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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 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 papers (Baral and Hoffman, 1971; Langlois and Sullivan, 1970; Scott and Bridge, 1971; Scott and Patterson, 1967). These reviews emphasize the great flexibility of hydrocracking; it is capable of desulfurizing vacuum residua, making lubricating oils (Gilbert and Walker, 1971), demetalizing catalytic cracker feed, cracking gas oils to jet fuel and gasoline, or cracking naphtha to LPG. Yields of different 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 desired (and undesired) products obtained from this process are crucial to its economic success. A method for predicting 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; Stangeland and Kittrell, 1972; Zhorov, 1971). Usami (1972) has recently used a similar technique for describing the products 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 compounds that can be characterized solely by boiling point. These compounds are then segregated into fixed boiling

ranges of 50°F each. Such a segregation is illustrated in 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 products. 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 previous 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 conversion below a chosen temperature is achieved. If liquid recycle operation is being simulated, the resulting reaction mixture at this point is “distilled” to separate the products from the uncracked feed remaining in the bottoms. 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 reactor 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 triInd. Eng.

Chem., Process Des. Develop., Vol. 13, No. 1 , 1974

71

Develop.] = C exp[-O.. Eng.3) and k(0. so large variations in shape must be allowed in the model. be zero a t 0°F and also a t 50-100°F below the TBP of the feed component.. angular product distribution matrix. For any specific application the method chosen for evaluating k . will depend on feed composition and on catalyst character.50 strongly and react faster than do lighter ones. 1968) to eq 2 can be used where the time independent D.O0693(TBP. For any value of the parameter A. This range is normalized by is the additional effect of adsorption on relative reaction the expression rates. This corresponds roughly to a removal of C4. the end result being a desired size distribution. the product distribution curve must. 1962). the shape of the product distribution curves depends strongly on feed type (Langlois and Sullivan. k ( T ) is greater than one unless A is negative.. Vol. large particles are broken into smaller ones. Since A usually lies in the range 0-1. Here. the lightest products considered here are the butanes which appear in the 0-50°F boiling range.[T + A ( T ' . Chem. Too many adjustable parameters make the method unwieldly..I = for 1 I = J D. 100°F increase in feed TBP above 250"F.The rate constants are defined in terms of the parameter A. B. For each while the product distribution is controlled by B a n d C. The choice of distribution function is influenced by several factors and assumptions. = Ofori <J and the time dependent E. were found to be adequate when used in physically rea[C. Above T = l. (Ratude paport.. there is a strong increases in k as The heavier products are distributed from 50°F up to a boiling point increases. The distribution of products obtained by cracking each component is the other important functionality that determines the usefulness of the model..(t) = exp(-k. . = 1-1 1-1 for I >J 11... 1970). 600 -F 800 loo0 TBP. heavier hydrocarbons adsorb more TBP. If all cracking rate constants are distinct. An expression for k was needed that could reflect these differences with a minimum number of parameters. A.. determines to a large extent the success of the model. respectively. The yield of butane usually increases as the TBP of the feed compound becomes lighter (Langlois and Sullivan. 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. and p. 1974 . Here. After several expressions were tried. and P. k . smooth product distribution function will not describe yields of all light products. Also.%0)] (3) sonable but arbitrary expressions for the k . Second. Description of a feed stock as discrete components. normal paraffins of a given molecular weight crack more 72 where T = TBP/1000 and ko = 1...T)1 (1) Figure E. one function is used to describe the butane yield. . of the values given by eq 4.t).: 0 15 c.. the butane yield The rate of hydrocracking for pure normal alkanes indrops by a factor of 2.. 