A Kinetic Model for the Prediction of Hydrocracker Yields

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.

Introduction ranges of 50°F each. Such a segregation is illustrated in

Hydrocracking is one of the most versatile processing
steps available to modern refineries. It is also one of the
fastest growing. Installed capacity has increased from 1000
bbl/day in 1960 to 770,000 as of June 1970 (Baral and
Hoffman, 1971). The history and rationale for this rapid
growth have been well summarized in severa! recent pa-
pers (Baral and Hoffman, 1971; Langlois and Sullivan,
1970; Scott and Bridge, 1971; Scott and Patterson, 1967).
These reviews emphasize the great flexibility of hydro-
cracking; it is capable of desulfurizing vacuum residua,
making lubricating oils (Gilbert and Walker, 1971), deme-
talizing catalytic cracker feed, cracking gas oils to jet fuel
and gasoline, or cracking naphtha to LPG. Yields of dif-
ferent products from existing plants can be varied over
fairly broad ranges in response to changes in demands.
Currently, the highest volume product is gasoline. The
strong emphasis today on low sulfur fuel oils, however, is
causing a shift toward a heavier product slate (Scott and
Bridge, 1971). Hydrocracking has the yield flexibility to
help meet these changes in product demands.
In most of its applications, the relative amounts of de-
sired (and undesired) products obtained from this process
are crucial to its economic success. A method for predict-
ing these yields as well as correlating them is the subject
of this paper.
To date, the most common approach to the problem of
predicting yields has been to select a small number of
products and devise various parallel and series reactions
to produce them. Parameters are chosen to best fit some
data. This technique has been used successfully to predict
yields from fluid catalytic cracking units (Nace and
Weekman, 1971; Pachovsky and Wojciechowski, 1971;
Weekman, 1969; Weekman and Nace, 1970) as well as
from hydrocrackers (Orochoko, 1970; Qader, 1970; Stange-
land and Kittrell, 1972; Zhorov, 1971). Usami (1972) has
recently used a similar technique for describing the prod-
ucts from thermal cracking. A major disadvantage to this
approach is that a change in product specifications (e.g.,
reducing the initial boiling point of jet fuel) or in the
number of products (e.g., eliminating a heavy naphtha
cut) requires reformulating the model and refitting the
data.
Model Description
In the model discussed here, the feed and product
streams are assumed to contain a continuum of com-
pounds that can be characterized solely by boiling point.
These compounds are then segregated into fixed boiling
Figure 1. The contents of any range, e.g., 100-15OoF, are
then treated as a single compound. Each is characterized
solely by the true boiling point (TBP) of the end of the
range. The number of these ranges is selected to span the
entire boiling range of interest (0-1100°F here), provide
the required resolution, and still allow the program to fit
on an available computer. Each compound undergoes a
first-order reaction to produce a spectrum of lighter prod-
ucts. Polymerization reactions, which would form heavier
products, are insignificant and can be ignored.
The cracking reactions can be thought of as occurring in
a long series of differential reactors as shown in Figure 2.
The feed to any reactor is the total effluent from the pre-
vious reactor. It includes products as well as unreacted
feed. Thus, products formed in one reactor are feeds to
succeeding reactors and can crack further. This closely
approximates the events occurring in a hydrocracker.
After each reaction step, the reaction mixture becomes
lighter. Cracking is terminated when the required conver-
sion below a chosen temperature is achieved. If liquid
recycle operation is being simulated, the resulting reac-
tion mixture at this point is “distilled” to separate the
products from the uncracked feed remaining in the bot-
toms. This heavier material is mixed with enough fresh
feed to make a new charge of feed for another pass
through the reaction sequence. The entire process for
cracking, distilling, and recycling is continued until the
recycle bottoms composition reaches a steady state.
Mathematical Development
The change in the amount of the ith component is the
result of its cracking plus the contributions from the
cracking of all heavier components.
1-1
where the heaviest component is F I . The first-order rate
constant is k , ; and the fraction of this lighter component,
F,, formed by cracking a heavier component, F,, is PLJ.
Note that k , and P,, are assumed to be independent of re-
actor residence time. This set of equations, one for each
component, can be written as a single matrix differential
equation
where F(t) is the vector containing the weight fractions of
all components, I is the identity matrix, P is the lower tri-

