Reactive Distillation

Introduction Reactive distillation is a unit operation in which chemical reaction and distillative separation are carried out simultaneously within a fractional distillation apparatus. Reactive distillation may be advantageous for liquid-phase reaction systems when the reaction must be carried out with a large excess of one or more of the reac-tants, when a reaction can be driven to completion by removal of one or more of the products as they are formed, or when the product recovery or by-product recycle scheme is complicated or made infea-sible by azeotrope formation.

For consecutive reactions in which the desired product is formed in an intermediate step, excess reactant can be used to suppress additional series reactions by keeping the intermediate-species concentration low. A reactive distillation can achieve the same end by removing the desired intermediate from the reaction zone as it is formed. Similarly, if the equilibrium constant of a reversible reaction is small, high conversions can be achieved by use of a large excess of reactant. Alternatively, by Le Chatelier's principle, the reaction can be driven to completion by removal of one or more of the products as they are formed. Typically, reactants can be kept much closer to stoichiometric proportions in a reactive distillation. When a reaction mixture exhibits azeotropism, the recovery of products and recycle of excess reagents can be quite complicated and expensive. Reactive distillation can provide a means of breaking azeotropes by altering or eliminating the condition for azeotrope formation in the reaction zone through the combined effects of vaporization-condensation and consumption-production of the species in the mixture. Alternatively, a reaction may be used to convert the species into components that are more easily distilled. In each of these situations, the conversion and selectivity often can be improved markedly, with much lower-reactant inventories and recycle rates, and much simpler recovery schemes. The capital savings can be quite dramatic. A list of applications of reactive distillation appearing in the literature is given in Table 13-23.

Although reactive distillation has many potential applications, it is not appropriate for all situations. Since it is in essence a distillation process, it has the same range of applicability as other distillation operations. Distillation-based equipment is not designed to effectively handle solids, supercritical components (where no separate vapor and liquid phases exist), gas-phase reactions, or high-temperature or high-pressure reactions such as hydrogenation, steam reforming, gasification, and hydrodealkylation.

Simulation, Modeling, and Design Feasibility Because reaction and separation phenomena are closely coupled in a reactive distillation process, simulation and design is significantly more complex than that of sequential reaction and separation processes. In spite of the complexity, however, most commercial computer process modeling packages offer reliable and flexible routines for simulating steady-state reactive distillation columns, with either equilibrium or kinetically controlled reaction models. [Venkataraman et al., Chem. Eng. Prog., 86(6), 45 (1990)]. As with other enhanced distillation processes, the results are very sensitive to the thermodynamics model chosen and the accuracy of the VLE data used to generate model parameters. Of equal, if not more significance is the accuracy of data on reaction rate as a function of temperature. Very different conclusions can be drawn about the feasibility of a reactive distillation if the reaction is assumed to reach chemical equilibrium on each stage of the column or if the reaction is assumed to be kinetically controlled [Barbosa and Doherty, Chem. Eng. Sci., 43, 541 (1988)]. Tray holdup

TABLE 13-23 Applications of Reactive Distillation


Distillation Butanol


Methyl acetate from methanol and acetic acid General process for ester formation

Dibutyl phthalate from butanol and phthalic acid Ethyl acetate from ethanol and butyl acetate Recovery of acetic acid and methanol from methyl acetate by-product of vinyl acetate production Nylon 6,6 prepolymer from adipic acid and hexamethylenediamine MTBE from isobutene and methanol TAME frompentenes and methanol Separation of close boiling 3- and 4-picoline by complexation with organic acids Separation of close-boiling meta and para xylenes by formation of tert-butyl meta-xyxlene Cumene from propylene and benzene General process for the alkylation of aromatics with olefins Production of specific higher and lower alkenes from butenes

4-Nitrochlorobenzene from chlorobenzene and nitric acid Production of methylal and high purity formaldehyde

