Acetic Acid 1

Separation & Purification Reviews
ISSN: 1542-2119 (Print) 1542-2127 (Online) Journal homepage: http://www.tandfonline.com/loi/lspr20
Acetic acid production and purification: critical

review towards process intensification
Parimal Pal & Jayato Nayak
To cite this article: Parimal Pal & Jayato Nayak (2016): Acetic acid production and purification:
critical review towards process intensification, Separation & Purification Reviews, DOI:
10.1080/15422119.2016.1185017
To link to this article: http://dx.doi.org/10.1080/15422119.2016.1185017
Accepted author version posted online: 04

May 2016.
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Download by: [University of Lethbridge] Date: 04 May 2016, At: 21:11

Acetic acid production and purification: critical review towards
process intensification
Parimal Pal*, Jayato Nayak
Environment & Membrane Technology Laboratory, Department of Chemical Engineering
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National Institute of Technology, Durgapur, India-713209
Submitted on January 2, 2016; revised on March 13, 2016; accepted on April 26, 2016.
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Short running title: Acetic acid production and process intensification
Downloaded by [University of Lethbridge] at 21:11 04 May 2016
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Abstract
The 1980-2015 literature has been critically reviewed to examine how acetic acid manufacturing
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practice has progressed over these 35 years and whether this important organic acid
manufacturing sector is in the right track to ensure sustainable business. Amidst growing
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environmental awareness and emerging regulations all over the world, a paradigm shift in
production strategy in favor of green processes appears imminent. Literature reveals that despite
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huge worldwide demand, conventional manufacturing practices still largely revolve around
multi-step and multi-phase unit operations which fail to ensure clean production environment.
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Production process is still dominated by a chemical synthesis route where multiple traditional
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unit operations like distillation, evaporation, absorption, filtration, crystallization, acid and alkali
treatments are required involving huge energy, material, manpower, and capital consumption.
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On the other hand, prospects for process intensification through adoption of membrane
technology in downstream separation and purification appear to have brightened. Emergence of
tailor-made and highly selective membranes in fouling free modules has opened up new avenues
towards green production that has the potential of ensuring sustainable business. This paper
directs further research towards process intensification.
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Keywords: acetic acid, membrane reactor, microfiltration, nanofiltration, scale-up.
*Corresponding Author (P. Pal, E-mail: parimalpal2000@yahoo.com or
ppal.nitdgp@gmail.com); Fax: +91343-254-7375: Tel: +91343-275-4088.
1. INTRODUCTION
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Acetic acid (ethanoic acid) is traditionally used as a food preservative, an excellent solvent or
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an intermediate ingredient for a variety of commercial grade chemicals (1). Acetic acid has
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recently attracted attention of many researchers towards process intensification. Global demand
of virgin acetic acid market stands at 13 million tons in 2015 which is forecasted to extend
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approximately to 18 million tons by 2020, showing a compound annual growth rate of around 5% (2).
According to 2015 market research, the market price of acetic acid varies within US $1200 and $1600
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per ton in different countries of the world (2). The major use of acetic acid is in the oxidative
production of vinyl acetate monomer (VAM) which polymerizes as poly vinyl acetate for
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extensive use in paints and adhesives. VAM is a key ingredient in emulsion polymers, resins,
and intermediates used in coatings, textiles, wires and acrylic fiber items. The condensation
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reaction of acetic acid produces acetic anhydride, a typical acetylation agent, which is
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subsequently used to produce cellulose acetate, used in synthetic textiles and also for silver-
based photographic films. Most commonly derived esters of acetic acid are ethyl acetate, n-butyl
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acetate, isobutyl acetate, and propyl acetate which are frequently used as solvents for
inks, paints and coatings. Glacial acetic acid is an excellent polar protic solvent which is
frequently used as a solvent for recrystallization to purify organic compounds (3). Acetic acid is
used as a solvent in the production of terephthalic acid (TPA) which is the raw material for
polyethylene terephthalate (PET). Vinegar which is mainly a 4-6% diluted acetic acid solution is
2
directly used as a flavoring agent for foods and also as food preservatives (4). Production of
acetic acid is picking up keeping in pace with the rising demand through the efforts of big world
players like Celanese, BP Chemicals, China Petrochemical, Dow chemical, Millennium
Chemicals, Monsanto, Sterling Chemicals as well as through hundreds of smaller producers. Acetic acid
production routes mainly depend on petroleum-derived stocks such as methanol, acetaldehyde, butane
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or ethylene (5).
The submerged fermentation based Orleans method and the Frings-acetators based German
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method are some developments towards green production regimes. But only a small percentage
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of the global demand can be currently met from such eco-friendly technologies which still do not
have provision for efficient downstream purification. The major challenge in developing
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sustainable technology is achieving cost effectiveness and efficient downstream processing in a
green environment (6, 7). Thus the concept of process intensification steps in that it promises
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minimum consumption of material and energy while offering higher engineering flexibility as
well as higher purity of the products (8, 9). Process intensification is the need of the hour in
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chemical manufacturing sector replacing old, inefficient, energy intensive technologies with
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smaller, safer and modular designed equipment with high scale up possibilities (10, 11).
This paper has reviewed critically the traditional routes of acetic acid production highlighting
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the major drawbacks associated with those processes while simultaneously presenting the state-
of-the-art of development of novel technologies with special emphasis on membrane based

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technologies towards sustainable business.
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2. CONVENTIONAL ROUTES FOR ACETIC ACID
PRODUCTION
Conventional acetic acid production plants have largely followed chemical synthetic
routes. Fermentation-based microbial production has recently drawn attention of researchers but
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robust plants with microbial production approach are yet to be commissioned in large scale.
2.1 Chemical synthesis approach
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The most widely accepted route for the chemical synthesis is methanol carbonylation also
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called Monsanto process. Methanol in the presence of a rhodium based carbonyl catalyst reacts
with carbon monoxide producing acetic acid in the temperature and pressure ranges of 150-
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200°C and 30-50 bar, respectively (12). The rhodium based catalytic reaction was later replaced
in the Cativa process (BP chemicals) by the use of iridium catalyst without changing the
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reactants and the reaction conditions. The iridium catalyst was proved to be more economic as it
allowed the use of less water in the reaction mixture and suppressed the water gas shift reaction.
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The Cativa process resulted in good yields of acetic acid (85%) and methanol (58%) (13). As
presented in Figure 1, a number of chemical reaction units (main reactor, secondary reactor,
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bubble loop reactor and catalyst recovery units) and unit operations (absorption, distillation,
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dryer, condenser and re-boiler) are involved in a Cativa process plant.
The distillation of the synthetic mixture is a critical step. Because of the presence of a
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tangent pinch on the pure water end in the liquid-vapor phase diagram of acetic acid and water,
separation of the binary mixture water-acetic acid by direct distillation is not suitable for
industrial applications. This could be overcome via heterogeneous azeotropic distillation adding
a water soluble stripper (14, 15), like ethylene dichloride, n-propyl acetate, n-butyl acetate (16),
isobutyl acetate (14, 15), ethyl acetate (17), or vinyl acetate. Recent researches support p-xylene
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to be an outstanding one for its capability of formation of a heterogeneous azeotrope with water.
It can carry higher amount of water in the azeotrope resulting in very high concentration of acetic
acid as the end-product (18, 19). While using other stripping additives, undesirable impurities
and contaminants used to get produced inside azeotropic distillation units (20). The main
drawback of azeotropic distillation is the requirement of larger diameter columns compared to
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simple distillation units, which allows increased vapor volume flow with high recycle rates for
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the azeotropic agent. The design, optimization and simulation involve additional care in control
as compared to simple distillation. The azeotropic distillation operational complexity and costs
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are high.
Acetaldehyde oxidation is another process of acetic acid production where petroleum

