Appendix B Information for the Preliminary Design of Eleven Chemical Processes The purpose of the process designs contained in this appendix is to provide the reader with a preliminary description of several common chemical processes. The designs provided are the result of preliminary simulation using the CHEMCAD process simulation software and often contain simplifying assumptions such as ideal column behavior (shortcut method using the Underwood Gilliland method) and in some cases the use of ideal thermodynamics models (k-value = ideal gas, enthalpy = ideal). These designs are used throughout the book in the end-of-chapter problems and provide a starting point for detailed design. The authors recognize that there are additional complicating factors, such as non-ideal phase equilibrium behavior (such as azeotrope formation and phase separation), feed stream impurities, different catalyst selectivity, side reaction formation, and so on. The presence of any one of these factors may give rise to significant changes from the preliminary designs shown here. Thus, the student, if asked to perform a detailed process design of these (or other) processes, should take the current designs as only a starting point and should be prepared to do further research into the process to ensure that a more accurate and deeper understanding of the factors involved is obtained. Following is alist ofthe sections and projects discussed in this appendix. Bl Dimethyl Ether (DME) Production, Unit 200 B2 Ethylbenzene Pi ion, Unit 30 B3 ‘Styrene Production, Unit 400 BS _ Production of Maleic Anhydride from Benzene, Unit 600 B& Ethylene Oxide Production, Unit 700 BZ _ Formalin Production, Unit 800 B.8 _ Batch Production of L-Phenylalanine and L-Aspartic Acid, Unit 900 B9 —_ Aaaylic Acid Production via the Catalytic Partial Oxidation of Propylene B.10 Production of Acetone via the Dehydrogenation of I 1 Alcohol Bu PB ion of He 1m Propyk uten B.1 Dimethyl Ether (DME) Production, Unit 200DME is used primarily as an aerosol propellant. It is miscible with most organic solvents, has a high solubility in water, and is completely miscible in water and 6% ethanol [1]. Recently, the use of DME as a fuel additive for diesel engines has been investigated due to its high volatility (desirable for cold starting) and high cetane number, The production of DME is via the catalytic dehydration of methanol over an acid zeolite catalyst. The main reaction is (B11) 2CH,OH > (CHy),0 + H,0 rehomed OME In the temperature range of normal operation, there are no significant side reactions. B.1.1 Process Description A preliminary process flow diagram for a DME process is shown in Figure B.1.1, in which 50,000 metric tons per year of 99.5 wi% purity DME product is produced. Due to the simplicity of the process, an operating factor greater than 0.95 (8,375 hvyr) is used. Figure B.1.1 Unit 200: Dimethyl Ether Process Flow Diagram soi oto e Fresh methanol, Stream 1, is combined with recycled reactant, Stream 14, and vaporized prior to being sent to a fixed-bed reactor operating between 250°C and 370°C. The single-pass conversion of methanol in the reactor is 80%, The reactor effluent, Stream 7, is then cooled prior to being sent to the first of twodistillation columns: T-201 and T-202. DME product is taken overhead from the first column. The second column separates the water from the unused methanol. The methanol is recycled back (o the front end of the process, and the water is sent to waste water (reatment {0 remove trace amounts of organic compounds. Stream summaries, utility summaries, and equipment summaries are presented in Tables B. Table B.1.1 Flow Table for DME Unit 200 Comore orl eee oe Bee, Se ae 2 oet ine Table B.1.2 Utility Summary Table for Unit 200 eiie20)~=CtO~SCROSS~SCRO:=SCEOT=SCSC*C RO Pavkqls —BMEAWig/d 1BSVAg/m THAR HGR ODER DADRA 2470 Table B.1.3 Major Equipment Summary for Unit 200eat Exchangers Fling head, con ste sella be design Freres sticun a tee Qe rasan ‘anim pressare ating of 15 bar pam An inom Foatinghendcabon to selland be design Proce stream nts and shel (= 2050 7h ‘simi psoas 15 bar em Toainghend-cabon ce shlhant ube design ‘Process staat inst = 12am aMh Maxinsom presarertng of 14 bar A=22080 ating head ctber sel shane der voce strnm in sel Q=2450MI/h “Maximum pressure ating of 1 bar Pao pam A Reciprocating electee deve Catone omens 72 KW tata) Gavetfcent Frese out = 1850 Pam AB Centitygal/elcrc dive ‘Catbonsteel Rower= LO KW (actual) Phe rene ot = 11 BaP 208 xed has, cabon te shel and tube desig Freer tam tall = 140 Min Maximum pressare rating of 10 bar A=s30nF “loainghesd carbon ste shel-an-ube design Process steam in shell, Q= 5750 ‘asim presoare rating of 1 bar e207, Aa tate oan hea, carb sel shel and tube sig Process stam in sl g= 590 M7h Maxi poetic gk? a Anasa? Feng ed, carbo sts shal anc tbe dng rower stent in sell = 120 Mi7n Maximum pressute wot aman Contnfugal/ cleric dave Catone Fimor = 3 2KW (act) aise eticent Pressurecnt= 16boe‘Reactor Rao Carbon tel Pacha ston 72. high lsd with ‘Maximum prssure rating of 47 bar Towers 201 aon set 2258 sew tayaplon bole 2hintray spacing ‘Cols ight = 15.8 Diameter = 079m Mecienast preamt ai of 106 bor v.01 Horizontal Carbon tet Tenth = 342m Diameler = L14e9 Manimam presire rating hae Horizons) Catton sicet Diameter = 198 0 ‘Manimuny presse rating of 1336 B.1.2 Reaction Kinetics ‘The reaction taking plac mildly exothermic with a standard heat of reaction, Al 20 Can sie 'Sskeve trays pls reborn condenser isin tay spacing Golan height = 149m Diameter = O87 v.03 Caton ste Length = Diameter = 08 nt Mavimnins presse ating of 7 bar Hgqe(25°C) = -11,770 ki/kmol. The equilibrium constant for this reaction at three different temperatures is given below: T a 73K 2000) 928 K (300°C) 520 673K (400°C) M7 ‘The corresponding equilibrium conversions for pure methanol feed over the above temperature range is greater than 99%, Thus this reaction is kinetically controlled at the conditions used in this process. The reaction takes place on an amorphous alumina catalyst treated with 10.2% silica. There are no significant side reactions at less than 400°C. At greater than 250°C the rate equation is given by Bondiera and Naccache [2] as: (B.1.2)=r, ‘methanol = ky exp] ep [Pm where ky = 1.21 * 10° kmol/(mPcat-h.kPa), Ey = 80.48 kJ/mol, and Pneinanot = Partial pressure of methanol (kPa) Significant catalyst deactivation occurs at temperatures greater than 400°C, and the reactor should be designed so that this temperature is not exceeded anywhere in the reactor. The design given in Figure B.LI uses a single packed bed of catalyst, which operates adiabatically. The temperature exotherm occurring in the reactor of 118°C is probably on the high side and gives an exit temperature of 368°C. However, the single-pass conversion is quite high (80%), and the low reactant concentration at the exit of the reactor tends to limit the possibility of a runaway. In practice the catalyst bed might be split into two sections, with an intercooler between the two beds. This has an overall effect of increasing the volume (and cost) of the reactor and should be investigated if, catalyst damage is expected at temperatures lower than 400°C. In-reactor cooling (shell-and-tube design) and cold quenching by splitting the feed and feeding at different points in the reactor could also be investigated as viable alternative reactor configurations B13 imulation (CHEMCAD) Hints The DME-water binary system exhibits two liquid phases when the DME concentration is in the 34% to 93% range [2]. However, upon addition of 7% or more alcohol, the mixture becomes completely miscible over the complete range of DME concentration, In order to ensure that this non-ideal behavior is simulated correctly, it is recommended that binary vapor-liquid equilibrium (VLE) data for the three pairs of components be used in order to regress binary interaction parameters (BIPs) for a UNIQUAC/UNIFAG thermodynamics model. If VLE data for the binary pairs are not used, then UNIFAC can be used to estimate BIPs, but these should be used only as preliminary estimates. As with all non-ideal systems, there is no substitute for designing separation equipment using data regressed from actual (experimental) VLE. B.1.4 References 1. “DuPont Talks about Its DME Propellant,” Aerosol Age (May and June 1982). 