Ind. Eng. Chem., Process Des. Develop., Vol. 13, No. 1 , 1974 71
 : 0 15
-
c, 010
0.05
0 TBP,
0 2w 4%
TBP,
Figure 1. Description of a feed stock as discrete components.
D i f f e r e n t i a l Reactors
Feed
7 ber of parameters. After several expressions were tried,
I the following function was chosen
Recycle Liquid
Figure E. Hydrocracking represented by a series of differential re-
actors.
angular product distribution matrix, and K is the diago-
nal matrix having the ki's on the diagonal.
This formulation of the problem is identical with that
developed by Herbst (1968) and Herbst and Fuerstenau
(1968) for the study of comminution in ball mills. Here,
large particles are broken into smaller ones, the end result
being a desired size distribution. If all cracking rate con-
stants are distinct, a simple solution (Herbst, 1968) to eq
2 can be used
where the time independent D,, is given by
1-1
k P,,,
I), = 1k---Dn,
,-k
?I
I,, =
1-1
11, = F (0)-
/,I = 1 tion curve must, in general, be zero a t 0°F and also a t
D,, = Ofori
and the time dependent E,(t) = exp(-k,t). This solution
is very convenient to use since the determination of yields
a t various residence times does not require reevaluation of
the matrix D, but only the vector E ( t ) . This solution can
readily be applied to polymerization processes by chang-
ing the ordering of components: let Fl be the lightest
rather than the heaviest component.
For any specific application the method chosen for eval-
uating k , and P,, determines to a large extent the success
of the model. Too many adjustable parameters make the
method unwieldly, and too few make it inflexible. In the
following development, three parameters, A, B, and C,
were found to be adequate when used in physically rea-
sonable but arbitrary expressions for the k , and p,,.The
rate constants are defined in terms of the parameter A,
while the product distribution is controlled by B a n d C.
The rate of hydrocracking for pure normal alkanes in-
creases in the ratio 1/32/72/120 for C ~ / C ~ O / C ~ ~ / C ~tude
(Ra-
paport, 1962). Thus, there is a strong increases in k as
boiling point increases. For mixtures of compounds, there
is the additional effect of adsorption on relative reaction
rates. In general, heavier hydrocarbons adsorb more
strongly and react faster than do lighter ones. Also, nor-
mal paraffins of a given molecular weight crack more
72 Ind. Eng. Chem., Process Des. Develop., Vol. 13, No. 1, 1974
'F
600 800 loo0
-F
Figure 3. Cracking rate function.
slowly than do the corresponding isoparaffins or cyclic
r- compounds. Thus, k , will depend on feed composition
h and on catalyst character. An expression for k was needed
that could reflect these differences with a minimum num-
CJ h ( T ) = k,,[T + A ( T ' - T)1 (1)
where T = TBP/1000 and ko = 1. For any value of the pa-
rameter A, k ( 0 ) = 0 and k(1) = l. Above T = l, k ( T ) is
greater than one unless A is negative. Since A usually lies
in the range 0-1.0, k varies from a linear to a cubic func-
tion as shown in Figure 3. Pure compound data (Scott and
Bridge, 1971) indicate that the cracking rate decreases
rapidly for hydrocarbons boiling below 250°F. Here, this is
simulated by setting k ( T ) = 0 for T 5 0.25. The values of
k for the next two heavier components are then adjusted
to minimize the abrupt change in k from zero to those
given by eq 4. k(0.3) and k(0.35) are reduced to 33 and
78%, respectively, of the values given by eq 4.
The distribution of products obtained by cracking each
component is the other important functionality that de-
termines the usefulness of the model. The choice of distri-
bution function is influenced by several factors and as-
sumptions. First, the lightest products considered here are
the butanes which appear in the 0-50°F boiling range.
Second, the minimum reduction in boiling point obtained
for I >J by cracking a molecule is 50-100°F. This corresponds
roughly to a removal of C4. Third, the shape of the prod-
uct distribution curves depends strongly on feed type
(Langlois and Sullivan, 1970); so large variations in shape
for I = J
must be allowed in the model. Thus, the product distribu-
<J 50-100°F below the TBP of the feed component. The total
area under the curve between these intercepts must be
one, and the shape must be flexible.
One complicating feature of actual product distribu-
tions is that the yield of butanes ( 0 4 0 ° F ) is higher than
that for pentanes (50-100°F). The yields of the heavier
liquid components are also higher than those for the pen-
tanes. Thus, a single, smooth product distribution func-
tion will not describe yields of all light products. Here,
one function is used to describe the butane yield, and an-
other handles all heavier product. The yield of butane
usually increases as the TBP of the feed compound be-
comes lighter (Langlois and Sullivan, 1970). This we have
described by the equation
[C,] = C exp[-O.O0693(TBP,,,,,, - %0)] (3)
where [C4] is the weight fraction of butanes. For each
100°F increase in feed TBP above 250"F, the butane yield
drops by a factor of 2. The parameter C sets the magni-
O of this yield.
The heavier products are distributed from 50°F up to a
point 100°F below TBPreed. This range is normalized by
the expression
TBP,,,,,,i - 50
 Y

