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Hydrocracking Model
Hydrocracking Model
Hydrocracking Model
Bruce E. Stangeland
Chevron Research Company, Richmond, Caiifornia 94802
A description of the yield changes that occur during hydrocracking is complicated by the large number
of different molecules involved. Here a kinetic model is discussed that represents this wide spectrum of
compounds as a series of 50°F boiling range cuts. Each of the heavier cuts cracks v i a a first-order
reaction to form a series of lighter cuts. One parameter describes the effect of boiling point on the rate
constant. Two other parameters determine what products will be generated as each cut cracks. With a
feed distillation and values for these three parameters, the model predicts product distillation curves as
a function of conversion level for both once-through and recycle liquid operation with a standard error
of about 1%. Values for these parameters are given for a variety of feeds and catalysts. They depend
on catalyst type and feed paraffin content.
Ind. Eng. Chem., Process Des. Develop., Vol. 13, No. 1 , 1974 71
: 0 15
-
c, 010
0.05
0 TBP, 'F
0 2w 4% 600 800 loo0
TBP, -F
Figure 3. Cracking rate function.
Figure 1. Description of a feed stock as discrete components.
72 Ind. Eng. Chem., Process Des. Develop., Vol. 13, No. 1, 1974
Y
k
m
c
Y. F r a c t i o n a l P r o d u c t
Boiling Range
"0 10 20 30 40 M 60 70 80 90 1W
The liquid product distribution function chosen for use Y i e l d o f C,+. W t 9!
here is Figure 5 . Comparison of measured and predicted yields for once-
P ( Y )= [,+ + B(?, - ?'?)](1 - [C4]) (7) through hydrocracking.
500
i
L
e
c
20 30 40 50 50 70 80 W
o0r Y Y
1
10
1
20
'
30
1
40 M
1 1
50 70
1 1
80
I
93
I
100
SecoPd-Stage Conversion, X, Y i e l d of C,+, W t %
Figure 7 . A comparison of predicted and measured jet yields from Figure 8. T h e effect of feed boiling range on product distribution.
a two-stage hydrocracker. T h e effect of conversion levels on yields. Comparison of model and d a t a .
Filled symbols indicate data. with ( 5 6 ) t h e jet yield in parentheses.
Contour lines represent model predictions.
LGO remaining in the product. This is in contrast to the
"theoretical" yields shown as a dashed line, which were
feed to the second-stage unit. The 550"F+ product from determined simply by adding the products from the LGO
the second stage was recycled back to become part of the and HGO in a 3:l ratio. If the two feed components crack
second-stage feed again. Many combinations of first- and independently of each other, then this would be the actual
second-stage conversions were simulated in order to build combined yield from this feed blend. The theoretical yield
up the jet yield contours shown in Figure 7. These agree of 300°F- product is 5070, while the actual yield was only
fairly well with the available data shown as circles. 32%. Thus, adding a heavy component to a lighter one
The maximum for jet production occurs a t low second- shifts the yields toward heavier products. This suggests
stage conversion, Xz, and about 30% first-stage conver- that the cracking of the two components is not indepen-
sion, XI.This corresponds to a small first-stage and a dent; but rather the cracking of the HGO is enhanced,
large second-stage reactor. The amount of second-stage while that for the LGO is retarded. Preferential adsorp-
feed decreases both as Xz increases a t constant XI and as tion and reaction of the heavier material would produce
XI increases a t constant Xz.Thus, as one moves up or to this effect. In the model this is described by a rate con-
the right in Figure 7, the overall feed rates and size of the stant that increases with boiling point.