Agreda et al., Chem. Eng. Prog., 86(2), 40 (1990) Simons, "Esterification" in Encyclopedia of Chemical Processing and Design, Vol 19, Dekker, New York, 1983 Berman et al., Ind. Eng. Chem., 40, 2139 (1948) Davies and Jeffreys, Trans. Inst. Chem. Eng., 51, 275 (1973) Fuchigami, J. Chem. Eng. Jap., 23, 354 (1990)

Jaswal and Pugi, U.S. Patent 3,900,450 (1975)

DeGarmo et al., Chem. Eng. Prog., 88(3), 43 (1992) Brockwell et al., Hyd. Proc., 70(9), 133 (1991) Duprat and Gau, Can. J. Chem. Eng., 69, 1320 (1991)

Shoemaker and Jones, Hyd. Proc., 67(6), 57 (1987) Crossland, U.S. Patent 5,043,506 (1991) Jung et al., U.S. Patent 4,709,115 (1987)

Belson, Ind. Eng. Chem. Res., 29, 1562 (1990) Masamoto and Matsuzaki, J. Chem. Eng. Jap., 27, 1 (1994)

and stage requirements are two important variables directly affected by the form of the reaction model chosen.

When an equilibrium reaction occurs in a vapor-liquid system, the phase compositions depend not only on the relative volatility of the components in the mixture, but also on the consumption (and production) of species. Thus, the condition for azeotropy in a nonreactive system (yt = x, for all i) no longer holds true in a reactive system and must be modified to include reaction stoichiometry:


x¡ = mole fraction of component i in the liquid phase y¡ = mole fraction of component i in the vapor phase vi = stoichiometric coefficient of component i (negative for reac-tants, positive for products)

Phase compositions that satisfy Eq. (13-128) are stationary points on a phase diagram and have been labeled reactive azeotropes by Barbosa and Doherty [Chem. Eng. Sci., 43, 529 (1988)]. At a reactive azeotrope the mass exchange between the vapor and liquid phase and the generation (or consumption) of each species is balanced such that the composition of neither phase changes. Reactive azeotropes show the same distillation properties as ordinary azeotropes and therefore affect what products are achievable. Reactive azeotropes are not easily visualized in conventional y-x coordinates but become apparent upon a transformation of coordinates which depends on the number of reactions, the order of each reaction (e.g., A + B ^ C or A + B ^ C + D), presence of nonreacting components, and the extent of reaction. The general vector-matrix form of the transform for C reacting components, with R reactions, and I nonreacting components has been derived by Ung and Doherty [Chem. Eng. Sci., 50, 23 (1995)]. For the transformed mole fraction of component i in the liquid phase, X¡, they give

X, - V^VRef) 1XRef 1 - vV(VRef)-1XRef\' where vT = row vector of stoichiometric coefficients of component i for each reaction vRe f = square matrix of stoichiometric coefficients for R reference components in R reactions xRe f = column vector of mole fractions for the R reference components in the liquid phase vttot = row vector composed of the sum of the stoichiometric coefficients for each reaction

An equation identical to (13-129) defines the transformed mole fraction of component i in the vapor phase, Y,, where the terms in x are replaced by terms in y.

The transformed variables describe the system composition with or without reaction and sum to unity as do xt and y,. The condition for azeotropy becomes X, = Yt. Barbosa and Doherty have shown that phase and distillation diagrams constructed using the transformed composition coordinates have the same properties as phase and distillation region diagrams for nonreactive systems and similarly can be used to assist in design feasibility and operability studies [Chem. Eng. Sci., 43, 529, 1523, and 2377 (1988a,b,c)]. A residue curve map in transformed coordinates for the reactive system methanol-acetic acid-methyl acetate-water is shown in Fig. 13-76. Note that the nonreac-tive azeotrope between water and methyl acetate has disappeared, while the methyl acetate-methanol azeotrope remains intact. Only

Hno3 Txy Curve
FIG. 13-76 Residue curve map for the reactive system methanol-acetic acid-methyl acetate-water in chemical equilibrium.

