Reactive Distillation

MICHAEL SAKUTH, Sasol Solvents Germany GmbH, Moers, Germany DIETER REUSCH, Degussa AG, Marl, Germany RALF JANOWSKY, Degussa AG, Mobile, Alabama, United States

1. 2. 2.1. 2.2. 3. 3.1. 3.2.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . Mathematical Modeling of Reactive Distillation Processes . . . . . . . . . . . . . . . . . Equilibrium-Based Models . . . . . . . . . . . . Rate-Based Models . . . . . . . . . . . . . . . . . . Design of Reactive Distillation Processes . . Procedures for Process Design Studies . . . Flow sheet for Process Development . . . . .

. 264 . . . . . . 265 265 266 267 267 269

4. 4.1. 4.2. 4.3.

Industrial Applications . . . . . . . . . . . . . . . Commercial Packing Structures . . . . . . . . Industrial Catalytic Distillation Processes . Novel Application of CD with regard to Process Intensication . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . .

. 270 . 270 . 272 . 275 . 275

Symbols and Abbreviations aj: ctj: E: fijL: kj: kij: Lj: Lj1: NijL: Nj : Ntj: NC: Q L: QV: rij: SjL: Vj: Vj1: Xi: xij: xijI: specic interfacial area, m /m mixture molar densities, kmol/m3 energy transfer rate, W feed ow rate of component i to stage j in the liquid phase, kmol/s matrix of mass transfer coefcients, m/s equilibrium ratio of component i on stage j liquid ow rate from stage j, kmol/s liquid ow rate to stage j, kmol/s liquid phase mass transfer rate of component i, kmol/s vector of mass transfer rates, kmol/s total mass transfer rate, kmol/s number of compounds liquid phase heat loss, W vapor phase heat loss, W reaction rate of component i on stage j, kmol/s ratio of liquid sidewithdrawal vapor ow rate from stage j, kmol/s vapor ow rate to stage j, kmol/s transformed liquid phase composition of component i mole fraction of component i in liquid phase of stage j liquid mole fraction of component i in interface
2 3

xj: Yi: yij: yijI: yj: DH r : ni: n T:

vector of liquid mole fractions transformed vapor phase composition of component i mole fraction of component i in vapor phase of stage j vapor mole fraction of component i in interface vector of vapor mole fractions heat of reaction, J/kmol stoichiometric coefcient for component i sum of stoichiometric coefcients dened by Equation 9

Superscripts I: L: V: Interface liquid phase vapor phase

Subscripts B: D: F: P: R: i: bottom distillate feed product reference component component number

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.c22_c01.pub2

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j: t:

stage number total

Abbreviations and Acronyms AIBN: CD: DIPB: ETBE: HB: HETP: Azobisisobutyronitrile Chemical distillation Diisopropylbenzene Ethyl tert-butyl ether High-boiling Height equivalent to a theoretical plate

LB: Low-boiling MB: Medium-boiling MESH: Material balance/equilibrium condition/ summation equation/heat balance MTBE: Methyl tert-butyl ether RD: Reactive distillation RWD: Reaction with distillation TAME: tert-Amyl methyl ether TAEE: tert-Amyl ethyl ether TIPB: Triisopropylbenzene

1. Introduction
Reactive distillation (RD) is a process in which a catalytic chemical reaction and distillation (fractionation of reactants and products) occur simultaneously in one single apparatus. Reactive distillation belongs to the so-called processintensication technologies. From the reaction engineering view point, the process setup can be classied as a two-phase countercurrent xedbed catalytic reactor. In the literature this integrated reaction separation technique is also known as catalytic distillation (CD) or reaction with distillation (RWD). According to [1], CD is a process in which a heterogeneous catalyst is localized in a distinct zone of a distillation column. RD is the more general term for this operation, which does not distinguish between homogeneously or heterogeneously catalyzed reactions in distillation columns. RWD is a trademark of the Koch Engineering Company for reactive distillation technology that uses their KataMax packing structures. A brilliant overview on the current status of RD technologies, modeling, industrial applications, etc., can be found in [2]. The present article exclusively deals with RD processes that operate with a heterogeneous catalyst system, i.e., CD technology. The most important advantage of CD technology for equilibrium-controlled reactions is the elimination of equilibrium limitation of conversion by continuous removal of products from the reaction mixture. It is the application of Le Chateliers principle to displace the chemical equilibrium by increasing the concentrations on the one side of the reaction, i.e., the reactants, and decreasing it