1. k ( 0 ) = 0 and k(1) = l.. 1971) indicate that the cracking rate decreases rapidly for hydrocarbons boiling below 250°F.25... Pure compound data (Scott and Bridge. and another handles all heavier product.. For mixtures of compounds. Figure 1. Thus. The total area under the curve between these intercepts must be one. the minimum reduction in boiling point obtained by cracking a molecule is 50-100°F.35) are reduced to 33 and 78%. In the following development. D i f f e r e n t i a l Reactors Feed rh 7 I CJ Recycle Liquid slowly than do the corresponding isoparaffins or cyclic compounds. Third. a single. this is simulated by setting k ( T ) = 0 for T 5 0. First. where [C4] is the weight fraction of butanes.0. the following function was chosen h ( T ) = k. is given by I). there point 100°F below TBPreed. No. k(0.05 0 0 2w 4% TBP. = k P. The yields of the heavier liquid components are also higher than those for the pentanes. a simple solution (Herbst.i . Process Des.. In general.. and K is the diagonal matrix having the ki's on the diagonal. Thus. Thus. The parameter C sets the magnicreases in the ratio 1/32/72/120 for C ~ / C ~ O / C ~ ~ / C ~ O of this yield. 1970). One complicating feature of actual product distributions is that the yield of butanes ( 0 4 0 ° F ) is higher than that for pentanes (50-100°F). 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. three parameters. 1k---Dn.-k ?I I. and C. Thus. 'F Figure 3. This solution can readily be applied to polymerization processes by changing the ordering of components: let Fl be the lightest rather than the heaviest component. 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. and the shape must be flexible. Cracking rate function.. in general. Here. 13. k varies from a linear to a cubic function as shown in Figure 3. and too few make it inflexible. but only the vector E ( t ) . This we have described by the equation Ind. - 010 0. Hydrocracking represented by a series of differential reactors. . = F (0) /.

P(y>-.12%. interpolation is usually safer than extrapolation. Again. which cracks its feed to extinction below some specified recycle cut point. W r The actual yield of any 50°F interval is obtained by suba tracting the value of P(>)t the beginning of the interval from that a t the end.Y k c m Y.?'?)](1 . F r a c t i o n a l P r o d u c t Boiling Range Figure 4. Data Fitting and Interpolation Sets of data a t three conversion levels are shown in Figure 5 for hydrocracking of a raw California gas oil in oncethrough liquid operation. which constitutes the hydrocracking yield model. 73. However. Subsequently. Comparison of measured and predicted yields for extinction recvcle cracking below 550°F. The 550"F+ product from the first-stage model was the fresh Ind. Comparison of measured and predicted yields for oncethrough hydrocracking. In general. such as the Richmond Refinery Isomax Unit. The first stage denitrifies and partially cracks the feed to the second stage. The butane yield depends primarily on the parameter C. 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. where we had obtained additional data. 61. yield = P ( y ) . (4) providing a consistent method for describing cracking rate constants on feeds that have a boiling range gap between the conversion reference temperature and the feed initial point. it is also influenced by A and B since this yield is a strong function of the amount of liquid boiling below about 600°F. and the standard deviation was 1. the agreement is quite good and probably close to experimental error. The parameter B usually lies in the range from -2 to +l. No.+ effluent from the reactor. includes two stages of reactors. It has been used in several capacities to increase our understanding of the hydrocracking process. Different values of B can either reflect changes in feed type (naphthenic to paraffinic) or in catalytic type (selective to random cracking). these parameters were used to predict yields a t 87% conversion. . This. This corresponds to removing small side chains from cyclic compounds. Even so. conversion for this feed and can be used to estimate yields on similar feeds. Applications Equations 3-8 were converted into a computer program. These include: (1) estimating yields a t a desired conversion level by interpolating among data taken a t other severities. The maximum error for this prediction was 5. 