= i those azeotropes containing either all the required reactants or products will be altered by the reaction (water and methyl acetate can back-react to form acetic acid and methanol, whereas methanol and methyl acetate cannot further react in the absence of either water or acetic acid). This reactive system consists of only one distillation region in which the methanol-methyl acetate azeotrope is the low-boiling and acetic acid is the high-boiling node.

The situation becomes more complicated when the reaction is kinetically controlled and does not come to complete-chemical equilibrium under the conditions of temperature, liquid holdup, and rate of vaporization in the column reactor. Venimadhavan et al. [AIChE J., 40, 1814 (1994)] and Rev [Ind. Eng. Chem. Res., 33, 2174 (1994)] show that the existence and location of reactive azeotropes is a function of approach to equilibrium as well as the evaporation rate.

Mechanical Design and Implementation Issues The choice of catalyst has a significant impact on the mechanical design and operation of the reactive column. The catalyst must allow the reaction to occur at reasonable rates at the relatively low temperatures and pressures common in distillation operations (typically less than 10 atmospheres and between 50°C and 250°C). Selection of a homogeneous catalyst, such as a high-boiling mineral acid, allows the use of more traditional tray designs and internals (albeit designed with allowance for high-liquid holdups). With a homogeneous catalyst, lifetime is not a problem, as it is added (and withdrawn) continuously. Alternatively, heterogeneous solid catalysts require either complicated mechanical means for continuous replenishment or relatively long lifetimes in order to avoid constant maintenance. As with other multiphase reactors, use of a solid catalyst adds an additional resistance to mass transfer from the bulk liquid (or vapor) to the catalyst surface, which may be the limiting resistance. The catalyst containment system must be designed to ensure adequate liquid-solid contacting and minimize bypassing. A number of specialized column internal designs, catalyst containment methods, and catalyst replenishment systems have been proposed for both homogeneous and heterogeneous catalysts. A partial list of these methods is given in Table 13-24.

Heat management is another important consideration in the implementation of a reactive distillation process. Conventional reactors for highly exothermic or endothermic reactions are often designed as modified shell-and-tube heat exchangers for efficient heat transfer. However, a trayed or packed distillation column is a rather poor mechanical design for the management of the heat of reaction. Although heat can be removed or added in the condenser or reboiler easily, the only mechanism for heat transfer in the column proper is through vaporization (or condensation). For highly exothermic reactions, a large excess of reactants may be required as a heat sink, necessitating high-reflux rates and larger-diameter columns to return the vaporized reactants back to the reaction zone. Often a prereactor of conventional design is used to accomplish most of the reaction and heat removal before feeding to the reactive column for final conversion, as exemplified in most processes for the production of tertiary amyl methyl ether (TAME) [Brockwell et al., Hyd. Proc., 70(9), 133 (1991)]. Highly endother-mic reactions may require intermediate reboilers. None of these heat-management issues preclude the use of reactive distillation, but must be taken into account during the design phase. Comparison of heat of reaction and average heat of vaporization data for a system, as in Fig. 13-77, gives some indication of potential heat imbalances [Sundmacher et al., Chem. Eng. Comm., 127, 151 (1994)]. The heat neutral systems (-A Hreact = A Hva„(avg)) such as methyl acetate and other esters can be accomplished in one reactive column, whereas the MTBE and TAME processes, with higher heats of reaction than vaporization, often include an additional prereactor. One exception is the catalytic distillation process for cumene production, which is accomplished without a prereactor. Three moles of benzene reactant are vaporized (and refluxed) for every mole of cumene produced. The relatively high heat of reaction is advantageous in this case as it reduces the overall heat duty of the process by about 30 percent [Shoemaker and Jones, Hyd. Proc., 57(6), 57 (1987)].