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stock derived acetaldehyde is oxidized to acetic acid in presence of metal catalysts like cobalt
or chromium, at 150°C temperature and 55 bar pressure. Though the obtained yield is about
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95%, some major by-products like ethyl acetate, formic acid, and formaldehyde are also
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produced (21). A schematic diagram of such a plant is presented in Figure 2.
Partial oxidation of ethane to acetic acid was studied over molybdenum-vanadium

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based catalysts like Mo 1 V 0:25 Nb 0:12 Pd 0:0005 O x at temperatures between 220 to 300°C and
pressures between 12 and 15 bar (22-24). It is observed that the production of acetic acid
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increased significantly with the co-feeding of water into the reactor. The reaction kinetics is
close to first order and could be explained by an Eley-Rideal-redox kinetic model (23).
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Introducing titania base and trace amounts of palladium metal produced a 10 time increase in
the acetic acid synthesis rate compared to the production rate without Pd/SiO 2 /TiO 2 support
(25). Production cost for partial oxidation of ethane to acetic acid was evaluated by Soliman et
al. (26) where they suggested cheaper methods for oxygen production necessary to be
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developed because oxygen supply consumed 70% of all raw material costs. A yield of 50-65 %
acetic acid through low temperature oxidation (60°C) of ethane (27) could be achieved
employing H 2 O 2 with m-nitride di-iron phthalocyanines as catalyst.
The reaction conditions and by-products formed in conventional chemical technologies
have been presented in Table 1 and the unit operations involved in those processes have been
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presented in Table 2. In these chemical synthesis routes, the raw materials like methanol,
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acetaldehyde or hydrocarbons are derived from petroleum stocks. Direct discharge of wastes
and by-products (acetic acid, water, butane, iso-butyl acetate and propionic acid), lead to severe
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environmental pollution. The expensive catalysts used in these processes need continuous
regeneration or replacement along with downstream separations to obtain desirable pure acetic
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acid. This involves many evaporation and condensation units which eventually increase the
cost of production.
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2.2. Fermentation for production of acetic acid
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The fermentative pathway for the production of acetic acid has the potential of using
renewable carbon sources. The most widely used submerged fermentative process for the
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commercialized vinegar synthesis is German method which employs the Frings acetator for
speeding up the acetic acid synthesis rate (6, 7). A schematic of such a process has been
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presented in Figure 3. In this process, a generator is used which is an upright tank filled with
beech wood shavings, charcoal, and grape pulp or alcohol concentration of about 12% (v/v) (7).
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Though the alcohol to acetic acid yield of about 98% is achieved, this process is slow requiring
about a week to produce the desired concentration (28). Another drawback is the demand for
pure substrates to maintain the quality of acetic acid which in turn increases the cost of
production. Fermentation based production techniques have some fundamental advantages
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such as easy process control in a simple design, involvement of low personnel cost and absence
of high energy consuming units.
Most of the literature on fermentative production revolves around use of finished
carbohydrates and alcohol as the carbon source as benchmark substrates. Through glycolysis
pathway, glucose gets degraded to pyruvate in the presence of enzymes. Following hetero-
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fermentative pathway, acetylphosphate forms which in presence of the enzyme acetate kinase,
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directly produces acetic acid. Acetylphosphate in presence of co-enzyme A, also forms
acetaldehyde. Produced molecules of acetaldehydes in presence of different dehydrogenase
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enzymes finally produce acetic acid via the Wood–Ljungdahl pathway (29). The
characteristics of different microbial strains producing acetic acid are presented in Table 3. The
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complete metabolic pathway of acetic acid production has been presented in Figure 4.
Investigations to find the best combination of microbial species for acetic acid
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production have been conducted. Tang et al.(30) reported the production of acetic acid from
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whey using an association of Streptococcus lactis and Clostridium formico-aceticum at a
temperature of 35°C where, at higher pH 7.6 the acetic acid yield was 95% along with a rate of
production of 1.0 g.L-1.h-1 within 20 hours. The use of a mixed culture of Saccharomyces
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cerevisiae and Acetobactor pasteurianus for acetic acid production from pure glucose was
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investigated by Wang et al. (31) where the first one helped to ferment glucose to ethanol and
the latter one produced acetic acid by fermentation of the produced ethanol in a batch (yield
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58.3%, productivity 0.26 g.L-1.h-1) and fed batch (yield 31.4%, productivity 0.36 g.L-1.h-1)
culture system. Another research focus in this context has been on finding cheap carbon
sources. Witjitra et al. (32) found that high substrate concentrations (50-100 g.L-1) primarily
inhibit the growth of microbes. Ultra-filtered ethanol silage, corn steep liquor and hydrolyzed
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soy flour were proved to be truly effective in enhancing microbial growth and acetate
production for a limited cost. Parrondo et al. (33) proposed to use whey lactose supplemented
with additional carbohydrates in a mixed batch culture of Kluveromyces fragilis and
Acetobacter pasteurianus under non-neutralizing condition where 50 g.L-1 acetic acid were
obtained with an ultimate acetic acid yield of about 84%. Huang et al.(34) reported the use of a
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co-culture of Lactococcus lactis and Clostridium formico-aceticum in a fed batch fibrous bed
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bioreactor which was proved to be advantageous due to its long term performance while
eliminating clogging and channeling problems inside the reactor. The mixed culture systems
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have the inherent problems of controlling and maintaining the optimum conditions for microbes
as well as safeguarding the cultures from contamination. Mixed culture approaches thus
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encountered difficulty in industrial scale implementation.
Acetogenic anaerobic bacteria of the two main genres Acetobacterium and Clostridium
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go through the Wood–Ljungdahl pathway for the synthesis acetyl-CoA from CO 2 or carbon
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monoxide during the production of acetates (35-37). Although the rate of production of
valuable products is low, it provides ecological advantage and sustainability by reducing

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greenhouse gases (35). Cell-recycled repeated batch culture of acetogenic Moorella sp.
HUC22-1 exploiting syngas (H 2 :CO 2 volume ratio 4:1) was reported to produce acetate at a
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rate of 0.4 g.L-1.h-1 (37). DNA isolation and genetic modification (38, 39) can elevate the
acetate synthesis rates up to 1.2 g.L-1.h-1 for Acetobactor woodii (40).

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Continuous separation and purification of acetic acid from fermentation broth without
disturbing microbial health can also be achieved by using membranes. Conventional
purification technologies are energy-intensive due to involvement of a number of unit
operations like fractional distillation, condensation and crystallization which are not at all eco-
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friendly. A judicial combination of highly selective membranes has the potential of offering
high purity product substantially reducing the cost of energy.
2.3. Limitations to the conventional production schemes of acetic acid
Conventional production plants are robust and involve multiple unit operations with
little flexibility in operation to adapt to a fluctuating marketing demand. Special and high
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quality materials of construction are mandatory to build the reactors which can withstand very
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high temperature and pressure while carrying out multiphase chemical reactions. Catalysts
used in these processes are expensive that is why the perfect selection and renewal of catalysts
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become essential. Purification of desired acetic acid is performed by high energy consuming
red processes like distillation, flash distillation, azeotropic distillation, absorption and drying
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(5, 13). Thus the complete process technology is highly complex and expensive requiring huge
involvement of man power and proper process safety. Release and dumping of waste acids or
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by-products (harsh chemicals) like, propanoic acid, butyric acid, butanone, ethyl acetate, formic
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acid and dichloroacetic acid in open environment results in severe environmental pollution.
Fermentation based processes are eco-friendly but very slow with a low productivity. Raw
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materials used in fermentation based techniques are over-priced whereas the high purity of the
end product is not always guaranteed in conventional fermentation based acetic acid production
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plants (41, 42).
So, a novel, eco-friendly and green process is urgently required. It must be flexible,
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economically attractive with reduced energy consumption while satisfying all the objectives of
process intensification. Amidst the tough competitions in the global market, the cost of
production has to be brought down to a significantly low level in the current regime of
emaciated profit margin in chemical and allied process industries. Literature shows that
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reported success stories of novel technologies promising clean production regime while
offering attractive returns are not many and a lot needs to be done towards opening such
sustainable avenues of chemical production (11, 41).
3. MEMBRANE BASED PROCESSES
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3.1. Operational aspects
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The novelty of membrane based processes lie in their capability of eco-friendly
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production with high degree of purity in very simple plant configuration that drastically cuts off
the total capital investment. This technology involves membranes as a selective barrier while
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transporting target molecules (liquid, vapor or gas) at different mass transfer rates which is
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basically controlled by the permeability of the barrier towards the membrane (43). Membrane
based processes are simple to design and flexible to operate.