k
m
c
Y. F r a c t i o n a l P r o d u c t
Boiling Range

Figure 4. Product distribution function.

"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.

The actual yield of any 50°F interval is obtained by sub-

tracting the value of P(>)a t the beginning of the interval W r

from that a t the end.

yield = P ( y ) - P(y>-,)
The parameters B and C determine the shape of the yield
curve. The parameter B usually lies in the range from -2
to +l. The differential of eq 7 is shown in Figure 4 a t sev-
eral values of B. At B = -2, the maximum yields occur
near TBPreea/2 for each component. This represents a
high probability of cracking molecules in half. A t B = 0,
the distribution is linear. This corresponds to removing
small side chains from cyclic compounds. Different values
of B can either reflect changes in feed type (naphthenic to
paraffinic) or in catalytic type (selective to random crack-
ing). or both. The butane yield depends primarily on the
parameter C. However, it is also influenced by A and B
since this yield is a strong function of the amount of liq-
uid boiling below about 600°F.
Applications
Equations 3-8 were converted into a computer program,
which constitutes the hydrocracking yield model. It has
been used in several capacities to increase our under-
standing of the hydrocracking process. These include: (1)
estimating yields a t a desired conversion level by interpo-
lating among data taken a t other severities; (2) maximiz-
ing jet yield in a two-stage plant by varying conversion
levels; (3) estimating yields for feeds that have not yet
been tested; (4) providing a consistent method for de-
scribing cracking rate constants on feeds that have a boil-
ing range gap between the conversion reference tempera-
ture and the feed initial point; (5) suggesting a way to de-
scribe the effects of different catalysts and feeds on kinet-
ics and yields.
Each of these applications is discussed in some detail
in the remainder of this paper.
Data Fitting and Interpolation
Sets of data a t three conversion levels are shown in Fig-
ure 5 for hydrocracking of a raw California gas oil in once-
through liquid operation. This plot represents a simulated
TBP distillation of the C,+ effluent from the reactor. Pa-
rameters were selected that gave the best fit to all the
data simultaneously. The predicted yields based upon
these parameters are shown as solid lines for conversions
of 50, 73, and 92% below 550°F. In general, the agreement
is quite good and probably close to experimental error.
Note that the model accurately describes the changes in
shape for these distillation curves from convex up a t low
severity to convex down a t high severity. This initialized
model can easily be used to generate yields a t any other
(8)
6d
0 ~ ' ' ~ ' i ~ ~ I
0 10 M M 40 M 60 70 80 90 1W
Y i e l d o f C,+ ht %
Figure 6. Comparison of measured and predicted yields for ex-
tinction recvcle cracking below 550°F.
conversion for this feed and can be used to estimate yields
on similar feeds.
Extinction recycle operation is represented by the data
on a denitrified California gas oil shown in Figure 6.
Again, parameters were selected to give the best fit to the
data. Here, the agreement is also quite good. The buildup
of material just above the 550°F recycle cut point is accu-
rately predicted a t all conversion levels (31, 61, and 78%).
So is the depletion of jet fuel in the 400-550°F boiling
range, which appears as a convex down curve below 550°F
and increases with conversion. This initialized model can
also be used to simulate yields on other similar feeds. The
maximum error for the fit of these three sets of data was
4.9%, and the standard deviation was 1.01%. Subsequent-
ly, these parameters were used to predict yields a t 87%
conversion, where we had obtained additional data. The
maximum error for this prediction was 5.270, and the
standard deviation was 1.12%. Thus, the quality of the
prediction was almost as good as was the original fit. Even
so, interpolation is usually safer than extrapolation.
Optimizing Two-Stage Yields
A common configuration for a commercial hydrocrack-
er, such as the Richmond Refinery Isomax Unit. includes
two stages of reactors. The first stage denitrifies and par-
tially cracks the feed to the second stage, which cracks its
feed to extinction below some specified recycle cut point.
As the first-stage severity increases, the feed to the second
stage becomes lighter. This, in turn, shifts the product
distributions from each stage. The combined yields from
such a two-stage plant were simulated using the models
initialized to the data shown in Figures 5 and 6. The
550"F+ product from the first-stage model was the fresh

