Separation Processes C. JUDSON KING Profeator of Chemical Engineering University of California, Berkeley Menaw-nut aoox company — INTY New Yor San Faneco St Louie Disteldod London Monee” Panama. Syaney TorontoAcASE MisTORY ‘The separation of ethylbenzene from styrene by distillation represents an interesting case where a crucial compromise must be made between factors governing efficiency and capacity of a distillation column. ‘As shown in Figures 12-28 and 12-29, styrene is manufactured from ethylbenzene by catalytic dehydrogenation (Stobaugh, 1965). Fresh and recycle ethylbenzene are mixed with superheated steam and are fed to a catalyst-containing reactor at 1200 to 1400°F and a pressure near atmospheric. In the reactor ethylbenzene is converted to Inydrogen and styrene at a conversion of 35 to 40 percent per pass: H 4 €LcH, —> C=CH +H Ethylbenzene Styrene Cooling steps following the reactor separate condensed steam from hydrocarbon product, and then separate condensed aromatics from the hydrogen product and other light hydrocarbon gases. The reaction selectivity is over 90 percent to styrene; however, some benzene and toluene are formed as cracking by-products and must be removed as a first distillation step. The following towers separate styrene from unconverted ethylbenzene and separate styrene from heavier tars (polymerization by-products). The separation of ethylbenzene from styrene presents unique difficulties. Styrene polymerizes readily and can therefore foul the reboiler, bottom trays, etc. Even in the presence of polymerization inhibitors, styrene polymerizes at temperatures greater than about 100°C. As a result it has been necessary to run the ethylbenzene-styreneCAPACITY AND EFFICIENCY OF CONTACTING DEVICES 09 Water Refrigerant Vent gases (H,, etc) Ethylbenzene Recycle ethylbenzene Bach Styrene stil storage Styrene product Fig. 12-28 Typical process for manufacture of styrene from ethylbenzene. column under vacuum so as to hold temperatures down. On the other hand, the relative volatility of ethylbenzene to styrene is not great, and so a large number of plates is required for the distillation, Consequently there is a large pressure drop through the tower, and this factor places a lower limit on the absolute pressure in the reboiler and, hence, on the reboiler temperature. If steps arc taken to reduce the pressure drop per. plate, the plate efficiency may also drop, with the result that more plates are required and the pressure drop goes back up. A history of efforts to cope with the efficiency and capacity problems associated with ethylbenzene-styrene distillation has been given by Frank (Frank, 1968; Frank et al., 1969) and is reproduced here.' “Joseph C. Frank, Early Developments in Styrene Process Disillation Column Design, Styrene Section, Midland Division, The Dow Chemical Company, Midland, Michigan. Reprinted with permission of The Dow Chemical Company.10 SEPARATION PROCESSES 12.28 A section of Dow Chemicals styrene complex at Midland, Michigan. (Courtesy The Dow ‘Chemical Co., Midland, Mich.) In the development of the Dow styrene process using the catalytic dehydrogenation of ethylbenzene, one of the most important process unit operations is distillation. Inthe alkylation ‘ection distillation columns separate the benzene and polyethylbenzenes for recycle and produce an ethylbenzene of over 99 weight percent purity. ‘With the ethylbenzene dehydrogenation step giving a crude product of about 40 weisht percent styrene, distillation columns are used to separate and purify the benzene and toluene, Separate for recycle the ethylbenzene and purify a styrene monomer to ever increasing purity ‘specifications. "The most difficult fractionation problemencountered isthe separation of styrene from the ‘unreacted ethylbenzene. With an atmospheric boiling point for ethylbenzene of 136.2°C and for styrene of 145.2°C, the temperature difference for this distillation is 9°C, and the relative volatility is less than 1.3. Vacuum operation improves this relative volatility to the range of 1.34 to 1.40. Today this would be considered an easy distillation column design