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UNDERSTANDING OF MEMBRANE

ASSISTED HYBRID SEPARATION


PROCESSES
Submitted By : Antarim Dutta Under the Supervision of :
Registration No : 2016CL04 Dr. Shabih-Ul-Hasan
Chemical Engineering Department Assistant Professor, ChED
M.Tech 2nd Year, 3rd Sem MNNIT. Allahabad
MNNIT, Allahabad

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CHEMICAL ENGINEERING DEPARTMENT, MNNIT 1
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CONTENTS
INTRODUCTION (Slide No : 3)

PRINCIPLE OF REACTIVE DISTILLATION (Slide No : 5)

MEMBRANE ASSISTED SEPARATION PROCESSES (Slide No : 7)

PERVAPORATION Concept (Slide No : 8)

PERVAPORATION verses VAPOR PERMEATION (Slide No : 10)

CASE STUDY (TITTLES) (Slide No : 12)


CASE STUDY 1 ( PRODUCTION OF ETHYL TERT-BUTYL ETHER(ETBE)) (Slide No : 13)
CASE STUDY 2 (PRODUCTION OF N-BUTYL ACETATE) (Slide No : 19)
CASE STUDY 3 (SEPARATION OF AZEOTROPIC MIXTURES) (Slide No : 27)
CASE STUDY 4 (N-PROPYL PROPIONATE SYNTHESIS) (Slide No : 31)

CONCLUSION (Slide No : 36)

FUTURE RECOMMENDATIONS (Slide No : 38)

REFERENCES (Slide No : 39)

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CHEMICAL ENGINEERING DEPARTMENT, MNNIT 2
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INTRODUCTION
The current concerns about sustainability of fossil fuels, in addition to the legislation aimed at reducing
greenhouse gas emissions, have forced the industry to search for renewable fuels with smaller carbon footprints
to replace (either completely or partially) the conventional fuels (Bardin et al., 2014).

The number of design and processing requirements in the chemical and biochemical industries are increasing to
adapt to rapidly changing markets and the global competition, as well as to shift toward more sustainable
production and to meet the need for new and innovative products. Hence, more efficient processes are needed.

This need led to the introduction of process intensification. Process intensification is a tool for the targeted
enhancement of involved phenomena at different scales to achieve a targeted benefit (Lutze et al., 2010b). The
four scales for these systems are the
Process/Plant level
The operation and equipment level
The phase and functional level, and
fundamental and molecular level (Lutze et al., 2010b; Freund and Sundmacher, 2008).

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Reactive and membrane-assisted distillation can achieve higher efficiencies and high capacities. They are
believed to be important technologies for retrofitting existing processes and for incorporation into future
processes for efficient and flexible(bio)chemical production.

Especially for equilibrium reactions like esterification, ester hydrolysis and etherification, the combination of
reaction and separation within one zone of a reactive distillation column is a well-known alternative to
conventional processes with sequential reaction and separation steps (Hiwale et al., 2004; Kaibel et al., 2005).

Hybrid separations integrate two different unit operations that complement each other to solve a defined
separation task (Franke et al., 2008). This arrangement enables the use of each unit operation in the operating
window in which it outperforms all others.

The overall goal in the reaction step is to achieve the highest production efficiency and yield of the desired
product at the lowest possible cost during safe operation. High efficiency and selectivity may also simplify the
downstream separation steps. The overall goal of the separation steps is to maximize the purity and recovery of
the products at the lowest costs.

This paper aims to provide an overview of past and current research regarding reactive and membrane-assisted
distillation, including pervaporation and vapor permeation, to provide a personal opinion of future research
trends, needs and challenges for these technologies.

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PRINCIPLE OF REACTIVE DISTILLATION
Reactive distillation integrates reaction and distillation within one apparatus (Sundmacher and Kienle, 2003). Hence,
both phenomena occur at the same time and place.

Identifying a common operating window between the reaction and separation that provides acceptable and controllable
reaction rates and appropriate volatilities to ensure high concentrations of reactants and low concentrations of products
in the reactive zone is difficult.

Multiple motivations underlie the application of this concept (Sundmacher and Kienle, 2003; Taylor and Krishna, 2000;
Gorak et al., 2007):
Improved Conversion.
Circumventing/Overcoming of azeotropes.
Reduced side-product formation.
Direct heat integration and avoidance of hot spots.
Capital savings.
Decreased catalyst amount.