on the other, i.e., the product side. The chemical composition at this equilibrium point can be calculated by means of the Gibbs energy of reaction at a given temperature. Activities must be used to recalculate the composition from the equilibrium constant (i.e., the molar fractions of the components). Usually, a partially converted reaction mixture, close to chemical equilibrium, leaves the xed-bed reactor section and enters the CD column in the fractionating zone to ensure the separation of products from feedstock components. The fractionated unconverted feedstock components enter the catalytic section in the CD column for additional or total conversion. The catalyst packing zone is installed in the upper or lower-middle part of the column, with normal distillation sections above and below. CD technology has several advantages over conventional operating methods, such as a xedbed reactor connected to a fractionating column, in which the distillate or bottoms have to be recycled after further separation steps for a total overall conversion. Apart from increased conversion, the following benets can be obtained [1]:
.

The most important benet of CD technology is the lower capital investment, because two process steps can be combined and carried out in the same device (so called process intensication). Such integration leads to lower costs for pumps, piping and electrical instrumentation. If CD is applied to an exothermic reaction, the reaction heat can be used to vaporize part of the surrounding liquid, which represents three

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fundamental advantages: The maximum temperature in the structured catalytic packing is limited to the boiling point of the reaction mixture, so that the danger of hot spots is reduced signicantly (so-called Siedek uhlung). Also, extremely simple and reliable temperature control is achieved. In addition, the integration of reaction heat in the distillation process leads to energy savings by reducing reboiler duty. Product selectivity can be improved owing to fast removal of reactants or products from the reaction zone. Thus, the probability of consecutive reactions, which may occur in the conventional operation mode, is generally lowered. If the reaction zone in the CD column is located above the feed point, poisoning of the catalyst can be avoided. This leads to longer catalyst lifetime compared to the conventional mode of operation. The possibility to break azeotropes in the vapor - liquid equilibrium, because reactants or products can act as entrainers or because the azeotropes can simply disappear.

In the literature, it can be found that endothermic reactions are not suitable for the CD technology, because the reaction heat condenses part of the vapor stream. Although endothermic reactions require more reboiler duty and therefore exhibit no large energy savings, there are no restrictions with regard to the application of this technology [3]. Chemical reactions, which may benet from CD technology, should fulll the above-mentioned criteria in general. Reactions of this type include, for example, etherications, esterications, transesterications, hydrations, hydrolysis, condensations, hydroisomerizations, oligomerizations, alkylations, transalkylations, and selective 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 as normal distillation processes, have been modeled by using the equilibrium-stage concept for a century. Therefore, early works on reactive distillation also used the equilibrium-stage model to simulate reactions with superimposed distillation. The principal assumption of the equilibriumstage model is that the vapor and the liquid stream that leave the stage are in thermodynamic equilibrium. In most real distillation columns, of course, the residence time is too short to reach total equilibrium. For this reason, efciencies have been introduced into the model (e.g., Murphree efciency, vaporization efciency, etc.) to account for the nonideal behavior. MESH (i.e., Material balance, Equilibrium relationship, Summation of all substances, and enthalpy balance H) equations are used to simulate conventional distillation columns (! Distillation, 1. Fundamentals, Section 4.3). To introduce the chemical reaction superimposed to the distillation further equations are needed to simulate reactive distillation processes (! Reaction Columns, Chap. 2.). The simplest way to consider chemical reactions is to use the equilibrium constant Ki, but many reactions are not fast enough to reach chemical equilibrium in

There are three important constraints for applying CD technology to catalytic chemical reactions:
.