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• Microfiltration membranes can easily separate microbial cells, having higher molecular
weight and size though these membranes have large pore size (between 50 nm and 5 µm)
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and a low pressure pump with 1 to 4 bar pressure building capacity can be used.
• Ultrafiltration membranes have pore size between 2 and 50 nm and a pump able to reach 5
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to 9 bar is required to separate cells, proteins and fats. In both microfiltration and
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ultrafiltration, the separation is based on size exclusion or sieving mechanism (8).
• Nanofiltration (NF) membranes have an average pore size of 1 nm and the separation is
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partly based on size exclusion and dominantly on Donnan exclusion mechanisms. High
pressure pumps (more than 10-20 bar) are required for fluid circulation and pressure
filtration.
• Reverse osmosis (RO) membranes are usually non porous and a high pressure pump
generating transmembrane pressure above 20 bar is necessary. Nanofiltration is a relatively
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newly developed technology which is mostly practiced for the separation of tiny neutral
impurities and charged particles (microbial cells, proteins, unconverted sugar, salts, metal
ions and the additional supplementary nutrients) present in aqueous solutions while
increasing the final product purity in the permeate stream (43, 44). Rejection through this
membrane is mainly due to electrostatic interaction between negatively charged membrane
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surface (polyelectrolytes like polyamides) and ions in feed solution. Solution diffusion
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(44) is the mechanism of separation, followed by the nanofiltration and reverse osmosis
technology. The RO technology can separate the same materials as what is done by NF.
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But the RO membranes are much costly with higher requirements of high pressure pumps
and power supply than the NF membranes. Operating at moderate pressure, using NF
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technology, high rejection of unwanted materials can be obtained satisfying high end
product purity (44, 45).

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Membranes often suffer due to fouling problem resulting from accumulation of coarse
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sized particles over the membrane surface. However, this can be effectively minimized in
designs with better hydrodynamics such as flat sheet cross flow membrane modules where the
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feed liquid flows parallel to the active surface of the membrane enabling high sweeping action
unlike in case of dead end modules where the feed flow is perpendicular to the membrane
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surface. A schematic flow diagram in Figure 5 provides an idea of integration of any kind of
membrane modules (micro, ultra, nano or reverse osmosis) in a single stage with a fermenter.
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While operating in continuous mode employing such a membrane integrated fermenter,
continuous removal of produced acid from fermentation broth could be performed while setting
the pH value at a fixed level. The very modular design offers great flexibility in scale of
operation as any number of modules can be used at a given time. The integration of membrane
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units with the fermenter as separation and purification stages culminates in the development of a
hybrid plant of simple configuration. One major advantage of use of membranes in bioprocess
engineering is the possibility of separation-purification at ambient temperature at significantly
reduced operating pressure than in conventional chemical technologies. Thus the use of
membrane technology turns green a process and indeed paves the way of process intensification
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(11, 46).
3.2. Microfiltration and ultrafiltration of fermentation broth
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The main challenging aspect during batch fermentation while producing acetic acid is
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overcoming the problem of product inhibition where the acidic product inhibits the growth of
microbes. Thus the general practice so far has been controlling pH in the fermentation medium
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by adding alkali. This however, produces acetate salts instead of direct acid necessitating
further acidification of the produced salts. Acetic acid has an acid dissociation constant pK a of
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4.76 and it is observed that at higher pH, complete dissociation occurs. Microfiltration and
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ultrafiltration of fermentation broth is very effective in recovering the acid and recycling
microbial cells. The problems related to substrate-product inhibitions could be substantially

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reduced if continuous withdrawal of acid product in a membrane-integrated fermentation unit is
done (47). Lowering of pH in fermentation broth results in decrease in permeate output and
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vise-versa. Thus pH becomes a key parameter during microbial fermentation and also during
membrane based separation-purification. While operating in continuous mode, continuous

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recycle of microbial cells with fresh feed addition to the fermenter helps the microbes to be in
an active state of exponential growth phase resulting in high microbial concentration and high
productivity inside the fermenter (48). Continuous withdrawal of acetic acid helps to prevent
pH lowering to the inhibition level of the fermentation broth increasing cell viability inside the
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fermentation unit. This kind of cell harvesting using microfiltration or ultrafiltration for its
subsequent recycling leads to a high cell concentration into the fermenter but often an excessive
buildup of cells increases the viscosity and causes lowering of flux output from filtration unit.
This problem could be largely overcome by cell bleeding from the recycle stream (8).
Due to size based separation in microfiltration or ultrafiltration membranes, chances of
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membrane fouling are very high. Fouling ultimately leads to high concentration polarization
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with a drastic declination in the resultant permeate flux. The solute and solvent fluxes in
permeate in case of micro and ultrafiltration are coupled in nature which indicates that an
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increased applied pressure can increase solvent and solute fluxes through membranes. Torang
et al. (49) proposed a shear enhanced cross flow ultrafiltration module for the separation of
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cells and proteins from fermentation broth where it was observed that the chances of fouling
and the effect of concentration polarization were significantly reduced. In a cross flow
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membrane module, as the feed fluid is allowed to flow parallel to the membrane imparting a
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very high sweeping action over the membrane surface providing a very little scope of formation
of concentration polarization layer. Fouling is a very serious problem which keeps a firm
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negative impact on permeates flux and membrane cleaning. Appropriate hydrodynamics and
back-flushing techniques can reduce fouling and delay the onset of fouling layer on the
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membrane surface (50, 51). Membrane material constituents are also key factors in minimizing
fouling problem. Polyethersulfone membranes foul more quickly than polyamide membranes.
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Ceramic membranes being non-porous suffer very quick fouling though complete disinfection
is achievable using these membranes (52). Polyvinylidene difluoride membranes are also prone
to fouling but the problem of concentration polarization and the effect of fouling could be
effectively minimized by generating shear stress over while controlling the tangential flow over
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the membrane (53). Different designs of cross flow membrane modules like hollow fiber (54)
or spiral wound (55) were successful in improving the quality of the final product removing
color, turbidity and other components present in the fermentation broth. Schematic diagrams of
different membrane modules have been represented in Figure 6.
Ultrafiltration membrane performance was observed on the rice husk derived
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hydrolysates aiming towards the separation of acetic acid from carbohydrate components (56).
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Biopolymer ultrafiltration membranes, in which polyethersulfone was blended with cellulose or
chitosan showed excellent rejection of acetic acid (75-84%). A cell recycle bioreactor coupled
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with a hollow fiber ultrafiltration membrane made of polysulfone module was developed by
Mostafa (57). It was observed that the addition of NaCl in fermentation broth affected the
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microbial health, resulting low acetic acid yield but increments in Na 2 SO 3 concentration helped
to elevate the product yield at a higher level. In batch system the acetic acid production
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suffered due to low substrate to product yield (maximum 55%). This kind of membrane
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integrated scheme was highly significant as it allowed continuous acetic acid production at high
dilution rate with high cell bleeding ratio where high cell viability was achieved with high
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concentration and productivity of acetic acid.
3.3. Electrodialysis
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In most of the fermentation based production techniques, addition of alkali is practiced
to control pH for enabling high microbial cell activity in the optimum pH medium. This results
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in generation of acetate salts instead of acetic acid itself. To overcome such problems of salt
formation, electro-dialysis based processes turn to be the only option to regenerate acetic acid
from any form present in fermentation broth. It is an electro-membrane process in which
selective transport of ions occurs through an ion permeable membrane from one solution to the
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other based on the potential differences across the electrodes (58). For the recovery of organic
acid from fermentation broths, this process is highly applied. Easier separation of organic acids
with a high purity and concentration could be expected from an electrodialysis system (59).
Recent development in electrodialysis technology has been applied for the product recovery in
the field of organic acid production. Acetic acid, lactic acid, propionic acid etc. could be easily
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separated, recovered and concentrated using such technology (59, 60). While maintaining pH
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of a fermentation broth, alkaline solutions like NH 4 OH and NaOH is used that could also be
recovered and recycled by electrodialysis. Thus the simultaneous reduction of environmental
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pollution with less involvement of money could be attained (61,62).
Chukwu and Cheryan (63) employed a microfiltration system followed by an