2. Bondiera, J., and C. Naccache, “Kinetics of Methanol Dehydration in Dealuminated H- mordenite: Model with Acid and Basic Active Centres,” Applied Catalysis 69 (1991): 139-148, B.2 Ethylbenzene Production, Unit 300‘The majority of ethylbenzene (EB) processes produce EB for internal consumption within a coupled process that produces styrene monomer, The facility described here produces 80,000 tonne/yr of 99.8 ‘mol% ethylbenzene that is totally consumed by an on-site styrene facility. As with most EB/styrene facilities, there is significant heat integration between the two plants. In order to decouple the operation of the two plants, the energy integration is achieved by the generation and consumption of steam within the two processes. The EB reaction is exothermic, so steam is produced, and the styrene reaction is endothermic, so energy is transferred in the form of steam. B.2.1 Process Description [1, 2] The PED for the EB process is shown in Figure B.2.1. A refinery cut of benzene is fed from storage to an on-site process vessel (V-301), where it is mixed with the recycled benzene. From V-301, it is pumped to a reaction pressure of approximately 2,000 kPa (20 atm) and sent to a fired heater (H-301) to bring it to reaction temperature (approximately 400°C). The preheated benzene is mixed with feed ethylene just prior to entering the first stage of a reactor system consisting of three adiabatic packed-bed reactors (R- 301 to R-303), with interstage feed addition and cooling. Reaction occurs in the gas phase and is exothermic. The hot, partially converted reactor effluent leaves the first packed bed, is mixed with more feed ethylene, and is fed to E-301, where the stream is cooled to 380°C. prior to passing to the second reactor (R-302), where further reaction takes place. High-pressure steam is produced in E-301, and this steam is subsequently used in the styrene unit. The effluent stream from R-302 is similarly mixed with feed ethylene and is cooled in E-302 (with generation of high-pressure steam) prior to entering the third and final packed-bed reactor, R-303. The effluent stream leaving the reactor contains products, by- products, unreacted benzene, and small amounts of unreacted ethylene and other noncondensable gases. The reactor effluent is cooled in two waste-heat boilers (E-303 and E-304), in which high-pressure and low-pressure steam, respectively, is generated. This steam is also consumed in the styrene unit. The two~ phase mixture leaving E-304 is sent to a trim cooler (E-305), where the stream is cooled to 80°C, and then to a two-phase separator (V-302), where the light gases are separated and, because of the high ethylene conversion, are sent overhead as fuel gas to be consumed in the fired heater. The condensed liquid is then sent to the benzene tower, T-301, where the unreacted benzene is separated as the overhead product and returned to the front end of the process. The bottoms product from the first column is sent to 7-302, where product EB (at 99.8 mol% and containing less than 2 ppm diethylbenzene (DEB]) is taken as the top product and is sent directly to the styrene unit. The bottoms product from T-302 contains all the DEB and trace amounts of higher ethylbenzenes. This stream is mixed with recycle benzene and passes through the fired heater (H-301) prior to being sent to a fourth packed-bed reactor (R-304), in which the excess benzene is reacted with the DEB to produce EB and unreacted benzene. The effluent from this reactor is mixed with the liquid stream entering the waste-heat boiler (E-303). Figure B.2.1 Unit 300: Ethylbenzene Process Flow Diagram= ge ki Stream summary tables, utility summary tables, and major equipment specifications are shown in Tables B2I-B23. Table B.2.1 Stream Table for Unit 300 Stream Number Temper rests Vapor male faction Tota kmol/h Total g/t Flowrates in kmol/h Ethylene Ethane Propylene Benzene Toluene Ettytbenaane 14-DiBtiBenzene Stream Number i 250 noo a0 2 20 ano 0 yo 1000 7761328195 sx00 700 aw 00 00 00 00“sew Temp CO Pras bP Vapor male fraction “otal mol/l Total igi Flowrates in kmol/h Ethylene Ethane Propylene enzene Tekan Ethybenzene Lacbitehienzene ‘Stream Number Temp CO, Pees KPa Vapor mote faction Total kmol/t Tota kg Flowrates in kmol/h Ethylene Ethane Propylene Benzene Taha Ethybenzene Lpieshenzene Stream Name lorate g/) stream Nome ‘lsat (8) os7 nr. Be 7958 19680 as200 Peery sia 2000 sees 79 00 05t me) 200-200 2850785 Bee 9225 oor 1037 20 1390 19a neo 1400 0000 ms 13 ssa 14852 000000) 200000 200000) a) 000008) wr 0st 0m 1035 fw to E302 ss Ipsto F308 a bw to E302 at onto te307 TSS 766 MA noo 11001050 a ies ama ima Won aby BRIS os: 00 app 700 0g 0.00 200 oo 00) S36 Teds 168.23, ov wish 9 ams was ao fs 6 ata zman 20000 20000 oo 00 ao i203 nny 31996 46165 09 00) ao 09 000 am 009 00) 000 most 98789878 am om 00) om om 09 0M Table B.2.2 Utility Summary for Unit 300 bfwto—_fwto E303 F304 aan 52h hpsto —cwto 308 &309 3m sa * Throttled and desuperheated at exchanger Table B.2.3 Major Equipment Summary for Unit 300 ian 1030 6% 18 ea 0 a0 oa mss 00 00 00 a ne 135 a onto E305, 118500‘eat Eichangess Eso Asm 1-2 hanger, Roan head stainless sel, recent i tae Qe 1967 MPH ‘Maximus pressure rating 0/2200 Pa a8 mt 1Zeschanger, lating hed, stainless sel Process in fe Qe 2s2M/5 “Maximus pressure ating of 2200 a Ex Aa 36m Tez enchanges, ating ead, stanss sel Processes tes = 1008078 ‘Maxima pressure rating of 2200 kPa oy A= 158m? 1B eschanger, fixed head carbon sto Process san i ube Qa 1237 M/s “Maximum pressorerting of 2200 kPa 508, And? 1-2 euchanger ating head, cabo soe Proce alream shel ga ssa3Mi74 Maxietum pecscure ating of 2210 Pe Asa 12exchanger fxd head can ste) Process stream in shh 29309 M75 Maxitum pevssre rating of 2210 XP eo A= Som 1-2uachanger, sting hed, carbon ste Process stream in shel = 7270/4 Maximum pressure rating of 200 kPa e508 annem! 2exchanger fixed hea carbon ses) Process stream in sho Q=s2si M74 Maximum peessre rating of KPaeat Exchangers Process steam in shell 282M Maximum pressure rating of200 KPa Fired Heater 301 Regiuired heat hood = 22376 MI/h Deeg (mon heat load = 35,009 MJ? Tubes = Stairlens see T3Iuthermal efficiency Maximum pressure rating of2:200 KPa Pumps P01 AB Pot a8 Postve displacement /eletie dive Cenviigal/euctre dive Carbon tel Carbon steel ‘ctl powor = 15 BW ‘Actual power = 4 RY Eifency 75% Fcecy 80s P3302 AB Pas AB ‘Cental eect dive Positive displacement electric drive Carbon sted Carbon sel ‘Actual power = 1KW Saul power =2.7 KW Eicieny 7% ‘iirey 75% 303.48 Goneitagal cece drive Carbon sel ‘Actual power =1kW Eicieney 75% Reactors Raot 903 ‘516 stainless tel packed bed, 2505 ‘molecular seve catalyst 20m 1m long, 172 mdiameter “Maximum prose rating of 2.20) kPa “Maximum allowable catalyst temperature su R302 36 stainless tel packed bed, 25605 ‘molecular seve catalyst sm 2mlong, 185m diameter ‘Maximum pressure rating of 2200 kPa “Maximum allowable catalyst temperature = 50 316 stainless steel packed bed, SMS molecular sieve extalyst vam? 12m omg 197 m diameter -Mosimam pressure rating of 2.200 Pa “Moin allseable catalyst temperature 0c Rot 36 stainless steel packed bed, SMS molocularsiewe exalyst vais7m S milong.095 m diameter ‘Maximum pressure rating of 2.200 Pa ‘MMximum allowable catalyst temperature 5c (continued)Towers 301 Tene Carbonstel Caxbon sted IBSS seve trays plus rebilerand total 7688 sive trays pas boiler and wil conden condense? {2%effcent ays sStecfcent trays Feed on tay 19 Food on ray 56 Adaltional fed ports on rays Wand 24 ‘Adlon ee ports on trays 0 and 62 Reflux ratio = 0.5605 {Sin tray spacing Colum eight = 28.96 m Diameter= 15m Reflux ratio = 03874 2hin way spacing mui pressure eating of 300 KPa Maximum pressure rating of 310 KPa Vesssle voi v-303 Carbonstee! Carbon see Horizontal, Hlrizonta L/D= L/D=3 7m Vear7m imum operating pressure = 250 kPa ‘Maximum operating pressure = 900 KPa v-302 v0 Carbon stool with $8 demistr Carbon see Verical Horizontal UD=3 LD=3 Y= 10m" Vesam Moximun operating pressure ‘Main operating pressure» 300 KPa B.2.2 Reaction Kinetics The production of EB takes place via the direct addition reaction between ethylene and benzene: (B21) CoH + GH > CHGHs benzene ethylene etiylhenzene The reaction between EB and ethylene to produce DEB also takes place: (B.2.2) COHSCoHs + CoH, > CoH,(CH3)2 efylenzene ethylene diethybenzene Additional reactions between DEB and ethylene yielding triethylbenzene (and higher) are also possible. However, in order to minimize these additional reactions, the molar ratio of benzene to ethylene is kept high, at approximately 8:1. The production of DEB is undesirable, and its value as a side product is low. In addition, even small amounts of DEB in EB cause significant processing problems in the downstream styrene process. Therefore, the maximum amount of DEB in EB is specified as 2 ppm. In order to maximize the production of the desired EB, the DEB is separated and returned to a separate reactor in‘which excess benzene is added to produce EB via the following equilibrium reaction: (B23) CiH,(CyHy): + CH, 2C,HCy diethylbenzene benzene ethylbenzene The incoming benzene contains a small amount of toluene impurity, The toluene reacts with ethylene to form ethyl benzene and propylene: (B24) GgH;CHs + 2CjH, > CcHeCoH + CH toluene elilbenzene propylene The reaction kinetics derived for a new catalyst are given as (B25) ke Ch pene Cte ChoereC tense CbeB where iis the reaction number above (B.2.i), and the following relationships pertain. bog koow be de kealikoat 3 28a Pasco" > 01 4 100 Saxo 200 1 0 The units of r; are kmol/s/m?