The use of CD technology is only possible if the temperature window of the vapor liquid equilibrium is equivalent to the reaction temperature. By changing the column operating pressure, this temperature window can be altered. The exibility in the operating temperature of a CD column is not only restricted by the fact that two phases are required for the distillation process. Also the thermal stability of the catalyst can limit the upper operating temperature. Because of the necessity of wet catalyst pellets, the chemical reaction must take place entirely in the liquid phase. As it is very expensive to change the catalyst in the structured packing of a CD column, only catalysts with a long lifetime are suitable for this process.

As a fourth constraint CD technology is somehow difcult to model mathematically, which complicates the scale-up from technical plant scale to full production scale as well [2].

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and summation equations (S equations, see above) for each component i:

X
i

yI ij 1 0;

as well as
X
i

xI ij 1 0

Figure 1. Nonequilibrium based stage model without feed and side streams

must be fullled. To simulate the reactive distillation process, an expression for the reaction rate rij f (temperature, concentrations/activities) must be added. For catalytic distillation the chemical reaction is taken into account in the material balance of the bulk liquid phase
L L 1sL j Lj xi;j xi;j1 Lj1 fij Nij rij 0

one theoretical stage. Therefore, it is often necessary to use kinetic expressions, which describes the reaction rate as a function of temperature and concentration activities of each component of the reaction scheme.

2.2. Rate-Based Models

To describe the real phenomena of mass transfer in distillation processes in more detail, a secondgeneration nonequilibrium model was developed by KRISHNAMURTHY and TAYLOR [4]. A nonequilibrium stage (Fig. 1) represents either a single tray or a section of packing in a column. Contrary to the equilibrium-based stage model, this rate-based model treats the vapor and liquid phases separately and combines them by means of a mass transfer rate and a heat transfer rate through the interfacial area. The total mass transfer rates are:
  V l V NjV cV tj kj aj yj yj Ntj yj   L l L NjL cL tj kj aj xj xj Ntj xj 1 2

where NjV or NjL are the vectors of molar uxes of the vapor or liquid stream, respectively, ctj are the molar densities, kj are the matrices of mass transfer coefcients, aj is the specic interfacial area, and NtjV or NtjL are the total mass transfer rate of the vapor or liquid stream, respectively [5]. At the interface of each stage j phase equilibrium (E equation, see above):
Kij xlij ylij 0 3

where sjL is the liquid side-withdrawal and fijL is the feed ow rate of component i to stage j in the liquid phase. For many catalytic distillation processes, liquid catalyst mass transfer must also be considered. The reaction heat DHr which is produced (exothermic reaction) or consumed (endothermic reaction) is considered in the heat balance of the liquid phase (see Fig. 1). YUXIANG AND XIEN [6] used this nonequilibrium stage model with simplied expression of the reaction kinetics based on concentrations to simulate the synthesis of MTBE, which they investigated experimentally in a column lled with catalyst granules in cloth pockets. The results of their simulation agreed fairly well with the experiments. However, SUNDMACHER AND HOFFMANN [7] investigated MTBE formation over a broad concentration range and found that the macrokinetics could be correctly described only by using liquid-phase activities for the intrinsic reaction kinetics and liquid solid mass transfer. The equilibrium-based stage model is an excellent pragmatic approach to simulate reactive distillation processes, especially those systems with homogeneous reactions. This model is part of all available process simulators (e.g., RADFRAC in ASPEN-PLUS, Aspen Technology, Inc.). For a detailed study of the superimposed distillation and interactions between reaction with mass transfer a rate-based approach is usually preferred (e.g., RATEFRAC in ASPEN-PLUS,

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Figure 2. Model complexity in simulation of reactive distillation systems

Aspen Technology, Inc.). Due to its complexity and the fact that only limited data are available on mass-transfer coefcients, this approach does not nd a broad usage. Furthermore, small deviations in these coefcients can have a severe negative impact on the simulation results [8]. (see Fig. 2)