problem, but in the early 1930's it was a very difficult design problem. In addition, styrene monomer as the bottom product ofthis distillation step polymerizes rapidly atthe temperatures encountered in the distillation column even at the best vacuum conditions commercially available. ‘The first step in solving this problem was the development of an efficient inhibitor to this polymerization and adding this inhibitor to the distilation column with the feed and reflux ‘streams, Sulfur was the inhibitor used and adding it high in the distillation column was one of the basic Dow patents on this process. "The first commercial styrene plant had a single shower deck low-pressure-drop column to make the ethylbenzene-styrene separation. Because of poor efficiency, this column proved inadequate and a econd section was added. Later, a third section was added with 3-inch bubble ‘cap tray design. Even operating with these three sections in series, the separation was inadequateCAPACITY AND EFFICIENCY OF CONTACTING DEVICES on with 2 to 5% ethylbenzahe in the bottom product. This ethylbenzene had to be removed inthe batch finishing sts ‘Acarefu study ofthe problem at this point showed that, to make the required separation beeween ethylbenzene and siyfen, at least 70 of the most eficent design bubble cap trays A0ailable were necessary, Even with the ue of small -n,dlametereaps and low st immersion, the prestue drop with this numberof rays was too high. With the minimum overhead vacuum 0f35 mm Hg which would allow forcondensing of the ethylbenzene ina water-cooled condenser, thecolumn pressure drop was too high to gives aaisfactoryrebolle temperature From laboratory checks of the rat of polymerization of styrene monomer and of the reaction rate forthe sulfuratyene reaction under conditions encountered Inthe rebolle, it Fig. 12-30 Primary-secondary column system for styrene. (Courtesy The Dow Chemical Co., Midland, Mich.) Overhead 16,700 Ibe 65am H orc” 41 trays, eft diameter Bas 21,550 Ib/he aes ‘3% styrene "| 54 mm Hg, per tray 286 mm Hg, Bottoms 10,850 Ibe (02% ethylbenzene (109000 + 16,700 + $8700)165) ‘Steam requirement Sano 2.80 Ibflb styreneor SEPARATION PROCESSES Fig. 12-31 Three sets of primary-secondary column distillation units for styrene at the Dow Midland Plant. (Courtesy The Dow Chemical Co., Midland, Mich.) was decided that the bottoms temperature in this column must be held below 90°C. Later ‘experience and data have shown thatthe operation is satisfactory at a much higher temperature it the residence time is kept low, but, at that time, 90°C was set as the maximum design temperature ffcient bubble cap trays could be designed for 3 mm Hg per tray pressure drop: therefore for 70 actual trays, this would give a column pressure drop of 210 mm He. Ifthe minimum top pressure is 35 mm Hg then the reboiler pressure would be 245 mm Hg, The resultant temperature was 108 to 110°C and was much too high. ‘After the study of several schemes, it was decided to split the required trays into two columns operating in series with complete condensing of the overhead vapors of each column s0 that vacuum of 35 mm Hg could be maintained at the top of each column. This spit was made with 4 trays in the primary column and 35 trays in the secondary column since the most critical bottorn temperature was that in the secondary column. [Figure 12-30] shows this primary and secondary column set up with atypical set of opera- ting data. A photograph of three such two-tower units isshown in [Figure 2-31). The first unit ‘was put into operation at the Midiand styrene plant in 1941. The operation of this system was an immediate success. With 76 bubble cap trays and 6 to I reflux ratio (and Tower) they gave ‘200d separation with the ethylbenzene being removed from the bottoms so that the frst over- head product from the batch stills was specification styrene, and within a few years we were finishing most of the styrene monomer in a continuous finishing stil feeding secondary bottoms. ‘Additional plants using the primary and secondary column system came rapidly as the World War II Rubber Program styrene