-reactor, the units of C; are kmol/m?-gas, and the units of k, ; vary depending upon the form of the equation. B.2.3 Simulation (CHEMCAD) Hints A CHEMCAD simulation is the basis for the design. The thermodynamics models used were K-val = UNIFAC and Enthalpy = Latent Heat. It should be noted that in the simulation a component separator was placed after the high-pressure flash drum (¥-302) in order to remove noncondensables from Stream 16 prior to entering 1-301. This is done in order to avoid problems in simulating this tower. In practice, the noncondensables would be removed from the overhead reflux drum, V-303, after entering T-301,As a first approach, both towers were simulated as Shortcut columns in the main simulation, but subsequently each was simulated separately using the rigorous TOWER module, Once the rigorous TOWER simulations were completed, they were substituted back into the main flowsheet and the simulation was run again to converge. A similar approach is recommended. The rigorous TOWER module provides accurate design and simulation data and should be used to assess column operation, but using the shortcut simulations in the initial trials speeds up overall conversion of the flowsheet. B.2.4 References 1. William J. Cannella, “Xylenes and Ethylbenzene,” Kirk-Othmer Encyclopedia of Chemical Technology, on-line version (New York: John Wiley & Sons, 2006). 2. “Ethylbenzene,” Encyclopedia of Chemical Processing and Design, vol. 20, J. J. MeKetta, ed. (New York: Marcel Dekker, Inc., 1984), 77-88. B.3 Styrene Production, Unit 400 Styrene is the monomer used to make polystyrene, which has a multitude of uses, the most common of which are in packaging and insulated Styrofoam beverage cups. Styrene is produced by the dehydrogenation of ethylbenzene. Ethylbenzene is formed by reacting ethylene and benzene. There is very little ethylbenzene sold commercially, because most ethylbenzene manufacturers convert it directly into styrene. B,3.1 Process Description [1, 2] The process flow diagram is shown in Figure B.3.1. Ethylbenzene feed is mixed with recycled ethylbenzene, heated, and then mixed with high-temperature, superheated steam. Steam is an inert in the reaction, which drives the equilibrium shown in Equation (B.3.1) to the right by reducing the concentrations of all components, Because styrene formation is highly endothermic, the superheated steam also provides energy to drive the reaction. Decomposition of ethylbenzene (o benzene and ethylene, and hydrodealkylation to give methane and toluene, are unwanted side reactions shown in Equations (B.3.2) and (B.3.3). The reactants then enter two adiabatic packed beds with interheating, The products are cooled, producing steam from the high-temperature reactor effluent. The cooled product stream is sent to a three-phase separator, in which light gases (hydrogen, methane, ethylene), organic liquid, and water exit in separate streams. The hydrogen stream is further purified as a source of hydrogen elsewhere in the plant. The benzene/toluene stream is currently returned as a feed stream to the petrochemical facility. The organic stream containing the desired product is distilled once to remove the benzene and toluene and distilled again to separate unreacted ethylbenzene for recycle from the styrene product. Figure B.3.1 Unit 400: Styrene Process Flow Diagram(B3.1) CHSCaHs 3 CHGCoHy + Hy cdiyberene styrene hydragen (B.3.2) CyHsCyHs 2+ CH, + CoH, atfeylbenzene — benzene ethylene (B3.3) C,H: CyH, + H, 4+ CHsCH, + CH, ethylienzene Iydrogent toluene methane The styrene product can spontaneously polymerize at higher temperatures. Because product styrene is sent directly to the polymerization unit, experience suggests that as long as its temperature is maintained at less than 125°C, there is no spontaneous polymerization problem, Because this is less than styrene’s normal boiling point, and because low pressure pushes the equilibrium in Equation (B.3.1) to the right, much of this process is run at vacuum, Stream tables, utility summaries, and major equipment summaries are given in Tables B.3.1, B.3.2, and B.3.3, respectively. Table B.3.1 Stream Tables for Unit 400‘Stream Number 1 2 3 4 5 6 ‘Temperature (C) rr ) Presure (kPa) re a Vapor mole action o 0 1 1 1 1 ‘Tol fow (kg/h) 19AIT_ SHAH SiaiD PTB UIT oH ‘Tori fow (kml/h) —IKRSOSITR SIPS 2A IRB Component flows Water oo oo wea aoe Eahybosene mo sk7sa7 tt Siyrene oo 12«12 a Hydrogen a Bervene 18 18s a0 Toluene lf 2a ona Enhylene er ee) Methane oo aoa ‘Stream Number 7 8 9 © tH Temperature (C) re) wo Pressure kPa) xs mw 1 Vapor moe fraction 14 1 1 1 Toul ow (kg/h) 4412914420 198010 189010 19809910 Total ow (ensi/R) —-§ONO_——$OO0-—-«SSIZG SLATS? HT Component flows Wier sx soo) No) Ethybonzene 00 on 512731 BML 58635, Siyrene 00 00125888 AEMT Hyde oo aaa) Benzene o> okt Toluene oo ops Bihylene eo 09) sas Methane 0000 aHStream Number ‘Tempera Pressure (At) YYapoe ma action Total lw (hg) Tot ew kot) Component flows Water Ethylene ‘irene Fygrogen ewer Toluene thyene Methane Stream Number TespesnareCC) Prete (Ata) Vopor male action “Totals kg/h) Total hw (hol /h) Component flows Water Ethybenasne Hysrogen Benzene Toe pene Methane stream No. Temperature °C) Pressure (AP) Vapor mole feation Total flow (kg) Total How (kmol/) Component flows Worer ehyibenzeme Styrene Hiydragin Benzene Toluene Euhylene Methane ‘Table B.3.2 Utility Summary for Unit 400 Boe ee nw o 6 6 mus Bo 1 1 ems ro 991) WMO HHI 682_ BANS RTS Re7 M27 BD? 7143 SITR TRE sm S00 Sak ORS 36% 36M KM HIS OO ee ee) ee eee) 3787787 ma mat mo om eh wm 1 0 69 o 9 9 ee ms3 5178 maa 197 ma 00k no as6a6 mR IRAE OM no ime Onna 9 m0 wk oo 7s 7s 0D 37000 sl 000 a ee ee ee) on ISS “sm mm 1 a0 mye Sina zs agama 497 mB wou 00a) op 3a mst a) SR ooo saa oo a oo 7s 00 © oo m9) wy oo 00) oo a9Eon E403 E404 E405 hos theshps biwips ow TT Soky/h TASH A/H TA TIO K/h 9ST TE Kg E408 e407 408 e409 Ips ow re ow ABSTSRg/h TUBE Ah 1638053g/—8ATS.ANE Kg ‘Table B.3.3 Major Equipment Summary for Unit 400 ‘Compressors and Drives cor ‘D-401478 (not shown on PFD) Cation ste! lecue/explsion prool W362 kW Wea kW Ph adiabatic ficione stu etlcieney eat Exchangers E406 Carkon ste! A= 787 a aig i Scan a [shell 2 ube passes Q=ss126I/n E07 Caron tot a=iDm ‘Sam in fl proce Mal abs Condensing sel, ew i tubes T shell-2 ube paces 1 shell-2 tbe passes 9237 M7 Q=aL1cI/n E03 0s S16 stainless soe Caron tet 42006 me a-oame Boiling in shel process ld in ttes Bolling in shel, condensing in tubes 1 abel 2 fe panes 1 sll 2 tale pasen Q= 128 Q=3Hl1G/n F409 Carbon tet A= 680m Boing in shel process uid in tubes ‘Condensing shel ew in tubes 1 sell™2 fib pases Toefl 2 fe pester Q= s58GI/m Q= 3067 ras Carbon tet A= 20m win shel, proces ui in tubes Titel ~2te pes Q-389GI/h Tired Heat nao Fires hoster refractory ‘Carbon ste! tubes Dasign Q= 8826 MV ‘Max 0 = 100 MW * See Figure B.3.1 and Table B.3.1 for shell-and-tube side pressures.Pump: Cane ive Ents Caton set Comet Wate kW acto Ws a8 ctu metcent mreficent Catt Canty item tee Siete Wan kW ta Wet 7S (tinh octet reticent Paws ae P06 ential lec ve Cntiagal loci deve Caton tel ‘Catone! W=20 ct Wz Wat) reticent Broeligert Reason Riots Rass Bitten el pcke estar sl pk a Gynecol pet (mm 92min) Cyn tye pi (32 em) Void acts Voit actor = Votan vem Sreatort in port 20? Seats pra at 0m? [2 meal 36meiameter 20m 30 mame “Towers ot 02 Exon et Caen Sener ays “cose (E409) Section eed tata cquent try 38 Bef ratio 258 Structured packing hin tray spacing, 2 weirs cnt ‘Columa eight =92 = 25 Diameter =i m ‘Top dames =26 ETP =03m Batt diameter = 27 Height = 345m [tapered coir Vessels tot 03 Carbon tel Horizontal ‘Carbon Stel L/p=3 ‘vein V=5a? Horizon] Carbon Stel B,3.2 Reaction Kinetics The styrene reaction may be equilibrium limited, and the equilibrium constant is given as Equation (B24). (B34)ef) Ink = 15.5403 - 4852.6 where Tis in K and P is in bar. ‘The equilibrium calculation is given as: CFigCHs CyHeCaHy + H, 1 0 0 be * * total = N+ 1 +x includes N moles of inert steam (B35) xP K=G@-ywettn where P is in bar. Equation (B.3.5) can be used to generate data for equilibrium conversion, x, versus P, T, and N. ‘The kinetic equations are adapted from Snyder and Subramaniam [3]. Subscripts on r refer to reactions in Equations (B.3.1)-(B.3.3), and the positive activation energy can arise from nonelementary kinetics; itis thought that perhaps these kinetics are an elementary approximation to nonelementary kinetics. (B36) 17 daix stool -2™%)p, (B37) 5 exp( 7804 r= 0755 exp( “Rr )PiPhn (B38) 4 =721x 1tep( 2),(B39) 26857 JP Pe r= 123exp(-" ar | where p is in kPa, Tis in K, R = 1.987 cal/mol K, and r; is inmol/m?