Reactive Distillation Case Studies

Chemical Engineering and
Processing: Process Intensification

A systematic framework for the feasibility
and technical evaluation of reactive
distillation processes
REACTIVE DISTILLATION(RD)
• Combines reaction and separation into a single
operating unit .
• Represents one of the most important industrial
applications of the multifunctional reactor concept.
ADVANTAGES OF RD
• Economical profit: significant reduction of capital
and operating costs, major energy savings .
• Environmental gains: emissions reduced by 20%
or more as compared to a classic setup (e.g.
reactor followed by distillation column) .
• Social benefits: improvement on safety, health
and society due to the reduced reactive holdup,
low chances of runaway sensitivity and lower
space footprint.
TECHNIQUES FOR RD PROCESS DESIGN
• Simulation : It involves specifying the inputs,
operating variables and equipment sizes and solving
for the resulting outputs .
• Synthesis Design : It involves specifying the inputs
and selected outputs, operating variables and also
design variables, and determine whether a feasible set
exits for the given product specifications (Mixed-
integer nonlinear programming (MINLP) and fixed-
point methods are two approaches used for the
synthesis design methods. )
SIMULATION METHODS
Equilibrium modeling Rate-based modeling
•The vapor and liquid are assumed to be in Compared to equilibrium modeling, rate-
equilibrium. based modeling offers accuracy in design
•In practice, the theoretical number of of a column as it accounts for :
stages obtained from equilibrium model •Vapor–liquid equilibrium only at the
calculations is converted to the required interface between the bulk liquid and
real number of stages, either through the vapor phases,
overall efficiency of a tray or by the height • A transport-based approach to predict the
equivalent of a theoretical plate (HETP) flux of mass and energy across the
for packed columns. interface
•This is a useful approach to simulate a • The real hydrodynamic situation of
binary system or an existing column. either a tray or a packed column
However, this approach is not reliable to •Column is designed more realistic as
simulate a multi-component system or an compared to EQ modeling, thereby
existing column with different operating reducing the capital and operating costs
conditions •Rate-based model is complex as
compared to EQ
Problem statement
• The problem is how to determine quickly but reliably
when RD is a technically feasible alternative for an
existing or a new chemical process.
• To solve this problem a systematic framework is
developed in this work through which the technical
feasibility, the process limitations, the working
regime, internal and model requirements for RD
process can be quickly and reliably evaluated .
• A major advantage of this approach is its applicability
to a wide range of all-scale processes and
multiproduct environments .
• The framework for technical evaluation provides
guidelines for the process limitations, the working
regime, internal and model requirements for RD
process .
CASE STUDIES
Methyl acetate hydrolysis
• During the production of poly vinyl alcohol (PVA), a
large quantity of methyl acetate–water mixture (1.68
kg/kg PVA) is produced as by-product .
• At the industrial scale, the mixture of methyl acetate
and water is further hydrolyzed in order to recover the
methanol and acetic acid.
• This process is operated far below the critical pressure
of the components while the difference between the
reaction and separation temperatures is less than 50
◦C. The chemicals present in this process are close
boiling components. Methyl acetate is the lightest
reactant and forms strong binary azeotrope with
methanol .
TECHNICAL CONSTRAINTS
• This thermodynamic behavior clearly suggests that it
is very difficult to keep methyl acetate in the reactive
zone. Moreover, the relative volatility is less than 1.1
for the binary pair of methyl acetate and water.
Hence, it is not likely to obtain high purity methanol
in a single RD column.
• Due to these technical constraints the conventional
RD process is not technically feasible, even though
RD is suitable for the reverse reaction.
SOLUTION
• However, a RD process with additional distillation columns
could be a possible alternative for this process .
• Fuchigami developed a RD process using an ion-exchange resin
catalyst .
• The reactive distillation column is operated under total reflux in
order to recover the methyl acetate from the binary azeotrope
methyl acetate-methanol.
• The stripping section of the column strips the whole amount of
methyl acetate hence the bottom product is essentially free of
methyl acetate and contains only methanol, water and acetic
acid.
• This ternary mixture obtained in the bottom of the RD column
can be easily separated by two additional distillation columns.
• Another viable alternative is a non-conventional RD process
carried out in a reactive dividing-wall columns.
Toluene hydro-dealkylation process
• In the conventional process of hydro-dealkylation
(HDA) of toluene to benzene, the main reaction
requires 20–25 bar and 400 ◦C, whereas the RD
column is operated at 30 bar and about 280 ◦C in the
reactive zone .
• Comparison of the traditional and RD processes
indicates that RD allows significant simplification of
the flowsheet, with a reduction in the number of
distillation columns from five to three, as well as the
eradication of the reactor vessels .
The selectivity of toluene over xylene is improved
and by-product formation is reduced by RD
compared to the traditional process. However, the
optimal reactions vs. separation conditions are
significantly different and the pressure required by
the RD column is higher.
Fatty acid methyl esters (FAME)
process
• Fatty acid methyl esters (FAME) – the main
components of biodiesel fuel – can be directly
produced by esterification of free fatty acids (FFA)
with methanol or bioethanol .
• Conventionally, biodiesel is produced batch-wise
using homogeneous catalysts that have many
associated problems, such as neutralization followed
by expensive separations and leading to salt waste
streams.
• The RD process powered by solid catalysts offers
unique advantages, such as higher productivity,
efficient use of the raw materials and the equipment, no
catalyst related issues, elimination of alcohol excess,
recovery and recycle, as well as significantly lower
capital and operating costs.
• Sulfated zirconia was considered as solid acid catalyst.
• High purity products are obtained in the top and the
bottom of the RD, while complete conversion of the
reactants is achieved.
• The RD process is technically feasible due to the
favorable overlapping of the operating conditions (e.g.
temperature, pressure) required for the reaction and
separation, respectively.
• The reaction is slightly exothermal hence the heat of
reaction is being used in situ for the evaporation and
removal of products.
• Moreover, the equilibrium constant, reaction rates and
relative volatility are at high levels.
• Remarkable, important energy savings are possible
(over 45%) while the capital investment can be reduced
by up to 40–60% as compared to conventional processes
• Therefore, in this case, the RD process proves to be not
only technologically feasible, but at the same time
economically attractive .
Unsaturated polyesters synthesis
• The synthesis of polyester is carried out by reacting
different anhydrides and diols with various physical
and chemical properties.
• Maleic anhydride and propylene glycol react and
produce polyester and water.
• This is an equilibrium limited process and can be
intensified by continuously separating water by-
product from the reaction medium, thus shifting the
equilibrium to the product side.
• RD could be an alternative for the traditional batch
reactor coupled with distillation column.
• RD could be an alternative for the traditional batch
reactor coupled with distillation column
• The RD column is operated at one bar, which is
significantly lower than the critical pressure of the
components.
• The chemical equilibrium constant over the RD
column is ranging from 32 to 62 for given respective
reaction temperatures, which are in line with the
chemical equilibrium constant for the conventional RD
process as recommended
• All these important criteria (separation temperature,
operating pressure, equilibrium constant and production
rate) fulfill the requested requirements for an
economically attractive RD process.

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Chemical Engineering and

Processing: Process Intensification

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