Ind. Eng. C h e m . , Process Des. Develop., Vol. 13, No. 1 , 1974 73

 w 45 wt 3W-5Wr Jet
80 ---F---\
-
20 30 40 50 50 70 80 W
SecoPd-Stage Conversion, X,
Figure 7 . A comparison of predicted and measured jet yields from
a two-stage hydrocracker. T h e effect of conversion levels on yields.
Filled symbols indicate data. with ( 5 6 ) t h e jet yield in parentheses.
Contour lines represent model predictions.
feed to the second-stage unit. The 550"F+ product from
the second stage was recycled back to become part of the
second-stage feed again. Many combinations of first- and
second-stage conversions were simulated in order to build
up the jet yield contours shown in Figure 7. These agree
fairly well with the available data shown as circles.
The maximum for jet production occurs a t low second-
stage conversion, Xz, and about 30% first-stage conver-
sion, XI.This corresponds to a small first-stage and a
large second-stage reactor. The amount of second-stage
feed decreases both as Xz increases a t constant XI and as
XI increases a t constant Xz.Thus, as one moves up or to
the right in Figure 7, the overall feed rates and size of the
two-reactor plant decreases; and the products become
lighter. In general, conversions should be kept below
about 70% conversion in both stages because of the rapid
decrease in jet yield above this level. Total C g + liquid
yield also decreases while the gas yield increases. The
curves are not symmetric because the yields from the two
stages are not identical. Thus, a t XI = 60. X2 = 30, the
jet yield is 60%; while at XI = 30, X2 = 60, the yield
drops to 56%. Similar studies could be made, for example,
a t a 400°F recycle cut point to maximize the amount of
heavy naphtha and minimize the yield of light naptha and
gases.
Mixtures of Feeds
A basic assumption in this model is that the same pa-
rameters should describe the yields for similar feeds even
if their boiling ranges differ. The feed to each successive
differential reactor shown in Figure 2 grows progressively
lighter, but the same parameters are used in each. Sets of
data were obtained on three gas oil feeds to confirm the
validity of this assumption. A 600-700°F light gas oil
(LGO) and a 750-900°F heavy gas oil (HGO) were dis-
tilled from the same crude. These, together with a 3:l
blend of LGO:HGO, were all studied in the same experi-
mental run a t the same reactor conditions. The resulting
yields are shown as symbols in Figure 8. These data on
the LGO, together with some additional data taken a t
lower severity, were used to select the model parameters
that best described the LGO data. These same parameters
were then used to predict yield distributions on the two
heavier feeds as well. These predictions are shown as solid
lines. The model fits all of the data quite well except for a
deviation a t the heavy end of the HGO. This success
tends to confirm the assumption in the model.
The yields on the feed blend are accurately described
by the model even to the large amount (20%) of 600-700°F
74 Ind. Eng. Chem., Process Des. Develop., Vol. 13, No. 1, 1974
-- Thwretical Yield for
500
i
L
e
c
o0r Y Y
1
10
1
20
'
30
1
40 M
1 1
50 70
1 1
80
I
93
I
100
Y i e l d of C,+, W t %
Figure 8. T h e effect of feed boiling range on product distribution.
Comparison of model and d a t a .
LGO remaining in the product. This is in contrast to the
"theoretical" yields shown as a dashed line, which were
determined simply by adding the products from the LGO
and HGO in a 3:l ratio. If the two feed components crack
independently of each other, then this would be the actual
combined yield from this feed blend. The theoretical yield
of 300°F- product is 5070, while the actual yield was only
32%. Thus, adding a heavy component to a lighter one
shifts the yields toward heavier products. This suggests
that the cracking of the two components is not indepen-
dent; but rather the cracking of the HGO is enhanced,
while that for the LGO is retarded. Preferential adsorp-
tion and reaction of the heavier material would produce
this effect. In the model this is described by a rate con-
stant that increases with boiling point.
Rate Constant Vs. Residence Time
The normal approach to describing hydrocracking ki-
netics involves the first-order reaction of a feed to prod-
ucts that boil below some reference temperature. Integra-
tion of the appropriate differential equation leads to the
familiar expression for rate constant
h= LHSV I n
1 -
___
x,, (9)
1 - x
where LHSV is a measure of residence time, Xo and X are
the amounts of material in the feed and product, respec-
tively, that boil below some chosen temperature. This
equation has been successfully used in many situations. It
is not very satisfactory, however, when a gap exists be-
tween the feed initial boiling point and the reference tem-
perature. As an example, consider the problem of describ-
ing the cracking of a nominal T50"F+ deasphalted oil. It
had 13R boiling below 850°F and 1% below 7OO"F, but
none below 600°F. Thus, eq 9 would predict the same
value for k a t 50% conversion below 550°F as for 50% con-
version below 400°F. Intuitively, the latter case should re-
quire a higher severity.
Sets of data a t three different severities were used to
calculate the values of k from eq 9 for four reference tem-
peratures. The hydrocracking model, which was initial-
ized to best fit these data, generated a residence time, t,
a t each of the three severities. These times are plotted in
Figure 9 US. the corresponding values of k . At X = 50%. eq 9
gives a value of h = 0.693 for any cut temperature below
600°F. However, the hydrocracking model indicates that the
residence time required to achieve a conversion of 50%
below 400°F is 3.1 times that needed a t a conversion of 50%
below 550°F. This compares favorably with the experi-
mentally measured value of 2.4. Thus, this approach shows
promise as a more general way of describing cracking and
 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.