two-reactor plant decreases; and the products become Rate Constant Vs. Residence Time
lighter. In general, conversions should be kept below
about 70% conversion in both stages because of the rapid The normal approach to describing hydrocracking ki-
decrease in jet yield above this level. Total C g + liquid netics involves the first-order reaction of a feed to prod-
yield also decreases while the gas yield increases. The ucts that boil below some reference temperature. Integra-
curves are not symmetric because the yields from the two tion of the appropriate differential equation leads to the
stages are not identical. Thus, a t XI = 60. X2 = 30, the familiar expression for rate constant
jet yield is 60%; while at XI = 30, X2 = 60, the yield
h= LHSV I n
1 -
___
x,, (9)
drops to 56%. Similar studies could be made, for example,
1 - x
a t a 400°F recycle cut point to maximize the amount of
heavy naphtha and minimize the yield of light naptha and where LHSV is a measure of residence time, Xo and X are
gases. the amounts of material in the feed and product, respec-
tively, that boil below some chosen temperature. This
Mixtures of Feeds equation has been successfully used in many situations. It
A basic assumption in this model is that the same pa- is not very satisfactory, however, when a gap exists be-
rameters should describe the yields for similar feeds even tween the feed initial boiling point and the reference tem-
if their boiling ranges differ. The feed to each successive perature. As an example, consider the problem of describ-
differential reactor shown in Figure 2 grows progressively ing the cracking of a nominal T50"F+ deasphalted oil. It
lighter, but the same parameters are used in each. Sets of had 13R boiling below 850°F and 1% below 7OO"F, but
data were obtained on three gas oil feeds to confirm the none below 600°F. Thus, eq 9 would predict the same
validity of this assumption. A 600-700°F light gas oil value for k a t 50% conversion below 550°F as for 50% con-
(LGO) and a 750-900°F heavy gas oil (HGO) were dis- version below 400°F. Intuitively, the latter case should re-
tilled from the same crude. These, together with a 3:l quire a higher severity.
blend of LGO:HGO, were all studied in the same experi- Sets of data a t three different severities were used to
mental run a t the same reactor conditions. The resulting calculate the values of k from eq 9 for four reference tem-
yields are shown as symbols in Figure 8. These data on peratures. The hydrocracking model, which was initial-
the LGO, together with some additional data taken a t ized to best fit these data, generated a residence time, t,
lower severity, were used to select the model parameters a t each of the three severities. These times are plotted in
that best described the LGO data. These same parameters Figure 9 US. the corresponding values of k . At X = 50%. eq 9
were then used to predict yield distributions on the two gives a value of h = 0.693 for any cut temperature below
heavier feeds as well. These predictions are shown as solid 600°F. However, the hydrocracking model indicates that the
lines. The model fits all of the data quite well except for a residence time required to achieve a conversion of 50%
deviation a t the heavy end of the HGO. This success below 400°F is 3.1 times that needed a t a conversion of 50%
tends to confirm the assumption in the model. below 550°F. This compares favorably with the experi-
The yields on the feed blend are accurately described mentally measured value of 2.4. Thus, this approach shows
by the model even to the large amount (20%) of 600-700°F promise as a more general way of describing cracking and
74 Ind. Eng. Chem., Process Des. Develop., Vol. 13, No. 1, 1974
m
f
1
>-
-2 roenitrificationCatalyst
? =HydrocrackingCatalyst, First Stage m,
*Hydrocracking Catalyst, Second Stage
I
I 1 I I I
0 10 2 0 3 0 4 0 %
0 2 Paraffins i n F e e d , V o I "
Figure 10. T h e dependence of m o d e l p a r a m e t e r s o n feed a n d
catalyst type.
Figure 9 . C o r r e l a t i o n of f i r s t - o r d e r r a t e constant w i t h m o d e l resi- tion of a two-stage plant suggests ways to increase jet
dence t i m e . yields. The residence time that appears in the model can
be used to represent processing severity in the case of feed
kinetics than does eq 9. It handles gap as easily as feed over- gap.
Extensions might include relating the residence time to
lap; and where both methods apply, it correlates well with
the standard first-order kinetics. the hydrogen consumption due to cracking and describing
yields from thermal cracking, coking, or fluid catalytic
Catalyst and Feed Effects cracking. It could also prove to be a useful model to incor-
porate into a refinery simulator program.
