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10.- Procesos de Intensificacin

Membrane:

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Multifunctional Reactors

The potential of multifunctional s ystems for PI is obvious. In multifunctional systems

different processes are coupled in one piece of equipment, usually reaction and separation or
several separation processes The most important benefit of incorporating two different functions
in one piece of equipment, of course, is reduction of the capital investment: why not place catalyst
particles on the trays of the distillation column?

One process step is eliminated, along with the associated pumps, piping, and instrumentation.
Other benefits depend on the specific reaction. In reactive distillation, optimal heat integration is
possible. Equilibrium limited reactions are an obvious class of reactions that would benefit from
the continuous removal of one of the products in situ.

Reactive Distillation

Reactive distillation involves a combination of reaction and distillation in a single column. If the
reaction is catalyzed, the process is referred to as catalytic distillation. Reactive distillation is a
two-phase flow process with gas and liquid flowing in countercurrent mode. If a solid catalyst is
present, this requires special catalyst morphology.

In the bulk chemical industry, catalytic distillation is already employed in a number of processes,
for example, for the production of MTBE (methyl tert-butyl ether) and other butyl ethers, the
production of cumene and ethylbenzene, and hydrogenation of aromatics [35]. An example of the
use of reactive distillation in the production of fine chemicals is the synthesis of
acetoacetarylamides [37].

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Production of MTBE

The formation of MTBE by etherification of isobutene with methanol (Section 6.3.4) is an

equilibrium-limited exothermic reaction:

In this reactor the largest part of the conversion takes place at relatively high temperature (high
reaction rate, low equilibrium conversion), while the remainder takes place in the catalytic
distillation column at lower temperature (low reaction rate, high equilibrium conversion). The
MTBE formed is continuously removed from the reaction section. Methanol, isobutene, and the
inert hydrocarbons flow upward through the catalyst bed and then to a rectification section, which
returns liquid MTBE. Isobutene conversions of over 99% can thus be achieved

An additional advantage of catalytic distillation is that the exothermic heat of reaction is directly
used for the distillative separation of reactants and products. Hence, perfect heat integration is
achieved: the heat of reaction does not increase the temperature resulting in near-isothermal
operation in the reaction zone.

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Production of Ethylbenzene

Ethylbenzene is produced by alkylation of benzene with ethene:

Main reactions during alkylation of benzene with ethene. B = benzene; EB = ethylbenzene;

DEB = diethylbenzenes; PEB = polyethylbenzenes.

Effect of ethene:benzene mole ratio on the alkylation of benzene to ethylbenzene (T = 500 K;

p = 1 bar; the E/B mole ratio of industrial processes is indicated).

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a) The Homogeneous Liquid Phase Process

The conventional liquid phase alkylation process is based on a homogeneous aluminum chloride
(AlCl3) catalyst. Although new plants are not built anymore, still a considerable amount of
ethylbenzene is produced by this process.
The catalyst system in this process consists of AlCl3 and HCl (which acts as a catalyst promoter).
HCl needs only be present in small quantities and is supplied as ethyl chloride.
Dry benzene, the catalyst complex, and ethyl chloride are fed to the alkylation reactor, which is an
empty vessel with an internal lining of corrosion-resistant brick. Ethene is spared into the liquid in
the reactor.
Alkylation takes place in the liquid phase. Excess benzene (22.5 mol/mol ethene) is used in order
to limit oligomerization of ethene and the formation of polyethylbenzenes. The reactor effluent is
mixed with recycle polyethylbenzenes and fed to the transalkylation reactor. In the transalkylation
reactor the polyethylbenzenes, mainly di- and tri- ethylbenzene, are converted to ethylbenzene.
The soluble catalyst complex is recycled to the alkylation reactor. The alkylate is treated with
caustic to neutralize any HCl still present, remove residual AlCl3, and to ensure that the alkylate is
free of chlorinated compounds. The crude ethylbenzene product, still containing benzene and
polyethylbenzenes, is then separated by distillation.

MonsantoLummus liquid phase alkylation process for the production of ethylbenzene.

