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Reactive Distillation

Reactive Distillation

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Published by 5161440
Reactive Distillation
Reactive Distillation

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Published by: 5161440 on Feb 22, 2013
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Ó
2012Wiley-VCHVerlagGmbH&Co.KGaA,Weinheim
Reactive Distillation
M
ICHAEL
S
AKUTH
,
Sasol Solvents Germany GmbH, Moers, Germany
D
IETER
R
EUSCH
,
Degussa AG, Marl, Germany
R
ALF
J
ANOWSKY
,
Degussa AG, Mobile, Alabama, United States
1. Introduction
. . . . . . . . . . . . . . . . . . . . . . . . . 264
2. Mathematical Modeling of ReactiveDistillation Processes
. . . . . . . . . . . . . . . . . . 265
2.1. Equilibrium-Based Models
. . . . . . . . . . . . . 265
2.2. Rate-Based Models
. . . . . . . . . . . . . . . . . . . 266
3. Design of Reactive Distillation Processes
. . . 267
3.1. Procedures for Process Design Studies
. . . . 267
3.2. Flow sheet for Process Development
. . . . . . 269
4. Industrial Applications
. . . . . . . . . . . . . . . . 270
4.1. Commercial Packing Structures
. . . . . . . . . 270
4.2. Industrial Catalytic Distillation Processes
. . 272
4.3. Novel Application of CD with regard toProcess Intensification
. . . . . . . . . . . . . . . . . 275
References
. . . . . . . . . . . . . . . . . . . . . . . . . . 275
Symbols and Abbreviations
a
 j
: specific interfacial area, m
2
 /m
3
c
tj
: mixture molar densities, kmol/m
3
: energy transfer rate, W
 f 
ij
L
: feedowrateofcomponentitostagejinthe liquid phase, kmol/s
 j
: matrix of mass transfer coefficients, m/s
ij
: equilibrium ratio of component i onstage j
 L 
 j
: liquid flow rate from stage j, kmol/s
 L 
 j
À
1
: liquid flow rate to stage j, kmol/s
 N 
ij
L
: liquid phase mass transfer rate of com-ponent i, kmol/s
 N 
 j
: vector of mass transfer rates, kmol/s
 N 
tj
: total mass transfer rate, kmol/sNC: number of compounds
Q
L
: liquid phase heat loss, W
Q
V
: vapor phase heat loss, W
ij
: reaction rate of component i on stage j,kmol/s
 j
L
: ratio of liquid sidewithdrawal
 j
: vapor flow rate from stage j, kmol/s
 j
þ
1
: vapor flow rate to stage j, kmol/s
 X 
i
: transformedliquidphasecompositionof component i
 x
ij
: mole fraction of component i in liquidphase of stage j
 x
ij
I
: liquid mole fraction of component i ininterface
 x
 j
: vector of liquid mole fractions
i
: transformed vapor phase compositionof component i
 y
ij
: mole fraction of component i in vaporphase of stage j
 y
ij
I
: vapor mole fraction of component i ininterface
 y
 j
: vector of vapor mole fractions
D
 H 
: heat of reaction, J/kmol
i
: stoichiometric coefficient for compo-nent i
T
: sum of stoichiometric coefficients de-fined by Equation 9
Superscripts
I: InterfaceL: liquid phaseV: vapor phase
Subscripts
B: bottomD: distillateF: feedP: productR: reference component
i
: component number
DOI: 10.1002/14356007.c22_c01.pub2
 
1. Introduction
Reactive distillation (RD) is a process in which acatalytic chemical reaction and distillation (frac-tionation of reactants and products) occur simul-taneously in one single apparatus. Reactivedistillation belongs to the so-called ‘process-intensification technologies’’. From the reactionengineering view point, the process setup can beclassified as a two-phase countercurrent fixed-bed catalytic reactor.In the literature this integrated reaction –separation technique is also known as catalyticdistillation (CD) or reaction with distillation(RWD). According to [1], CD is a process inwhich a heterogeneous catalyst is localized in adistinct zone of a distillation column. RD is themore general term for this operation, which doesnot distinguish between homogeneously or het-erogeneously catalyzed reactions in distillationcolumns. RWD is a trademark of the KochEngineering Company for reactive distillationtechnology that uses their KataMax packingstructures. A brilliant overview on the currentstatus of RD technologies, modeling, industrialapplications, etc., can be found in [2].The present article exclusively deals with RDprocesses that operate with a heterogeneous cat-alyst system, i.e., CD technology. The mostimportant advantage of CD technology for equi-librium-controlled reactions is the elimination of equilibrium limitation of conversion by continu-ous removal of products from the reaction mix-ture. It is the application of Le Chatelier’s prin-ciple to displace the chemical equilibrium byincreasing the concentrations on the one side of the reaction, i.e., the reactants, and decreasing iton the other, i.e., the product side. The chemicalcomposition at this equilibrium point can becalculated by means of the Gibbs energy of reaction at a given temperature. Activities mustbe used to recalculate the composition from theequilibrium constant (i.e., the molar fractions of the components).Usually, a partially converted reaction mix-ture, close to chemical equilibrium, leaves thefixed-bed reactor section and enters the CDcolumn in the fractionating zone to ensure theseparation of products from feedstock compo-nents. The fractionated unconverted feedstock components enter the catalytic section in the CDcolumn for additional or total conversion. Thecatalyst packing zone is installed in the upper orlower-middle part of the column, with normaldistillation sections above and below.CD technology has several advantages overconventional operating methods, such as a fixed-bed reactor connected to a fractionating column,in which the distillate or bottoms have to berecycled after further separation steps for a totaloverall conversion.Apart from increased conversion, the follow-ing benefits can be obtained [1]:
.
The most important benefit of CD technologyis the lower capital investment, because twoprocess steps can be combined and carried outin the same device (so called ‘‘process intensi-fication’’). Such integration leads to lowercosts for pumps, piping and electricalinstrumentation.
.
If CD is applied to an exothermic reaction, thereactionheatcanbeusedtovaporizepartofthesurrounding liquid, which represents three
 j
: stage numbert: total
Abbreviations and Acronyms
AIBN: AzobisisobutyronitrileCD: Chemical distillationDIPB: DiisopropylbenzeneETBE: Ethyl
tert 
-butyl etherHB: High-boilingHETP: Height equivalent to a theoretical plateLB: Low-boilingMB: Medium-boilingMESH: Material balance/equilibrium condition/ summation equation/heat balanceMTBE: Methyl
tert 
-butyl etherRD: Reactive distillationRWD: Reaction with distillationTAME:
tert 
-Amyl methyl etherTAEE:
tert 
-Amyl ethyl etherTIPB: Triisopropylbenzene
264 Reactive Distillation Vol. 31
 
