen compounds, in the con-
centrations normally found present, do not Interfere. Molybdenum, boron and tungsten are
Interferences and catalysts containing these elements cannot be analyzed by this method.
Sulfur concentrations as low as 0.005% can be determined by this procedure.

The sample is weighed into a combustion boat and is inserted into a ceramic
tube contained in a high temperature resistance furnace. The products of decomposition
are swept from the tube by a stream of oxygen into an absorber containing hydrogen
peroxide. The sulfuric acid formed is titrated with barium perchlorate using Thorin as the
indicator.

Precision
Based on 6 pairs of catalyst samples which had been finely ground, and con-
tained 0.02 to 0.06% sulfur, the estimated standard deviation was found to be 0.002%
sulfur.

Duplicate analyses should not differ by more than 0.007% sulfur on finely-ground
samples (95% probability). The precision is poorer on non-uniform or unground catalysts.

Time for Analysis

The total elapsed time for an analysis Is one hour.

 SAMPLING OF GASOLINES, DISTILLATE FUELS
AND C3' C4 FRACTIONS
UOP METHOD 516.66
Scope

This is an outline of the sampling techniques necessary for obtaining, in a

stainless steel cylinder, an air•free sample of a liquid hydrocarbon. Samples may consist
of liquefied natural gases, high vapor pressure, natural gasolines, various liquefied
petroleum gases, air-unstable gasolines or other liquid hydrocarbon products which
require rigorous exclusion of air.

Outline
Proper sampling techniques are specified to obtain an uncontaminated, air-free
sample in a suitable container; viz., a double-valved, stainless steel cyclinder. The cylinder
is mounted vertically near the sampling point and connected to the plant sample line by
steel tubing or pipe. The connecting lines are flushed with the sample, which is then
allowed to flow upward through the cylinder. Several volumes of sample are discarded
before closing the sample cylinder valves of the cylinder.

Identification and Shipment

Properly identify each sample by attaching a tag to the cylinder giving company
name and location, time and date of sampling, identity of stream sampled, sample
pressure and tests required. Crate the cylinder to protect the valves from being opened or
damaged in shipment. Affix a "Red Label" or other proper shipping label (as prescribed by
Interstate Commerce Commission regulations) to the crate.

Notes and Precautions

Samples taken in containers found leaking either during or after sampling should
be discarded and new samples taken In leak-free cylinders.

Consult the current Interstate Commerce Commission regulations for applicable

specification for shipment. Consult ASTM Methods D 270, D 1145 and D 1265, if necessary,
for procedures for measurement and sampling of petroleum and petroleum products.

For liquid samples taken in the above manner it is mandatory to immediately

provide a safe outage in the cylinder to prevent thermal expansion and cylinder rupture.
Follow the recommendations in this method to safely provide that outage.

F-46
 GAS ANALYSIS BY GAS CHROMATOGRAPHY
UOP METHOD 539-73
Scope
This method Is for determining the composition of a wide variety of gaseous
hydrocarbon mixtures obtained from refining processes or from natural sources, including
minor concentrations of the composite of CS olefins and Ce + hydrocarbons. 1•Butene is
not resolved from isobutylene and argon is determined as a composite with oxygen. The
lower limit of detection for a single component is 0.1 mol-%.

Outline of Method
All the constituents of a total gas sample cannot be resolved by a single
chromatographic column. Therefore in this procedure, 3 columns are connected In series
with appropriate coupling valves. Each column is used to separate a specific portion of the
total sample. The first column is able to resolve gases in the C3 - Cs boiling range. The
second column separates the components in the intermediate boiling range — carbon
dioxide, ethylene, and ethane — while the third resolves the light gases — hydrogen,
oxygen + argon (composite), nitrogen, methane, and carbon monoxide.

Precision
Based on 7 replicate determinations, the estimated standard deviations (esd) In
Table 2 were calculated for the components listed.