Figure 3. Transformation of coordinates for a equilibrium reaction A B

C
i xR xi nv R T xR 1 nn R

Xi

3. Design of Reactive Distillation Processes

3.1. Procedures for Process Design Studies
Only a few systematic methods are available for the process design of multifunctional units such as reactive distillation columns. One method is the concept of reactive distillation lines with reactive azeotropes by BUZAD AND DOHERTY [9], BESSLING ET AL. [10] AND STICHLMAIER et al. [11]. A brief description of this method is given below. More details can be found in [2]. Figure 3 shows the transformation of coordinates for the equilibrium reaction A B
C. This transformation reduces the equilibrium concentration of component C to a single point on the line of the transformed coordinates A and B. Mathematically one can dene a chemical equilibrium reaction by Equation (7):
na Anb B . . .
np P . . . ; 7

Yi

i yR yi nv R T yR 1 nn R

where R is a chosen reference component. R can be reactant or a product component. The stoichiometric coefcient nT in these equations is dened as:
nT
NC X i1

ni

10

Both the vapor and liquid molar fractions of component P are set to zero, i.e., XP YP 0. According to Equation (8), the transformed composition coordinates fulll the unity constraints:
NC X i1

Xi

NC X i1

Yi 1

11

where ni are the stoichiometric coefcients of the reactants A, B, etc., and the desired products P, etc. The transformed liquid and vapor coordinates for an arbitrary component i, i.e., Xi and Yi, are given by Equation (8) [12].

By using these transformed coordinates for the feed components A and B, the mass balance and operating lines of a distillation column can be set up in the same way as for a system without a reaction. It reveals that feasible top and bottom compositions have to meet the lever rule (! Distillation, 1. Fundamentals, Section 4.1) through the feed concentration and an appropriate distillation line, as shown in Figure 4. This is the same procedure as for conventional nonreactive systems.

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is increased, a reactive azeotrope appears along line AB (Fig. 6). According to UNG and DOHERTY [13] this reactive azeotrope is characterized by identical vapor and liquid transformed-concentration coordinates (Eq. 12).
Xi Yi 12

Figure 4. Application of the concept of reactive distillation lines. As mass balance must be fullled, the feed concentration XF is located on a straight line between the transformed concentrations XD and XB.

Figure 5 shows reactive distillation lines for the equilibrium reaction A B

C in the presence of an inert component D. Note that product C is no longer necessary, because of the transformed-concentration coordinates between A and B (see Eq. 8). For a given feed concentration F, two process layouts can be derived. In design type I, component C decomposes, and B can be separated from A and D. With design type II, component C is formed, and the inert component D is separated from a mixture of A and B, which is in chemical equilibrium with C. If the equilibrium constant of the reaction A B
C

In this case the reactive azeotrope and the inert component D are nodes; components A and B are saddles. Therefore, in contrast to Figure 5, it is not possible to realize design type I (decomposition of C). Only design type II, i.e., the formation of C and separation of D at the top and A, B, and C at the bottom of the RD column, is feasible. The concept of reactive distillation lines with reactive azeotropes can also be extended to several other reaction types and to nonideal reactive distillation systems as well. In collaboration between the chemical industry and different European universities (EU-research project Brite-Euram), two computational tools have been developed for the design of RD processes, namely SYNTHESIZER and DESIGNER. SYNTHESIZER is based on the above-mentioned analogy between normal distillation processes and RD processes. It investigates the feasibility of RD for an existing process during re-engineering or in the planning stage for a new process. DESIGNER gives a more precise

Figure 5. Reactive distillation lines for an equilibrium reaction A B

C in the presence of an inert component D (LB low-boiling, MB medium-boiling, HB high-boiling)

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Figure 6. Reactive distillation lines for an equilibrium reaction A B

C in the presence of an inert component D with a reactive azeotropic point (LB low-boiling, MB medium-boiling, HB high-boiling).

insight into the RD process with respect to column parameters (e.g., column diameter, etc.). It contains calculation procedures with equilibrium-based stage models as well as rate-based models for a specic process design [14].

