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Critical Reviews in Environmental Science and Technology, 35:429–467, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1064-3389 print / 1547-6537 online
DOI: 10.1080/10643380590966181
Production and Recovery of Lactic Acid

for Polylactide—An Overview
A. N. VAIDYA, R. A. PANDEY, S. MUDLIAR, M. SURESH KUMAR,

T. CHAKRABARTI, and S. DEVOTTA
National Environmental Engineering Research Institute, Nehru Marg Nagpur, India
In the recent past the ultimate disposability of synthetic plastics has

been a greater environmental concern, and it has triggered the
R&D efforts in the designing of material with an environmentally
friendly life cycle by integrating material design concepts with ul-
timate disposability, resource utilization, and conservation. Tra-
ditionally, all plastics have been manufactured from nonrenew-
able petroleum resources, and these plastics are nonbiodegradable.
Conventional disposal methods include incineration and secured
landfill, which are associated with many environmental problems,
such as production of dioxins. The continued depletion of landfill
space and problems associated with incineration have led to the
development of biodegradable plastics such as polylactides (PLA),
which are manufactured from lactic acid that in turn is produced
from starch. Although production processes for lactic acid and PLA
are well known, very few processes have been commercialized and
still the cost of PLA is not competitive with synthetic plastics. The
crux of the PLA production technology is the fermentative produc-
tion of optically active lactic acid and its recovery. Many processes
are reported in the literature and through patents for the recovery
of optically active lactic acid and still offer an extensive scope for
research and development. This article critically reviews the pro-
duction and recovery processes for lactic acid and PLA production.
KEY WORDS: biodegradable plastic, fermentation, lactic acid, life

cycle, PLA, recovery
Address correspondence to A. N. Vaidya, National Environmental Engineering Research

Institute, Nehru Marg Nagpur 440 020, India. E-mail: atulvaidya33@hotmail.com
429
430 A. N. Vaidya et al.
I. INTRODUCTION
Growing environmental concerns, regulations, and social demands through-

out the world have triggered a paradigm shift in the industry to develop the
processes and materials compatible with the environment. This necessitates
attention to designing materials with an environmentally friendly life cycle,
integrating material design concepts with ultimate disposability, resource uti-
lization, and conservation. In the recent past the ultimate disposability of
synthetic plastics has been a great environmental concern. Traditionally, all
plastics are manufactured using crude oil as the very basic material, and
this is a nonrenewable resource. Manufacturing of conventional plastics in
petrochemical industries consumes more than 270 million tonnes of oil and
gas every year worldwide. Known global reserves of crude oil are expected
to run dry in the near future, but the economic impact of their depletion
could be realized much sooner. Therefore, an emergent need has been re-
alized for shifting the policies toward minimizing the resource consumption,
and employing alternative renewable resources for fuels and chemicals in-
cluding synthetic plastics. As a result, research in the recent past is directed
toward the development of alternative processes for the production of plas-
tics utilizing renewable raw material sources and thereby conserving nonre-
newable resources and minimizing the environmental deterioration caused
by the production and disposal of synthetic plastics. Most of the synthetic
plastics that are in wide use are either nonbiodegradable or partially degrad-
able. The existing disposal methods, therefore, include secured landfill and
incineration. The disposal of plastic materials by incineration generates air
pollutants/wastes of environmental concern, namely, dioxins, toxic hydrocar-
bons, and so on. The continued depletion of landfill space is posing severe
restriction on the secured landfill disposal of plastic. Therefore, developing a
biodegradable plastic is viewed as an environmentally and ecologically sound
approach. Plant materials, such as corn, potato peels, sago, and others, or
even waste from food processing products can also be used for the pro-
duction of biodegradable plastics. These raw materials for the biodegradable
polymers contain starch-based constituents, which are fermented to produce
the lactic acid. The lactic acid is further converted into lactide, which serves as
a monomer for production of polylactide (PLA), a prominent biodegradable
polymer. The production of PLA encompasses:
r Utilization of renewable resources that leads to conservation of the

nonrenewable resource base.
r Production of biodegradable materials that follow the concept of “cradle
to grave.”
The primary focus of this article is to reveal the present status
of lactic acid and PLA production and its use. The article covers the
Production and Recovery of Lactic Acid for Polylactide 431
history of development of PLA: types of raw materials used for produc-

tion of PLA via lactic acid, production and recovery processes available,
environmental benefits derived from the use of PLA, and probable im-
pacts of PLA on the environment. Based on the information available,
the future research needs in different areas pertaining to PLA are also
envisaged.
II. PROCESSES FOR PRODUCTION OF LACTIC ACID

A. Chemical Processes for Lactic Acid Production
General properties of lactic acid are given in Table 1. Lactic acid
can be prepared by a variety of chemical reactions. Many of these
reactions are of scientific interest only, and very few have been
commercialized. These reactions can be classified broadly in six
categories:
r Hydrolysis of lactic acid derivatives, for example, esters or nitriles.