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electrodialysis unit containing 20 cation exchange and 20 anion exchange membranes for the
recovery of acetate salts. After the electrodialysis, the concentration of calcium acetate was
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enriched about three fold. Yu et al.(64) recovered acetic acid from waste water using an
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electrodialysis cell where after every anion-exchange layers of the bipolar membranes single
cation exchange membranes (negatively charged) were arranged. After imposing an electrical
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field, acetate ions cross the anion exchange membrane and hydrogen ions cross the bipolar
membrane produced a concentrated acetic acid solution. It was observed that with the increase
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in removal ratio of concentrated acetic acid solution, the current efficiency decreased (65).
Faster transport of hydroxyl ions than the acetic ions was the main reason of obtaining low
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current efficiency and low concentration of recovered acetic acid. As a matter of fact, this low
current efficiency (about 40%) during the process with the back diffusion of acetic acid through
anion exchange membrane remained being the demerits of this work. A schematic of such
bipolar membrane electrodialysis system is represented in Figure 6D.
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While using bipolar electrodialysis membranes for the acetic acid production from
aqueous solution of sodium acetate, cell configuration is a remarkable issue considering the
product yield, current efficiency, and energy consumption (66). Next to the bipolar
membranes, cation exchange membranes, anion exchange membranes and both cation and
anion exchange membranes were arranged. The best throughput was obtained when the bipolar
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membrane was coupled with a negatively charged cation exchange membrane. Compared to
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any other bipolar electrodialysis membrane configuration, the foretold one produced the highest
current efficiency (93.1%) with the highest acetic acid yield (77%) at the lowest electrical
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energy consumption of 3.14 kWh for per kg production of acetic acid. Despite all the research
attempts on electrodialysis to establish the potential of product recovery in an efficient and eco-
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friendly way, this technology suffers from the drawback of high energy consumption. Due to
the poor conductivity of the organic phase, power consumption in electrodialysis is always very
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high. No electrodialysis process is so robust to ensure high purity product as the fermentation
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derived acetic acid always remain mixed with the salts where the selective separation of salts
with the extraction and purification of acetic acid is a difficult job.

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3.4. Nanofiltration and reverse osmosis of fermentation broth
Microfiltration of microbial bodies from the fermentation cannot yield high purity
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acetic acid. Extraction of acetic acid from the mixture of salts, unconverted sugar and nutrients
from aqueous substrate is critical but essential. Nanofiltration and reverse osmosis can play
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crucial roles in separation of those impurities (charged or uncharged solutes, tiny sized
impurities). In case of these specific separation techniques, the sieving mechanism and the
electrostatic charge repulsion mechanism both govern the separation (67). Recovery of organic
acids by the separation and purification employing NF is a relatively new class of the pressure-
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driven membrane processes where it stands being a viable alternative of conventional unit
operations like solvent-extraction, ion-exchange, flash distillation, absorption, evaporation and
distillation. Researches on nanofiltration have widely been performed in the areas of
desalination, wastewater treatment, dye recovery and separation of products generated in
biological pathways (67, 68). Salts of metal ions present in the feed solution could be
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effectively rejected by NF membranes due to the presence of a polyelectrolyte layer on the
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active surface of the membrane causing high negative charge (99). While using nanofiltration
of any type of feed solution, the electrostatic charge repulsion leads to the repulsion of ions of
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same charges and attraction towards the ions of opposite charges along with the sieving
mechanism of separation, (depending on the characteristics of the solute). NF treatment of

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organic acids was proved to be strongly depending on the hydrodynamic conditions of feed
solution and the nature of solutes present in it (67).

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Han and Cheryan (70, 71) performed downstream processing of acetate fermentation
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broth using a dead end stirred filtration cell involving round shaped flat sheet nanofiltration
membranes. NTR 729 membrane showed high glucose rejection (99%) with a significant salt
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(NaCl) rejection capacity of 75% under all operating conditions. Experimental surveys with
nanofiltration membranes to study the rejection characteristic by the presence of different

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electrolytes (72) and at different pH levels of acetic acid were also reported. Bellona et al. (73)
observed that at low pH ranging within 3 to 4 rejection of acetic acid was within 20% but over
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this range, there reported a huge rise in rejection values (more than 60%). A spiral wound
Desal-5 DK nanofiltration membrane module was employed for the separation of acetic acid
from xylose in a synthetic model solution (74) where with the increase of the solute
concentration, the solvent permeability decreased. This specific membrane was found to have
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an isoelectric point of 4.1 which makes it to be negatively charged when the pH of the feed is
kept higher than this value and positively charged one over this value. At pH 2.9, the major
extent of acetic acid is in its undissociated molecular form (99%) and the intermolecular
interactions between acetate ions and zeta potential of membrane. The same spiral wound
Desal-5 DK nanofiltration membrane module was employed for the extraction of acetic acid
t
ip
from sugars in dilute acid rice straw hydrolysates (75). They observed that the separation
cr
performance during nanofiltration was temperature dependent and the performance decreased
when the operating temperature was increased from 25°C to 40°C with a significant decline in
us
permeate flux. Maiti et al. (76) observed through experimental investigations that flat sheet
modules are able to generate high flux with better separation than spiral wound modules.
an
Reverse osmosis is a high pressure driven (15- 40 bar) and relatively mature technology
which is widely used for desalination, waste water treatment and water purification
M
applications. By the proper use of reverse osmosis, over 99% removal efficiency for different
ed
salts, inorganic and organic matters could be achieved in acetic acid production. Electrolytes
could be separated out aiming towards production of highly concentrated acid acetic solutions.
pt
Hausmanns et al. (77) studied the rejection of acetic acid using composite polyamide reverse
osmosis membranes in a spiral wound module. It was observed that for the monocarboxylic
ce
acids, rejection increased with the increase in molecular weight and acetic acid suffered a
rejection of about 47%. Ragaini et al. (78) showed that reverse osmosis could be a highly
Ac
efficient option for the separation of acetic acid (>70% rejection) from water at low
temperature of 21°C and applied transmembrane pressure of 17 bar. Diltz et al. (79) used a thin
film composite polyamide RO membrane (Dow Chemical Co., FILMTEC FT30) in a spiral
wound single-pass configuration for the post-treatment of an anaerobic fermentation broth with
18
acetic acid as model compounds. The highest rejection of acetic acid was observed to be
90.3% at an operating pressure of 55 bar with a low recovery factor without recirculation of
acetic acid. Recirculation of acetic acid with the feed mixture reduced the rejection to about
80% with a two fold increase in recovery of acetic acid at high pressure (from 18% at 27.5 bar
to 37% at 55 bar). Li et al. (80) developed a combined process comprising of only
t
ip
nanofiltration and reverse osmosis (using commercial membranes) for separation and
cr
concentration enrichment of organic acid from fermentation broth.
3.5. Nanofiltration membranes as low cost membranes with high degree of purification
us
Rejection of solutes by nanofiltration membranes is largely due to electrostatic charge
repulsion (Donnan effect) (45, 67-68, 81) where separation by steric hindrance (size
an
exclusion) is very limited. Rejection of the solutes also depends on solution hydrodynamics
and properties of the solute molecules. Retention of neutral solutes is totally based on size
M
exclusion. Two characteristic parameters of membrane (effective pore radius, thickness–
ed
porosity ratio) and one characteristic parameter of solute (stoke radius) are needed to be
considered in explaining the transport of uncharged solutes (undissociated acetic acid,