3.2. Flow sheet for Process Development

Figure 7 shows a ow sheet as a conceptual basis for the development of a CD process. The key feature of this ow sheet is the feasibility study followed by pilot plant experiments (optional) and a basic engineering concept. After using the above-mentioned tools for process synthesis and design (see Section 3.1), the parameters of a kinetic model must be determined in an appropriate experimental setup. Simulation studies with a simple equilibrium-based stage model, such as RADFRAC (ASPEN-PLUS), should reveal the optimal feed point to the CD column, the operating conditions of the CD column, and the position of the reaction zone in the CD column. As a rst approximation, these studies can be carried out by using equilibrium constants to incorporate the chemical reaction into the column (less complex model simulation, see Fig. 2.). For a

more detailed investigation, it is recommended to use an appropriate activity-based reaction expression with the determined kinetic parameters in a conventional simulator. In pilot plant experiments, which are carried out in a CD column with an inner diameter of 50 100 mm, the simulation studies are examined. As the process is iterative, these experiments are needed to check and to improve the simulations. As the last step of the feasibility study, all obtained results are fed into a nal simulation to decide whether an RD or conventional setup (e.g., reaction section followed by separation steps with internal recycle streams) should be applied. Preferably, a rate-based model, such as for example RATEFRAC (ASPEN-PLUS), is used to check whether any mass-transfer limitations interfere with the removal of reactants. Such limitations can cause undesired consecutive reactions in the reaction zone. As it is reported by some authors [2] it should be mentioned that predictive scale-up procedures from lab-scale experiments (50 80 mm inner diameter column) to pilot-plant scale (%300 mm inner diameter column) already reveal some evident deviation in conversion, e.g., for methyl acetate synthesis or MTBE decomposition in a CD column. The origin of this effect is up to now not fully understood.

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Figure 7. Flow sheet for the process development of a CD technology (CSTR continuous stirred tank reactor) (*: see Chapter 1)

The possible reasons for the observed deviations, discussed in [2], could be:
. . .

version, if scale-up calculations are made. These studies can facilitate improvement of the reliability of such simulations.

reduced reaction rates due to incomplete catalyst wetting, mass-transfer limitations, or maldistribution, etc.

4. Industrial Applications
4.1. Commercial Packing Structures
All commercial CD packing structures have in common that the catalyst is located in a distinct

Sensitivity studies of different CD column parameter can help to understand the order of magnitude of the deviations on the overall con-

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zone of a distillation column. Apart from the problem of positioning these packing structures, adequate contact between catalyst surface and liquid phase must be ensured. Nowadays, in most industrial processes macroporous acidic ion-exchange resins are used, but any other solid catalyst pellet can be placed in the pockets of a structured packing. As the entire catalyst structure must be removed from the distillation column to exchange the catalyst, one evident prerequisite for the catalyst is a long lifetime (more than about three years). Catalyst replacement means shutting down whole plants which results in a signicant loss of costs and operating time. CD Tech Catalyst Bales. This type of spatial conguration in a distillation column was rst developed and commercialized by CR & L (Chemical Research & Licensing Company) in 1980 [15]. It is now licensed by CD Tech (Chemical Distillation Technologies), a joint venture between CR & L and ABB Lummus Crest. In this technology the catalyst is supported in a berglass cloth, which is wrapped with stainless steel wire mesh. The demister wire mesh has two tasks. First, it stabilizes the berglass packing; second, it provides the void space necessary for distillation. These berglass cloths are rolled into catalyst bales and stacked on sieve trays in the column (Fig. 8).