13.270.01%. "0 10 20 30 40 M 60 70 80 90 1W The liquid product distribution function chosen for use here is Y i e l d o f C.[C4]) (7) Figure 5 . Product distribution function. This initialized model can also be used to simulate yields on other similar feeds. So is the depletion of jet fuel in the 400-550°F boiling range. . The differential of eq 7 is shown in Figure 4 a t several values of B. Extinction recycle operation is represented by the data on a denitrified California gas oil shown in Figure 6. Develop. the distribution is linear. the agreement is also quite good. and 92% below 550°F.. The buildup of material just above the 550°F recycle cut point is accurately predicted a t all conversion levels (31. or both. As the first-stage severity increases. the feed to the second stage becomes lighter. A t B = 0. 1 . The combined yields from such a two-stage plant were simulated using the models initialized to the data shown in Figures 5 and 6. (2) maximizing jet yield in a two-stage plant by varying conversion levels. and the standard deviation was 1. This plot represents a simulated TBP distillation of the C. 6d 0 ~ 0 10 M M ' ' ~ ' 40 M 60 70 80 90 1 W i ~ ~ I Y i e l d o f C. Here. W t 9! P ( Y )= [. 1974 73 .+ ht % Figure 6. which appears as a convex down curve below 550°F and increases with conversion.+. Parameters were selected that gave the best fit to all the data simultaneously. the quality of the prediction was almost as good as was the original fit. C h e m . in turn. Eng. At B = -2. and 78%). This represents a high probability of cracking molecules in half. (5) suggesting a way to describe the effects of different catalysts and feeds on kinetics and yields. shifts the product distributions from each stage. Process Des. (3) estimating yields for feeds that have not yet been tested. This initialized model can easily be used to generate yields a t any other Optimizing Two-Stage Yields A common configuration for a commercial hydrocracker. Vol. the maximum yields occur near TBPreea/2 for each component.) (8) The parameters B and C determine the shape of the yield curve.9%. The predicted yields based upon these parameters are shown as solid lines for conversions of 50. Each of these applications is discussed in some detail in the remainder of this paper.+ + B(?. parameters were selected to give the best fit to the data. The maximum error for the fit of these three sets of data was 4. Thus.

. the 2 2 jet yield is 60%. A comparison of predicted and measured jet yields from a two-stage hydrocracker. Many combinations of first. a t each of the three severities.-- w t 3W-5Wr Jet -. At X = 50%.693 for any cut temperature below 600°F.4. T h e effect of conversion levels on yields. X = 30.. a t a 400°F recycle cut point to maximize the amount of heavy naphtha and minimize the yield of light naptha and gases. Vol. The model fits all of the data quite well except for a deviation a t the heavy end of the HGO. W t Figure 7 . Figure 8. The maximum for jet production occurs a t low secondstage conversion. The theoretical yield of 300°F.w 80 45 -. These agree fairly well with the available data shown as circles. In the model this is described by a rate constant that increases with boiling point. Eng. These. In general. Thus. eq 9 gives a value of h = 0. Develop.Thus. Chem. 1 . a t XI = 60. Residence Time The normal approach to describing hydrocracking kinetics involves the first-order reaction of a feed to products that boil below some reference temperature. The hydrocracking model. XI. This is in contrast to the "theoretical" yields shown as a dashed line. together with a 3:l blend of LGO:HGO. the latter case should require a higher severity. T h e effect of feed boiling range on product distribution. Intuitively. The resulting yields are shown as symbols in Figure 8. The feed to each successive differential reactor shown in Figure 2 grows progressively lighter. It had 13R boiling below 850°F and 1% below 7OO"F. the yield I drops to 56%. generated a residence time.x (9) Mixtures of Feeds A basic assumption in this model is that the same parameters should describe the yields for similar feeds even if their boiling ranges differ. but none below 600°F. It is not very satisfactory. the corresponding values of k . and about 30% first-stage conversion. consider the problem of describing the cracking of a nominal T50"F+ deasphalted oil.