plants were built and started up in 1943 with cight sets of these stills in the Texas plant, four ses in the Los Angeles plant, and two sets in the Sarni plant of Polymer Corporation. Also, all of our styrene know-how was furnished through government agencies (Rubber Reserve Co.) to our competitors at that time.CAPACITY AND EFFICIENCY OF CONTACTING DEVICES a3 ‘ofthe World War I, a third larger unit was installed at Midland using 76 bubble cap trays with 41 trays in the prima and 35 trays in the secondary. The operating data are shown in Figure 12.30, Aiso in 1961 a new distillation unit was installed in the Texas plant with a primary and secondary column, with $0 dual flow trays in each column, ‘The primary-secondary column system with condensing and reboiling of the vapors, ‘between the columns takes more steam and cooling water (or air) utilities than a single column. If the reflux ratio or L/ below the feed tray is maintained the same in the secondary as in the primary column, then the steam required will be twice that required in a single column system ‘When designing the primary and secondary colurnn system, it was noted from study of the McCabe-Thiele diagram that the reflux in the secondary column could be muck lower with the requirement of only two or three more trays in this section, Almost all secondary columns have been designed inthis manner with the steam load on the secondary at about 65° ofthat required for the primary column. You will also note on Figure 12-30 that the secondary columnis smaller in diameter, ie. 9-foot diameter as compared with an L-foot diameter for the primary column. Fig. 12-32 Two duplicate single-columm distillation units for the separation of ethylbenzene and styrene each using 10 Linde seve trays, (Courtesy, The Dow Chemical Co., Midland, Mich)CHPUN ‘peopprpe “09 poonusyg og ayy Katana) ‘9104 umaprow 9 ouOUULfind Yin ouaAKiE sof ayeks sumpod-2}2uS EEE “BLA uaoied 14 0 wao1ed 14 66 wu2oned ua 79 auazuaq uN 96 oKo0L)o00've a1 uortonposd 000/02 ywonrasrnbos wreang ‘001 + 00cSE owyar Ws ‘suaakis QUAL TET = uaorad 1 oe uakis usoiad 1m 046 suacuaqidey sw] 005 EST xO YASNAGNOD A3TOOO-lV ‘skei 2purt wasnganoo inaa({___[) sf wnnoea 01 142), 2/41 005°8L1 20deA peoquAO, ouCAPACITY AND EFFICIENCY OF CONTACTING DEVICES en ‘The use of a single column for the ethylbenzene-styrene separation had often been dis- ccussed after our styrene know-how became more extensive, and it was found that these columns ‘could be operated at higher pressure and higher bottoms temperatures. The sieve tray or valve tray could be designed for lower pressure drop (in the range of 2 mm Hg per tray), but we were never convinced that tray efficiencies could be obtained ina high enough range to give the required separation. The sieve tray design was very dificult because most design data were extrapolated {rom atmospheric pressure correlations. Also with the low design pressure the sieve tray is very close to the weeping range and, furthermore, requires a minimum foam (or liquid) depth on the ‘ray. Either of these conditions can give poor tray efficiency. ‘We had several reports in the 1950's of our competitors using a single column for this separation with valve teay design, but results were not available to us, and reports on operation did not appear to be very good. In 1963 the Linde Division of Union Carbide announced that they were offering for sale their know-how on sieve tray design which had been developed over the years in their design of ‘oxygen and liquid air plants, The Dow Sarnia plant was at this time actively working on a styrene plant expansion and sent out an inquiry to Linde among others. Mr. Garrett and Mr. Bruckert of Linde came to Sarnia in January 1964 and outlined their tray design know-how and made preliminary proposals for design ofa single column unit for the ethylbenzene-styrene separation, Linde required a secrecy agreement before making a formal proposal. The agreement ‘was made and, after a formal proposal was made, the first order with Linde for a single column using Linde Trays was placed for the Sarnia plant. In March 1964, Linde was invited