-reactor s. ‘You should assume that the catalyst has a bulk catalyst of 1282 kg/m? an effective diameter of 25 mm, and a void fraction = 0.4 B.3.3 Simulation (CHEMCAD) Hints Results for the simulation given here were obtained using SRK as the k-value and enthalpy options in the thermodynamics package. B.3.4 References 1. Shiow-Shan Chen, “Styrene,” Kirk-Othmer Encyclopedia of Chemical Technology, on- line version (New York: John Wiley & Sons, 2006). 2. “Styrene,” Encyclopedia of Chemical Processing and Design, vol. 55, J. J. McKetta, ed. (New York: Marcel Dekker, Inc., 1984), 197-217. 3, Snyder, J. D., and B, Subramaniam, “A Novel Reverse Flow Strategy for Ethylbenzene Dehydrogenation in a Packed-Bed Reactor,” Chem. Engr. Sci. 49 (1994): 5585-5601 B.4 Drying Oil Production, Unit 500 Drying oils are used as additives to paints and varnishes to aid in the drying process when these products are applied to surfaces. The facility manufactures drying oil (DO) from acetylated castor oil (ACO). Both of these compounds are mixtures. However, for simulation purposes, acetylated castor oil is modeled as palmitic (hexadecanoic) acid (C,sH,,COOH) and drying oil is modeled as 1-tetradecene (C4Fp,). In an undesired side reaction, a gum can be formed, which is modeled as 1-octacosene (Cagle). B.4.1 Process DescriptionThe process flow diagram is shown in Figure B.4.1. ACO is fed from a holding tank where it is mixed with recycled ACO. The ACO is heated to reaction temperature in H-501, The reaction does not require a catalyst, since it is initiated at high temperatures. The reactor, R-501, is simply a vessel with inert packing to promote radial mixing. The reaction is quenched in E-501. Any gum that has been formed is removed by filtration. There are two holding vessels, V-502 A/B. One of them is used to hold reaction products, while the other one feeds the filter (not shown). This allows a continuous flow of material into Stream 7. InT-501 the ACO is Figure B.4.1 Unit 500: Drying Oil Process Flow Diagram, separated and recycled, and in 7-502, the DO is purified from the acetic acid. The contents of Streams 11 and 12 are cooled (exchangers not shown) and sent to storage. Stream summary tables, utility summary tables, and major equipment specifications are shown in Tables B41-B43. Table B.4.1 Stream Tables for Unit 500Steam Number Temp CO) ros hPa) Vapor mote ato eerie kg) ‘lowrate tka) Component flowrates(kimal/t) Actieaid ‘Tetradacen (Drying) Hecadecanoic Acid (ACO) stream Number Temp CO) Vapor efron ovorae (kg) owrae ka?) Component flowrates(kiol/t) Acti acid Tetradcene (Drying 1) Mexadecnoic Acid (ACO) stream Number Tempco) Pres APA) Vapor mote econ lwrateky/h) ovorate hol /) Component flowratss (kina) Acetic aid Telrad (Drying 0) oxadecsnoic Acid (ACO) Gum Stream Number ‘Temp CO) Pres (KPa) Vapor mole faction Flowrate /) lowrate (ml/h) Component flowrates (kmol/h) ‘Aceticactd TTetradecene (Drying OW) Hexadecanoie Acid (ACO) E501 E502 ‘wins Diver A a as «ss 5 en 30 wes an 3538 dareto? 108 10 ras nw ox ox ope aco 3 1700 5) 000 orto 3840 ooo 0.06 a4 000 503 ium ask ams om ea 6 vse 70) 000 ry longo 10zK08 ox ox 638 oa e888 deri" noma 10 u sams sooo sa crue 86H 3s om oa 62s 00% oo ast eo 000 oo ry 7003 11000 000 074.0 3340 0.00 096 334 00 Table B.4.2 Utility Flow Summary for Unit 500 E504 «£505 thos ow 4 sa 1500 wozm10 on ne Asie? 2a 1250) R08 38 os oa nos 00 E506 istoDostkg/h — T26HOlg/h ASA Kg/H —ABkg/h—-SHOBKg/ 2088 Ag Table B.4.3 Major Equipment Summary for Unit 500 ede Heo “Tota het ty required = 13219 24 Design capacity = #0 Caton ste tes | ser thrmaleteknsy eat Exchangers ES Est Anza Ants? {-aenchanpr ating he, tains sel 1.2 exchange, festing hes, anes st Froese aren nas Fremesieansta dha reas n/n Qa79Mi7n es bs Aasr5 me Anass "exchanger tinged, sani extanger, ating hed sais te Treen steam inal Tron steam nah Qos Min @=20%/n Est Ete 422988 Aaa ne {exchanger floating hed, nies 1 exhange, ating hed tanks ta Procesateam abel Prsts seam tubes Qe 0B M7 Qa MIContiogal/eectee drive Carbon eo! over = 09 KW facta!) Pietcent [NPSH, at clesign flow = 14 fofliguic 502.018 Contifogal/eece drive Stale steel Poveer= 1 EW (ct) 0 efficient Reactor Stainless ste vessel Vals Si mlong 053m diameter Stainless sel Besnew trays pls cbiler and condenser ficient Mays Tota condenser Feed on tay = 32 Refs rit 015 Banteay spacing, 22.n weirs Coloma teaght 217 a Dieter =2 1 m blow fod ar 0.5 hove teed vot Horizont Carbon steel Des v-230" v.so2 Vertical Stainless sel Lp=s Pomp P01 A Psa ae Cental /elactle dive Stains tel Power = OBKW (octal) srs ethcient P01 AB Stains ste electric drive Power =03 KW (atl) ‘a elicit PSI at design ow = 12 ofiguid rs Stains stl "Bisiowe trays pls rb and condenser S2helfcient trys “ota condenser Feed on tray = 23 Refs ratio= 052 TDi tay spacing, 28-n wets (Colas ah Dinmeter= 045m Vessels Horizontal Stains lel L=3 V-230" 501 Horton Carbon steel =a V=03m° ‘The reactions and reaction kinetics are adapted from Smith [1] and are as follows. (B41) CyskyCOOH(D “+ CHSCOOH(g) + CHa! ACO (B42) acetic acd Do2CyyHog(l) > CosFls(8) bo gum where (B43) Cac (B44) =n = ky and (B45) k, = 5.538 X 10 exp(-44,500/RT) (B46) ky 10 exp(—88,000/RT) The units of reaction rate, r;, are kmol/m’s, and the activation energy is in cal/mol (which is equivalent to kcal/kmol), B.4.3 Simulat n (CHEMCAD) Hints If you want to simulate this process and 1-octacosene is not a compound in your simulator’s database, you can add gum as a compound to the simulator databank using the following physical properties: molecular weight = 392 boiling point = 431.6°C For the group contribution method add the following groups 1 — CH, group 25 > CHy groups CH group1 =CH-group B.4.4 Reference 1, Smith, J. M., Chemical Engineering Kinetics, 3rd ed. (New York: John Wiley & Sons, 1981), 224-228. B.5 Production of Maleic Anhydride from Benzene, Unit 600 Currently, the preferred route to maleic anhydride in the United States is via isobutene in fluidized-bed reactors. However, an alternative route via benzene may be carried out using a shell-and-tube reactor, With catalyst in the tubes and a cooling medium being circulated through the shell. B.5.1 Process Description A process flow diagram for the reactor section of the maleic anhydride process is shown in Figure B.5.1 Berzene is vaporized in E-601, mixed with compressed air, and then heated in a fired heater, H-601, prior to being sent to a packed-bed catalytic reactor, R-601, where the following reactions take place Figure B.5.1 Unit 600: Maleic Anhydride Process Flow Diagram(B5.1) C\Hy + 4.50, CGH,O, + 2CO, + 2H,C ioe ne alec antite (B.5.2) C,H, + 750,“+6CO, + 3H,0 benzone (B5.3) yO, + 30,2400, + HO inact (B.5.4) Cabs + 150,7% CoH,O, + 21 ozone unos Al the reactions are highly exothermic. For this reason, the ratio of air to benzene entering the reactor is kept very high. A typical inlet concentration (Stream 6) of approximately 1.5 vol% of benzene in air is used, Cooling is achieved by circulating molten salt (a mixture of sodium nitrite and sodium nitrate) cocurrently through the shell of the reactor and across the tubes containing the catalyst and reactant gases. This molten salt is cooled in two external exchangers—E-602 and E-607—prior to returning to the reactor. The reactor effluent, Stream 7—containing small amounts of unreacted benzene, maleic anhydride, quinone, and combustion products—is cooled in E-G03 and then sent to an absorber column, T-601, which has both a reboiler and condenser. In T-601, the vapor feed is contacted with recycled heavy organic solvent (dibutyl phthalate), Stream 9. This solvent absorbs the maleic anhydride, quinone, and small amounts of water. Any water in the solvent leaving the bottom of the absorber, T-601, reacts with the maleic anhydride to form maleic acid, which must be removed and purified from the maleic anhydride. The bottoms product from the absorber is sent to a separation tower, T-602, where the dibutyl phthalate is recovered as the bottoms product, Stream 14, and recycled back to the absorber. A small amount of fresh solvent, Stream 10, is added to account for losses. The overhead product from T-602, Stream 13, is sent to the maleic acid column, T-603, where 95 mol% maleic acid is removed as the bottoms product. ‘The overhead stream is taken to the quinone column, T-604, where 99 mol% quinone is taken as the top product and 99.9 mol% maleic anhydride is removed as the bottoms product. These last two purificationcolumns are not shown in Figure B.5.1 and are not included in the current analysis. ‘Stream summaries, utility summaries, and equipment summaries are presented in Tables B.5.1-B.5.3. ‘Table B.5.1 Flow Summary for Unit 600 ‘ream Nomber 72 3 «56 7 Tempe) x» 2» esis mm mama Total ms 2) 22 Ba Ze ZH Tord ig/s so ama man ma Flonrates in ke Mibicatysiike 00 OD re) Dbuivphiaie ona 0 eo Wore op aoa v2 91a, Ogg on a0 6 -09 xa ‘inane wo ad 07 a7 Catundiwile Dad 8 mas 1083 Sedu 00000 0000 Scum tae op ao awe ow Stream Number . 