KataMax and KataPak Technology. Analogous catalytic packing congurations were developed in 1991/1992 independently by Koch Engineering Company as KataMax technology [16] and by Gebr uder Sulzer [17] as KataPak technology. Here the catalytic section in the CD column has a conventional corrugated structure, wire-cloth distillation packing which contains appropriate catalyst pellets for the desired reaction. The solid catalyst is held in an envelope of meshed and crimped screen, sealed at the edges. These envelopes are stacked together in modular blocks, so that the crimp of one envelope has a 90 degree angle of inclination to the crimp of the next. In this architecture, channels are formed for the rising vapor ow and descending liquid ow. At the intersections, they provide intensive mixing of vapor and liquid phases and radial distribution in a block. It is reported [18] that the performance parameters of the KataMax packing (i.e., the hydraulic and mass transfer efciencies) are similar to those of standard distillation devices (e.g., the Flexipac packing). At liquid loadings of 10 50 m3m2h1 catalyst contact efciency exceeded 75 90 %. Catalyst contact efciency is the ratio of the rate constant of the catalyst in the packing to the rate constant of the catalyst in a stirred tank reactor for a simple liquid-phase rst-order reaction at the same temperature. Usually the catalyst content of KataMax or KataPak lies between 20 and 25 vol. %. For KataMax a HETP value (height equivalent to a theoretical plate) between 0.4 and 0.6 m can be used for simulation. For KataPak the HETP is 1.0 m at normal F factors (! Distillation, 2. Equipment, Section 2.2). The specic surface area of KataMax is 210 m2/m3 and of KataPak, 85 or 125 m2/m3 (KataPak-S 170.Y or KataPakS 250.Y, respectively). The benets of this type of packing are a very good distribution of liquid and vapor phases at a low pressure drop, efcient contact of the reactants with catalyst pellets and instantaneous distillative removal of reactants. Therefore, it combines excellent separation performance with an efcient mass and heat transfer for chemical reaction. MultiPak Technology. This structured catalyst packing was developed by the company Montz in 1998 in cooperation with the University of Dortmund [19]. In MultiPak technology the

Figure 8. CD Tech catalyst bales

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stacks are built up of alternating layers of meshed, but not crimped, catalyst envelopes and crimped structured distillation sheets. From the viewpoint of reaction and fractionating behavior, it has the same performance as KataMax or KataPak. The advantage of MultiPak is the identical geometric structure in an 80-mm laboratory packing and a 300- or 1000-mm pilot plant packing. Therefore, scaleup from pilot plant experiments to industrial plants is much easier. It is claimed that a dened ow pattern of vapor and liquid is achieved by this construction. This has advantages when resins are used as catalyst. As there is only liquid phase in the catalyst envelopes, the pellets are completely wetted under process conditions, and there is no swelling or shrinkage due to alternating contact with vapor and liquid. The disadvantage is a higher pressure drop along the structured packing. Multichannel Packing [20]. Details on this type of catalyst packing were published in 2003 by BASF. The point of departure to develop these packings was to improve trickle-bed reactor performance by installing corrugated distillation packings inside the reactor and pouring catalyst particles into them. The catalyst particles are brought loose into the packing cavities, distributed under the inuence of gravity. By alternating packing layers of high and low specic surface areas (so called catalyst barrier layer) the catalyst could be held in a specic area of the CD column. The advantage of these packings is their simplicity and the ease of catalyst removal in case of deactivated catalyst. As the way of introducing the catalyst into a specic column segment is similar to a normal trickle-bed reactor, the authors describe also a simpler modeling in case of scale-up studies. However, if the catalyst size distribution is not 100 % uniform, some particles may enter the lower part of the CD column. Especially with reversible reactions, which can only be performed in a specic segment of a CD column setup (e.g., MTBE synthesis), the undesired reverse reaction could occur in the bottom, if catalyst particles are present there. Reactive Rings. The reactive rings of VEBA Oel [21] are based on packing bodies such as Raschig rings or Berl saddles. On the outer and inner surface of these bodies, macro-

porous ion exchange resins are bonded chemically or physically. For example, the active Raschig rings are prepared by using an opencelled sintered glass, which is impregnated with a mixture of styrene, a long chain alkane, pdivinylbenzene, and a radical starter (AIBN: azobisisobutyronitrile). After the polymerization procedure, the resin is sulfonated with chlorosulfonic acid to build up the active catalytic sites. These types of reactive rings have been used in an etherication process in a pilot plant column [7, 22]. Other Technologies. Another interesting, but as yet not commercialized, technology for immobilizing catalyst pellets in a distinct zone of a CD column is to incorporate a xed-bed in the downcomer of a conventional tray column [23].