pt
carbohydrate present in fermentation broth) through NF membranes (67). Rejection of
negatively charged ions are mainly based on Donnan effect and dependent on three
ce
parameters which are the effective pore radius, the thickness–porosity ratio and the effective
charge density of membrane (82). The solute and solvent fluxes in case of nanofiltration and
Ac
reverse osmosis are uncoupled in nature where increase in applied transmembrane pressure
increases solvent flux as well as rejection of solute.
In case of rejection of charged solute, the transport through membrane could be
efficiently described by the Donnan steric pore model which is developed based on the
19
extended Nernst Plank equation (83). The rejection of organic acids is also a function of feed
solution pH because increases in pH level higher than 4.76, the acetic acid pK a , form acetate
anions retained by the charged NF membrane. Zhou et al. (84) reported that sugar molecules
with high molecular weight, possess Stokes radiuses higher than that of acetic acid (0.19 nm).
During the nanofiltration of a mixture of acetic acid and monosaccharide, the latter and bigger
t
ip
one suffers higher rejection than the former at any operating condition. Apparent pore
cr
diameters of a polyamide NF membrane is also dependent on solution pH where with the
change in pH value of feed, the amount of protonation or deprotonation in the feed solution
us
change significantly. Higher pHs induce an increase in osmotic pressure along with ionic
strength in NF membranes. Moreover, at higher pH, the functional groups of organic acids
an
(carboxyl group) get ionized. Thus an increased thickness of the double layer of the charged
functional group over the membrane surface is formed resulting a reduction in the apparent
M
pore size of the membrane leading to a higher rejection of charged entities (67, 68).
3.6. Pervaporation
ed
Azeotropic distillation is essential for separation of acetic acid from water-acetic acid
pt
mixture. Pervaporation was proved to be a much energy saving procedure with low cost
involvement than the conventional azeotropic techniques. Li et al. (85) prepared synthetic
ce
mordanite membranes (made of ±-Al 2 O 3 ) for pervaporation of acetic acid and water mixture
which produced high separation factor (more than 1000), high flux of water (about 1200 g m-2
Ac
h-1) with the elevation of temperature up to 90°C. Aiming towards dehydration of acetic acid,
pervaporation was performed with polyphenyl sulfone membranes by Jullok et al.(86) where it
was observed that low content of polyphenyl sulfone (25 weight %) showed higher
hydrophilicity with a significantly degree of swelling detrimental to the process.
20
Zhou and Koros (87) reported that an increase in bore size (above 350 µm) for a fixed
length of hollow fiber module produced an increased water flux but the acetic acid flux
decreased. Swelling effect by acetic acid at the bore side were noted and found influencing the
acid permeability. Polyvinyl alcohol was proved to be a very good pervaporation membrane
material when cross-linked with hydrocarbons. Investigations were performed on cross-linking
t
ip
polyvinyl alcohol with formaldehyde (88), polyacrylic acid and malic acid (89). Polyvinyl
cr
alcohol membranes modified with malic acid with an optimum 17:3 volume ratio, operated at
40°C turned out to be a good option for the dehydration of a 20% acetic acid solution. The
us
degree of swelling of the membrane and the permeation rate of water increased with the
increase in feed concentration of acetic acid (up to 80% w/w) and then decreased. A very high
an
separation factor (34 to 3550) was achieved when polyvinyl alcohol membranes were cross-
linked with polyacrylic acid producing a permeate flux of 0.03–0.60 kg.m-2.h-1. Polycrystalline
M
silicate membranes with two kinds of porous supports (silicate/stainless steel support and ZSM-
ed
5 zeolite/alumina support) were investigated for the separation of acetic acid in 5 to 40 %
solutions (85). Sulfonated polybenzimidazole membranes were investigated for pervaporation

pt
dehydration of acetic acid (90). Thermogravitimetric analysis showed that the membrane was
highly stable up to 600°C. Such kind of novel pervaporation membranes produced a flux of
ce
0.207 kg.m-2.h-1 with a separation factor of 5460 while treating 1:1 weight ratio of acetic acid-
water feed solution at 60°C. However pervaporation remains fundamentally a slow process to
Ac
be implemented industrially.
4. MEMBRANE INTEGRATED HYBRID REACTOR
In acetic acid production, product self-inhibition is a serious issue. Membrane
bioreactors where a continuous stirred tank reactor or fermenter is coupled with acetic acid
21
permeable membranes like micro or ultrafiltration for cell retention and NF or RO for the final
purification purpose turns out to be a promising technology to overcome product inhibition due
to continuous extraction of the acid produced. By the wise selection of a membrane with high
degree of selectivity, very high degree of product purity could be assured. Use of NF
membranes is a very promising separation tool which can replace the conventional highly
t
ip
energy intensive separation-purification units like distillation, absorption, drying, flash
cr
distillation. Recycling cells allows to generate high cell concentration inside fermenter where
the cells used to live in a strong viable stage of exponential growth phase offering high
us
productivity. Where in the field production of acetic acid, ecofriendly upstream production
along with energy saving and flexible downstream processing are big challenges, membrane
an
integrated hybrid reactor systems come up with a step towards process intensification. By
eliminating the needs of separate purification units with a compact, modular and flexible design
M
with reduced capital investment, membrane based processes are able to generate highly pure
ed
acetic acid comparable with what was achieved with conventional processes. In fact, these
kinds of membrane integrated processes are able to satisfy all the aims of process
pt
intensification. Though fouling is a serious problem, it could be overcome by two-stage
membrane integration. But the research attempts on two stage membrane integration are
ce
scarce.
Park et al. (91) demonstrated a process of acetic acid production in a single continuous
Ac
stirred tank reactor integrated with a hollow fiber microfiltration filter module. The generation
of acetic acid was performed in a continuous scale with an ultimate concentration of 40 g. L-1at
a volume rate of 4 L.h−1 and a very high productivity of 160 g.h-1. Nishiwaki (92) showed a
steady-state fermentation scheme of a two-stage fermenter system, where a cell filtration unit
22
was attached with each fermenters for the continuous production of acetic acid. In the two-
stage recycle system, two fresh medium feed streams and the bleed were supplied to the second
fermenter. These kinds of membrane integrated bioreactor were proved to generate higher
productivity of acetic acid (150 g. L-1.h-1) at a volume rate of 3.7 L.h-1 with no bleeding.
However, though high productivity was achieved, the purity of the end product could not be
t
ip
assured because the microfiltration or ultrafiltration membranes used had high pore sizes
cr
through which small sized impurities or electrolyte solutions could easily permeate. For those
perspectives, nanofiltration of fermentation broth turned out to be a feasible option to enhance
us
the purity of end product acetic acid. A downstream processing work of Han and Cheryan (70,
71) with NTR 729 (from Nitto-Denko) membrane was extended for a fermentation broth where
an
fermentation was carried out with C. thermoaceticum on pure dextrose for the production of
acetic acid. The fermentation broth pH was maintained at 5.6 which yielded calcium
M
magnesium acetate. In this study, the fermentation broth was first clarified with hollow fiber
ed
microfiltration membranes followed by nanofiltration membranes attached with a series of high
and low rejection membranes. It was observed that without using any evaporator, this system
pt
was able to concentrate acetate solution at about three fold concentration.
Nayak and Pal (93) reported a very simple scheme of acetic acid production in a
ce
membrane integrated reactor system from cheese whey. Integration of microfiltration
membranes was done as a primary clarifier unit (for microbial bodies) and the permeate from
Ac
microfiltration was further treated with NF technology. Flat sheet cross flow modules as
represented in Figure 6C were used which enabled high permeate flux and long term operation
due to the high sweeping action over the membrane surfaces. The concentration of the
produced acetic acid was further enriched by nanofiltration exploiting NF-1 membranes. A
23
high productivity of 4.06 g. L-1.h-1 with a final acetic acid concentration of 96.9 g L−1 with 98%
purity was obtained. A continuous membrane based process technology as represented in
Figure 7 is able to ensure high output rate from a reaction unit which is highly economic due to
faster production. At high pH regime, NF membranes possess a very highly compact structure
resulting in high rejection. Nayak et al. (94) also drew a correlation that during steady
t
ip
permeation, the acetic acid rejection follows a positive correlation with membrane charge
cr
density. The design of flat sheet cross flow membrane module is so unique that the effect of
concentration polarization could be efficiently reduced by increasing the cross flow rate over
us
the membrane surface. The sweeping action of the fluid flow generated a greater convective
force enhancing the solvent flux during permeation (93). Though the cost of membrane itself
an
plays the major role in the final cost of a membrane based process but the use of highly
selective membranes with better mechanical strength and antifouling characteristics provides
M
the potential of ensuring high process intensification as compared to conventional production
ed
process (95).
Economic evaluations are required to seek whether a proposed scheme stands to be