Table 2

Allowable
Level, esd, Difference,
Component mol•% mol•% mol•%
Hydrogen 10 0.10 0.36
Nitrogen 20 0.02 0.07
Methane 10 0.03 0.09
Carbon monoxide 10 0.14 0.49

Carbon dioxide 10 0.03 0.10

Ethane 10 0.04 0.14
Propylene 10 0.02 0.05
n-Butane 10 0.03 0.09

Isopentane 3 0.03 0.11

CS Olefins t
Ce Plus f 4 0.04 0.14

r 47
 1
Ca AROMATIC ISOMER DISTRIBUTION
BY GAS CHROMATOGRAPHY
UOP METHOD 581.651
Scope
This method is for the determination of the relative distribution of isomers in C e
aromatic concentrates. It is limited to fractions which contain no C 10 non•aromatic
hydrocarbons, because certain C to components have the same retention times as the C e
aromatic isomers. C• aromatics, including isopropyibenzene and n-propylbenzene, are
resolved from Ce aromatics. Total non-aromatics, benzene, toluene and total CA aromatics
can be determined by UOP Method 394.

Outline of Method

The sample is injected into a chromatograph employing a column packed with

Chromosorb. The column temperature is 100 °C. The total elution time through o•xylene is
21 minutes.

Precision
Based on 6 pairs of analyses, the estimated standard deviations (esd) have been
calculated for the components at the concentrations listed in Table III.

Table HI

Concentra- Allowable
Component tion, wt-% esd Difference
p-Xylene 83 0-09 0.2

m•Xylene 17 0.07 0.1

F 46
-
 TOTAL CHLORIDE IN PETROLEUM OILS
BY SODIUM BIPHENYL REDUCTION WITH
POTENTIOMETRIC FINISH
UOP METHOD 588.65
Scope
This method is for the determination of total chloride in hydrocarbons containing
more than - 100 ppm sulfur. Both organic and inorganic chlorides, as well as bromides and
iodides, will be determined. Since bromides and iodides are rarely, if ever, present in
petroleum samples, the method treats all halogens as chlorides. This method is similar to
UOP Method 395 but has an additional step for removal of titratable sulfur and a poten.
tiometric finish.

This method works well on most samples. However, on samples with very poor
endpoints a potentiographic titrator must be used.

The method is applicable to samples with chloride concentrations of 1 ppm or

higher.

Precision

Based on a limited number of samples, duplicate determinations should not dif-

fer from the mean by more than 1.0 ppm in the 10-ppm range or 5.0 ppm in the 100-ppm
range.

The estimated standard deviation (esd) is 0.44 ppm in the 1.0- to 20.0-ppm range
based on the mean range for 5 duplicate determinations on heavy oil samples.

Time for Analysis

The total elapsed time is 2 hours per sample.

F.49
 INDIVIDUAL SATURATED HYDROCARBONS
THROUGH Co IN PETROLEUM DISTILLATES
BY GAS CHROMATOGRAPHY
UOP METHOD 690-73
Scope

This is a method for determining Ce , C7 or CB and lower boiling compounds, in

saturated liquid hydrocarbons. Low concentrations of benzene and toluene can be deter-
mined. Olefins interfere with the determination of the non-olefinic hydrocarbons and must
be removed from the sample by ASTM Method D 2002 or 2003 prior to analysis. The lower
li mit of detection for any single component is 0.1 weight per cent.

Outline of Method

The olefin-free sample is injected into the first column of a 2-column, 2-detector
system connected in series through a pressure backflushing system. The first column is
employed as a fractionator to separate the sample into light and heavy cuts of desired
boiling range. The light fraction is allowed to enter the analytical column while the heavy
cut is backflushed out of the fractionator column. Thus the boiling range of the fraction
taken for analysis may be limited to those compounds of analytical interest, when desired,
such as Ce - minus, Cy -minus or Ce -minus_ Samples having endpoints below 135°C may be
injected without backflushing If an analysis of the total sample is desired. The con-
centration of each component is obtained on an absolute basis by comparing the peak
area obtained for an internal standard to the areas obtained for the components in the frac-
tion analyzed.