fundamental advantages: The maximum tem-perature in the structured catalytic packing islimited to the boiling point of the reactionmixture, so that the danger of 
hot spots
isreduced significantly (so-called ‘Siedek 
uh-lung’’). Also, extremely simple and reliabletemperature control is achieved. In addition,the integration of reaction heat in the distilla-tion process leads to energy savings by reduc-ing reboiler duty.
.
Product selectivity can be improved owing tofast removal of reactants or products from thereaction zone. Thus, the probability of conse-cutive reactions, which may occur in the con-ventional operation mode, is generallylowered.
.
IfthereactionzoneintheCDcolumnislocatedabove the feed point, poisoning of the catalystcan be avoided. This leads to longer catalystlifetimecomparedtotheconventionalmodeof operation.
.
Thepossibilitytobreakazeotropesinthevapor- liquid equilibrium, because reactants or pro-ducts can act as entrainers or because theazeotropes can simply disappear.There are three important constraints for ap-plying CD technology to catalytic chemicalreactions:
.
TheuseofCDtechnologyisonlypossibleifthetemperaturewindowofthevapor liquidequi-librium is equivalent to the reaction tempera-ture. By changing the column operating pres-sure, this temperature window can be altered.
.
TheflexibilityintheoperatingtemperatureofaCD column is not only restricted by the factthat two phases are required for the distillationprocess. Also the thermal stability of the cata-lyst can limit the upper operating temperature.
.
Becauseofthenecessityofwetcatalystpellets,the chemical reaction must take place entirelyin the liquid phase.
.
Asitisveryexpensivetochangethecatalystinthe structured packing of a CD column, onlycatalysts with a long lifetime are suitable forthis process.As a ‘fourth constraint’CD technology issomehow difficult to model mathematically,which complicates the scale-up from technicalplant scale to full production scale as well [2].Intheliterature, itcanbefound thatendother-mic reactions are not suitable for the CD tech-nology, because the reaction heat condenses partof the vapor stream. Although endothermic reac-tions require more reboiler duty and thereforeexhibit no large energy savings, there are norestrictions with regard to the application of thistechnology [3].Chemical reactions, which may benefit fromCD technology, should fulfill the above-men-tioned criteria in general. Reactions of this typeinclude, for example, etherifications, esterifica-tions, transesterifications, hydrations, hydroly-sis, condensations, hydroisomerizations, oligo-merizations, alkylations, transalkylations, andselective hydrogenations.An excellent overview of the current status of published applications is given in [2].
2. Mathematical Modeling of Reactive Distillation Processes
2.1. Equilibrium-Based Models
Multicomponent separation processes, such asnormal distillation processes, have been modeledby using the equilibrium-stage concept for acentury. Therefore, early works on reactive dis-tillation also used the equilibrium-stage model tosimulatereactionswithsuperimposeddistillation.The principal assumption of the equilibrium-stagemodelisthatthevaporandtheliquidstreamthat leave the stage are in thermodynamic equi-librium. In most real distillation columns, of course, the residence time is too short to reachtotal equilibrium. For this reason, efficiencieshave been introduced into the model (e.g., Mur-phree efficiency, vaporization efficiency, etc.) toaccount for the nonideal behavior. MESH (i.e.,Material balance, Equilibrium relationship,Summation of all substances, and enthalpy bal-ance
) equations are used to simulate conven-tional distillation columns (
!
Distillation, 1.Fundamentals, Section 4.3).To introduce the chemical reaction superim-posed to the distillation further equations areneededtosimulatereactive distillationprocesses(
!
Reaction Columns, Chap. 2.). The simplestway to consider chemical reactions is to use theequilibrium constant
i
, but many reactions arenot fast enough to reach chemical equilibrium in
Vol. 31 Reactive Distillation 265

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