Fig. Reactive Distillation

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Fig. Methyl Acetate Reaction

Reactive distillation is used with reversible, liquid phase reactions. Suppose a reversible reaction
had the following chemical equation :

For many reversible reactions the equilibrium point lies far to the left and little product is
formed:

However, if one or more of the products are removed more of the product will be formed because
of Le Chatlier's Principle :

Removing one or more of the products is one of the principles behind reactive distillation.
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MEMBRANE ASSISTED SEPARATION PROCESS
Membrane technologies have recently emerged as an additional category of separation processes to the well-
established mass transfer processes. Membrane separation technologies offer advantages over existing mass
transfer processes.

Such advantages can comprise :


High selectivity;
low energy consumption;
moderate cost to performance ratio;
compact and modular design. Fig . Membrane Separation Illustration

In a membrane-separation process, a feed consisting of a mixture of two or more components is partially


separated by means of a semipermeable barrier (the membrane) through which one or more species move faster
than another or other species.

In membrane separations: (i) the two products are usually miscible, (ii) the separating agent is semipermeable
barrier, (iii) a sharp separation is often difficult to achieve.

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PERVAPORATION Concept
Pervaporation is a separation process, which is based on the selective transport through a dense membrane
combined with a phase change of the permeating components from liquid to vapor.

Fig. Overview of Pervaporation Process

In its simplest form, is an energy efficient combination of membrane permeation and evaporation.

It's considered an attractive alternative to other separation methods for a variety of processes.

For example, with the low temperatures and pressures involved in pervaporation, it often has cost and
performance advantages for the separation of constant-boiling azeotropes.

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Pervaporation involves the separation of two or more components across a membrane by differing rates of
diffusion through a thin polymer and an evaporative phase change comparable to a simple flash step.

A concentrate and vapor pressure gradient is used to allow one component to preferentially permeate across the
membrane.

A vacuum applied to the permeate side is coupled with the immediate condensation of the permeated vapors.

Pervaporation is typically suited to separating a minor component of a liquid mixture, thus high selectivity
through the membrane is essential.

Pervaporation can used for breaking azeotropes, dehydration of solvents and other volatile organics,
organic/organic separations such as ethanol or methanol removal, and wastewater purification.

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PERVAPORATION verses VAPOR PERMEATION
Separation via pervaporation (PV) or vapor permeation (VP) is based on a solution-diffusion mechanism across the
membrane.
Highlights of PV and VP Processes
Mixtures that at normal distillation form azeotropes and/or require a large number of theoretical stages can easily
and economically be separated even without the use of entrained agents (chemicals).

High product purity is obtained and no environmental pollution occurs.


Multicomponent mixtures with small difference in boiling points can be dehydrated effectively and economically.

The feed mixtures could be in either liquid or vapor form.


Low energy consumption is required.
Small units can operate economically exploiting the modular design of the membrane system.
High degrees of feed mixture flexibility.
High final product qualities are obtained
Modularly, compact design and factory-preassembled systems are simple to operate and can be started up and shut
down rapidly.

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Comparison between Pervaporation and Vapor Permeation
Pervaporation Vapor Permeation
The feed is a liquid. The feed is a mixture of vapor or vapor and gases.
Liquid-vapor phase change is required, involving the No change of phase and no significant temperature difference
enthalpy of vaporization. across the membrane are required.
Heat exchangers could be required. Heat exchangers can be dispensed with.
The driving force for PV process is the difference in The driving force is the partial pressures of the components
chemical potential, concentration gradient between phases on in the feed.
the opposite sides of the interfacial barrier.
There is no possibility of increasing the driving force by It is possible to increase the driving force by pressure
pressure in the feed compartment. augment.
Permeate must be volatile at operating conditions. Larger modules could be used and the scale-up of the MR
makes it easier.
The membrane is in contact with the liquid feed, so it could Long membrane lifetime since the membrane is not in direct
be poisoned during the reaction. contact with the reaction environment.
Highly swollen membranes could favor greater fluxes. Water permselectivity is increased, fluxes of water in certain
systems are higher and lower membrane area is required.