Craininq ModPl Residence Time, t

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
dence t i m e .
kinetics than does eq 9. It handles gap as easily as feed over-
lap; and where both methods apply, it correlates well with
the standard first-order kinetics.
Catalyst and Feed Effects
Data for many feed-catalyst combinations have been
analyzed in our laboratory in terms of the model discussed
here. Feed stocks have included cracked stocks from cok-
ers and fluid catalytic crackers, slack waxes, deasphalted
oils, and residua. Parameters from the bulk of our mod-
eling work, which involved straight run gas oils, suggest
the correlation with feed-paraffin content shown in Figure
10. The three catalysts included in this study appear to
each require separate correlations. The cracking rate pa-
rameter, A , is not a function of feed type but does depend
upon catalyst type. The denitrification catalyst has a
higher value of A than the two cracking catalysts. As
shown in Figure 3, this means that it has less tendency to
recrack its products, because its values of k drop rapidly
with decreasing boiling point.
The product distributions for these catalysts do depend
upon feed as well as on catalyst. As the paraffin content
increases, liquid products grow lighter as indicated by de-
creasing values of B. Also, the butane yield increases as in-
dicated by increasing values of C. This suggests that
paraffins are more prone to crack into two large fragments
than are cyclic compounds. As indicated in Figure 4, a
value of B = -2 indicates a high probability of making
two large fragments. The second-stage catalyst accent-
uates this trend toward lighter products. This explains
why the jet yields were high in the two-stage simulation
when the amount of second-stage product was low.
Extinction recycle as well as once-through hydrocrack-
ing data were obtained on some feed-catalyst combina-
tions. The primary difference was in the value of the pa-
rameter, A . I t was less for recycle than for once-through
cracking. This corresponds to a reduction in the relative
rate constant for the heavier portion of the reactor feed. It
reflects the presence of recycle bottoms in the feed.
Conclusions
A simple kinetic model for describing hydrocracking
yields has been developed that appears to have wide utili-
ty. It simulates the operation of actual reactors to the ex-
tent that it can describe the effects on yields of conversion
level, feed type and boiling range, and catalyst. Optimiza-
resi- tion of a two-stage plant suggests ways to increase jet
yields. The residence time that appears in the model can
be used to represent processing severity in the case of feed
gap.
Extensions might include relating the residence time to
the hydrogen consumption due to cracking and describing
yields from thermal cracking, coking, or fluid catalytic
cracking. It could also prove to be a useful model to incor-
porate into a refinery simulator program.
Acknowledgment
The author thanks Chevron Research Company for its
permission to publish this paper and thanks Professor T .
S. Mika for his help in solving the matrix equation.
Nomenclature
A = rate constant parameter, defined by eq 4
B = product distribution parameter, defined by eq 7
C = butane yield parameter, defined by eq 5
[C,] = butane yield, weight fraction
D = time-independent solution matrix, defined by eq 3
E = vector of rate terms, EL(t ) = exp( - k L t )
F , = weight fraction of component i
F = vector of component weight fractions
I = identitymatrix
k , = first-order rate constant for components i
K = diagonal matrix of the rate constants, k ,
k ( 2') = reaction rate function given by eq 4
P,,= the fraction of the cracked products from a heavier
component, j , that becomes a lighter component, i
P = lower triangular matrix of the P,,
P(,y) = product distribution function defined by eq 7
t = residence time
T = normalized boiling point, TBP/1000
TRP = boiling point of a component, "F
X = conversion, weight per cent
3' = normalized product boiling point, defined by eq 6
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Separation of Sulfur Dioxide and Nitrogen by Permeation through a Sulfolane