Data for many feed-catalyst combinations have been
analyzed in our laboratory in terms of the model discussed Acknowledgment
here. Feed stocks have included cracked stocks from cok-
ers and fluid catalytic crackers, slack waxes, deasphalted The author thanks Chevron Research Company for its
oils, and residua. Parameters from the bulk of our mod- permission to publish this paper and thanks Professor T .
eling work, which involved straight run gas oils, suggest S. Mika for his help in solving the matrix equation.
the correlation with feed-paraffin content shown in Figure
10. The three catalysts included in this study appear to Nomenclature
each require separate correlations. The cracking rate pa- A = rate constant parameter, defined by eq 4
rameter, A , is not a function of feed type but does depend B = product distribution parameter, defined by eq 7
upon catalyst type. The denitrification catalyst has a C = butane yield parameter, defined by eq 5
higher value of A than the two cracking catalysts. As [C,] = butane yield, weight fraction
shown in Figure 3, this means that it has less tendency to D = time-independent solution matrix, defined by eq 3
recrack its products, because its values of k drop rapidly E = vector of rate terms, EL(t ) = exp( - k L t )
with decreasing boiling point.
F , = weight fraction of component i
F = vector of component weight fractions
The product distributions for these catalysts do depend I = identitymatrix
upon feed as well as on catalyst. As the paraffin content k , = first-order rate constant for components i
increases, liquid products grow lighter as indicated by de- K = diagonal matrix of the rate constants, k ,
creasing values of B. Also, the butane yield increases as in- k ( 2') = reaction rate function given by eq 4
dicated by increasing values of C. This suggests that P,,= the fraction of the cracked products from a heavier
paraffins are more prone to crack into two large fragments component, j , that becomes a lighter component, i
than are cyclic compounds. As indicated in Figure 4, a P = lower triangular matrix of the P,,
value of B = -2 indicates a high probability of making P(,y) = product distribution function defined by eq 7
two large fragments. The second-stage catalyst accent- t = residence time
T = normalized boiling point, TBP/1000
uates this trend toward lighter products. This explains TRP = boiling point of a component, "F
why the jet yields were high in the two-stage simulation X = conversion, weight per cent
when the amount of second-stage product was low. 3' = normalized product boiling point, defined by eq 6
Extinction recycle as well as once-through hydrocrack-
ing data were obtained on some feed-catalyst combina- Literature Cited
tions. The primary difference was in the value of the pa- Baral, W. J., Hoffman, H. C., World Petrol Congr.. Proc.. 8th. Paper PD
rameter, A . I t was less for recycle than for once-through 12(1) (1971).
cracking. This corresponds to a reduction in the relative Gilbert, J. B., Walker, J., World Petrol. Congr.. Proc , 8th. Paper PD
12(4) (1971).
rate constant for the heavier portion of the reactor feed. It Herbst, J. A , , MS Thes's, University of California, Berkeley, 1968.
reflects the presence of recycle bottoms in the feed. Herbst, J. A , . Fuerstenau. D. W., A l M E Trans, 241, 538 (1968).
Langlois, G. E., Sullivan, R. F., Advan. Chem. Ser., No. 97, 38 (1970).
Conclusions Nace, D. M.. Weekman, V. W., Jr., lnd. Eng. C h e m , Process Des. De-
velop.. 1 0 , 530 (1971).
A simple kinetic model for describing hydrocracking Orochko. D. I., e t a l . . Khim. Tekhnol. Topl. Masel. 1 5 , No. 8, 2 (1970).
Pachovsky, R . A . . Wojciechowski, B. W., Can. J. Chem. Eng.. 49, 365
yields has been developed that appears to have wide utili- (1971 ) .
ty. It simulates the operation of actual reactors to the ex- Oader, S. A , , etal.. J. inst Petrol.. 56, No. 550, 187 (1970).
Rapaport, I . B.. "Chemistry and Technology of Synthetic Liquid Fuels,"
tent that it can describe the effects on yields of conversion 2nd ed, Israel Program for Scientific Translatlon. Ltd. Jerusalem,
level, feed type and boiling range, and catalyst. Optimiza- 1962.
Ind. Eng. Chem.. Process Des. Develop.. Voi. 13, No. 1, 1974 75
Scott, J. W . . Bridge, A. G . , Advan. Chem. Ser., No. 103 (1971). Zhorov, Yu. M., e t a / . . Int. Chem. Eng.. 11, 256 (1971).
Scott, J . W . , Patterson, N . J . , World Petrol. Congr., Proc.. 7th. 4, 97
(1967). Received f o r recieu April 27, 1973
Stangeland. B . E., Kittrell, J. R.. lnd. Eng. Chem., Process Des. Devel-
o p . , 11, 16 (1972). Accepted October 9, 1973
Usami, H., Hydrocarbon Process.. 103 (1972).