to come to Midland to present their story and make proposals for two columns for Midland’s planned plant modernization. The Linde proprietary Additions to the standard sieve tray along with their design experience and engineering know-how in tray design appeared to be the break-through required for the successful design of a single ig. 12-34 Learning curves for Midland plant styrene-ethylbenzene distillation units. (Courtesy, The Dow Chemical Co., Midland, Mich.) Single unit capacity, MIb/mo paonposd auauzis ques gt 1990 1955 196019651970 Years,SEPARATION PROCESSES ‘column forthe ethylbenzene-styrene separation. Linde had already designed a single column unit for the Union Carbide styrene monomer plant at Seadrift, Texas, which would be in operation before our design was finalized. There was extensive discussion and study of the Linde Tray design by Dow Engineers which was climaxed by a demonstration by Linde at theit Tonawanda Laboratory comparing the weeping tendency and stability of the Linde Tray as compared to a more standard sieve tray. This demonstration was convincing enough so that we gave Linde the {g0-ahead approval on the Midland columns in the summer of 1964, and the formal order was, placed in January 1965. Also added to the same agreement was an ordet for one column in ‘Texas and two columns for the Terneuzen styrene plant. ‘The two units for single column ethylbenzene-styrene distillation were started up in Midland in late 1965 and have met all production plant requirements from that date up to the present time, [Figure 12-32] is a photograph of these columns, and [Figure 12-33] shows typical ‘operating data for the columns at maximum production rates. In summary, we like to show our improvements in chemical process know-how in what ‘we calla "Learning Curve.” [Figure 12-34] shows our learning curve improvements in the sty- rene disilation process. Acknowledgment. The accomplishments discussed here have come from the cooperative efforts of many engineers and scientists, and the author gratefully acknowledges their contribu- tions and wishes io thank The Dow Chemical Company for permission to publish this discussion. REFERENCES ALLCh-E.: “Bubble-Tray Design Manual," American Institute of Chemical Engineers, New York, 1958. Bakker, C. A. P., P, M. van Buytenen, and W. J. Beek: Chem. Eng. Sci. 21: 1039 (1966). FH. Fentener van Vlissingen, and W. J. Beek: Chem. Eng. Si., 22: 1349 (1967). Bolles, W. L.andJ. R. Fair: Tray Hydraulics, in B.D. Smith, “Design of Equilibrium Stage Processes,” ‘chaps. 14-15, McGraw-Hill Book Company, New York, 1963, Bond, J. and M. B, Donald: Chem. Eng. Sci. 6:237 (1987). Brian, P. L, TJ. E. Vivian, and D. C. Matiatos: A..Ch.E. J. 13: 28 (1967). (Clark, M, W. and C. 3. King: AChE, 16: 69 (1970). Colburn, A. P.: Ind. Eng. Chem.,28: 536 (1936). Crawford, 1. W. and C. R, Wilke: Chem. Eng. Progr. 47: 423 (1951). Danckwerts, P. V., W. Smith, and H, Sawistowski: in “International Symposium on Distillation,” p. 7, Iastitution of Chemical Engineers, London, 1960. ‘and M, M, Sharma: The Chemical Engineer, no. 202, p. CE 244, October, 1966. and A. Tavares da Silva: Chem. Eng. Sci, 22: 1513 (1967). Danly, D. E.: In. Eng. Chem, Fundam., 12218 (1982) Davies, J. T.: Mass Transfer and Interfacial Phenomena, in T. B. Drew, J. W. Hoopes, and T. ‘Vermeulen eds,),““Advancesin Chemical Engineering,’ vol.4, Academic Press, New York, 1963. A.A. Kilner, and G. A, Ratcliff: Chem. Eng. Sci., 19: 583 (1964). Diener, D. A. and J. A, Gerster: Ind. Eng. Chem., Process Design Develop.,7: 339 (1968). Ells. S, R, M. and J. T. Shelton: in “International Symposium on Distillation,” p. 171, Institution of ‘Chemical Engineers, London, 1960. Fair, 3, R. and R. L, Matthews: Pearol. Refiner, 37 (4); 153 (1958). Petro|Chem. Engr. p.45,Sept. 196. Francis, R. C.and J. C. Berg: Chem. Eng. Sc, 22: 685 (1967). Frank, J. C.: Early Developments in Styrene Process Distillation Column Design, in “Professors’ ‘Workshop on Industrial Monomer and Polymer Engineering," The Dow Chemical Company, Midland, Michigan, 1968. 1G, R. Geyer, and H. Kehde: Chem. Eng. Progr., 65 (2):79 (1969),