+. the hydrocracking model indicates that the residence time required to achieve a conversion of 50% below 400°F is 3. As an example. but the same parameters are used in each. the overall feed rates and size of the two-reactor plant decreases. with ( 5 6 ) t h e jet yield in parentheses. however. 1974 .Thwretical Yield for 500 i L c e 20 30 40 50 50 70 80 X. as one moves up or to the right in Figure 7. conversions should be kept below about 70% conversion in both stages because of the rapid decrease in jet yield above this level. W o0r Y Y 10 1 20 1 ' 30 40 1 M 1 50 1 1 70 % 80 1 9 3 I I 100 SecoPd-Stage Conversion. These predictions are shown as solid lines.\ -.product is 5070. then this would be the actual combined yield from this feed blend. Comparison of model and d a t a . when a gap exists between the feed initial boiling point and the reference temperature. Sets of data were obtained on three gas oil feeds to confirm the validity of this assumption. Process Des. The amount of second-stage feed decreases both as Xz increases a t constant X and as I XI increases a t constant Xz. but rather the cracking of the HGO is enhanced.. while at X = 30. If the two feed components crack independently of each other. eq 9 would predict the same value for k a t 50% conversion below 550°F as for 50% conversion below 400°F. while the actual yield was only 32%. for example. that boil below some chosen temperature. Filled symbols indicate data. No. This corresponds to a small first-stage and a large second-stage reactor. The curves are not symmetric because the yields from the two stages are not identical. This suggests that the cracking of the two components is not independent. t. Total C g + liquid yield also decreases while the gas yield increases. LGO remaining in the product. Thus. Similar studies could be made. This equation has been successfully used in many situations. adding a heavy component to a lighter one shifts the yields toward heavier products. This success tends to confirm the assumption in the model. feed to the second-stage unit. The yields on the feed blend are accurately described by the model even to the large amount (20%) of 600-700°F 74 where LHSV is a measure of residence time. respectively. together with some additional data taken a t lower severity. were all studied in the same experimental run a t the same reactor conditions. and the products become lighter. Integration of the appropriate differential equation leads to the familiar expression for rate constant h= LHSV I n ___ 1 - x. X = 60. Rate Constant Vs. Sets of data a t three different severities were used to calculate the values of k from eq 9 for four reference temperatures. This compares favorably with the experimentally measured value of 2. X and X are o the amounts of material in the feed and product. These data on the LGO.1 times that needed a t a conversion of 50% below 550°F. were used to select the model parameters that best described the LGO data. Thus. which was initialized to best fit these data. Preferential adsorption and reaction of the heavier material would produce this effect. However. 13. Xz.F . which were determined simply by adding the products from the LGO and HGO in a 3:l ratio. this approach shows promise as a more general way of describing cracking and Ind. Contour lines represent model predictions. The 550"F+ product from the second stage was recycled back to become part of the second-stage feed again. while that for the LGO is retarded. Y i e l d of C.and second-stage conversions were simulated in order to build up the jet yield contours shown in Figure 7. A 600-700°F light gas oil (LGO) and a 750-900°F heavy gas oil (HGO) were distilled from the same crude. Thus. These same parameters were then used to predict yield distributions on the two heavier feeds as well. These times are plotted in Figure 9 US. 1.

Masel.. Khim.. Berkeley. 1. 49. 8.. J. This suggests that paraffins are more prone to crack into two large fragments than are cyclic compounds. Wojciechowski. TBP/1000 TRP = boiling point of a component. It reflects the presence of recycle bottoms in the feed. weight per cent 3' = normalized product boiling point. C h e m .. R . k . R. defined by eq 3 E = vector of rate terms. Ind.. Extensions might include relating the residence time to the hydrogen consumption due to cracking and describing yields from thermal cracking. C. deasphalted oils. 530 (1971). Tekhnol.. this means that it has less tendency to recrack its products. .. This explains why the jet yields were high in the two-stage simulation when the amount of second-stage product was low. 