Precision

Based on 7 replicate determinations, the estimated standard deviations (esd) in

the table were calculated for the components listed.

Concentra- Allowable
Component lion, wt-% sad, wt-% Difference, wt-%
n-Pentane 7 0.05 0.15
n-Hexane 6 0.04 0.13
Cyclohexane 3 0.04 0.14
n-Heptane 7 0.06 0.21
Methylcyclohexane 6 0.04 0.15
n-Octane 6 0.10 0.35

F-50
 CARBON ON CATALYST BY "LECO"
WR-12 WIDE RANGE CARBON DETERMINATOR
UOP METHOD 703-71
Scope

This method gives supplementary instructions for the determination of 0.01 to

80.0 wt-% carbon on catalysts.

It is necessary that the analyst be provided with the history of the sample so that
the proper sample preparation can be applied.

The sample is weighed In a ceramic crucible, mixed with accelerators and burned
in an induction furnace using oxygen carrier gas. The products of combustion pass
through a purifying train consisting of a dust trap, antimony metal for chloride removal,
manganese dioxide for sulfur removal, and a heated catalyst tube for conversiton of car-
bon monoxide to carbon dioxide and hydrogen to water. The carbon dioxide is adsorbed on
molecular sieves at ambient temperature. After the adsorption period is ended, the
molecular sieve column is rapidly heated to 600°F and the carbon dioxide eluted and
carried through the measuring thermistor by an auxiliary flow of oxygen. The output of the
thermistor bridge is integrated and read on a digital voltmeter and converted to percent
carbon by calculation.

Precision

The estimated standard deviation (esd) for carbon at different concentrations is

shown below.

For the 95% probability level, duplicate results by the same operator should not
be considered suspect unless they differ by more than the amounts shown in the
"allowable difference" column.

Allowable
Carbon Level Number of Number of esd, Difference,
°/• C Pairs Used Replicates % C %C
0.01 - 0.6 5 8 0.005 0.02
0.6 - 2 7 0.015 0.05
2-5 7 — 0.022 0.07
20 5 — 0.334 1.25

F. 51
 TOTAL SULFUR IN NAPHTHAS AND PETROLEUM
DISTILLATES BY OXIDATIVE PYROLYSIS AND
MICROCOULOMETRIC TITRATION
UOP METHOD 727-72
Scope

This method is for determining total sulfur in hydrocarbons at the 0.1 to 1-ppm
level and the 1•ppm or higher level. Samples may be analyzed directly If viscosity permits
injection by syringe. Samples having a high content of sulfur may be analyzed after
dilution with a suitable solvent. Halides in excess of 10 times the sulfur level, nitrogen con-
tent greater than 10% and heavy metals interfere with the analysis.

The sample is injected by a microliter syringe equipped with a repeating dispen-

ser into a flowing helium-oxygen stream and passed through a pyrolysis tube in a corn-
busion furnace. The sulfur dioxide formed passes into a titration cell and is titrated
iodometrically. The iodine consumed is replaced coulometrically. The amount of current
required to re-establish the iodine balance in the electrolyte is a measure of the total sulfur
in the sample.

Precision

Allowable
Sulfur Level, No. of esd, Difference
Type of Sample wt•ppm S Replicates wt•ppm S wt.ppm S
Hydrotreated
Naphtha 0.27 5 0.034 0.131
0.50 5 0.039 0.154
0.54 5 0.041 0.159
0.65 5 0.047 0.185
1.86 5 0.087 0.340
5.18 5 0.040 0.155
II

.. 5.77 5 0.070 0.275

6.24 5 0.151 0.590
II

.. 29.85 5 0.217 0.85

., 42.62 5 0.756 2.96
50.72 5 0.760 2.97
te

Time For Analysis

The elapsed time is 0.75 hour per analysis.

