Mody and Marchildon: Chemical Engineering Process Design Chapter 20 INTEGRATED REACTION AND SEPARATION

P:/CEPDtxt2007/CEPDtextCh20

On-going improvements in plant design include efforts at process integration and also process intensification !ntegration includes the use of heat exchange among hot and cold process streams to reduce the use of external heating and cooling" and also the com#ination of reaction and separation in a single process !ntensification is generall$ a ma%or step-change increase in the driving force or rate constant of a limiting aspect of a process &he present section descri#es one t$pe of integration" namel$ the com#ination of reaction and distillation 'reen (" )ohnson * and )ohn ( +,--- Decem#er. /Process !ntensification 0agnifies Profits1" Chemical Engineering p 22-73 4tan5ie6ic7 ( ! and 0oulin ) ( +2000 )anuar$. /Process !ntensification: &ransforming Chemical Engineering1" Chemical Engineering Progress p 22-38 9allale : +200, )ul$. /*urning *right &rends in Process !ntegration1" Chemical Engineering Progress p 30-8, &souris C and Porcelli ) ; +2003 Octo#er. /Process !ntensification < 9as !ts &ime =inall$ Come>1" Chemical Engineering Progress p ?0-??

P@ODAC& =EE D

@B

D:

D:

!t is ver$ common for a reactor to #e follo6ed #$ one or man$ separation devices" to separate product from outflo6 and to rec$cle un-reacted material to the reactor !t 6ould appear that com#ining all of these operations into a single vessel 6ould reduce the capital cost of the s$stem" #ut if the vessel is ver$ large and complicated and difficult to control" then the saving could Cuic5l$ #e reversed &he com#ination of operations has to provide some s$nerg$" e g " assisting the reaction #$ continuousl$ removing some inhi#iting component or assisting in the #rea5-up of an a7eotrope 4ometimes after considering the advantages of com#ining operations it is concluded that it is not a fruitful approach De consider three em#odiments of the commonl$ used term reactive distillation as 6ell as a ne6 term distillative polymerization

20. . Reaction!A""i"ted Di"tillation &his concept comprises the pre-reaction of one component in an other6ise difficult-toseparate mixture and the su#seCuent reversal of the reaction after separation &erril" 4$lvestre and Dohert$ +,-E?. have proposed it for the separation of a mixture of metaand para-x$lenes !n concept it apears as follo6s:

B C O L U M N A.C 1 C

A
C O L U M N 2

A + B

(nother application might #e to esterif$ a mixture of organic acids to reduce their melting point and ma5e them more easil$ distilla#le &erril D F" 4$lvestre F = and Dohert$ 0 = +,-E?. /4eparation of closel$ #oiling mixtures #$ reactive distillation" , &heor$1" !ndustrial and Engineering Chemistr$" Process Design and Development" vol 28" p ,022-,07,

20.2. Catalytic Di"tillation &his concept is #ased on three 7ones in a column: a central 7one pac5ed 6ith catal$st 6here reaction ta5es place" and an upper 7one and a lo6er 7one 6here separation of components ta5e place &he example 6hich is generall$ used is the production of the gasoline ox$genate additive 0&*E" meth$l tertiar$ #ut$l ether 0&*E is made #$ the reaction of methanol 6ith iso#ut$lene

Inert hydrocarbons Methanol "eed

Methanol

Methanol # inert hydrocarbons Catalyst Bed

Isobutylene and other inert! hydrocarbons MTBE$ %ethanol& MTBE a'eotro(e

a'eotro(e

Methly Tertiary Butyl Ether MTBE!

Manufacture of MTBE by Reactive Distillation

&he main consideration is to 5eep the methanol in the column 6hile letting the inert h$drocar#ons +6hich accompanied the iso#ut$lene. and the 0&*E product escape &he design of a catal$st s$stem that can sta$ intact in the middle of all this activit$ 6as a challenge (#ufares ( ( and Douglas P F +,--?. /0athematical modeling and simulation of an 0&*E catal$tic distillation process using 4PEEDAP and (4PE:PFA41" &rans ! Chem E " vol 73(" p 3-,2 !sla 0 ( and !ra7oCui 9 ( +,--2. /0odeling" anal$sis" and simulation of a meth$l tert#ut$l ether reactive distillation column" !nd Eng Chem @esearch" vol 3?+E." p 22-2270E

20.#. Reacti$e Di"tillation De reserve the term reactive distillation for s$stems in 6hich reaction and distillation are ta5ing place together throughout the column One of the earliest examples 6as the reaction of methanol and acetic acid to produce meth$l acetate +and 6ater as a #$product. &he standard process reCuired multiple distillation columns to purif$ the product" mainl$ #ecause of the a7eotropes that form #et6een it and 6ater and #et6een it and methanol =inall$" after consideration of man$ schemes the Eastman Chemical Compan$ came up 6ith the single vessel s$stem sho6n #elo6 &he internal composition profile is also sho6" 6ith the tra$s num#ered from the #ottom up (greda ; 9" Partin F @ and 9eise D 9 +,--0 =e#ruar$. /9igh-Purit$ 0eth$l (cetate via @eactive Distillation1" Chemical Engineering Progress p 80-82

MeOAc Enrichin. )OAc *ater E+traction MeOAc

,eaction MeO)

MeO) -tri((in. )2O

Manufacture of Methyl Acetate by Reactive Distillation

100 80 Mass % 60 40 20 0
0

Water MeOH

MeOAc

HOAc

Impuritie s

10

20

30

40

50

60

70

Tray Number MeOH i!e!ra" HOAc H2 O4 Co%(osition /ro"iles in Methyl Acetate ,eacti0e 1istillation

20.%. Di"tillati$e Poly&eri'ation &he use of a distillation column for pol$meri7ation ma$ seem unli5el$ #ut 6ith proper stirring of the #ottom stages viscosities up to ?0 pascal-seconds have #een handled &he conventional process for n$lon 22 reCuires the pre-mixing of adipic acid" hexameth$lene diamine and 6ater" 6ith the su#seCuent vapori7ation of 6ater of solution and also 6ater produced #$ reaction

2EE1 31 *ATE, 2EE132 Conventional

4A/OU,

generic process for making nylon

&he ne6l$ developed process introduces the main components at opposite ends a distillation column :o 6ater is added Dater of reaction comes out the top" n$lon pol$mer comes out the #ottom

2EE1 31 Process for Di-monomeric Polyamides US 5 !"# $"#

4A/OU,

2EE1 32 N5LON