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CASE STUDY
Sl. No. Tittle Author Journal Year

1. Comparative study of conventional, Adham Norkobilov, Chemical 2017


reactive-distillation and pervaporation Daniel Gorria, Enginnering &
integrated hybrid process for ethyl tert- Inmaculada Ortiz Processing : Process
butyl ether production Intensification
2. A thermally coupled reactive distillation Gregorius Rionugroho Chemical 2017
and pervaporation hybrid process for n- Harvianto, Faizan Engineering Research
butyl acetate production with enhanced Ahmadb Moonyong Lee and Design
energy efficiency
3. Optimisation-based design method for Katharina Koch, Daniel Chemical 2013
membrane-assisted separation processes Sudhoff, Stefan Kreisa, Enginnering &
Andrzej Gorak, Peter Processing : Process
Kreisa Intensification
4. Hybrid Separation Process Combination Carsten Buchaly, Peter Chemical 2007
of reactive distillation with membrane Kreis, Andrzej Gorak Enginnering &
separation Processing : Process
Intensification
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CASE STUDY 1 (Production of Ethyl tert-butyl ether(ETBE))
Tertiary alkyl ethers, such as methyl tert-butyl ether (MTBE) and ethyl tert-butyl ether (ETBE), are commonly used as
octane improvers for liquid fuels.

As consequence of the negative impacts that MTBE has on the environment, ETBE has become a popular alternative
oxygenate additive for gasoline. In addition, it has higher heating value and lower oxygen content, lower water
solubility and faster degradation in soils (Bardin et. al., 2014).

ETBE is produced on industrial-scale by a reversible reaction of isobutene (IB) and ethanol (EtOH) with a strong
acidic macroporous ion exchange resign in liquid phase at 10 bar.

A drawback in the conventional ETBE manufacture is the energy intensive product recovery process, making ETBE
expensive. The purification process of ETBE involves the separation of ETBE, mixed C4 hydrocarbons and unreacted
ethanol. Unfortunately, the unreacted ethanol forms azeotropic mixtures with ETBE that are difficult to separate by
distillation.

While distillation provides large capacities and simple operation, membranes potentially offer a high selectivity and
low energy consumption, as well as a compact and modular design (Sirkar, et. al., 2015).

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CHEMICAL REACTIONS IN THE PRODUCTION OF ETBE

4 8 + 2 6 6 14 ------------------------------------------- (1)

4 8 + 2 4 10 ---------------------------------------------- (2)

24 8 8 16 -------------------------------------------------------- (3)
Eq. 1 represents the etherification reaction, Eq. (2) represents the hydration of isobutene to form tert-butyl alcohol, and
Eq. (3) represents the dimerization reaction of isobutene to form di-isobutene.

The etherification reaction is limited by the thermodynamic equilibrium in the range of temperatures typically used in
the industrial field. Thus, the equilibrium conversion at 343 K for a stoichiometric mixture of reactants is only 84.7%
(Jensen, et. al., 1995; Sneesby, et. al., 1997).

The secondary reaction of isobutene dimerization (Eq. (3)) is favored at low concentration of ethanol and at high
temperature and is also equilibrium limited (Rehfinger et. al., 1990).

In the case of ethanol/ETBE mixtures, these compounds form an azeotropic mixture containing 20.4 wt% ethanol at
94.7 kPa and 65 C (Rarey, et. al., 1999).

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Fig. The conventional process for the production of ETBE with pressure swing distillation for product purification.

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Fig. Schematic diagram of the pervaporation integrated hybrid process.

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Fig. Schematic diagram of the reactive distillation process for ETBE production

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RESULTS AND DISCUSSION
Conventional Reactive Distillation Hybrid PV Separation
In the case of the conventional process The results of the process that There is an improvement in
(after heat integration) the consumption incorporates reactive distillation show productivity as the amount of unreacted
of heating utilities is mainly related to the an increase in production due to the fact ethanol recycled to the reaction zone is
reboiler thermal duties of the three that this process leads to 98.9% increased and also more than 99.9% of
distillation columns, which consume 2.4 isobutene conversion, much higher than the produced ETBE leaving the reactor
MW, 1.8 MW and 1.2 MW, respectively. the conversions reached in the other is recovered from the bottom of the
two alternatives. column.
Regarding the consumption of cooling
utilities, this consumption is mainly due In contrast the energy requirements are The consumption of heating utilities for
to the cooling needs in the condensers of much higher than the previous cases debutanizer column is around 2.5 MW.
the debutanizer column and the third due to higher reflux ratio is required to The adiabatic mode operation of the 7
column of the flowsheet, which consume ensure high conversion and at the same PV modules makes necessary the
2.2 MW and 2.6 MW (with heat time to achieve the target ETBE purity. reheating which consumes around 26
integration) respectively. kW. Cooling utilities for debutanizer
The energy requirements for column consumes 2.2 MW and partly
This means that for the conventional condensation (8.9 MW) and reboiler in the cooling of catalytic reactor (0.76
process it is necessary to supply 884 duty (9.2 MW) are appreciably greater MW). Energy to be removed to achieve
kWh 1 by means of hot utilities and than the consumption in the alternative the condensation of permeate stream
to remove 926 kWh 1 by means of cases. (35 kW).
cooling utilities.
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CASE STUDY 2 (PRODUCTION OF N-BUTYL ACETATE)
n-Butyl acetate is widely used in industry as a raw material for coatings and paints, a solvent for manufacturing
lacquers, a synthetic fruit flavoring for food products, and as a reagent for pharmaceutical and cosmetic formulations
(Liu et al., 2005).