4.2. Industrial Catalytic Distillation Processes

Catalytic distillation can be used in catalytic chemical reactions which are limited by a chemical equilibrium. There are various reactions that satisfy this criterion, but only for etherication, esterication, and alkylation (synthesis of ethylbenzene or cumene) is this technology applied on an industrial scale. An overview of further possible applications can be found in [1, 2, 22]. Etherication Processes (see also ! Methyl Tert-Butyl Ether). The application of CD technology to etherication is limited to synthesis of methyl tert-butyl ether (MTBE), ethyl tertbutyl ether (ETBE), tert-amyl methyl ether (TAME), and tert-amyl ethyl ether (TAEE). Because of their good octane enhancing properties and low volatilities these ethers are excellent gasoline blending compounds (so-called oxygenates). Reduction of the tetraethyllead content in gasoline in the mid-1970s led to a dramatic increase in the demand for octane enhancers, with MTBE being used increasingly. Driven by the U.S. Reformulated Gasoline Program, which mandated a minimum oxygen content in gasoline of 2 %, world MTBE production has reached ca. 19 106 t/a in 1997 [24]. The successful use of CD technology in MTBE production led to its worldwide establishment.

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Table 1. Overview of CD processes for ether production [27]

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Process (licensor) ETHERMAX (UOP) CDMTBE & CDTAME (CD-Tech) CDETHEROL (CD-Tech) CATACOL (IFP)
*

Process description xed-bed tubular reactor or adiabatic recycle reactor followed by a reactive distillation column with KataMax Packing adiabatic reactor operating at the boiling point followed by a reactive distillation column with CD Tech Bales adiabatic xed-bed reactor operating at the boiling point followed by a reactive distillation column with CD Tech Bales recycle reactor, xed-bed reactor followed by a reactive distillation column

Catalyst sulfonated ion-exchange resin acidic ion-exchange resin trifunctional ion-exchange resin acidic ion-exchange resin

Market share* ca. 32 % ca. 58 % ca. 10 %

For MTBE, produced by CD technology in 1997

It should be mentioned that end of 1997 California started to ban MTBE from the gasoline pool due to its effect as a water contaminant and its possible cause of health problems (see also ! Methyl Tert-Butyl Ether). In mid-2006 the U.S. Environmental Protection Agency terminated the legal requirement of using MTBE in the gasoline pool [25]. The production capacities of MTBE are therefore shrinking day-by-day. Table 1 summarizes processes for ether production based on CD technology. As shown in the simplied process ow diagram for the ETHERMAX process (Fig. 9), all processes have in common a reactor section followed by a CD column. There is no industrial process in which the whole conversion is performed in a single CD column. A partially converted mixture from the reactor section, which is nearly in chemical

equilibrium, enters the CD column below the catalyst packing zone to ensure the separation of the ether from the feed stream. The catalyst packing is installed in the upper middle of the column, with normal distillation sections above and below. Usually, the reaction of the isoalkene with methanol or ethanol is conducted in the presence of a slight stoichiometric excess of the alcohol. In addition to the advantages of a higher selectivity for the ether (lower formation of C8 and C10 dimers) and shifting of the chemical equilibrium to the product side, this leads to a secure process control. In the absence of the alcohol in the reaction zone of the CD column exothermic dimerization and oligomerization of the C4 and C5 alkenes takes place at high reaction rates. A sharp and excessive temperature rise (hot spot)