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b) The Zeolite-Catalyzed Gas Phase Process

The gas phase alkylation process is based on the zeolite ZSM-5. This catalyst contains pores of
molecular dimensions, enabling shape selectivity. The ethylbenzene molecules can diffuse freely
through the pores, whereas diffusion of the polyethylbenzene molecules is strongly inhibited
(product selectivity).
The catalyst deactivates due to coke deposition, which is favored by high temperatures.
Regeneration of the catalyst takes place by burning off coke in oxygen-poor air or suitable N2/O2
mixtures. This operation takes about 24 hours.
Benzene drying is not required since this catalyst is very resistant to water. A mixture of make-up
and recycle benzene is preheated and fed to a multistage fixed bed reactor. Part of the ethene
required is added at this point. The benzene/ethene ratio at the entrance of the reactor is higher
than in the AlCl3-catalyzed liquid phase process, namely 815 mol/mol. Cooling is performed by
quenching with cold ethene after each catalyst bed in order to control the temperature rise
resulting from the exothermic alkylation reaction.
Separation of the product stream takes place by distillation. Although the ZSM-5 catalyst is very
selective for ethylbenzene, the formation of polyethylbenzenes cannot be prevented completely.
The polyethylbenzene stream from the distillation section is mixed with benzene and fed to a
transalkylator where additional ethylbenzene is formed.

MobilBadger gas phase process for the production of ethylbenzene.

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c) Production of Ethylbenzeneby PI

Catalytic distillation is an alternative for the processes described for the production of
ethylbenzene. The selectivity strongly depends on the ethene/benzene ratio: at low values the
selectivity approaches 100%.
In this configuration a low concentration of ethene in the reactor is maintained because of the
recycle of unreacted benzene.
The heat of the highly exothermic alkylation reaction is now used directly in the distillation of
reactants and products: benzene evaporates from the liquid mixture in the top of the distillation
column. The vapor is then condensed in the overhead condenser and returned to the reactor. It is
claimed that this process requires only half the amount of energy compared to other processes,
while the investment costs are reduced by 25%.
Furthermore, due to the internal recirculation of excess benzene, there is no need to (externally)
recycle large amounts of benzene, reducing the operating costs of the process.

Simplified flow scheme of catalytic distillation process to produce ethylbenzene. PEBs =

poly(ethylbenzenes).

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Reaction and Membrane Separation

In a catalytic membrane reactor the presence of a membrane thanks to its permselectivity, affects
the course of the reactions, allowing improvements of either the achievable conversion (e.g.,
equilibrium-limited reactions) or the selectivity towards intermediate products (e.g., consecutive
reaction
schemes)
Three major application areas exist for catalytic membrane reactors:
yield enhancement of equilibrium-limited reactions: a reaction product is selectively
permeating through the membrane, thereby enhancing the per pass conversion compared
to conventional fixed bed reactors (e.g., for dehydrogenations);
selectivity enhancement: accomplished by selective permeation or controlled addition of a
reactant through the membrane (e.g., partial oxidations or hydrogenations);
membrane bioreactors: coupling membranes and biochemical reactions promoted by
(immobilized) enzymes or microorganisms.

Ethene Production

The first field for which membrane reactors have been conceived is in equilibrium enhancement. A
classical bench-scale example of the use of a catalytic membrane reactor, showing its potential, is
the dehydrogenation of ethane:

The reactor consists of a porous alumina membrane tube covered with platinum crystallites
showing good catalytic activity for dehydrogenation. The ceramic tube consists of a multilayered
composite porous alumina tube.
For the gases playing a role in the reaction, the gas flow rate as a function of the pressure drop
over the membrane. Clearly, the transport of hydrogen is much faster than that of ethane and
ethene. Hence, in principle, it is possible to shift the equilibrium to the side of ethene by removal
of hydrogen.

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Membrane reactor for the dehydrogenation of ethane

Conversion in a membrane reactor compared to thermodynamic equilibrium

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Production of Ethene Oxide Using a Catalytic Membrane Reactor

Catalytic membrane reactor for the partial oxidation of ethene to ethene oxide.

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Enzyme-Immobilised Polymer Membranes

Enzyme-immobilised polymer membranes

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Types of Zeolite Membrane Reactors

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Types of zeolite membrane reactor

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Equilibrium Displacement by Water Removal

The integration of a membrane and a reactor in the so-called packed bed enclosed membrane
reactor is based on the separation of a product while it is formed and is the most commonly
studied case of a membrane reactor. Since hydrophilic zeolite membranes are well known for their
capability to selectively separate water and in fact their only industrial application up to now is the
purification of solvents by removing water by pervaporation

ZMR with equilibrium displacement by water removal

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Reaction configurations for water removal

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