CHE 304 Optional Homework (Due May 27 2009) A basic simulation of the toluene hydrodealkylation process is required using

Provision. Deliverable ! (") Your own drawing of the PFD and a specification table for the toluene hydrodealkylation process. (2) PFD from the simulation (P !"#$#!%&. Stream Property Tables are required.

#oluene Hy$ro$ealkylation %ro&e

( evised from $enior Pro'ect of Patricia (uinones) *++*&

,he hydrodealkylation of toluene- (.DA& is a process used to produce ben/ene. ,he main reaction in the process is0 ,oluene 1 .* 2en/ene 1 3.4 ,oluene and hydrogen are converted in a reactor packed with catalyst to produce ben/ene and methane. ,ypically the reaction reaches a conversion of 5+6. ,he reaction is highly e7othermic and the typical operating conditions are 8++ 3 to 99+ 3) and *+ to 9+ bar. Figure shows the block diagram of the .DA process.
.* ecycle

'uel +a

Hy$ro(en ,ea&tor #oluene -eparator

)en*ene

Di tillation

,oluene ecycle

'i(ure "0 ,oluene .ydrodealkylation 2lock Flow Diagram

Analysis) $ynthesis) and Design of 3hemical Processes ichard ,urton) ichard 3. 2allie) :allace 2. :hiting) ;oseph A. $haelwit/. Prentice .all) P, . %ew ;ersey) -55<.

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,he .DA process begins with mi7ing fresh toluene with a stream of recycle unreacted toluene) the mi7ing is achieved in a storage tank. ,he toluene is then pumped to combine it with a stream of mi7ed hydrogen and fresh hydrogen gas. ,he mi7ture of hydrogen and toluene is preheated before it is introduced to the heater or furnace. #n the furnace the stream is heated to 9++ 3) the reaction temperature) then introduced into the reactor. ,he reactor is where the main reaction happens0 3=.< 1 .* > 39.9 1 3.4 ,his reaction is irreversible) and it requires catalyst. ,he catalyst consists of chromium or molybdenum o7ides) platinum or platinum o7ides) on silica or alumina. Another minor reversible side reaction* is often observed0 * 2en/ene > Diphenyl 1 .* ,he catalytic process occurs at lower temperatures and offers higher selectivity but requires frequent regeneration of the catalyst. ,he products are then cooled and introduced into a pair of separators that separate the unreacted hydrogen. Portion of the unreacted hydrogen is compressed and recycle back to the feed and the reactor. ,he products leaving the separators are then heated before being introduced into a distillation column) where toluene is separated from the stream and recycle to the feed. ,his allow for greater conversion. ,hen further fractionation separates methane and toluene from the ben/ene product. ,he heating requirements are achieved with low) high and medium pressure steam. ,he cooling requirements are achieve by cooling water at temperature of ?+ 3 and pressure of - bar. ,he process begins with the first phase of a process0 the reactor feed preparation. ,his begins with combining -+<.= kmol@hr of a fresh stream of toluene at *8 o3) and -.5 bar) with a recycle stream of unreacted toluene in a storage tank ,AB- at --* o3 and *.4? bar. ,oluene is then pumped through pump PB-) the discharge pressure of the pump must be *8.8 bar) this is pumped to a second storage tank ,AB* where toluene is combined with a combined stream of fresh and recycle of hydrogen. ,he new twoBphase stream is preheated in CB- to -9?.5 o3) high pressure steam at 48 barg is used for this purpose. ,he stream e7ists the preBheater as a oneB phase stream because the toluene was vapori/ed. ,he stream is then introduced into the heater) .B-) this fired heater is a type of furnace which uses air to combust fuel gas to produce enough heat to raise the temperature of the stream to 9++ o3. ,he reactor feed preparation has now been completed. ,he stream is at the desired pressure) *4.<- bar) and temperature) 9++o3) necessary for the reaction to occur. ,he stream is then introduced into the reactor B-) this reactor is a vertical vessel packed with catalyst. ,his is the main part of the process where the main reaction) which produces ben/ene) happens0 3=.< 1 .* > 39.9 1 3.4
*

D2en/eneE. AirkB!thmer Cncyclopedia of 3hemical ,echnology :illiam Fruscella. ;ohn :iley F $ons) #nc.) -55*.