0 0 we Dp mw ow Temp CC) wwe Pra ks 2m 8 om mm om Total imta sill OL saz zy salsa sooo Totals yee Me saw 28ST Tw IED ML Flomrate in kmol/h Mikicashpirike 00 DH] Dinipipniabe 0) Ow Nitogen oo ao) Oe ane on a0 80000 Open oo a0 ewww ‘since rT ee eT) Caudle 008d Nbc ackt oo ao aoa Savoie oo a0 80h ‘Sad ite 0p a0 0000) ca) asad 8a Table B.5.2 Utility Summaries for Unit 600 Ee0i E602 E608 E604 605 606 ie Bir ips —biwhps ow ps w VS0MI/h —167OOM/n SLA MI/ 8G 900MI/A 950/350 M/A BiLky/h 728k ASTI7g/h—-2OBHIORG/MTTZRTAG/H 7500 KR/ Table B.5.3 Equipment Summary for Unit 600‘Compressor and Drives coor D-0A/B not shown on PED) Cental fletee deve ectrie/explosionproot Gorbon ste w= 3200 88% int “Tote (prces) heat ty coi = 26800 MI. Design capacity = 32.000 KW Carbon ste bes 35% dermal ficancy Design presse = 300 KPa “eat Exchangers Eot Aa idone {enchange;dotingheod,sinlessiel Pacha ting head tiles set Q-L75IM/n Q=,80M7n Design premare = 00 kPa Design pressure = 4100 KP 1-2exchang, floating head, tals steel exchanger looting head, slaniess sce Fosenmean nate Irsesteam nse Qciero ne Osis Beal premure = 4108 Design prema =3004P 5408 a L:exchs looting, hend, stainless ste! {exch ning hed ile at exchanging hod stainles Tmcaceeen saad natin eter Q= 3140078 Design pressure» 4100 KP E-ot 421 088 0? {-2enchanget fend, sales see Press team nts Q= 8590078 Design pressure» 300 PaPam Peat am Centitagal/electeie drive Carbon et Poywor=113 KW (actu) 58 otisent Design pressure =300 kPa P02 08 Centiagal electric drive Stainless ste) Poveor~ 38 KW (actual) 68% ition Design presane = 200 kPa Peon Reciprocatng/letric drive Slain sie! oveer = 1 KW (ct) (8% efficent Dasign pressure = 200 kPa Reactor Reo Shell and. tube verti sign Stes sto) L=70m Daa8m 12,10 in diameter, 64m hngth catalyst fies abe Design presate Towers Tar Staines te! [sieve trays pus boiler and condenser Sie efficent ays Pasta conderser Feeds. tn 1 and 14 ets ato = 0.189 2hin tray spacing, 2: weirs ‘Calum eight 10 0, Diameter = 42-0 ‘Design pressone = 110K wor Versels vs Horizons] Carbon tet L=3som im Dasign pressure = 10 kPa von Horizons Staines ste) Laiam Dosim Dasign pressure = 10 kPa B.5.2 Reaction Kinetics F608 018 Central electri drive ‘Strinies se Povrer = 675KW (actus 87 eticent Design pressure =200 kPa Pes Cental electric deve ‘Shines se! oysor = 0.7 XW (act) Sr eticene Design pressure = 400 kPa P6068 Centitgal electric drive Staines sie) Tower = 24 KW (octal) estethcent Design pressure = a. 02 ‘Staniess ste! ‘2 sewo trays pls rbollor and condenser (5%. eflicent trays Total condenser Feed on tay 27 ets aio = 124 [Bin way spacing, Lin welts Colum eight = 18 Diameter = LOS m Disign presume = 10 KPa veo Horizontal ‘Stine ste! 1-390m Brim Design pressure = 10a ‘The reactions and reaction kinetics [3] given in Equations (B.5.1)-(B.S.4) are given by the expression (B55)= KCrercene OF —13 = KsCyaticantyirite where (B56) 7 X 106 exp(-25,143/RT) (B57) = 631 X 107 exp(-29,850/RT) (B58) 2.33 X 10' exp(-21,429/RT) (B59) 7.20 X 10° exp(-27,149/RT) The units of reaction rate, r;, are kmol/m*(reactor)s, the activation energy is given in cal/mol (which is equivalent to kcal/kmol), the units of k; are m’(gas)/m? (reactor)s, and the units of concentration are kmol/m*(gas). The catalyst is a mixture of vanadium and molybdenum oxides on an inert support. Typical inlet reaction temperatures are in the range of 350°C to 400°C. The catalyst is placed in 25 mm diameter tubes that are 3.2 m long. The catalyst pellet diameter is 5 mm, The maximum temperature that the catalyst can be exposed to without causing irreversible damage (sintering) is 650°C. The packed-bed reactor should be costed as a shell-and-tube exchanger. The heat transfer area should be calculated based on the total external area of the catalyst-filled tubes required from the simulation. Because of the high temperatures involved, both the shell and the tube material should be stainless steel. An overall heat transfer coefficient for the reactor should be set as 100 W/m?*C. (This is the value specified in the simulation.) B.5.3 Simulation (CHEMCAD) Hints The CHEMCAD simulation used to generate the PED shown in Figure B.5.1 has several simplifications that are valid for this system. The removal of trace amounts of noncondensables is achieved after theabsorber using a component separator, which avoids problems with column convergence downstream. The formation of maleic acid is simulated by using a stoichiometric reactor and setting the conversion of water to 1 Tower 1-601, the maleic anhydride scrubber, is simulated using the rigorous tower simulator. Tower T= 602, the dibutyl phthalate tower, is simulated using the Shortcut column module. Currently, we do not have any experimental vapor pressure data for the components in this simulation. It appears that the vapor pressures of the components differ widely, and no azeotropes are known at this time. For this reason, the ideal vapor pressure K-value option and the latent heat enthalpy option are used. In order to simulate the temperature spike in the reactor, the reactor is simulated as a cocurrent, packed- bed Kinetic reactor, with a molten salt stream as the utility. This configuration provides a greater temperature differential at the front end of the reactor, where the reaction rate is highest. Countercurrent flow could be investigated as an alternative. The kinetics given above are used in the simulation. ‘Dimensions of the reactor tubes are given in Section B.5.2. B5.4 References 1. Felthouse, T. R,, J. C. Burnett, B. Horrell, M. J. Mummey, and Y-J Kuo, “Maleic Anhydride, Maleic Acid, and Fumaric Acid,” Kirk-Othmer Encyclopedia of Chemical Technology, on-line version (New York: John Wiley & Sons, 2001), 2. “Maleic Acid and Anhydride,” Encyclopedia of Chemical Processing and Design, vol. 29, J. J. McKetta, ed. (New York: Marcel Dekker, Inc., 1984), 35-55. 3. Wohlfahrt, Emig G (une 1980): 83-90. “Compare Maleic Anhydride Routes,” Hydrocarbon Processing B.6 Ethylene Oxide Production, Unit 700 Ethylene oxide is a chemical used to make ethylene glycol (the primary ingredient in antifreeze). Itis also used to make polyethylene-oxide, and both the low-molecular-weight and high-molecular-weight polymers have many applications including as detergent additives, Because ethylene oxide is so reactive, ithas many other uses as a reactant. However, because of its reactivity, danger of explosion, and toxicity, it is rarely shipped outside the manufacturing facility but instead is often pumped directly to a nearby consumer. B.6.1 Process Description [1, 2] The process flow diagram is shown in Figure B.6.1. Ethylene feed (via pipeline from a neighboring plant) is mixed with recycled ethylene and mixed with compressed and dried air (drying step not shown), heated, and then fed to the first reactor. The reaction is exothermic, and medium-pressure steam is madein the reactor shell. Conversion in the reactor is kept low to enhance selectivity for the desired product. The reactor effluent is cooled, compressed, and sent to a scrubber, where ethylene oxide is absorbed by water. The vapor from the scrubber is heated, throttled, and sent to a second reactor, followed by a second series of cooling, compression, and scrubbing, A fraction of the unreacted vapor stream is purged, with the remainder recycled to recover unreacted ethylene. The combined aqueous product streams are mixed, cooled, throttled, and distilled to produce the desired product. The required purity specification is 99.5 wt% ethylene oxide. Figure B.6.1 Unit 700: Ethylene Oxide Process Flow Diagram Stream summary tables, utility summary tables, and major equipment specifications are shown in Tables B.6.1-B.6.3. ‘Table B.6.1 Stream Table for Unit 700‘Stream Number Temp 6) Pres ba) Vapor ole faction lossate (igh) lssrate (amo /9) Component flowrates (kmol/h) Bykne tiplne oie Carbon dinide oxygen Nitrogen Wate Stream Number Temp EO) Pres bor) Vapor ioe faction Alosate(ig/) Flviate (nah) Component flowrates (kaol/h) tyne Ethylene oxide carbon dowide Oxygen Nitrogen Water ones: 0 0.000 Wr3815 wo uo sams ao 5 aK 1.00 500.000 TABLAS uo som 4.10008 a0 =a som um 2000 71291 71291 00 oo oo 6 50) sa) 100 0000 7381s 00 00 som1.38 a005 00 3 wa 300 10 00000 wrss1as an an 00 estas 4009 a0 7 waat zai 100 500000 738108 ao oo an aaa .s0009 w rary 2m 10 00000 wrse1as 00 09 sass 4.0009 7281 mest oo 00‘Stream Number 2 ‘Temp (C) 263 Pre (toe) 200 Vapor mse faction 1.00 lovato igh) S408 losate (ms /5) 20129 Component flowrates (kmel/h) ayer 795 Ethylne onde pas carbon dioxide siz nye usa Nitrogen Mos302 Wier 99 ‘Stream Number a Tenp ec) a Pres (ba) 2545 Vapor mole faction 100 lwrate (ig) on3s80 lsat (meh) aa Component flowrates (kmol/h) tytn ran Ethylene onde an Carbon dioxide 36 Oxygen e209 Nitrogen 2R19138 Water 4882 10 10874 2680 100 vons.es) 3560859 nea a7 si71 esi 2819139 8 1% wr 2015 100 sons a8 amar 2a7 955 «20119 28191389 4882 a w iowa 2000 2650 2525 100 1.00 nsw Lense mans Bsa wwirsrmR8? a7 aR si 1956 ez eaons ws18139 8191.39 aus 4882 15 16 00 3796 an 1545 