r Hydrolysis of other 2-substituted propionic acids.
r Decarboxylation of certain derivatives of 2-methylmalonic acid.
r Reduction.
r Oxidation.
r Rearrangement and disproportionation.
TABLE 1. Properties of Lactic Acid
Product identification
CAS no. 50-21-5, 79-33-4 (L), 10326-41-7 (D)
EINECS no. 200-018-0
Formula CH3 CH(OH)COOH
Mol. wt. 90.08
H.S. code 2918.11
Toxicity Oral rat LD50: 3543 mg/kg
Synonyms 2-hydroxypropanoic acid;
1-hydroxyethanecarboxylic acid;
ethylidenelactic acid;
alpha-hydroxypropionic acid
Physical and chemical properties (99%)
Physical State Colorless to slightly yellow, syrupy liquid
Melting point 17◦ C
Boiling point 122◦ C
Specific gravity 1.2
Solubility in water Miscible
NFPA ratings Health 3, Flammability 1, Reactivity 1
Flash point 112◦ C
Stability Stable under ordinary conditions
Out of these, only the synthesis from lactic acid derivatives has been
commercialized.
Lactic acid can be liberated from most of its derivatives by suitable treat-
ment, however, there is no practical advantage, as lactic acid is the raw
material for these derivatives. Lactonitrile and lactic acid nitrate are the im-
portant exceptions, as these are not produced from lactic acid. Lactonitrile
is produced from acetaldehyde and hydrogen cyanide as an intermediate in
the production of acrylonitrile, and it is further hydrolyzed to lactic acid as
follows:
HCl
CH3 CHO + HCN −→ CH3 CHOH CN (1)
Acetaldehyde lactonitrile
HCl
CH3 CHOH CN + 2H2 O −→ CH3 CHOH COONH4 (2)
Ammonium lactate
→ CH3 CHOHCOOH
lactic acid
Unreacted or waste lactonitrile may be used as a raw material. In 1963,

Monsanto Chemical Company installed the first commercial the plant in
United States that produced technical-grade lactic acid (55 to 85% w/w).
In another route, propene is converted into α-nitropropionic acid by nitric
acid in the presence of oxygen. α-Nitropropionic is further hydrolyzed to
lactic acid. Reactions involved can be expressed as:
CH3 CH2 CH3 + HNO3 + O2 → CH3 CH (NO2 ) COOH (3)

α -Nitropropionic acid
CH3 CH (NO2 ) COOH + H2 O → CH3 CHOHCOOH (4)

Lactic acid
The commercial details of these reactions are not available.
B. Fermentation Processes for Lactic Acid Production

Industrial production of lactic acid, especially where pure optical isomers are
required, is presently carried out predominantly by fermentation process. The
production process can be divided into:
r Actual production of lactic acid by fermentation of a carbohydrate source.

r Downstream processing of the fermentation broth to obtain pure lactic
acid.
Several microorganisms have been isolated and used in the production

of lactic acid from the genera Lactobacillus, Streptococcus, and Pediococcus.
These organisms exhibit maximum productivity only within a very narrow
pH range. The fermentation processes are associated with the production of
lactic acid as well as other organic acids, which lower the pH of the fermen-
tation broth continually. Therefore, it is necessary during fermentation not
only to maintain optimum temperature but also to maintain a pH at constant
value, preferably in the range of 5.5 to 6.5. This is achieved by addition of
bases such as hydroxides or carbonates of alkali or alkaline earth metals, or
ammonia. Thus, the main constituent of fermentation broth is a salt of lactic
acid, and not pure lactic acid apart from salts of other organic acids, unre-
acted materials, nutrients, microorganisms, and so on. Such a fermentation
broth cannot be utilized for the further use, and therefore additional process-
ing steps are required to obtain pure lactic acid. The recent research work
in lactic acid production comprises mainly downstream processing, and var-
ious downstream processes have been developed and invariably patented
(Vickroy, 1985; Chahal, 1990).
I. RAW MATERIALS FOR LACTIC ACID PRODUCTION
Raw materials for lactic acid production should meet certain purity require-
ments besides being available at reasonable prices, since these are critical
for the further purification of the produced lactic acid. The choice of raw
materials largely depends on the intended application and the respective
costs of product purification. Various readily available mono- and disaccha-
ride materials are traditional substrates for lactic acid manufacturing. These
are
r Glucose (dextrose) and glucose syrups of varying qualities as end products

of starch conversion processes applying enzymes such as glucoamylases.
r Maltose as a product of specific enzymatic starch conversion applying α-
amylases and β-amylases from barley malt or other sources.
r Sucrose as end product, intermediate products (syrups, juices), and by-
product (molasses) of beet and cane sugar production.
r Lactose as a constituent of whey as the natural substrate of most lactic acid
bacteria.
Starch-based raw materials can be obtained from corn (maize), potatoes,

wheat, tapioca (cassava), and other plants. Starch cannot be utilized by com-
mon lactic acid bacteria, except Lactobacillus amylophilus and L. amylovorus.
Starch hydrolysis can be performed by either chemical or enzymatic meth-
ods, with chemical methods being abandoned for some time. Since maltose
is the main product of enzymatic hydrolysis, only a limited number of or-
ganisms are suitable of the fermentation process. Starch liquefaction and
saccharification are achieved, at present by the combined action of different