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Toluene + Hydrogen = Benzene + Methane ,his is a catalytic e7othermic reaction) and the temperature is controlled by in'ecting hydrogen into the reactor. .ydrogen is in'ected at 4+.4 kmol@hr 44.59o3 and *8.8 bar. ,he e7iting stream e7its at *4.<- bar and 9=-o3) it contains methane) ben/ene) toluene) and hydrogen. ,he one pass conversion is typically around =86. ,he process then continues to the separator feed preparation phase. ,his process phase begins with introducing the stream into a cooling water heat e7changer CB*. ,his heat e7changer cools the product stream to ?< o3) which condenses most of the toluene and ben/ene in the stream. ,he stream then proceeds to the final phase of the process0 the separation. #n this phase) the desired product is separated from the by products and the unreacted components. ,hat is) ben/ene is separated from unreacted toluene) unreacted hydrogen and the byBproduct methane. ,his is achieved by introducing the twoBphase stream containing ben/ene) methane) hydrogen and toluene into a highBpressure phase separator) FB-. #n this flash drum the vapor and liquid are separated. #n the overhead mainly hydrogen and methane e7its) and in the bottom some hydrogen) methane) and mainly all the toluene and ben/ene e7it. ,he overhead stream is split into two streamsG one stream is compressed to *8.8 bar in compressor 3B- and is recycle back to the feed and to the reactor) the other stream is a portion of the fuel gas stream. ,he separation happens at a temperature of ?<o3 and *?.5 bar. ,he partially separated stream is then introduced in a second separator) FB*) where mainly all the methane and hydrogen is separated in the overhead stream. ,his separator is a lowBpressure separator. ,he liquid e7iting the lowBpressure flash drum consist of mainly toluene and ben/ene and traces of dissolved hydrogen and methane. ,he separation is then completed by heating the stream in heat e7changer CB?) and then introducing it to a distillation column) ,B-. ,he stream is heated to a temperature of 5+o3 in CB?) low pressure steam is used for this purpose. ,he distillation column is used to purify the ben/ene product by separating all the unreacted components and the by products. ,his tower consists of 4* sieve trays) a reboiler CB9) a condenser CB8) a reflu7 drum FB?) and a reflu7 pump PB*. ,oluene e7its as a liquid in the bottom at a temperature of --*o3 and *.4? bar. ,he overhead containing ben/ene) traces of hydrogen and methane) is condensed in CB8 at a temperature of --* o3 and a pressure *.8 bar. 3ooling water is used to condense the vapor e7iting the column. A remaining hydrogen and methane are then separated in the reflu7 drum FB?G this vapor stream is combined with the other gases streams0 the overhead of the first separator FB-) and the overhead of the second separator FB*) which are combined to form the fuel gas. ,he liquid stream e7iting in the bottoms of the reflu7 drum is pumped to a discharge pressure of ?.? bar. ,he pumped stream is separated in two streams. !ne stream is feed to tray one of the column and the other stream is cooled down to ?<o3 in heat e7changer CB4. ,he cooled product stream is then sent to storage. -imulation De &ription Figure * shows the PFD of the simulationG the following description refers to this PFD. ,he simulation requires certain inputs for each type of equipment. ,able - is the desired inputs in stream $- and $-=) the toluene and hydrogen streams) and ,able * is the desired output streams $** and $*=.

-=

Fi&!re 3( Si)!lation Pro'e%% Flo* +ia&ra)

Hydrodealkytion of ol!ene
SP2 S14 C1 S12

Re'y'le Hydro&en

S13

S20 S15 S11 M5 S16 S17 M2 M4 S6 R1 S8 S7 S9 S25 M6 S22

F!el $a%

SP1

Hydro&en

S18

M3 S3

S4 S5 E1 E2 E5 S28

SC2

S2 S1 M1

F1 S23 S10

S26

ol!ene

P1

S27

F2 S19

E4

"en#ene

S21 E3 SC1 S24

ol!ene Re'y'le

'i(ure 20 $imulation PFD for the toluene hydrodealkylation process.