pt
implementable at industrial scale and for choosing the best pathway of production. This has
been performed for few cases. Efforts should be directed towards the development of a fully
ce
membrane-integrated fermentative process for operation in continuous mode under non-
neutralizing conditions where should be the provision for continuous cell separation and
Ac
recycle with further purification of directly produced acetic acid. Membranes should be so
designed to lessen the fouling problems due to concentration polarization. Thus a membrane-
integrated continuous production scheme keeps the potential of achieving the major goals of
process intensification in acetic acid manufacturing. To improve the concentration of produced
24
acetic acid along with high productivity and purity, multistage membrane cell recycle
bioreactors should be employed. Use of cheap and renewable raw materials as the alternate
resource of carbon and nitrogen should be searched to make the process more economic. By
choosing proper membrane modules incorporating membranes selected on the basis of
membrane material, producing high selectivity, permeability and rejection, researches should
t
ip
be performed in such a way that no additional purification steps will be needed. After
cr
understanding all such essential points, researches should be directed towards modeling,
simulation and scale up. Studies become necessary to judge how much the developed process
us
satisfies process intensification based on the process intensification parameters like energy
intensification and space intensification (96). An overall comparison of bioreactor

an
performances in previous literatures is given in Table 4.
5. ECONOMIC EVALUATION OF ACETIC ACID PRODUCTION IN

M
MEMBRANE-INTEGRATED PROCESSES
ed
There are very few studies on the techno-economic feasibility of the proposed systems.
Generally in a membrane integrated system, the main cost factor involved is the cost of
pt
membrane itself which could be minimized for a concerned process by choosing high
ce
selectivity membranes and proper designing of modular system units. Han and Cheryan (70,
71) showed a cost evaluation for the production of acetate salts in a fermentation based system.
Ac
The scheme was so designed that a final acetate concentration of 300 g L-1 was achieved from
that of 58.5 g L-1 present in fermentation broth. On the basis of 103 ton per day sodium acetate
production, while using microfiltration followed by two stages of NF for purification and
concentration steps, the cost of membranes were 85% of the annualized capital cost. This cost
was cut down to 60% of the capital cost when only the microfiltration and NF purification steps
25
were involved. Using simple configuration of microfiltration followed by single NF
technology, the cost was evaluated about 66.4 $ per ton of acetate where use of microfiltration
followed by two stages of NF technology resulted in a cost of 110.6 $ per ton of acetate. The
first configuration was preferred where the fermenter was coupled with a microfiltration and
then a single NF membrane system for purification. Chukwu and Cheryan (63) evaluated the
t
ip
cost of a downstream process where a microfiltration followed by an electrodialysis unit with a
cr
final stage evaporator system was attached with the fermenter. It was observed that the
electrodialysis system itself was bearing 90% of the total capital investment and using such
us
kind of design, the annualized operating cost for per ton of acetate was twofold higher than the
previously cited reference (70, 71). So, electrodialysis of acetate fermentation broth is not at all
an
economic due to high energy consumption and membrane cost. A single electrodialysis
membrane unit charges about 91% of the total annual operating cost of a whole acetate
M
production plant.
ed
For a membrane integrated hybrid system, major cost factors to be considered are: (i)
capital investment: fermenter, pumps, membrane modules, storage tanks, pipelines, power
pt
consumption, depreciation, civil investments and (ii) operating costs: raw materials, labor,
membrane, maintenance and utility (51). The scale up calculations could be performed as
ce
follows (95):
Aimed output per day ( kg )

Ac
Required number of modules =

Actual output per module per day ( kg )
Now, the required membrane area is:
Aimed output per day ( kg )

Output from a single module per day per unit surface area ( kg / m )
2
26
The cost calculation could be performed using the standard procedure of the sixth-tenth power
rule of scale-up (96):
0.6
 Size of high capacity equipment 
=
Cost of high capacity equipment Cost of small capacity equipment ×  
 Size of small capacity equipment 
t
The annualized capital cost could be calculated as:
ip
( Total capital cost
× Capital recovery factor )
cr
Annual output rate (kg per year)
 i (1 + i ) n 
us
where, Capital recovery factor =  
 (1 + i ) − 1 
n
‘n’ and ‘i’ were considered to be is the project life of the plant and the rate of interest as per
market statistics.
an
Total annual operating cost ($)
M
The annualized operating cost could be evaluated as:
Output per year (kg)
The overall cost of production could be obtained by adding the annualized capital cost with the
ed
annualized operating cost.
A cost evaluation (94) for production of fermentation derived acetic acid employing
pt
microfiltration for cell recycle and nanofiltration for purification of show that 57% of the
ce
operation cost is consumed by supplementary nutrients. The power consumption is only about
7% of operational cost where the membrane cost involved is about 24%. Use of renewable
Ac
wastes as carbon source can significantly reduce the overall cost of the process. By proper
scale up, the annualized production cost was evaluated to be 350 US $ per ton of acid where
Indian market, production cost of 98% pure technical grade acetic acid costs about 850 US
$/ton. The major cost factors involved has been presented in Figure 8. The use of cross flow
membrane systems attached with a fermenter is more economic from the perspectives of energy
27
consumption, installation and membrane replacement costing with capital investment resulting
in a reasonably high product output with high purity compared to all other technologies.
Efficiency of the used membranes could be recovered by cutting off the cost involved. Dey
and Pal (51) reported that membrane cleaning by backwashing and with a series of acid and
alkali wash could recover the efficiencies of the membranes to a great extent. Cleaning of each
t
ip
membrane was performed with 0.1 N NaOH and 10−2 molar HNO 3 solutions respectively then
cr
those were sterilized with 200 ppm NaOCl solution followed by rinsing with ultrapure water.
Further researches are still needed to be devoted towards finding some suitable but low cost
us
supplementary nitrogen rich nutrients which will be effective in minimizing the overall cost of
fermentation based technologies. An analytical assessment of the acetic acid production

an
describing advantages in cost saving, flexibility, pollutant emission leading towards
environmental friendliness in membrane integrated processes has been provided in Table 5.