Process Applications The production of esters from alcohols and carboxylic acids illustrates many of the principles of reactive distillation as applied to equilibrium-limited systems. The equilibrium constants for esterification reactions are usually relatively close to unity. Large excesses of alcohols must be used to obtain acceptable yields with large recycles. In a reactive-distillation scheme, the reac-

TABLE 13-24 Catalyst Systems for Reactive Distillation




Homogeneous catalysis

Liquid-phase mineral-acid catalyst added to column or reboiler

Esterifications Dibutyl phlalate Methyl acetate

Keyes, Ind. Eng. Chem., 24, 1096 (1932) Berman et al., Ind. Eng. Chem., 40, 2139 (1948) Agreda et al., U.S. Patent 4,435,595 (1984)

Heterogeneous catalysis

Catalyst-resin beads placed in cloth bags attached to fiberglass strip. Strip wound around helical stainless steel mesh spacer Ion exchange resin beads used as column packing

Etherifications Cumene

Smith et al., U.S. Patent 4,443,559 (1981) Shoemaker and Jones, Hyd. 57(6), 57 (1987)

Catalyst-resin beads placed in cloth bags attached to fiberglass strip. Strip wound around helical stainless steel mesh spacer Ion exchange resin beads used as column packing

Molecular sieves placed in bags or porous containers Ion exchange resins formed into Raschig rings

Granular catalyst resin loaded in corrugated sheet casings Trays modified to hold catalyst bed

Distillation trays consturcted of porous catalytically active material and reinforcing resins Method described for removing or replacing catalyst on trays as a liquid slurry Catalyst bed placed in downcomer, designed to prevent vapor flow through bed Slotted plate for catalyst support designed with openings for vapor flow

Ion exchanger fibers (reinforced ion exchange polymer) used as solid-acid catalyst High-liquid holdup trays designed with catalyst bed extending below tray level, perforated for vapor-liquid contact Catalyst bed placed in downcomer, in-line withdrawal/addition system

Etherifications Cumene

Hydrolysis of methyl acetate

Alkylation of aromatics MTBE

Dimethyl acetals of formaldehyde MTBE

None specified None specified Etherifications, alkylations None specified Hydrolysis of methyl acetate None specified None specified

Smith et al., U.S. Patent 4,443,559 (1981) Shoemaker and Jones, Hyd. 57(6), 57 (1987)

Crossland, U.S. Patent 5,043,506 (1991) Flato and Hoffman, Chem. Eng. Tech., 15, 193 (1992)

Zhang et al., Chinese Patent 1,065,412 (1992) Sanfilippo et al., Eur. Pat. Appl. EP 470,625

Wang et al., Chinese Patent 1,060,228 (1992) Jones, U.S. Patent, 5,133,942 (1992) Asselineau, Eur. Pat. Appl. EP 547,939 (1993)

Evans and Stark, Eur. Pat. Appl. EP 571,163

Hirata et al., Jap. Patent 05,212,290 (1993)

Reactive Distillation
FIG. 13-77 Similarity of heats of reaction and vaporization for compounds made by reactive distillation.

tion is driven to completion by removal of the water of esterification. The method used for removal of the water depends on the boiling points, compositions, and liquid-phase behavior of any azeotropes formed between the products and reactants and largely dictates the structure of the reactive-distillation flowsheet.

When the ester forms a binary low-boiling azeotrope with water or a ternary alcohol-ester-water azeotrope and that azeotrope is heterogeneous (or can be moved into the two-liquid-phase region), the continuous flowsheet illustrated in Fig. 13-78 can be used. Such a flowsheet works for the production of ethyl acetate and higher homologs. In this process scheme, acetic acid and the alcohol are continuously fed to the reboiler of the esterification column, along with a homogeneous strong-acid catalyst. Since the catalyst is largely nonvolatile, the reboiler acts as the primary reaction site. The alcohol is usually fed in slight excess to ensure complete reaction of the acid and to compensate for alcohol losses through distillation of the water-

Tert Amyl Alcohol
FIG. 13-78 Flowsheet for exters which form a heterogeneous minimum-boiling azeotrope with water.

ester-(alcohol) azeotrope. The esterification column is operated such that the low-boiling, water-laden azeotrope is taken as the distillation product. Upon cooling, the distillate separates into two liquid phases. The aqueous layer is steam-stripped, with the organics recycled to the decanter or reactor. The ester layer from the decanter contains some water and possibly alcohol. Part of this layer may be refluxed to the esterification column. The remainder is fed to a low-boiler column where the water-ester and alcohol-ester azeotropes are removed overhead and recycled to the decanter or reactor. The dry, alcohol-free ester is then optionally taken overhead in a final refining column.