aw 4956 a9 eaa7 on aga72 2000 on (continued)Stream Number a 18 Fo 20 Tempe) sist 2100 me 0) Pres ba 3000 2820 2850 2575 ape ok rcs ‘a0 10 1.0 1.00 lwrate hg) 8011 L015) lveratehmol/) IST SETS TOS TTAT Component flowrates (kmal/h) Ethylene mz 795 art Ethylene oxide 5 154s 75H Carbon dionide eas wos on Oxysn em aaah 610172 Nitrogen PRISA7. — DAIS 28; NBATD Water a8 is wi2 7a stream Number a 2 23 2 Temp CC) 500 an 250) sous61 Pres ne mas was sain son ‘Vapor me fraction 109 100 ‘0 10 “Tori kgyh o1Si69 1.015869 3—.008 084 Tot] ml/h ssu7ay Sata =n SNL Flowrates in km/h hyene ens oo 7008 Ethylene oxide vss uw 1296 Carbon ion eat ry os Oxygen soz «10172 no «1008 Nitogen auimaze — amnsare ho amaHa08 Water Tals 78 aN 696 ‘Steam Number a 26 7 Ey Temp (0) 26 a0 309 208 Pres bee) su00 soa sano m0 Vapor mole fection 0 1 10 140 oveate (ig/h) serge SIND SKIL lseate (mo/5) pom S738 S738 TSI738 Component lowrates (kmol/h) Ethylene os smo; saat aS Binylone oxide 16288 688 os 8 Carbon donide aot an aut sit Onyaen 143 BGR pa Niteogen 2os UBMs? gwan Water angisas a9 sayy sass ‘Stream Number 2 30 3 2 Temp CO) 5208 450) as 6A Pres ba) 100 Bn 100 1090 Vapor mole fsetion 200 om 200 200 lvrate(g/) 797 TM697 = 7R6IS ASE lverate (mel /h) sn3ess8—s036t48anasas 239 Component flowrates (kmel/h) tylene we 1 wz a9 Ethylene ode sin oa Carbon dose ane om 02 00 onygen 28 299 ayy a0 Nitrogen 535 535 535 00 Water sonm7s—somo7ssnoma7E as‘Stream Number 3 34 Temp ec) 1230, a0 Pres ae) 1050 1000 Vapor mate fection 00 100 Frat h/) m7 27 oysate (me /) sans? 953 Component lowrates (kmol/h) Bihylone oo zs Ethylene onde 28 00 Carbon donide 00 00 Osyge0 uo 288 Nitrogen uo 535 Water sosm39 00 Table B.6.2 Utility Summary for Unit 700 ow ow hes ow LAWATDKg/h —ASSBSTHRg/H ATG g/h—_5008727 eh ps ow ow bps UR kg/h ASDA g/h—SIRBIT Rglln RST p/h e709 R701 R702 ow ions ies aioka/h 13A7Bkg/h ———TDSIB Ash Table B.6.3 Major Equipment Summary for Unit 700 e701 e702 e708 E704 £705 £708 e707 £708Corben tel ‘Contig Power = 19 MW Ps adiabatic ficiency 702 Carbon steel Contig over = 25 MW SP adubatic eficteny C703 Carbon set ‘Contig Power “2.5MW Heat Exchangers Aa SSSA mt T-Zeachanger, laating hed, carbon ste Proce team ints O= 58487 Mh [-Zeschanger, Noting head, carbon ste! Proce ream in tubes Q=8320MI/n Ema A= 12062 4-2exchanger, floating hen, casbon sto! Proveve stam i tabs A= ato me ‘-2eachanger floating end, carbon see) Process teu in tubes 2 28,507 MI /t Ems f= 14082 mF Zeachanger, Noating head, carbon see Prowse ints (= 229590 MI/h 708 {Carbon tet ‘Centritgal Power = 35 MW PL adlabaic efickeney C705 ‘Carbo tet Contig Power 55 MW ‘Saban efkeney ‘nail efficeney Aa 16 m8 T-Zeschanger, fasting nd carbon ste) Process team in tes Q= 2074s Me En? An une? [-Zeschanger, Moning head, carbon see! rece stream in tes = 21493MI/n Ene A= Seem? 4-2 exchange, Mating hed, sales steel Proceve steam condenses in shell Q258HMI/n e709 Anise 1-dexchanger, ating head tains tel Process steam oll shell Q2 182M “Note that all compressors have electric-explosiomproof drives with a backup. These units are designated D-701 A/B through D-705 A/B but are not shown on the PFD.Pump Poo Ais Cnn electric rive Stains steel Power = 4 (actual) Strefcent ‘Reactors Reon Revon Carton sel shettand-tube packedbed Carb sl sella puck bat Spherical aly pelt 9mm diameter Spher eatast pelt mm deter Void actin 04 Vanitacton vad v= ann vee Tm tall,738 mata aos Soar al 88 ex Geico is ar bes aes 100 ie th etive catalyst 100 ie eth active catalyst 5 = 261790/h ps ma 78 Carton sel Stains scl OSB ee eye 7OSSsieve ray pls rebrand incenser reticent ays 3Wheficen trays Ferm pf an 20 “otal condenser 7) 2inuay Feed an nay 36 Coit he Rela tio = 089 Diameter = 54m 1intaay spacing, in wes 702 Carton set BWsSseve ays 2B effcent ays Foca on ays Tan 20 hain tray spacing in wees Colum height = 122m Dometer= 5667 Verse! v0 Stinies ste! B.6.2 Reaction Kinetics ‘The pertinent reactions (adapted from Stoukides and Pavlou [3]) are as follows. (B6.1) GH, +050, 30,H,0 (B6.2) CH, + 3.0,2CO, + 2H,0(B.6.3) C,H, + 2.50,—>2CO, + 2H,0 The kinetic expressions are, respectively, (B.6.4) . 1.96 exp(-2400/RT)P ie 1° 1 + 0.00098 exp(11,200/RT)Pay, B. 0.0936 exp(~6400/RT)Punre 21 + 0.00098 exp(11,200/RT)P, yin (B66) 4p, = 0142768 exp —6200/ RT Pion os % 1 + 0.000083 exp(21,200/RT) Prine ote ‘The units for the reaction rates are moles/m? s. The pressure unit is bar. The activation energy numerator is in cal/mol. The catalyst used for this reaction is silver on an inert support. The support consists of 7.5 mm diameter spheres that have a bulk density of 1250 kg/m? and a void fraction of 0.4. B.6.3 Simulation (CHEMCAD) Hints ‘The following thermodynamics packages are strongly recommended for simulation of this process. + K-values: Use a global model of PSRK but use UNIFAC as a local model for T-701 and T-702. + Enthalpy: Use SRK. B.6.4 References 1. Dever, J. P., K. F. George, W. C. Hoffman, and H. Soo, “Ethylene Oxide,” Kirk-Othmer Encyclopedia of Chemical Technology, on-line version (New York: John Wiley & Sons, 2004).2. “Ethylene Oxide,” Encyclopedia of Chemical Processing and Design, vol. 20, J. J MeKetta, ed. (New York: Marcel Dekker, Inc., 1984), 274-318. 3, Stoukides, M., and S. Pavlou, “Ethylene Oxidation on Silver Catalysts: Effect of Ethylene Oxide and of External Transfer Limitations,” Chem. Eng. Commun. 44 (1986): 53-74, B.7 Formalin Production, Unit 800 Formalin is a 37 wt% solution of formaldehyde in water. Formaldehyde and urea are used to make urea- formaldehyde resins that subsequently are used as adhesives and binders for particle board and plywood. B.7.1 Process Description [1, 2] Unit 800 produces formalin (37 wt% formaldehyde in water) from methanol using the silver catalyst process. Figure B.7.1 illustrates the process. Figure B.7.1 Unit 800: Formalin Process Flow Diagram Air is compressed and preheated, fresh and recycled methanol is pumped and preheated, and these two streams are mixed to provide reactor feed. The feed mixture is about 39 mole % methanol in ait, which is greater than the upper flammability limit for methanol. (For methanol, UEL = 36 mole 9%; LFL = 6 mole %,) In the reactor, the following (wo reactions occur. (B71)metal formatdenyte (B72) CH,OH HCHO +H, — AH, In = 20:3 keal/mole ethanol formaldehyde The reactor is a unique configuration, in which the silver catalyst is in the form of wire gauze, suspended above a heat exchanger tube bank. Because the net reaction is very exothermic, the heat generated in the adiabatic reactor section must be removed quickly, hence the close proximity of the heat exchanger tubes. The heat exchanger resembles a pool boiler, with a pool of water on the shell side. If the temperature of the effluent is too high, the set point on the steam pressure line is lowered to increase the vaporization of boiler feed water (BFW). In general, the liquid-level controller on the BEW is adjusted to keep the tube bundle fully immersed. ‘The reactor effluent enters an absorber in which most of the methanol and formaldehyde are absorbed into water, with most of the remaining light gases purged into the off-gas stream, The methanol, formaldehyde, and water enter a distillation column, in which the methanol overhead is recycled; the bottoms product is a formaldehyde/water mixture that contains <1 wt% methanol as an inhibitor, This mixture is cooled and sent to a storage tank, which is sized at four days? capacity. This storage tank is essential, because some of the downstream processes are batch. The composition in the storage tank exceeds 37 w(% formaldehyde, so the appropriate amount of water is added when the downstream process draws from the storage tank. This is not shown in the PFD (Eigure BI). Storage of formaldehyde/water mixtures is tricky. At high temperatures, undesirable polymerization of formaldehyde is inhibited, but formic acid formation is favored. At low temperatures, acid formation is inhibited, but polymerization is favored. There are stabilizers that inhibit polymerization, but they are incompatible with resin formation, Methanol, at concentrations between 5 wi% and 15 wt%, can also inhibit polymerizaton, but no separation equipment for methanol currently exists on site, and methanol greater than 1 wi% also causes defective resin production. With <1 w1% methanol, the storage tank Contents must be maintained between 35°C and 45°C. Stream summary tables, utility summary tables, and major equipment spe: BII-B23. ications are shown in Tables Table B.7.1 Stream Tables for Unit 800‘Stream Number 1 2 3 4 5 6 Tenn 2300 90006150 Pres bP ams 130071225 ND a2 ‘Vapor fection un an amo 10 Tota kg/h sainsh 246475 Manat aa BBA 9 Total kh uuso1 7692920 Component kmol/h ‘Methanal 00) 74m Sunt Oxygen sn 0) aw ey Formaldehyde oa oo ao oo a0 Water on aw ssl en) a0 Hydrogen ooo a ao 9 a0 Nitrogen us2e 0 a ag uss stream Number 1 8 ° 10 uo Temp eC) 2000174 ODD Pres Pe sm 2500 185001500000 aN ‘ape