The complexity of this process is due to the occurrence of two azeotropes, one between methanol and methyl acetate
(at 66.7 mol% methyl acetate) and one between n-butyl acetate and butanol (at 78.01 mol% butanol).

A single reactive distillation column can replace conventional multi-unit processes that require five times more energy
and capital investment (Taylor and Krishna, 2000).

The thermally coupled distillation (TCD) technique has proven to bean attractive method for reducing both the energy
and capital costs of distillation processes. TCD sequences are obtained through the implementation of interconnecting
streams (one in the liquid phase and the other in the vapor phase) between two columns.

Each interconnection replaces one condenser or one reboiler from one of the columns, providing potential capital and
energy cost savings (Long and Lee, 2014; Van Duc Longand Lee, 2013).

Luyben et al. (2004) has proposed a reactive distillation process for the enhanced production of n-butyl acetate with a
simpler process structure consisting of only three distillation columns that showed significant improvement in the
energy efficiency.

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Wang et al. (2008) combined the reactive distillation and thermally coupled distillation techniques and developed
thermally coupled reactive distillation (TCRD) as an attractive strategy to reduce the energy requirement of the
distillation columns in n-butyl acetate production.

However, all of these configurations have similar drawbacks in that methyl acetate and methanol are recycled back to
the main reactive distillation column as azeotropes, which limits the reaction and energy efficiency of the reactive
distillation column.

Pervaporation (PV), or vapor permeation, of organic mixtures has been widely used in industry to overcome difficulties
with mixtures such as azeotropes or close-boiling mixtures (Kujawski, 2000; Naidu and Malik, 2011), and it is
considered to be a good technique for separating methanol from methyl acetate (Sain et al., 1998). Steinigeweg and
Gmehling (2004) and Svandov and Markos (2011) have reported experimental and simulation studies on the
integration of reactive distillation and pervaporation separation for n-butyl acetate production.

They proved that in order to increase the conversion of methyl acetate to n-butyl acetate, the recycle stream to the
reactive distillation column should be concentrated into pure methyl acetate.

Various alternative that have been investigated are as follows:


1. RD + MC 4. Thermally coupled Reactive Distillation Column (TCRD)
2. RD + MC (opt) 5. TCRD (opt)
3. RD + PV (opt) 6. TCRD + PV (opt)
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Fig. Conventional reactive distillation process (RD + MC)for n-butyl acetate production.

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Fig . Conventional RD + MC (optimized) Process

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Fig. Optimized RD + PV hybrid process.

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Fig. Proposed system for thermally coupled reactive distillation with pervaporation (TCRD + PV).

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Fig. Optimized TCRD + PV hybrid process.

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RESULTS AND DISCUSSION

Fig. Comparison of capital costs for different process Fig. Comparison of TACs for different process
configurations. configurations.

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CASE STUDY 3 (SEPARATION OF AZEOTROPIC MIXTURES)
The separation of the ternary system acetone/isopropyl alcohol (IPA)/water by a combination of distillation and
membrane separation was chosen as a case study.

Between IPA and water, a homogeneous temperature minimum azeotrope exists with a water mole fraction of 0.3167
mol/mol and a boiling temperature of 80.4 at atmospheric pressure (1.013 bar) (Papa, et. al., 2010).

RESULTS AND DISCUSSION


With increasing water content in the feed mixture, a
strong increase of the permeate flux can be
observed.

The permeate flux also increases with rising feed


temperatures.