Methyl acetate cannot be produced in high purity using the simple esterification scheme described above. The methyl acetate-methanol-water system does not exhibit a ternary minimum-boiling azeotrope, the methyl acetate-methanol azeotrope is lower boiling than the watermethyl acetate azeotrope, a distillation boundary extends between these two binary azeotropes, and the heterogeneous region does not include either azeotrope, nor does it cross the distillation boundary. Consequently, the water of esterification cannot be removed effectively and methyl acetate cannot be separated from the methanol and water azeotropes by a simple decantation in the same manner as outlined above. Conventional sequential reaction-separation processes rely on large excesses of acetic acid to drive the reaction to higher conversion to methyl acetate, necessitating a capital- and energy-intensive acetic acid-water separation and large recycle streams. The crude methyl acetate product, contaminated with water and methanol, can be purified by a

Bubble Cap Distillation Column
FIG. 13-79 Integrated reactive-extractive distillation column for the production of methyl acetate.

number of the enhanced distillation techniques such as pressure-swing distillation [Harrison, US Patent 2,704,271 (1955)], extractive distillation with ethylene glycol monomethylether as the solvent [Kumerle, German Patent 1,070,165 (1959)], or azeotropic distillation with an aromatic or ketone entrainer [Yeomans, Eur. Patent Appl. 060717 and 060719 (1982)]. The end result is a capital- and energy-intensive process typically requiring multiple reactors and distillation columns.

The reactive-distillation process (Fig. 13-79) provides a mechanism for overcoming both the limitations on conversion due to chemical equilibrium as well as the difficulties in purification imposed by the water-methyl acetate and methanol-methyl acetate azeotropes [Agreda et al., Chem. Eng. Prog., 86(2), 40 (1990)]. Conceptually, this flowsheet can be thought of as four heat-integrated distillation columns (one of which is also a reactor) stacked on top of each other. The primary reaction zone consists of a series of countercurrent flashing stages in the middle of the column. Adequate residence time for the reaction is provided by high-liquid-holdup bubble-cap trays with specially designed downcomer sumps to further increase tray holdup. A nonvolatile homogeneous catalyst is fed at the top of the reactive section and exits with the underflow water by-product. The extractive-

distillation section, immediately above the reactive section, is critical in achieving high-methyl-acetate purity. As shown in Fig. 13-76, simultaneous reaction and distillation eliminates the water-methyl acetate azeotrope (and the distillation boundary of the nonreactive system). However, pure methyl acetate remains a saddle in the reactive system, and cannot be obtained as a pure component by simple reactive distillation. The acetic acid feed acts as a solvent in an extractive-distillation section placed above the reaction section, breaking the methanolmethyl acetate azeotrope, and yielding a pure methyl acetate distillate product. The uppermost rectification stages serve to remove any acetic acid from the methyl acetate product and the bottommost stripping section removes any methanol and methyl acetate from the water byproduct. The countercurrent flow of the reactants results in high local excesses at each end of the reactive section, even though the overall feed to the reactive column is stoichiometric. Therefore, the large excess of acetic acid at the top of the reactive section prevents methanol from reaching the distillate, while, similarly, methanol at the bottom of the reactive section keeps acetic acid from the water bottoms. Temperature and composition profiles for this reactive-extractive-distillation column are shown in Fig. 13-80a and b, respectively.

Alcohol Stripping Systems

FIG. 13-80 Reactive extracting distillation for methyl acetate production. (a) Composition profile. (b) Temperature profile.

FIG. 13-80 Reactive extracting distillation for methyl acetate production. (a) Composition profile. (b) Temperature profile.

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