550. G. J. W. A ... A . Develop. Also. Ser. This corresponds to a reduction in the relative rate constant for the heavier portion of the reactor feed. Gilbert. As the paraffin content increases. k ( 2 = reaction rate function given by eq 4 ' ) P. A l M E Trans. because its values of k drop rapidly with decreasing boiling point. Jerusalem. The cracking rate parameter. World Petrol. I. Optimiza- tion of a two-stage plant suggests ways to increase jet yields. and catalyst. Craininq ModPl Residence Time. defined by eq 5 [C.. As shown in Figure 3. . Extinction recycle as well as once-through hydrocracking data were obtained on some feed-catalyst combinations. It could also prove to be a useful model to incorporate into a refinery simulator program. Catalyst and Feed Effects Data for many feed-catalyst combinations have been analyzed in our laboratory in terms of the model discussed here. Topl. First Stage *Hydrocracking Catalyst. Proc. The denitrification catalyst has a higher value of A than the two cracking catalysts. Ltd. Process Des. 538 (1968). A . j . W. Advan. W. Herbst. Mika for his help in solving the matrix equation. No. MS Thes's. 1 0 . 187 (1970). It simulates the operation of actual reactors to the extent that it can describe the effects on yields of conversion level. 8th. lnd. Acknowledgment The author thanks Chevron Research Company for its permission to publish this paper and thanks Professor T . The residence time that appears in the model can be used to represent processing severity in the case of feed gap.. Sullivan. slack waxes. Chem. P(. a value of B = -2 indicates a high probability of making two large fragments. D. F. No. Chem. A . M. Paper PD 12(1) (1971). J. A . V o I " T h e dependence catalyst type. inst Petrol. As indicated in Figure 4. 365 (1971 ) . .. it correlates well with the standard first-order kinetics. B.. etal. Develop. Nace. "Chemistry and Technology of Synthetic Liquid Fuels.. Eng.o r d e r r a t e constant w i t h m o d e l dence t i m e . feed type and boiling range. S. Voi. = weight fraction of component i F = vector of component weight fractions I = identitymatrix k . 97.] = butane yield. H. S. A . resi- kinetics than does eq 9. Fuerstenau. and where both methods apply. 1962.. J. 8th. 38 (1970).. defined by eq 7 C = butane yield parameter. Pachovsky. Feed stocks have included cracked stocks from cokers and fluid catalytic crackers. and residua. Paper PD 12(4) (1971). Eng. I 1 -2 ? I 1 I I 0 0 2 10 2 0 3 0 4 0 I % Paraffins i n F e e d . World Petrol Congr. Proc . is not a function of feed type but does depend upon catalyst type. of m o d e l p a r a m e t e r s o n feed a n d C o r r e l a t i o n of f i r s t . 13.. Hoffman.. suggest the correlation with feed-paraffin content shown in Figure 10. J. the butane yield increases as indicated by increasing values of C. 1 5 . 241. No. J. It handles gap as easily as feed overlap. Nomenclature A = rate constant parameter.= the fraction of the cracked products from a heavier component. E. Herbst. weight fraction D = time-independent solution matrix. Orochko. D... University of California. liquid products grow lighter as indicated by decreasing values of B." 2nd ed. D.. Congr. Weekman. defined by eq 6 Literature Cited Baral. 1968. W. Second Stage m. V.. The primary difference was in the value of the parameter.y) = product distribution function defined by eq 7 t = residence time T = normalized boiling point. "F X = conversion. J. e t a l .. Process Des.. that becomes a lighter component. I t was less for recycle than for once-through cracking.f m > roenitrificationCatalyst =HydrocrackingCatalyst. coking. Jr. 56. 2 (1970).. 1974 75 . The second-stage catalyst accentuates this trend toward lighter products. Walker. t Figure 10. or fluid catalytic cracking. B. Langlois. which involved straight run gas oils. No. EL( ) = exp( . Parameters from the bulk of our modeling work. i P = lower triangular matrix of the P. Eng. I . The product distributions for these catalysts do depend upon feed as well as on catalyst. Chem. Figure 9 . Israel Program for Scientific Translatlon. Conclusions A simple kinetic model for describing hydrocracking yields has been developed that appears to have wide utility. Oader. The three catalysts included in this study appear to each require separate correlations. Can.k L t ) t F . B. Rapaport. = first-order rate constant for components i K = diagonal matrix of the rate constants. . defined by eq 4 B = product distribution parameter. .