An increase in the feed temperature of


approximately 20 doubles the permeate flux, e.g.,
the permeate flux at a feed water mass fraction of
15 mass% increased from 0.8 kg/hr at 60 to 1.6
Fig. Influence of feed temperature and water content
kg/hr at 77 C.
in feed mixture on total permeate flux.

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For all experiments, very high water content in the
permeate of above 98 mass% was reached.

This high water content reflects the high selectivity of the


2201D membrane, resulting from a high
degree of crosslinking in the active polymeric layer.

Fig. Influence of feed temperature and water content in


feed mixture on water content in permeate ,H2O
(right) for IPA/water mixtures at = 30 mbar.

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CONTINUES

Fig. Process configuration, equipment dimensions and operating conditions of the optimized hybrid pervaporation-distillation
process.

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The side stream is positioned at the packing height,
where the water content of the liquid phase is the
biggest.

The combined water-rich permeate stream reaches a


purity of 99.7 mole% of water due to the very water-
selective separation of the 2201D
membrane.

For the optimal hybrid pervaporation-distillation


process, a CPT value of 90.5 /ton is reached and the
total investment and operating costs of this process.

Fig. Concentration profile in the liquid phase along the


distillation column for the optimal hybrid pervaporation-
distillation process.

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CASE STUDY 4 (N-PROPYL PROPIONATE SYNTHESIS)
Equilibrium reactions like esterification, ester hydrolysis and etherification, the combination of reaction and separation
within one zone of a reactive distillation column is a well-known alternative to conventional processes with sequential
reaction and separation steps (Hiwale et. al., 2004; Kaibel et. al., 2005).

In several cases, non-ideal aqueousorganic mixtures are formed which tend to form azeotropes. They can be
overcome using membrane separations like pervaporation and vapor permeation since they are very selective and not
limited by vaporliquid equilibrium (Rautenbach et. al., 1997).

In their work, the heterogeneously catalyzed esterification of propionic acid (ProAc) with 1-propanol (POH) to n-
propyl propionate (ProPro) and water (2 ) is investigated:
3 8 + 3 6 2 6 12 2 + 2

The esterification reaction is reversible; the equilibrium constant is a weak function of temperature.

The chemical system shows complex thermodynamic phase behavior with several binary and ternary azeotropes as
well as miscibility gaps.

Due to two binary homogeneous azeotropes (1-propanol water, propionic acidwater), one binary heterogeneous (n-
propyl propionatewater) as well as one ternary heterogeneous (n-propyl propionate1-propanolwater) temperature
minimum azeotrope, a conventional process requires a complex separation train downstream of the reactor.

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Table Boiling points of pure components and azeotropic data at 1 atm (Buchaly et. al., 2007)

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Fig. Process Design of the hybrid process

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RESULTS

Fig. Influence of reboiler heat duty and reflux ratio, v, on product purity, xProPro,bottom (left) and propionic acid conversion,
XProAc (right).

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Fig. Influence of the mass fraction of water in the recycle on required


membrane area and reboiler heat duty.

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CONCLUSION
From Case Study 1
It can be concluded that the good performance of RD to carry out the reaction/separation stages simultaneously
contrasts with its high energy consumption. This suggests that there is still a lot of opportunity exists to explore
other options that allow energy savings in RD.
The PV hybrid process appears as the best option to achieve energy savings compared to the conventional
process, and it is also an attractive option to carry out a revamping of existing processes.

From Case Study 2


It can be said that by applying the pervaporation membrane, the azeotrope composition of the methanol-methyl
acetate successfully in the recycle stream had been eliminated, allowing high reaction conversion in the reactive
zone.
It was also found that the recycle flow rate and the split ratio are key variables for improving the energy
efficiency of the conventional configuration.
The energy efficiency was significantly improved by precise optimization of these variables for a fixed column
structure. Despite the fact that the proposed TCRD + PV configuration has slightly higher capital cost, it
exhibited a synergistic combination of the advantages of both TCRD and RD + PV configurations: i.e., (1) a low
recycle flow rate; (2) a high concentration of methanol in the liquid split stream, (3) a low concentration of
methyl acetate in the rectifying stages; and (4) high reaction con-version in the reactive distillation column.
The proposed TCRD + PV hybrid process reduced the energy consumption and TAC by 63.8% and 43.1%,
respectively.

