Académique Documents
Professionnel Documents
Culture Documents
T n many areas of the world residual fuel oil has become the principal
A
source of industrial, commercial, and utility fuel. In these services it
has historically been the marginal energy source with locally produced
coal or natural gas being the fuel of choice for economic reasons. How-
ever air pollution control regulations relating to fuel sulfur content have
limited many sources of coal, and in many important areas low cost
natural gas is becoming critically short in supply. Because of these fac-
tors, fuel oil consumption is growing rapidly, and in many instances at
a rate substantially above the normal growth in energy demand. This
growth in demand, coupled with increasingly stringent sulfur-content
specifications, is leading in the direction of a shortage in residual fuels,
particularly those of lower sulfur contents.
105
In Pollution Control and Energy Needs; Jimeson, R., et al.;
Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
106 POLLUTION CONTROL AND ENERGY NEEDS
the desired end-product. This paper considers some of the problems asso-
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
ciated with processing residual oils and presents some new developments
in the H-Oil process. Because of these new developments it is now pos-
sible to design a processing facility which can economically produce fuel
oils of 0.3% sulfur content interchangeably from a range of feedstocks
encompassing most of the commercially important residues. One of the
most significant aspects of these new developments involves the ability
to economically desulfurize the high metals-content residues from
Venezuela.
Adaptability. In the future the market for low sulfur fuel oil may
become less attractive for several reasons. Among these are: increasing
use of nuclear energy, installation of stack gas-desulfurization processes,
and increased availability of low sulfur fuels. Should this occur it would
be desirable to put to alternative use any facility installed today to de-
sulfurize fuel oil. At such a time, the market could revert to the tradi-
tional U.S. pattern in which high sulfur residual oil is a low value material,
and there would be a consequent economic incentive to convert it to
lighter products.
Considering these factors an optimum fuels-processing facility should
possess the following basic characteristics: the ability to process fuel oil
at low unit cost, the ability to handle a range of residual fuels as feed-
Downloaded by UNIV OF ARIZONA on January 8, 2013 | http://pubs.acs.org
and compared with the data. The second-order relationship more accu-
rately represents the situation. It must be remembered, however, that
this is an empiricism and data extrapolations must be treated with caution.
A practical consequence of the pseudo second-order model is that,
as market requirements dictate a lower sulfur content product, the reac-
tion rate in the final stages of a process will be quite low. With a second-
order model the reaction rate in the final incremental portion of a reactor
system will be only one-tenth at the 0.3% sulfur level what it would be
at the 1% sulfur level.
1.61 1 1 1 1 1 1 1 1 1 1
Downloaded by UNIV OF ARIZONA on January 8, 2013 | http://pubs.acs.org
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
.30
.20
A
GO
z .10
o
o
18° API
o
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
or 3.7%S
o 36ppmV
loppmm
CNJ
o FEED B: LIGHT VENEZUELAN ATM. RESIDUUM
If" A H
CO 2.1% S
Q_
230ppmV
30ppmNi
0 1 2 3 4
CATALYST AGE B/#
Figure 2. Variation of rate constant with catalyst age
liquid. Under certain conditions the mass action effect of this material
can strongly influence the overall rate of the desulfurization reaction.
Figure 3 shows the effect for one set of circumstances of H S partial 2
£ 2 3 4 5 6 7 8 9
°- H S CONCENTRATION IN EXIT GAS
2
M0L%
Figure 3. Effect of H S on reaction rate constant, Kuwait feed
M
tions. When operations are directed to achieving very low levels of sulfur
in the product, this effect—coupled with the other difficulties of such an
operation—can have important design consequences.
the low sulfur concentration present. At the same time the faster reac-
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
tions take place in a reactor in which the catalyst has reached its final
equilibrium level before being discarded. The line for the back-staging
of catalyst in a three-stage system, shown in Figure 4, indicates that by
this approach virtual equivalence is attained between the H-Oil system
and a theoretical plus-flow reactor.
Split Ho Recycle. A process flow scheme using the back-flow
catalyst/three-stage system is shown in Figure 5. This is basically the
reactor scheme which would be used within an H-Oil unit designed to
achieve very low sulfur contents. A further aspect of this system, shown
in Figure 5, is a split-recycle system. In this way, H S free-hydrogen 2
RECYCLE HYDROGEN
TO
SULFUR
HS
2
X REMOVAL
SPENT
CATALYST 1st 8 2nd STAGE
H-OIL
a D
REACTORS
FRESH
3rd STAGE CATALYST
H-OIL
REACTOR
UNSTABILIZED
LOW SULPHUR
FUEL OIL
2.5
Downloaded by UNIV OF ARIZONA on January 8, 2013 | http://pubs.acs.org
2.0
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
O
o
cr
Q. 1.5
FEED VENEZUELAN ATMOSPHERIC
RESIDUUM 200ppmV.