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#able "! #nput streams for the .DA process. .nput -tream! -" Holar ate0 -+<.= kmol@hr ,emperature0 *8 3 Pressure0 -.5 bar Holar 3omposition0 -.++ ,oluene -tream! -"7 Holar ate0 ?+-.+ kmol@hr ,emperature0 *8 3 Pressure0 *8.8 bar Holar 3omposition0 +.58.* +.+8 3.4 #able 2! !utput streams for .DA process. Output -tream! -22 Holar ate0 ?+4.- kmol@hr ,emperature0 ?8.= 3 Pressure0 *.8 bar Holar 3omposition0 +.++- 3=.< +.8<= .* +.4+? 3.4 +.++5 39.9 ,he inputs required in each type of equipment are shown in ,able ? ($pecification ,able&. #able 30 #nput data for process simulation.
Simulator Equipment Simulator Input Output Number Equipment Streams Streams M,1 Mi-er S1 S24 S2 M,2 Mi-er S17 S14 S16 M,3 Mi-er S16 S3 S4 M,4 Mi-er S6 S15 S7 M,5 Mi-er S11 S18 S20 M,6 Mi-er S20 S25 S22 P,1 P!). S2 S3 C,1 Co).re%%or S12 S13 E,1 Pre,5eater S4 S5 E,2 Heater S5 S6 E,3 Heat E-'5an&erS19 S21 E,4 Cooler S26 S27 E,5 Cooler S8 S28

-tream! -27 Holar ate0 -+8.9 kmol@hr ,emperature0 ?< 3 Pressure0 *.588 bar Holar 3omposition0 +.++4 3=.< +.559 39.9

Required Input Pre%%!re +ro. / 0 0ar Pre%%!re +ro. / 0 0ar Pre%%!re +ro. / 0 0ar Pre%%!re +ro. / 0 0ar Pre%%!re +ro. / 0 0ar Pre%%!re +ro. / 0 0ar 1!tlet .re%%!re / 2525 0ar3 Effi'ien'y 754 1!tlet .re%%!re / 2525 0ar3 Effi'ien'y 754 1!tlet 6i7!id Fra'tion / 0 1!tlet te).erat!re / 600 C 1!tlet te).erat!re / 90 C 1!tlet te).erat!re / 38 C 1!tlet te).erat!re / 38 C

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F,1 F,2 SP,1 SP,2 R,1 SC,1 SC,2

Fla%5 +r!) Fla%5 +r!) S.litter S.litter Rea'tor

S28 S10 S9 S13 S7

S9 S18 S11 S14 S8 S23 S25

Strea) Cal'2 S21 Strea) Cal'2 S23

S10 Pre%%!re / 2329 0ar3 e). / 38 C S19 Pre%%!re / 228 0ar3 e). / 38 C S12 Re'y'le %trea) flo*rate / 440 k&)ol85r S15 Re'y'le to t5e rea'tor / 40 k&)ol85r +!ty / 03 .rod!'t .5a%e%3 &lo0al te). / ,2222 C 754 'on9er%ion 19er5ead .rod!'t / 994 0en#ene3 S24 "otto)% .rod!'t / 98285 4 tol!ene S26 19er5ead .rod!'t / 1004 H23 1004 CH4