Figure 9. Simplied ow diagram for the ETHERMAX process

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causes irreversible catalyst deactivation and catalyst damage. The excess alcohol is collected in the overhead of the CD column and separated from the hydrocarbon stream by extraction with water. In the case of MTBE production, a conversion of up to 99.9 % is possible by using this technology, if sufcient ether is present at the bottom of the column. Because of a minimum boiling azeotrope in the binary MTBE methanol system, the ether carries the alcohol into the reaction zone of the CD column. This unusual vapor liquid behavior and the high difference in the heat of vaporization between C4 hydrocarbons and methanol are possibly responsible for the known multiple steady states in CD column operation [22, 26]. The TAME process usually gives a lower conversion of 91 95 % only. Esterication Processes. Esterication is a good example for the benecial use of the CD technology. In conventional methyl acetate production the recovery of methyl acetate from the reactor outlet stream is complicated, because methanol forms a low boiling azeotrope with water and the separation of water from unconverted acetic acid is difcult. Due to these separation problems, the old Eastman Kodak process used a reactor coupled with eight distillation columns and an extraction column [28]. In the reactive distillation process, almost pure methyl acetate can be collected in the overhead of a single CD column at acetic acid

conversions of greater than 99 %. The Eastman Kodak process uses sulfuric acid as catalyst [29], but a heterogeneous catalyst system (acid ionexchange resin) can also be used successfully [30]. The conceptual basis for the successful implementation of reactive distillation in methyl acetate synthesis is shown in Figure 10. There are four zones in the column, which ensure the fairly high conversion. Acetic acid is separated from methyl acetate at the top of the column (zone I). In zone II, an extractive distillation section below the acetic acid feed extracts water from methyl acetate. The reaction takes place in the middle of the column (zone III). At the bottom (zone IV) methanol is fed and stripped from descending byproduct water. Alkylation Processes. CD-technology is also applied for alkylation reactions in the case of ethylbenzene and cumene manufacture [1]. As the two processes are fairly similar, only the cumene process is discussed here. In the CDCUMENE process, CD Tech catalyst bales are lled with an acidic, wide-pore zeolite catalyst, for example, zeolite Y, b or w [31]. The bales are stacked in the middle of a distillation column. Below the reaction zone propene is fed; benzene is passed as reux to the top of the column. The propene concentration in the reaction zone is held fairly low to slow down a side reaction in which diisopropylbenzene (DIPB) and triisopropylbenzene (TIPB) are formed. The cumene product with impurities of

Figure 10. Methyl acetate synthesis with CD technology

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Figure 11. Transesterication of methyl acetate to butyl acetate with CD technology in a divided wall column

ethylbenzene and n-propylbenzene, is taken from the bottom of the column. The overhead pressure of the CD column is maintained at 5 bar. The advantages of CD technology in cumene synthesis are lower formation of oligo-isopropylbenzenes (DIPB and TIPB), higher catalyst lifetime, and a higher conversion of benzene [32]. The internal benzene recycle to the reaction zone, which is a result of the distillative cumene benzene separation in the lower portion of the column, ensures the observed higher conversion.

4.3. Novel Application of CD with regard to Process Intensication

Distillation columns with dividing walls are used with success in some chemical processes. An EU-research project named INSERT has been started to investigate if CD technology can also be applied advantageously to such distillation columns with divided wall internals [33]. The successful use of CD technology in a divided wall column is reported in [34] for the transesterication of methyl acetate to butyl acetate (Fig. 11.). This process can be performed in one column of this type instead of using one CD column followed by two normal distillation columns.

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Vol. 31
W. L. Luyben, C.-C. Yu: Reactive Distillation Design and Control, Wiley, Hoboken, NJ 2008. K. Sundmacher: Reactive Distillation, Wiley-VCH, Weinheim 2003.

Further Reading
C. A. M. Afonso: Green Separation Processes, Wiley-VCH, Weinheim 2005. Z. Lei B. Chen Z. Ding: Special Distillation Processes, 1st ed., Elsevier, Amsterdam 2005.