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From Case Study 3
It can be concluded that a design method was demonstrated for a case study to optimize a hybrid pervaporation-
distillation process for the separation of the azeotropic system acetone/isopropyl alcohol(IPA)/water.
Pervaporation experiments at varied feed composition and temperature were performed for IPA/water mixtures
using the hydrophilic polymer membrane 2210. The experimental results obtained were used to
identify and parameterize an empirical correlation of the hybrid pervaporation-distillation process.

From Case Study 4


It can be state that the theoretical and experimental investigation shows that the heterogeneously catalysed
synthesis of n-propyl propionate via a hybrid process consisting of reactive distillation and vapor permeation is
feasible.
One major result of this study is that the EQ model assuming chemical equilibrium is not sufficient for a proper
description of the n-propyl propionate synthesis in a reactive distillation column at laboratory and pilot-scale.
The NEQ model and the EQ model with reaction kinetics exhibit qualitatively similar results over a broad range
of catalyst volume fractions. For a detailed comparison of the NEQ model and the EQ model with reaction
kinetics, further studies are necessary.

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FUTURE RECOMMENDATIONS
As the comparative study done by Norkobilov et. al., 2017 showed that the energy requirements for the RD process is
highest among all the alternative processes. Heat integrated distillation column (HIDiC) is an advancement in this
respect, which seeks to maximize the energy efficiency of a heat pump design by making use of internal heat-
integration.

It is not easy to carry out a direct comparison between VP and PV efficiency; however, VP, similar to gas separation,
could exhibit some advantages over PV. For example, the evaporation energy could be supplied in a separate
evaporator thus avoiding the use of heat exchangers. Then, a more favourable fluid dynamics allows the use of larger
modules with consequent benefits in terms of cost reduction. The processes which have been improved by integrating a
VP unit are mainly natural gas or organic solvents dehydration as well as water separation from air and its recovery
from the waste stream.

In a hybrid process, several possibilities exist to implement the PV or VP modules and the membrane separation
devices and the reactor can be separated into two units or integrated into a single one. For Example, Membrane
Reactor, Membrane distillation.

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Fig. Direct Contact Membrane Distillation Fig. Sweeping Gas Membrane Distillation

Fig. Air Gap Membrane Distillation Fig. Vacuum Membrane Distillation

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Fig. Examples of reactor-membrane separator configurations.

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REFERENCES
Bardin, M. E., El-Dein Hussin, A.M.T.A., Gushchin, P. A., Vinokurov, V. A., Burluka, A. A., 2014. Technical aspects of
ethyl tert-butyl ether (ETBE) for large-scale use as gasoline improver. Energy Technology 2, 194204.

Buchaly, C., Kreis, P., Gorak, A., 2007. Hybrid separation processesCombination of reactive distillation with
membrane separation. Chemical Engineering and Processing 46, 790799

Frank, M., 1990. Auslegung und Optimierung von Pervaporationsanlagen zur Entwsserung von Lsungsmitteln und
Lsungsmittelgemischen, PhD Thesis, University of Aachen, Germany.

Freund, H., Sundmacher, K., 2008. Towards a methodology for the systematic analysis and design of efficient
chemicalprocesses: Part 1. From unit operations to elementary process unctions. Chemical Engineering and Processing
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Gorak, A., Hoffmann, A., Kreis, P., 2007. Prozess intensivierung: Reaktive und Membran-untersttzte Rektifikation.
ChemieIngenieur Technik 79, 15811600.

Harvianto, G. R., Ahmad, F., Lee, M., 2017. A thermally coupled reactive distillation and pervaporation hybrid process
for n-butyl acetate production with enhanced energy efficiency. Chemical Engineering Research and Design 124, 98-113.

Hiwale, R. S., Mahajan, Y. S., Bhate, N. V., Mahajani, S. M., 2004. Industrial applications of reactive distillation. Recent
trends, International Journal Chemical Reaction Engineering 2.

Kaibel, G., Miller, C., Holtmann, T., Schoenmakers, H., 2005 Reaktivdestillation, Chemical Engineering Technology
77(11), 17491758.

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Koch, K., Sudhoff, D., Kreis, S., Gorak, A., Kreis, A., 2013. Optimisation-based design method for membrane-assisted
separation processes. Chemical Engineering and Processing 67, 2 15.

Lutze, P., Gani, R., Woodley, J.M., 2010b. Process intensification: a perspective on process synthesis. Chemical
Engineering and Processing 49, 547558.

Liu, K., Tong, Z., Liu, L., Feng, X., 2005. Separation of organic compounds from water by pervaporation in the
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