 PARAFFIN AND NAPHTHENE DISTRIBUTION BY
CARBON NUMBER OF SATURATED PETROLEUM
DISTILLATES BY GAS CHROMATOGRAPHY
UOP METHOD 741-74
Scope
This method is for determining the distribution of paraffins and naphthenes by
carbon number in C and lower mixtures of saturated hydrocarbons. Hydrocarbon mix-
tures with endpoints above about 385 °F (196 eC) will contain C tz hydrocarbons which can-
not be accurately measured; analysis should not be attempted. Aromatic and olefinic
hydrocarbons interfere with the determination of the saturated hydrocarbons and must be
removed from the sample prior to analysis.

Outline of Method
The saturated hydrocarbon sample is injected into a gas chromatograph em-
ploying a column packed with molecular sieves_ The column temperature is li nearly in•
creased from 250 to 450°C. The weight- or liquid volume•percent concentration of each
saturated hydrocarbon type, by carbon number. is obtained from the measured areas of the
recorded peak groups, adjusted for deviation in response by the use of factors.

Precision

The allowance difference between replicate determinations should be 1.0 wt% or

less for most components.
 117013

HYDROCARBON TYPES IN PETROLEUM

FRACTIONS BY CHROMATOGRAPHY

UOP Method 777-77

Scope

This method describes a procedure for determining paraffin,

olefin, and aromatic hydrocarbon types in stabilized yasolines or
fractions therefrom. Paraffins and naphthenes are determined by
carbon number with cyclopentane, methylcyclopentane, and cyclo-
hexane determined individually. C6 minus hydrocarbons can be
reported either individually or by carbon number. Aromatics are
determined by carbon number through C 8 with the C9+ determined
as a composite. Olefins are reported undistributed.

Determination of C8 aromatic isomer distribution and/or (.:7 and C8

saturate isomers is optional, and may be determined if desired.

Outline of Method

A stabilized sample is subjected to gas chromatographic analyses to

determine the aromatic content and the C5 minus content of a high
olefinic sample, or the C6 minus content of a low olefinic sample.
The sample is analyzed by Fluorescent Indicator Adsorption (FIA)
to determine the total olefin content. A breakdown of the
saturates to determine the percentages of paraffins and
naphthenes by carbon number is accomplished by processing the
sample through silica gel to obtain a saturates fraction and
analyzing this portion by gas chromatography. Densities of the
sample and of the various fractions are determined as necessary
for calculations. A more detailed breakdown of t he C 8 aromatic
isomers and/or the C7 and C8 saturate isomers can he obtained by
additional gas chromatographic analyses, when required.
 BROMINE NUMBER OF PETROLEUM
DISTILLATES AND COMMERCIAL ALIPHATIC
OLEFINS BY ELECTROMETRIC TITRATION
ASTM D-1159
Scope
This method determines the bromine number of petroleum distillates sub-
stantially free of materials lighter than ICA and which have 90% points under 620 F, The
magnitude of the bromine number is an indication of the quantity of bromine-reactive con-
stituents, not an Identification of such. A known weight of the sample is titrated with a
standard bromine-bromate solution.

Definition: Bromine No. is the number of grams of bromine which will react
with 100 g of sample.
Bromine Index is the number of milligrams which will react with 100
g of the sample.

Precision
Repeatability and reproducibility charts should be consulted in an ASTM book of
standards when laboratory results are in question. These numbers depend on type of
distillate and their physical properties.

F•55
 SULFUR IN PETROLEUM PRODUCTS
(LAMP METHOD)
ASTM D-1266
Scope
This method determines the total sulfur in liquid petroleum products in con-
centrations above 0.002 weight percent. The procedure involves burning the sample in a
closed system using a suitable lamp apparatus. An artificial atmosphere composed of
70% CO2 and 30% 0 2 Is used to burn the sample to prevent formation of nitrogen oxides.
The oxides of sulfur are then oxidized to sulfuric acid. Sulfur as sulfate is determined
acidimetrically by titration or gravimetrically by precipitation as barium sulfate.