M
6. CONCLUSIONS
ed
Over the last two decades, several studies have been conducted to develop a production
scheme for acetic acid by fermentative process using cheap, renewable carbon sources in an
pt
eco-friendly approach. Investigations for process intensification are absolutely essential for
ce
development of a novel and sustainable technology in the present era of emaciated profit
margin in a highly competitive global market. Future studies should explore further
Ac
developments including synthesis and use of better membranes offering still higher selectivity,
flux and durability at reduced cost. It thus transpires that several studies have been taken up in
the recent past towards evolution of green manufacturing processes for production of acetic
acid and a majority of such research activities have revolved around developing membrane
based technology as evolution of new tailor-made membranes and modules with high flux,
28
selectivity and durability have opened up new avenues of low cost downstream processing with
promise of high degree of product purity. However, scale up confidence is still limited and
more modeling and simulation studies with economic assessment need to be done to raise scale
up confidence. There is a vast scope for improving the existing membrane-based technologies
with development of better membranes and modules with higher mechanical strength at
t
ip
reduced cost. Studies on construction of new membrane based plants are absolutely necessary
cr
to trap the huge potential of membrane based technology in developing eco-friendly, smaller,
more compact, flexible and safer plants with higher profit margin compared to conventional
us
plants.
Acknowledgement
an
Authors are thankful to the Department of Science and Technology (DST, India) and Ministry
M
of Human Resource Development (MHRD India) for all the necessary funds and supports.
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pt
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ip
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Ac
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ip
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M
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ip
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us
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using combination of nanofiltration and reverse osmosis membranes. Appl. Biochem.
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ip
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cr
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Ac
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acid dehydration by pervaporation. Chem. Eng. Res. Des., 40: 263-267.
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by pervaporation using poly (vinyl alcohol) membranes modified with malic acid. Chem.
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495.
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ip
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cr
Enhancement of acetic acid production in a high cell-density culture of Acetobacter aceti.
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us
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an
Nayak, J. and Pal, P., (2013) Transforming Waste Cheese-Whey into Acetic Acid through
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M
2984.
ed
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acetic acid from cheese whey in a multi-stage membrane-integrated bioreactor. Biochem.

pt
Eng. J., 93: 179-195.
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ce
manufacturing acetic acid and whey protein from waste cheese whey, J. Cleaner Prod.,
112(1): 59-70.
Ac
96. Pal, P. and Dey, P., (2013) Process intensification in lactic acid production by three stage
membrane integrated hybrid reactor system. Chem. Eng. Process., 64: 1-13.
40
Figure 1. Schematic diagram of a Cativa process plant for production of acetic acid
t
ip
cr
us
an
M
ed
pt
ce
Ac
41
Figure 2. Flow diagram of an Ethylene or Acetaldehyde oxidation plant for the
production of acetic acid.
t
ip
cr
us
an
M
ed
pt
ce
Ac
42
Figure 3. Left: Schematic diagram of a generator used in German method of food
grade acetic acid production. Right: photograph of an actual Fring's
fermentor
t
ip
cr
us
an
M
ed
pt
ce
Ac
43
Figure 4. Metabolic pathway of acetic acid production from glucose through
fermentation.
t
ip
cr
us
an
M
ed
pt
ce
Ac
44
Figure 5. Schematic diagram of a single stage membrane based continuous
fermentation system.
t
ip
cr
us
an
M
ed
pt
ce
Ac
45
Figure 6. Schematics of different membrane modules; A : Hollow fiber membrane
module, B: Spiral wound membrane module, C: Flat-sheet cross flow
membrane module, D: A bipolar electrodialysis cell configuration. M:
metal ion. AC: acetate radical.
t
ip
cr
us
an
M
ed
pt
ce
Ac
46
Figure 7. A promising continuous fermentative two stage membrane integrated
scheme for high purity acetic acid production representing high process
intensification.
t
ip
cr
us
an
M
ed
pt
ce
Ac
47
Figure 8. Major cost factors involved in acetic acid production in a membrane
integrated bioreactor; A: Operational cost, B: Capital cost.
t
ip
cr
us
an
M
ed
pt
ce
Ac
48
Table 1. Conventional Chemical Routes: conditions and by products.
Process Raw Catalyst Reaction Yield By-product
Name Material Used Condition (%)
Usage (oC, bar)
Monsanto CH 3 OH, CO [Rh (CO) 2 I 2 ]-AsPh 4+ 150-200, 30-50 95 HCOOH, HCHO
t
RhCl 3 .3H 2 O, Rh 2 O 3
ip
Cativa CH 3 OH, CO Ir 2 (CO) 8 150-200, 30-50 95 HCOOH, HCHO
cr
Acetaldehyde CH 3 CHO,O 2 Co(C 2 H 3 O 2 ) 2 150, 55-60 95 CH 3 COOC 2 H 5 ,
-Oxidation HCOOH, HCHO
us
Butane Oxidation C 4 H 10 , O 2 CrO 5 , CoO 2 150-230, 50-60 50 C 2 H 5 COOH,
HCOOH
Ethylene Oxidation C2H4, O2 Pb, Pb-Pt 150-160, 80 87 CH 3 CHO, CO 2
an
M
e d
pt
ce
Ac
49
Table 2. Unit operations involved in a conventional Cativa Plant for production of acetic acid
production.
Sl. No Unit operations Overall Remarks
t
ip
1 Main Reactor Dependence on petroleum
2 Flash Drum feed stock, Energy intensive as
cr
3 Secondary Reactor high temperature and high pressure
us
4 Bubble loop Reactor are required during reaction and
5 Recovery unit for feed phase changing phenomena are
and catalyst involved, high cost of individual
6
an
Distillation column units, strong requirement of process
7 Condenser use of expensive catalysts,
M
8 Reboiler generation of waste and direct
9 Dryer disposal in environment, huge
ed
10 Iodide recovery unit involvement of skilled persons.

pt
ce
Ac
50
Table 3.Characteristics of different microbial strains producing acetic acid (substrate: glucose).
Genus Species Growth conditions Fermentation

(Temperature, pH) products
300C, pH 6
t
Acetobactor Acetobacter aceti Acetic acid
ip
Acetobacter pasteurianus 300C, pH 6 Acetic acid
Acetobacter xylinum 300C, pH 6.5 Acetic acid
cr
Acetobacter suboxydans 300C, pH 6.2 Acetic acid
Acetobacter woodii 25-350C, pH 6-7 Acetic acid
us
Thermoanaerobacter Acetogenium kivui 660C, pH 6.4 Acetate
Thermoanaerobacter ethanolicus 690C, pH 5.8-8.5 Acetate, lactate, ethanol
Thermoanaerobacter finnii 650C, pH 6.5-6.8 Acetate, lactate, ethanol
an
Thermoanaerobacter brockii 650C, pH 7.5 Acetate, lactate, ethanol
Thermoanaerobacter acetoethylicus 650C, pH 5.5-8.5 Acetate, lactate, ethanol
70-730C, pH 6.4-7.0
M
Acetomicrobium Acetomicrobium faecalis Acetate, lactate, ethanol
Acetomicrobium flavidum 580C, pH 6.2-8.0 Acetate, lactate, ethanol
Acetothermus Acetothermus paucivorans 580C, pH 5.8-8.5 Acetate
55-600C, pH 6.6-7.5
Clostridium Clostridium thermoaceticum
e d
Clostridium stercorarium 650C, pH 7.3
600C, pH 7.0
Acetate
Acetate, lactate, ethanol

pt
Clostridium thermocellum Acetate, lactate, ethanol
Clostridium thermocopriae 600C, pH 6.5-7.3 Acetate, lactate, ethanol
Clostridium thermosaccharolyticum 55-620C, pH 6.5-7.0 Acetate, lactate, ethanol
ce
Clostridium thermosuccinogenes 580C, pH 7.6 Acetate, lactate, ethanol,

succinate, butyrate
650C, pH 7.3
Ac
Clostridium stercorarium Acetate, lactate, ethanol