fection 1 uw u uw no 10 Tots km/h Muso4 24586 7AUS2 7a 25TH SABA Total kg/h wminst 73S RNS RNS HOD A Component kmol/h ‘Methane 0 25S a8 Oxygen ans ane Sts ons Feemaldehye oo 00 aeons? oo Watee ee Hysrogen oa 166 186 1.466 Nitrogen S28 S28 SHB T1828 ‘Stream Number 13 1% 5 16 78 Temp eo) wae Fae UMA CSRNDH Pres kPa sno 1000 isp as000 800200 Vapormole faction a) ao a0 09 a0 “Total kg/h AERIS GSS S705 S8HTE 38ND 66 ‘Total mol/h 19687 «7807386 7RSG 73S 230 Component kmol/h Methanol i071 090900) Oxygen a TT} Formaldeiyde 26302632} gS) Waree 6M = S81 ns ta0g3m0a3 a 0” = 0m = om om oo 0m ammo ‘Table B.7.2 Utility Stream Flow Summary for Unit 800‘Compressor sor Carbon set Centritgal Power = 189 AY haf) Avetiant Heat Exchangers eso AS 1 2eachang, lating hand extn steal Process stream inset Qeaii Ny ‘anim prssuse rating of 350 kPa Esa Assam? exchange, ating nd exon seal Procese stream in tes Qa 7575 MH/h ‘Maximum presse rating of 350 KPa saa A= 216m 1-2enchanger, lating head carbon steel Process steam in she 983.23 MI7h ‘Maximum pressure rating of 350 kPa Reactors 801, Heat-Eschanger Portion An uodi ‘Counterfow caching, Noatng head carbon tee recess seu in tes Qa 8925 Mh ‘Masimam pasate rating oF 380 KPa Paps Pn vB Contritugalelectic deve Carbon ste! Power =033W etic Ps A Centrifugal electric drive (Carbon ste! Power =17 4W SPeeticent e801 e802 5-803 E204 os hos or np 20 ig/k——_ASABg/h——_— 2550/8949 kg/h £805 £806 R201 ow ow br ops TST iy/h STi «STB g/h Table B.7.3 Major Equipment Summary for Unit 800 601.4 fot shown on PRD) Blectie/explesionpao! We 15 KW 98% cficent Ee A= 573m 12eacharyger, kettle rebilr staiss see Process stot ish Qa a75MI/n ‘Maimum pressure rating of 250 Pa Ems Ane wt 1.2excharge, lating he sales seo Process stonn in shel (Q= BASMI/h ‘Maximum priscure rating of250 kPa Ess Anda 12eachanyger, lating he, sane seo Process teem ites Qe 1187 M75 ‘Maximum prssure rating of 00 kPa 901, Resetor Portion Thin layers of iver wire gauze suepended lve heat exchanger tue bank Ps AM Contritugal elect deve Staines st) Power =053W Peieticentca Component Formaldehyde water Methanol 10am B,7.2 Reaction Kinetics Due to the very high temperature and large surface area of the wire gauze, the reaction may be considered to be instantaneous. B.7.3 Simulation (CHEMCAD) Hints Solutions of formaldehyde and water are very non-ideal. Individually, the volatilities are, from most volatile to least volatile, formaldehyde, methanol, and water. However, formaldehyde associates with water so that when this three-component mixture is distilled, methanol is the light key and water is the heavy key. The formaldehyde will “follow” the water. The ESDK K-value package in CHEMCAD simulates this appropriately and was used for the simulation presented here. Latent heat should be used for enthalpy calculations. The expert system will recommend these choices. Alternatively, the data provided in ‘Table B.7.4 can be used directly or to fit an appropriate non-ideal VLE model, Table B.7.4 K-values for Formaldehyde/Water/Methanol System [2] oh eal Component Formaldehyde water Methanol 0am 10273 When simulating an entire process, we recommend first using the Shortcut distillation column within the process for the methanol-water/formaldehyde distillation. A rigorous column solver should then be usedas a separate item to simulate the column based on the results obtained from the shortcut column. However, due to the non-ideality of the thermodynamics, the actual column simulation using the rigorous column will probably requite many more stages than predicted by the shortcut simulation, possibly twice the number. Once the parameters for the rigorous column have been established, the Shortcut column can be replaced by the rigorous column and the simulation rerun to get a converged simulation. B.7.4 References 1. Gerberich, H. R., and G. C. Seaman, “Formaldehyde,” Kirk-Othmer Encyclopedia of Chemical Technology, on-line version (New York: John Wiley & Sons, 2004), 2. “Formaldehyde,” Encyclopedia of Chemical Processing and Design, vol. 23, J. J. McKetta, ed. (New York: Marcel Dekker, Inc., 1984), 350-371. 3. Gmebling, J, U. Onken, and W. Arlt, Vapor-Liquid Equilibrium Data Collection, Chemistry Data Series (Aqueous-Organic Systems, Supplement 1), vol. 1, part 1a, DECHEMA, 1981, 474-475. B.8 Batch Production of L-Phenylalanine and L-Aspartic Acid, Unit 900 Phenlyalanine and L-aspartic acid are amino acids. When they bond together, the corresponding di- peptide methyl ester is aspartame, known by the brand name Nutra-Sweet or Equal. Production of both amino acids can be accomplished via fermentation of genetically altered bacteria. Production rates of 1,000 and 1,250 tonnes/yr of L-aspartic acid and L-phenylalanine are desired B.8.1 Process Description To accomplish a fermentation process, bacteria must grow in the presence of appropriate nutrients that facilitate the production of the desired product. In a processing context, the fermentation reactor must first be primed with the bacteria and the nutrients. The nutrient feed includes the reactant that the bacteria metabolize to produce the desired amino acid. Air is also sparged into the fermenter as a source of oxygen. All of these feeds are passed through sterilization filters prior to entering the reactor. The bacteria are then allowed to multiply, and the desired product, an amino acid in this case, is produced. In this process, both products are extracellular. After the desired production level of the amino acid is reached, the fermentation broth pH is lowered by addition of sulfuric acid, the bacteria are removed from the fermentation broth by filtration, and the product stream is sent to a holding tank. The addition of acid Litrates the amino acid, making it positively charged. The addition of acid is done only for phenylalanine, because L-aspartic acid bypasses the ion exchange column and is crystallized directly via precipitation from solution. In this process, both amino acids are produced in the same facility. Because fermentation is involved and production levels are low compared with typical commodity chemicals, batch processes are involved. Inbatch processes, the key variable is the batch time, or the length of time that the unit is allowed to run. For example, in a batch reactor, the batch time is analogous to the space time in a continuous reactor. The separation sequence is @ continuous process, which is accomplished by a continuous feed from the holding tank. This is not uncommon in batch facilities, because many separation processes are more easily accomplished in the continuous mode. The separation sequence for the two amino acids differs slightly. Phenylalanine is isolated using ion exchange followed by crystallization; in contrast, L-aspartic acid is crystallized directly from the filtered fermentation broth. For phenylalanine, it is adsorbed on the ion exchange resin and subsequently eluted using a basic solution. The addition of base neutralizes the positive charge to promote desorption from the ion exchange resin. For both amino acids, filtration follows crystallization. The product is then sent to storage. The process is shown in Figure B.8. Figure B.8.1 Unit 900: Amino Acid Process Flow Diagram The use of batch processing requires batch scheduling of the type discussed in Chapter 3, which allows use of the same equipment to manufacture both amino acids in the same facility. In this description, only the PED, reactor calculations, and general descriptions of the separation units are presented. The design of individual equipment, the utility consumption, and the production schedule for the plant are left as exercises for the student. A description of a process to produce four amino acids (including the two amino acids inthis process) in the_~—same_— facility is. available at This process description includes possible batch schedules for both the reactors and the separation section. B.8.2 Reaction KineticsL-Aspartic Acid. The reaction of fumaric acid to form L-aspartic acid is an enzymatic conversion carried out using the aspartase activity of bacteria Escherichia Coli (E. Coli) cells according to the following reaction, (B81) C,H,O, + NH,"="°C,H,NO, furaric acid Le-aspartic acid ‘The bacteria cells are suspended in a matrix polyacrylamide gel, and the reacting species must diffuse in and out of the matrix. The diffusivities of the substrate (fumaric acid) and product (L-aspartic acid) in the gel decrease as their concentrations increase due to the tendency of the gel to shrink at low pH. The kinetic model for this reaction follows a Michaelis-Menten form for a reversible reaction, which rearranges to (B82) 1 ES Va Vamox Cra is the concentration of fumaric acid (kmol/m4). ‘Cay is the concentration of L-aspartic acid (kmol/m’). ‘Cy: is the concentration of ammonium ions (kmol/m?). where K is a reaction equilibrium constant (m'/kmol). V, is the apparent rate of production