CO 1.0
FEED: DE METALLIZED
VENEZUELAN
ATMOSPHERIC RESIDUUM
40_ ppm V.
0.5
0 2 4 6 8 10 12
CATALYST AGE,BBL OF OIL/LB OF CATALYST
Figure 6. Comparison of catalyst deactivation in desulfurizing virgin and
demetallized Venezuelan atmospheric residues
bed principle which is then followed by one or more H-Oil stages using
conventional catalysts.
Figure 6 shows the effect of using this newly developed procedure in
the processing of Venezuelan oil. The upper curve in Figure 6 shows the
desulfurization of a medium Venezuelan residual oil as a function of
catalyst age. The lower curve represents the performance of the same
oil over the same catalyst after it has been processed through the newly
developed demetallization procedure. The advantages of such an opera-
tion are obvious, and this procedure makes the processing of these oils
at low rates of catalyst use practical. This procedure removes the limits
previously placed on residue processing by metals content and all of the
presently produced crudes can be considered for the production of low
Downloaded by UNIV OF ARIZONA on January 8, 2013 | http://pubs.acs.org
sulfur fuels.
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
.90
o
o
LU
CO
g
ZD
LU
CO
Q-
.01
.75 .80 .85 .89
xlO"
T(°R)
NAPHTHA
FUEL GAS HS FREE
2
HS ELEMENTAL
LIGHT SULFUR
2
SULFUR
ENDS RICH , PLANT
PROCESSING GAS
ATMOSPHERIC
_ RESID H-OIL
UNIT
FUEL OIL
STABILIZER
LOW SULFUR
FUEL OIL
The data developed in this illustration have been based on the con-
ventional H-Oil catalyst. If one of the newer catalysts referred to earlier
were used, the same results would be achieved at somewhat lower invest-
ment and at substantially reduced rates of catalyst use.
Base Operation. The feedstock flexibility of the plant is illustrated
by the data in Table I. Using the identical plant, we show the ability of
this facility to process Venezuelan, Kuwait, and West Texas atmospheric
residues as well as West Texas vacuum residue to produce a 0.3% sulfur
fuel oil product. The capacity of the plant varies with each of these
Power, kW 12,700
Steam, lbs/hr 6
65,000
Cooling water, gal/min 4,750
Boiler feed water, gal/min 135
Catalyst and chemicals (other than H-Oil), $/day 225
Labor, men/shift 6
a
Supplied from H-Oil gases and light ends.
b
Net external steam requirement.
$/SD
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
Fuels Refinery
73 16 89
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
52 4 56
120 18 138
° After plant fuel consumption.
FUEL GAS
NAPHTHA FOR
SNG OR PETROCHEMICAL
PROnilfiTlflN »
T TURBINE FUEL
WHOLE
^CRUDE HYDROGEN HYDROGEN
PR00UCTI0N
.FUEL GAS
HgS ELEMENTAL
LIGHT RICH SULFUR SULFUR
ENDS PLANT
PROCESSING GAS
H-OIL
UNIT
FUEL OIL
STABILIZER
LOW SULFUR
FUEL OIL
the flexibility necessary to handle raw crudes from various sources and
to enable the processor to meet the varying requirements of the markets
which may be imposed on him with changing product specifications and
product requirements.
Acknowledgments
Literature Cited
Downloaded by UNIV OF ARIZONA on January 8, 2013 | http://pubs.acs.org
1. Beuther, H., Schmid, B. K., World Petrol. Cong., Proc., 6th, Frankfurt, 1963,
Section III, paper 20-PD7.
Publication Date: August 1, 1974 | doi: 10.1021/ba-1973-0127.ch010
2. Griswold, C. R., Van Driesen, R. P., Amer. Petrol. Inst., Div. of Refining,
May 11, 1966, paper 53-66.
3. Van Driesen, R. P., Rapp, L. M., World Petrol. Cong., Proc., 7th, Mexico
City, 1967, paper I.P. No. 32.
4. Johnson, A. R., Papso, J. E., Hippeli, R. F., Nongbri, G., Amer.Petrol.Inst.,
Div. of Refining, May 15, 1970, Houston, Tex., papers 48-70.
5. Johnson, A. R., Papso, J. E., Hippeli, R. F., Wolk, R ., Ann. Meetg., Nat.
Petrol. Refiners Ass., March 21-23, 1971, San Francisco, Calif., paper
AM-71-17.
RECEIVED February 15, 1973.