Precision

Samples should contain in the range of 0.01% to 0.4% sulfur

Repeatability: duplicate results by same operator should not differ by more than
0.005%.

Reproducibility: results by two laboratories should not differ by more than 0.010
+ 0.025S where S = the total sulfur content, weight percent, of the sample.
 KNOCK CHARACTERISTICS OF MOTOR FUELS
BY THE RESEARCH METHOD
ASTM D 2699
Scope

This method determines the knock characteristics of motor gasolines, intended

for use in spark-ignition engines. A Research Octane Number (RONC) of 100 or lower is the
volume percent of iso-octane in a blend with n-heptane that matches the knock intensity of
the unknown sample. For numbers above 100, a comparison Is made to isooctane and
millilitres of tetraethyllead required to match knock intensity.

Summary of Method

The RONC of a gasoline is determined by comparing its knocking tendency with

these for blends of reference fuels of known octane. Knock intensity is measured by an
electronic detonation meter on a testing unit consisting of a single-cylinder engine.

Repeatability
Data for limits on duplicate results by the same operator have not been de-
veloped.

Reproducibility

Results by different laboratories should be considered suspect if their difference

is greater than the limits shown below

Ave. Research Octane No. Level Limits

80 1.2
85 0.9
90 0.7
95 0.6
100 0.7
105 1.1

F•57
 SAMPLE CONTAINERS
OCTANE LOSS
It has been found that sample collection in clear bottles, which are left exposed
to sun light (or ultra violet li ghting) either direct or Indirect, and whether or not the sample
-

has been treated with oxidation inhibitors, will result in a severe loss of octane rating
within a very short time. Every effort must therefore be made to see that only the brown or
amber sample bottles are used for daily samples and more important that all samples ship-
ped to UOP for analysis are taken in amber bottles, are kept in a cool dark place until
packaged for shipment, and are shipped as soon as possible after sampling.

F 58
 SUNLIGHT AND OCTANE RATINGS
I. Effect of Fuel Type
Peroxide No. Octane No., F-1 Clear
Hours exposure (a) 0 6 54 121 169 217 0 6 54 121 169 217
Platformate, 0.21 11.1 1 3.2 12.6 15.5 22.1 88.3 84.7 84.1 83.7 - 82.0
Polymer, (Inhib.1 0.26 12.3 1 4.4 17.4 28.0 30.6 96.7 94.8 94,4 94.2 - 92.0
Cat. Crackea,TInfilb.) 0.29 3.54 5.30 4.60 5.82 8.72 98.8 91.4 91.4 - - 90.6
Thermal Cracked, (Inhib.) 3.49 5.41 8.40 12.0 11.9 13.2 72.4 72.0 72.2 - - 70.3
Reference Fuel (b) 0.02 0.73 0.85 0.83 1.90 2.02 130.7 78.7 - - - 79.2

(a) First 6 hours of exposure was to direct sunlight.

-
n Following 211 hours was continuous exposure, 24 hrs. per day.
All samples unleaded in clear glass bottles.

(b) 80% isooctane. 20% n-heptane.

II. Effect of Inhibitor and Brown Bottles on Platformate.

Peroxide No. Octane No.. F-1 Clear
Hours exposure lc) 0 6 10 0 6 10
No Inhibitor, Clear bottle 0.06 6.20 6.90 88.3 86.5 86.0
No Inhibitor, Brown bottle 0.06 0.32 1.56 88.3 88.3 88.3
15 lb UOP N5, Clear bottle 0.04 4.35 7.40 88.3 86.7 86.0
15 lb UOP N5, Brown bottle 0.04 0.21 0.42 8.8.3 88.7 88.7

(c) First 3 hours of exposure was to sunlight.

Next 3 hours was to diffuse daylight.
Next 4 hours was to sunlight.