of L-aspartic acid (kmol/lvkgegel). Veamax is the apparent maximum rate of production of L-aspartic acid (kmol/h/kge gel). K, 11s the apparent Michaelis constant for the reaction (kmol/m?). Reaction rate parameters have been modified from reference [1] and are used for the current process using a 1.0 M substrate solution at a reaction temperature of 32°C. .68C 724 FAD 7 = CAD Vio oun = ‘oma = 459K = 88.7 m‘/kmol at 32°C Cunt; = 2.04C rq It should be noted that the relationship Cv: = 2.04Cpq can be achieved only in a batch reactor by measuring the concentration of fumaric acid and adjusting the ammonia concentration with time. This approach is assumed here; however, if a fixed amount of ammonia is initially added to the reactor, then the relationship between yi; and Cp, must be found from the material balance and substituted in Equation (B.8.2). Substituting the above values into Equation (B.8.2) and using the conversion, X, of fumaric acid (Cra = Cpa o(I-X) and Cag = CraoX), we get (B.8.3) [ (1 = 2X) 1— (2 + 123CH)X + 123CH38, “Ww dt 150 a) Vis the volume of the reacting mass in the reactor (m?). Wis the weight of the gel (ke) = VC1-2)P bead: where cis the void fraction of beads in the reacting mass. P bead is the bead density (kg/m?) Substituting into Equation (B.8.3) we have (B84) (1-2X) (1 + 123Cpi4) — (2 + 123CH)X. For the specified initial concentration of fumaric acid of 1.0M = 1 kmol/m? and with p peqq ~ 1,000 kg/m? and assuming a voidage of 0.5, Equation (B.8.4) simplifies to (B aK _y yf (1-28) at "La —125x.Separating variables and integrating Equation (B.8.5) yield the conversion as a function of batch reaction time, This relationship is shown in Figure B.8.2. Figure B.8.2 Conversion of Fumaric Acid to L-Aspartic Acid as a Function of Reaction Time —= 0s oa os oz Conversion of Fumarie Acid, X on 2.0 ° 10 20 30 40 5c Batch Resetion Time, h Preliminary Sizing of Reactor R-901. For a conversion of 45% (90% of equilibrium), a reaction time of approximately 30 hours is required. Assuming that an additional 5 hours is required for filling, cleaning, and heating, the total reactor step time is 35 hours. Using a reactor size of 37.9 m? (10,000 gal) and assuming a 90% fill volume and a voidage of 0.5, the amount of fumaric acid fed to the batch is (37.9)(0.9)(0.5) = 17.04 m?, or 17.04 kmol (17.04 x 116 1977 kg). The amount of L-aspartic acid produced = (17.04)(0.45) = 7.67 kmol = (7.67)(133) = 1020 kg Production rate of L-aspartic acid from a 10,000 gallon reactor is 1020 kg/batch using a batch time of 35 hr, L-Phenylalanine. L-phenylalanine is produced via fermentation using a mutant Brevibacterium lactofermentum 2256 (ATCC No. 13869) known as No. 123 [2]. The rate equations for biomass (bacteria, X), substrate (mainly glucose, S), and product (L-phenylalanine, P) are described by Monod Kinetics. (B86)(B87) dt (B88) aE dt where X is the concentration of bacteria (kg/m’). Sis the concentration of substrate (glucose) (kg/m*). P is the concentration of product (L-phenylalanine) (kg/m). Hm is the maximum specific growth rate (hr™). K, is the Monod constant (kg/m*). Ygs is biomass yield. Yps is product yield. According to Tsuchida et al. [2], for a culture medium containing 13% glucose, 1% ammonium sulfate, and 1.2% fumaric acid (plus other trace nutrients etc.) the yield of L-phenylalanine was 21.7 mg/ml after 72 he of cultivation at a temperature of 31.5°C. This represents a yield of approximately 16.7% from glucose by weight. Other amino acids are also produced in small quantities (<5 kg/m’), with Lysine making up approximately 50%. To obtain a kinetic model of the growth of bacteria and subsequent production of L-phenylalanine and depletion of glucose, the parameters in Equations (B.8.6)-(B.8.8) were back calculated to give best-fit profiles of X, S, and P compared to published values ([2], Figure 4). The parameter values are shown in Table B.8.1, and the profiles are plotted in Figure B.8.3. Table B.8.1 Best-Fit Parameters for Monod Kinetics Using Brevibacterium lactofermentum 2256 (ATCC No. 13869) Strain No. 123Parameter value Sagi aus? ; anridkg/e 0bg/r Figure B.8.3 Concentration Profiles as a Function of Reactor Time °0 0 oo Concentration of S, kglm> Concentration of X and P, kgim? a 20 40 60 0 Reaction Time, hr Preliminary Sizing of Reactor R-901. For a reaction time of approximately 60 hours, the final concentration of L-phenylalanine is 21.0 kg/m®, Assuming an additional 5 hours for filling, cleaning, and heating gives a total reactor step time of 65 hours. Using a 37.9 mi (10,000 gal) reactor for the fermentation and assuming that a 90% fill volume is used, the volume of reactants is (37.9)(0.9) = 34.11 nr. ‘The amount of L-phenylalanine produced in a 60 h batch reaction is (34.11)(21.0) = 716 kg. Production rate of L- of 65 hr. ispartic acid from a 10,000 gallon reactor is 716 kg/batch, with a reactor step time Preliminary Information on Other Equipment. As mentioned in the process description, the production of both L-aspartic acid and L-phenylalanine follows similar paths. A brief discussion of the unit operations involved with the separation and purification of the final products is in order, because these operations are not typical of the unit operations covered in this text. Size information is not included for the equipment described next; however, estimates of processing times, where applicable, are given. Filtration of Bacteria, After reaction, the bacteria must be filtered from the mother liquor prior to storage. The bacteria tend to give rise to slimy filter cakes, and the filtration of such material is bestaccomplished using a rotary drum filter utilizing a precoat. Typical precoating materials are dolomite, perlite, and cellulose, and these are applied to the drum in a two-stage process prior to filtration, The precoating process involves depositing a layer of the precoat material (515 cm thick) on the drum prior to the filtration operation. Once the precoat has been applied, the filtration starts, and the biomass forms a thin layer on the precoat. This layer of biomass is continuously removed, along with a thin layer of the precoat material, using a sharp-edged “Doctor” blade. Additional information is given at hup://www.solidliquid-separation.com [3]. Without doing detailed calculations, it is difficult to determine the time required for the precoat stage and filtration stages. For this project you may assume that these steps take 25 h and 5 h, respectively. Intermediate Storage. The fermentation broth (free of solids, or biomass) leaving the filters is stored in an intermediate storage tank prior to being sent to the ion exchange column (for L-phenylalanine) and on to the crystallizer. The use of an intermediate storage vessel allows the remainder of the process to operate as a continuous process. Ion Exchange Column, ‘The ion exchange columns operate as semibatch processes. Hydrochloric acid is added to the L-phenylalanine-containing solution and is passed through freshly regenerated ion exchange resin such as DOW’s Dowex Marathon C [4]. The resin captures the positively charged amino acid. Once the bed is full, it is backwashed with a basic solution of ammonium or sodium hydroxide, which breaks the resin amino acid bond. The resin is subsequently washed free of the hydroxide, and the cycle starts again. Continuous Crystallizer and Filtration, Draft tube baffle crystallizers can be used for the crystallization of L-aspartic acid and L-phenylalanine. These crystallizers offer the advantages of high circulation rates for efficient mixing. Fines removal is facilitated through the use of baffles, and a certain amount of product classification (crystal size control) is obtained through the elutriating leg. Batch crystallizers could also be used, but product quality and efficiency suffer. The saturated liquid from the crystallizer, containing amino acid crystals, is sent to a filter (such as a rotary drum filter), where the crystals are removed and sent for washing, drying, and packaging, The saturated liquid is returned to the crystallizer for further product recovery, thereby increasing the efficiency of the operation. Both amino acids can be crystallized at temperatures greater than 100°C. Therefore, the crystallization may take place at ambient pressure by removing the excess water through evaporation, The solubilities of L-aspartic acid and L-phenylalanine at 100°C are 67 g/liter and 100 giliter, respectively. B.B.3 References 1. Takamatch, T., K. Yamashita, and A. Sumi, “Kinetics of Production of L-aspartic Acid by Aspartase of Immobilized E. Coli Cells,” Japanese Journal of Fermentation Technology 58, no. 2 (1980): 129-133. 2, Tsuchida, T., K. Kubota, Y. Morinaga, H. Matsui, H. Enei, and F. Yoshinga, “Production of L-phenylalanine by a Mutant of Brevibacterium lactofermentum 2256,” Agric. Bio. Chem. 51, no. 8 (1987): 2095-2101. 3. hutp://www,solidliquid-separation.com.