Plasticized Vinylidene Fluoride Film

Dennis R. Seibel and F. P. McCandless*

Department of Chemical Engineering, Montana State University, Bozeman, Montana 59715

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
The permeability coefficient of-a gas in a polymeric film
is considered to be a function of both solubility and diffu-
sion coefficients. Thus, membrane selectivity may be
greatly influenced by the relative solubilities of the com-
ponents to be separated in the film. In view of this it
seemed appropriate to investigate the inclusion of an SO2
solvent as a plasticizer in a relatively impermeable poly-
mer in a study of the separation of SO2 from other gases
by gas permeation. A similar technique was recently used
t o make a permeation membrane selective for aromatics
in the separation of aromatic and naphthenic hydrocar-
bons by vapor permeation (McCandless, 1973).
Experimental Section
The permeation cell and the apparatus for permeability
measurement have been described in detail (McCandless,
1972) although the flux measurement procedure was mod-
ified somewhat to facilitate the measurement of the per-
meate which contained u p to about 90% S 0 2 . The per-
meating gas was allowed to vent to the atmosphere
through a l/B-in. nylon tube and through an oil seal while
the system reached steady state. To measure the perme-
ation rate, oil was drawn into the calibrated vent tube
and the position of the oil-gas interface was timed. Sampl-
ing for gas analysis was done using a gas-tight syringe
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
kept the feed gas composition nearly constant for most runs
although a t some conditions the flux and separation factor
were such that about 30% of the feed SO2 was removed
through the membrane.
The feed gas mixtures were made by pressurizing a cyl-
inder from commercial grade (99.9%j gases (Matheson
Gas Products). Analysis of the feed and permeate was ac-
complished with a thermal conductivity gas chromato-
graph using a Proapak Q-S column (Waters Associates,
Inc.). The chromatograph was previously calibrated using
known gas mixtures.
The accuracy of permeation measurements using a sim-
ilar apparatus has been reported to be of the order of *5Yc
(Stern, et al., 1963).
Membrane Manufacture
The membranes were made as follows. A casting solu-
tion was prepared by dissolving appropriate amounts of
vinylidene fluoride resin (Kynar, Grade 301, Pennwalt
Corp.) and sulfolane (Phillips Petroleum Co.) in di-
methylformamide. A ratio of dimethylformamide/resin of
5.7 ccjg was used throughout the study. Gentle heating
at about 100" aided dissolution. The films were then cast
on a 9.5 x 5 x 3/16 in. glass plate between three thickness-
es of masking tape by pouring the mixture on the glass
plate and distributing it evenly by drawing a glass rod
down the plate with the rod resting on the masking tape.
This was then placed in an electrically heated oven held
a t about 105" for 20 min to evaporate the solvent. The
plate was cooled to room temperature before stripping the
film from the plate for mounting in the test cell. The re-
sulting films were about 1 mil thick.
Results
Vinylidene fluoride resin was chosen as the film materi-
al because of its relative impermeability. Hence, it was
felt that the membrane selectivity and permeation rate
would largely be controlled by the properties of the plasti-
cizing agent because of the high solubility of SO2 (0.65
lb/lb of sulfolane at 20" and 1 atmj in the material. It has

76 Ind. Eng. Chem., Process Des. Develop.,Vol. 13, No. 1, 1974