Weekman, V , w , , J ~ , lnd,
, them,, Process Des, 385 Presented a t the 164th National Meeting of the American Chemical
(1969) Society, Division of Petroleum Chemistry. Kew York, N. Y., Aug
Weekrnan, V . W., J r . , Nace. D. M . , A l C h E J . . 16, 397 (1970). 1972.
Vinylidene fluoride plasticized with sulfolane (tetrahydrothiophene 1 , l -dioxide) was found to be an ef-
fective membrane for the separation of SO2 from a binary mixture with NP. Depending on permeator
conditions, actual separation factors varying from about 30 to 100 and fluxes varying from 0.02 to 1.86
scfd/ft2 were observed for the optimum membrane composition containing about 8.2 wt % sulfolane.
Feed gas pressures of 100 to 500 psig were investigated. The membrane selectivity is highly dependent
on feed and membrane composition, and on permeator pressure.
Introduction and Background Gas Products). Analysis of the feed and permeate was ac-
The permeability coefficient of-a gas in a polymeric film complished with a thermal conductivity gas chromato-
is considered to be a function of both solubility and diffu- graph using a Proapak Q-S column (Waters Associates,
sion coefficients. Thus, membrane selectivity may be Inc.). The chromatograph was previously calibrated using
greatly influenced by the relative solubilities of the com- known gas mixtures.
ponents to be separated in the film. In view of this it The accuracy of permeation measurements using a sim-
seemed appropriate to investigate the inclusion of an SO2 ilar apparatus has been reported to be of the order of *5Yc
solvent as a plasticizer in a relatively impermeable poly- (Stern, et al., 1963).
mer in a study of the separation of SO2 from other gases
by gas permeation. A similar technique was recently used Membrane Manufacture
t o make a permeation membrane selective for aromatics The membranes were made as follows. A casting solu-
in the separation of aromatic and naphthenic hydrocar- tion was prepared by dissolving appropriate amounts of
bons by vapor permeation (McCandless, 1973). vinylidene fluoride resin (Kynar, Grade 301, Pennwalt
Corp.) and sulfolane (Phillips Petroleum Co.) in di-
Experimental Section
methylformamide. A ratio of dimethylformamide/resin of
The permeation cell and the apparatus for permeability 5.7 ccjg was used throughout the study. Gentle heating
measurement have been described in detail (McCandless, at about 100" aided dissolution. The films were then cast
1972) although the flux measurement procedure was mod- on a 9.5 x 5 x 3/16 in. glass plate between three thickness-
ified somewhat to facilitate the measurement of the per- es of masking tape by pouring the mixture on the glass
meate which contained u p to about 90% S 0 2 . The per- plate and distributing it evenly by drawing a glass rod
meating gas was allowed to vent to the atmosphere down the plate with the rod resting on the masking tape.
through a l/B-in. nylon tube and through an oil seal while This was then placed in an electrically heated oven held
the system reached steady state. To measure the perme- a t about 105" for 20 min to evaporate the solvent. The
ation rate, oil was drawn into the calibrated vent tube plate was cooled to room temperature before stripping the
and the position of the oil-gas interface was timed. Sampl- film from the plate for mounting in the test cell. The re-
ing for gas analysis was done using a gas-tight syringe sulting films were about 1 mil thick.
through a silicon rubber septum in the vent line.
During a test a feed gas rate 'of about 1.5 scfd was main-
tained through the high-pressure side of the cell. This rate Results
kept the feed gas composition nearly constant for most runs Vinylidene fluoride resin was chosen as the film materi-
although a t some conditions the flux and separation factor al because of its relative impermeability. Hence, it was
were such that about 30% of the feed SO2 was removed felt that the membrane selectivity and permeation rate
through the membrane. would largely be controlled by the properties of the plasti-
The feed gas mixtures were made by pressurizing a cyl- cizing agent because of the high solubility of SO2 (0.65
inder from commercial grade (99.9%j gases (Matheson lb/lb of sulfolane at 20" and 1 atmj in the material. It has