,he thermodynamic system used for this simulation was the $oaveB edlichBAwong ($ A&. ,he simulation starts with combining the fresh toluene stream $- with the recycle toluene stream $*4 in the mi7er HB- to form stream $*. ,his mi7er simulates the mi7ing that happens in ,AB- in the original PFD figure *. ,he stream $* is then pumped (PB-& to *8.8 bar and is combined in a mi7er HB? with stream $-9) this stream is a mi7ture of fresh feed hydrogen mi7ed with unreacted hydrogen) it also contains traces of toluene ben/ene and methane. Pump PB- is simulated with an efficiency of =86. Hi7er HB? simulates the mi7ture of the liquid phase and gas phase that happens in ,AB* in the original process. ,he stream $-9 is the outlet of mi7er HB*) this mi7er combines the fresh stream of hydrogen $-= and the unreacted recycle stream of hydrogen $-4. ,o simulate the mi7ers only the pressure drop is required) which in this case is + bar. ,he two phase stream e7iting the mi7er HB? is then introduced into heat e7changer CB- in the tube side. .ighBpressure stream is used in this heat e7changer in the shell side to heat up the tube side process stream $4 to an outlet temperature of -9?.5 3. ,he outlet stream $8 is a oneBphase stream of all vapor. ,he pressure drop for all the heat e7changers are set to be +.?48 bar to simulate a real heat e7changer. ,he process stream is then introduced into the heater CB*) where it is heated up to 9++ 3. ,his temperature is the required temperature that will allow the reaction to happen in the reactor. ,he now heated up stream $9 is combined with recycle compress hydrogen $-8 in mi7er HB4. $ince the reaction is highly e7othermic) the temperature is controlled by in'ection of quench hydrogen at the reactor) this is simulated by the use of mi7er HB4. ,he feed is then introduced to the main part of the process the reactor B-. A conversion reactor is used to simulate this stoichiometric reactor. ,he reaction stoichiometry must be entered in order to appropriately use this reactor. ,his reactor type is used since only the reaction is known) no other data equilibrium data is known. #n order to simulate an e7othermic reactor the duty of the reactor must be specified to be /ero 2tu@hr. Also the toluene conversion of =86 must be entered. ,his is the typical conversion that is realistic for this process. ,he process stream now containing a high amount of ben/ene e7its the reactor at 9=-o3) this temperature must be decreased in order to separate the unreacted components with the products. ,his is achieved by introducing the product stream $< to heat e7changer CB8. #n this heat e7changer the process stream is cooled to ?< o3) by using cooling water. ,he outlet stream) $*<) is a twoBphase stream that is introduced into the first separator FB-. ,his knock out drum separates mostly all hydrogen and methane and it also contains traces of toluene and ben/ene. ,he pressure and temperature of this flash drum must be specified to *?.5 bar and ?<o3.

*+

,he overhead stream $5 is then split into two streams $-- and $-* in splitter $P-. For this splitter an estimate of what is recycled back is given in table ?. ,able ? shows the estimates needed for the recycle streams $-*) and $-8) for splitters - and *. $tream $-* is compressed in a compressor of efficiency of =86 to a pressure of *8.8 bar. ,he compressed gas $-? is then introduced into splitter $PB*) which splits the splitter into stream $-4 and $-8. $tream $-4 is mi7ed with the fresh feed of hydrogen) and stream $-8 is used to control the temperature of the reactor. ,he amount of the splits is given in ,able ?. ,he stream $-- is part of the fuel gas. ,he bottom stream $-+ of the separator F- is introduce into the second separator F*) which separates more hydrogen and methane from ben/ene and toluene. ,he liquid bottom stream $-5 is then heated up in heat e7changer CB? to 5+ o3. ,he overhead stream $-< is combined with the overhead of the first separator FB- in mi7er HB8 to makeup portion of the fuel gas. $tream $-5 is then introduced into a distillation column) which is simulated by a stream calculator) $3-. #n this piece of equipment the separation required must be specified. #n this case 556 of the ben/ene must e7it at the overhead and 5<.<86 of the toluene must e7it at the bottom of the separation unit. ,he temperature and pressure of the overhead and the bottom must be specified in order for the simulation to be properly represented. ,he temperatures are --*o3 and *.4? bar. ,he bottoms of this stream calculator $*4 is the recycle toluene that is mi7ed in H- with the fresh toluene feed. ,he overhead of this separator is then introduced into another stream calculator $3*) which simulates the condenser and reflu7 drum and pump of the distillation tower. ,his stream calculator separates all the hydrogen and methane in the overhead $*8) from the toluene and ben/ene in the bottoms $*9. ,he stream $*8 is then combined in a mi7er H9 with the rest of the gas that composes the fuel gas. ,he stream $*9 is then introduced into a heat e7changer C4 where the ben/ene product is cooled down to ?<o3 before is sent to storage. ,able 4 lists the results of the material balance of each stream in the simulation.