Zhorov. J ~ . . B . Proc. .86 scfd/ft2 were observed for the optimum membrane composition containing about 8.Vol. Int.. E. . To measure the permeation rate. J. and on permeator pressure. 7th. Gentle heating at about 100" aided dissolution. membrane selectivity may be greatly influenced by the relative solubilities of the components to be separated in the film. lnd. Montana State University. A ratio of dimethylformamide/resin of 5. Gas Products).. 4. Process Results Vinylidene fluoride resin was chosen as the film material because of its relative impermeability. M . M. . Seibel and F. 97 (1967). Usami. J .. lnd. Weekman. Scott. A l C h E J . . No. 1963). Aug 1972.. 1973 Presented a t the 164th National Meeting of the American Chemical Society. 103 (1971). 397 (1970). Hence.02 to 1. Eng. Advan.. Patterson.2 wt % sulfolane. Montana 59715 Vinylidene fluoride plasticized with sulfolane (tetrahydrothiophene 1 . Received f o r recieu April 27. Introduction and Background The permeability coefficient of-a gas in a polymeric film is considered to be a function of both solubility and diffusion coefficients.. J r .. W. World Petrol.) and sulfolane (Phillips Petroleum Co. Y. Membrane Manufacture The membranes were made as follows. 1. In view of this it seemed appropriate to investigate the inclusion of an SO2 solvent as a plasticizer in a relatively impermeable polymer in a study of the separation of SO2 from other gases by gas permeation. During a test a feed gas rate 'of about 1. W . Chem. The membrane selectivity is highly dependent on feed and membrane composition. The plate was cooled to room temperature before stripping the film from the plate for mounting in the test cell. No. N. Sampling for gas analysis was done using a gas-tight syringe through a silicon rubber septum in the vent line. 13.5 x 5 x 3/16 in. Thus. A. 385 (1969) Weekrnan. w . 11. A similar technique was recently used t o make a permeation membrane selective for aromatics in the separation of aromatic and naphthenic hydrocarbons by vapor permeation (McCandless.7 ccjg was used throughout the study. l -dioxide) was found to be an effective membrane for the separation of SO2 from a binary mixture with NP. glass plate between three thicknesses 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. The films were then cast on a 9. . W . The chromatograph was previously calibrated using known gas mixtures. Yu. Chem. Feed gas pressures of 100 to 500 psig were investigated.. Pennwalt Corp. 256 (1971). The permeating gas was allowed to vent to the atmosphere through a l/B-in. Nace. Process Des. 11... Experimental Section The permeation cell and the apparatus for permeability measurement have been described in detail (McCandless. Bozeman. . H. N . Stangeland. McCandless* Department of Chemical Engineering... 16. e t a / . J . 103 (1972). The accuracy of permeation measurements using a similar apparatus has been reported to be of the order of *5Yc (Stern. Chem.5 scfd was maintained through the high-pressure side of the cell. 1973). Bridge.. it was felt that the membrane selectivity and permeation rate would largely be controlled by the properties of the plasticizing agent because of the high solubility of SO2 (0. Develop. 1972) although the flux measurement procedure was modified somewhat to facilitate the measurement of the permeate which contained u p to about 90% S 0 2 . The feed gas mixtures were made by pressurizing a cylinder from commercial grade (99.Scott. Eng.9%j gases (Matheson 76 Ind.). actual separation factors varying from about 30 to 100 and fluxes varying from 0.. Analysis of the feed and permeate was accomplished with a thermal conductivity gas chromatograph using a Proapak Q-S column (Waters Associates. Congr. oil was drawn into the calibrated vent tube and the position of the oil-gas interface was timed. Chem. J. them.. Hydrocarbon Process. Eng. Inc. 1973 Accepted October 9. 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. 1974 . . P.) in dimethylformamide. The resulting films were about 1 mil thick. G . et al. Grade 301. D. It has Des.65 lb/lb of sulfolane at 20" and 1 atmj in the material. . 16 (1972). Ser. Depending on permeator conditions. .. Division of Petroleum Chemistry. Kittrell. This was then placed in an electrically heated oven held a t about 105" for 20 min to evaporate the solvent. V . V . Separation of Sulfur Dioxide and Nitrogen by Permeation through a Sulfolane Plasticized Vinylidene Fluoride Film Dennis R. nylon tube and through an oil seal while the system reached steady state. Develo p . Kew York. A casting solution was prepared by dissolving appropriate amounts of vinylidene fluoride resin (Kynar. R. Process Des. .

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