Calorimator fervidus 680C, pH 7.0-7.5 Acetate
Moorella thermoautotrophica 55-600C, pH 5.7 Acetate
Saccharomyces Saccharomyces cerevisiae 28-32, pH 4-6 Acetic acid
51
Table 4. A comparative summary of bioreactor performances for acetic acid production.
Raw Microorganisms Type and mode Dilution Concentration of Yield Productivity Reference
Material used of fermenter rate (h-1) Acetic acid (g L-1) (g g-1) (g L-1h-1)
t
ip
Whey lactose S. lactis+ Batch CSTR NA 30.0 0.95 0.4 (30)
C. formicoaceticum
cr
Whey +lactose A. pasteurianus Shaker flask NA 47.62 0.34 0.5 (33)
Dried whey K. fragilis Shaker flask NA 25.84 0.5 0.14 (57)
us
Glucose C. thermoaceticum Batch CSTR NA 39.0 0.39 0.5 (32)
Basal medium Acetobacter Batch and 4.0 40 0.91 120.0 (97)
an
+acetic acid aceti M23 continuous
+ethanol CSTR
M
Basal medium Acetobacter Continuous 0.73 30-56 0.9-0.95 15-35 (98)
+acetic acid aceti M23 CSTR
+ethanol
Date extract
Glucose
Acetobacter aceti
Mutant
e
Continuous d
Continuous CSTR 0.06-0.24
0.006-0.03
46.5-50
30-45
0.9-0.96
0.8-0.9
2.8-11
0.4-4.6
(99)
(100)
pt
C. thermoaceticum CSTR
Cheese whey Acetobacter aceti Continuous CSTR 0.1-0.5 42-28 0.98-0.82 4.2-2.1 (93)
ce
Ac
52
conomic and environmental assessment of conventional acetic acid production processes vis-à-vis membrane- integrated
Assessment Conventional Production Conventional Electrodialysis Membrane-

Parameters Chemical Technologies process fermentation integrated
integrated technology fermentation
fermentation
a) Type of Non- Non- Renewable + Renewable+
Feed renewable renewable Non- Non-renewable
renewable
t
b) Operational Fixed Flexible Flexible Flexible
Production production as production as production as
ip
capacity,
Flexibility Not flexible per market per market per market
demand demand demand
cr
c) Space 0.5 m2/ton 0.2 m2/ton 0.3 m2/ton 0.09 m2/ton
acetic acid acetic acid acetic acid acetic acid
requirement
us
d) Capital US US $ US $ US $ 300/ton
$8600/ton 1500/ton 3500/ton acetic acid
acetic acid acetic acid acetic acid
investment
e) Cost of feed
f) Cost of
Energy 5500
US$ 480 /ton
acetic acid
1000 kWh/ton
acetic acid
an
US$ 450 /ton
acetic acid
3400 kWh/ton
acetic acid
US$ 480 /ton
acetic acid
55.76
kWh/ton
US$ 23
/ton acetic
acid
M
kWh/ton acetic acetic acid
acid involved
g) Cost of US$ US$ 900- US$ 700- US$ 300/ton
600-800/ton 1500/ton 800/ton acetic
acetic acid acetic acid acid
ed
Production
h) Product Low Purity 85-95% 98%
purity 95-99% due to the lack
proper of
pt
downstream
units
i) Emission of Propanoic No emission Ethyl acetate, No pollutant
pollutants acid, Butyric productivity metal acetates emission
ce
Dichloroacetic acid,
acid, carbon- Butanone,
di-oxide Ethyl acetate,
Formic acid,
Ac
j) Major cost Downstream High cost of Electricity and Except

enhancing processing, feed but low electrodes membranes
factors electrical 90% cost of consume costs other
energy production are pretty low
involvement
for production,
high cost of
feed and
individual
units
53

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Separation & Purification Reviews

ISSN: 1542-2119 (Print) 1542-2127 (Online) Journal homepage: http://www.tandfonline.com/loi/lspr20

Acetic acid production and purification: critical

Parimal Pal & Jayato Nayak

To link to this article: http://dx.doi.org/10.1080/15422119.2016.1185017

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Download by: [University of Lethbridge] Date: 04 May 2016, At: 21:11

Parimal Pal*, Jayato Nayak

Environment & Membrane Technology Laboratory, Department of Chemical Engineering

technology in downstream separation and purification appear to have brightened. Emergence of

directs further research towards process intensification.

*Corresponding Author (P. Pal, E-mail: parimalpal2000@yahoo.com or

ppal.nitdgp@gmail.com); Fax: +91343-254-7375: Tel: +91343-275-4088.

players like Celanese, BP Chemicals, China Petrochemical, Dow chemical, Millennium

of-the-art of development of novel technologies with special emphasis on membrane based

technologies towards sustainable business.

2.1 Chemical synthesis approach

dryer, condenser and re-boiler) are involved in a Cativa process plant.

drawback of azeotropic distillation is the requirement of larger diameter columns compared to

Acetaldehyde oxidation is another process of acetic acid production where petroleum

produced (21). A schematic diagram of such a plant is presented in Figure 2.

Partial oxidation of ethane to acetic acid was studied over molybdenum-vanadium

employing H 2 O 2 with m-nitride di-iron phthalocyanines as catalyst.

The reaction conditions and by-products formed in conventional chemical technologies

production. Fermentation based production techniques have some fundamental advantages

of high energy consuming units.

Most of the literature on fermentative production revolves around use of finished

acetaldehyde. Produced molecules of acetaldehydes in presence of different dehydrogenase

whey using an association of Streptococcus lactis and Clostridium formico-aceticum at a

with additional carbohydrates in a mixed batch culture of Kluveromyces fragilis and

valuable products is low, it provides ecological advantage and sustainability by reducing

acetate synthesis rates up to 1.2 g.L-1.h-1 for Acetobactor woodii (40).

disturbing microbial health can also be achieved by using membranes. Conventional

purification technologies are energy-intensive due to involvement of a number of unit

high purity product substantially reducing the cost of energy.

2.3. Limitations to the conventional production schemes of acetic acid

plants (41, 42).

sustainable avenues of chemical production (11, 41).

3. MEMBRANE BASED PROCESSES

based processes are simple to design and flexible to operate.

ultrafiltration, the separation is based on size exclusion or sieving mechanism (8).

generating transmembrane pressure above 20 bar is necessary. Nanofiltration is a relatively

membrane is mainly due to electrostatic interaction between negatively charged membrane

product purity (44, 45).

While operating in continuous mode employing such a membrane integrated fermenter,

engineering is the possibility of separation-purification at ambient temperature at significantly

3.2. Microfiltration and ultrafiltration of fermentation broth

microbial cells. The problems related to substrate-product inhibitions could be substantially

reduced if continuous withdrawal of acid product in a membrane-integrated fermentation unit is

membrane based separation-purification. While operating in continuous mode, continuous

Due to size based separation in microfiltration or ultrafiltration membranes, chances of

different membrane modules have been represented in Figure 6.

Ultrafiltration membrane performance was observed on the rice husk derived

concentration and productivity of acetic acid.

In most of the fermentation based production techniques, addition of alkali is practiced

from any form present in fermentation broth. It is an electro-membrane process in which

recovered and recycled by electrodialysis. Thus the simultaneous reduction of environmental

Chukwu and Cheryan (63) employed a microfiltration system followed by an

bipolar membrane electrodialysis system is represented in Figure 6D.

with the extraction and purification of acetic acid is a difficult job.