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#able 4! $imulation Haterial 2alance

Stream Name Stream Des ription !"ase #emperature !ressure $lo%rate &omposition #O'(ENE )2 *E#)+NE )2O +IR ,EN-ENE Stream Name Stream Des ription !"ase #emperature !ressure $lo%rate &omposition #O'(ENE )2 *E#)+NE )2O +IR ,EN-ENE Stream Name Stream Des ription !"ase #emperature !ressure $lo%rate &omposition #O'(ENE )2 *E#)+NE )2O +IR ,EN-ENE Stream Name Stream Des ription !"ase #emperature !ressure $lo%rate &omposition #O'(ENE )2 *E#)+NE )2O +IR ,EN-ENE S1 S2 S3 S4 S5 S6 S7 S8 ol!ene 6i7!id 6i7!id 6i7!id Mi-ed :a.or :a.or :a.or :a.or C 252000 482242 492160 432219 1632905 6002000 5862293 6712015 ";R 12900 12900 252500 252500 252155 242811 242811 242811 <$,M168HR 1082700 1442653 1442653 8452265 8452265 8452265 8852653 8852653 12000 02000 02000 02000 02000 02000 S. 02993 02000 02000 02000 02000 02007 S1/ 02993 02000 02000 02000 02000 02007 S11 02170 02618 02206 02000 02000 02005 S12 02170 02618 02206 02000 02000 02005 S13 02170 02618 02206 02000 02000 02005 S14 02163 02617 02215 02000 02000 02006 S15 02041 02495 02337 02000 02000 02127 S16 :a.or 362672 252500 7002612 02001 02745 02249 02000 02000 02005 S25

C ";R <$,M168HR

:a.or 6i7!id :a.or :a.or :a.or :a.or :a.or 382000 382000 382000 382000 442958 442958 442958 232900 232900 232900 232900 252500 252500 252500 7402254 1452400 3002254 4402000 4402000 3992612 402388 02001 02591 02399 02000 02000 02009 02243 02004 02021 02000 02000 02732 02001 02591 02399 02000 02000 02009 S1. 02001 02591 02399 02000 02000 02009 S2/ 02001 02591 02399 02000 02000 02009 S21 02001 02591 02399 02000 02000 02009 S23 02001 02591 02399 02000 02000 02009 S24

S17 S18 Hydro&en :a.or :a.or C 252000 382000 ";R 252500 22800 <$,M168HR 3012000 32117 02000 02950 02050 02000 02000 02000 S26 02007 02165 02766 02000 02000 02063

6i7!id :a.or Mi-ed :a.or 6i7!id :a.or 382000 352487 902000 1122000 1122000 1122000 22800 22800 22455 22155 22425 22500 1422283 3032371 1422283 1062329 352954 02731 02248 02000 02005 02000 02000 02747 02001 02587 02403 02000 02000 02009 02248 02000 02005 02000 02000 02747 02004 02000 02007 02000 02000 02989 02970 02000 02000 02000 02000 02030 02000 02023 02977 02000 02000 02000

S27 S22 S28 "en#ene F!el $a% 6i7!id 6i7!id :a.or Mi-ed C 1122000 382000 352661 382000 ";R 32300 22955 22500 242466 <$,M168HR 1052598 1052598 3042102 8852653 02004 02000 02000 02000 02000 02996 02004 02000 02000 02000 02000 02996 02001 02585 02404 02000 02000 02009 02041 02495 02337 02000 02000 02127

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