α-amylases of bacterial origin and of fungal glucoamylases.
Sucrose-derived raw materials are also suitable as raw materials for lac-
tic acid fermentation, and molasses is the cheapest raw material. Most of
the known homofermentative organisms of Lactobacillus can utilize sucrose,
with L. bulgaricus and L. helveticus being notable exceptions.
Lactose poses a limitation as a raw material due to its low concentration
in the most readily available whey, and in addition expensive purification
procedures have impeded the successful utilization of whey. The fact that
whey represents a considerable environment load has stimulated the de-
velopment of modern technologies of whey concentration and fractionation,
such as ultrafiltration and electrodialysis. These, in turn, have exerted a strong
stimulus on fermentation research laboratories, as may be seen from the re-
cent literature (Roy et al., 1986; Boyaval et al., 1987; European Patent 265409,
1988; Leh and Charles, 1989a, 1989b; Kulozik et al., 1992; Chiarini et al., 1992;
Boergardts et al., 1994).
2. MICROORGANISMS USED IN LACTIC ACID PRODUCTION
Substantial information related to the genetics of lactic acid bacteria and

possible applications of genetic engineering is available (Devos and Vaughan,
1994; Fitzsimons et al., 1994; Wel et al., 1995). Although all prerequisites for
developing a recombinant DNA system have been thoroughly investigated,
industrial production of lactic acid apparently still relies on producer strains
that are selected empirically, on the basis of raw material.
Lactic acid bacteria utilize either the well-known EMP pathway of glu-
cose metabolism to produce lactic acid as the major end product, or use
pathways of pentose metabolism resulting in the formation of lactic acid plus
other products such as acetic acid, ethanol, and CO2 . In 1919, Orla-jensen
proposed the terms “homofermentative” and “heterofermentative” for the re-
spective organisms. The industrial production of lactic acid is mostly carried
out by homofermentative bacteria; however, the homofermentative behavior
of certain strains may change to heterofermentative under the growth-limiting
levels of carbon source (De Vries et al., 1970). The temperature range for op-
timal growth of mesophilic lactic acid bacteria is from 28 to 45◦ C and that of
thermophilic lactic acid bacteria is 45–62◦ C. Organisms operating at higher
temperatures are preferred because of reduced risk of contamination during
fermentation; however, most of the microbial strains are sensitive to pH. Ac-
cording to Buchta (1994), lactic acid fermentation is strongly inhibited at pH
5 and ceases at pH values below 4.5. Lactic acid bacteria differ in their ability
to produce D-(−)-, L-(+)-, and DL-lactic acid, depending upon the presence
of respective lactate dehydrogenases and racemases (Garvie, 1980; Teuber,
1993).
Lactic acid bacteria have complex nutrient requirements. These com-

prise many of the known vitamins, amino acids, and even small peptides
(Barton-Wright, 1952). Therefore the fermentation media needed for lactic
acid production is quite complex and expensive, too. In order to create
reproducible conditions, it is recommended that one maintain cultures of
producer organisms on standard culture media, such as MRS medium, which
is available from several sources (Merck 106600500, 106610500; Oxoid CM
395; Difco 0881).
For glucose as a raw material, any homofermentative member of the
genus Lactobacillus may be used. The preferred organism, however, is Lac-
tobacillus delbrueckii, now designated as Lactobacillus delbrueckii ssp. Del-
brueckii (Teuber, 1993; Hammes et al., 1991). The organism can also utilize
sucrose and is thus suitable for the fermentation of sucrose or molasses, but
it cannot utilize lactose. In contrast, Lactobacillus delbrueckii ssp. Bulgari-
cus utilizes lactose but not sucrose and has been used for the conversion
of lactose, that is, whey. Lactobacillus helveticus, on the other hand, utilizes
lactose but not sucrose, and thus represents another useful organism for the
conversion of whey. Lactobacillus delbkueckii ssp. lactis, formerly known as
L. lactis, may be used in fermentation of glucose, sucrose, and lactose. With
respect to starch, which cannot be fermented by lactic acid bacteria and has
to be hydrolyzed prior to fermentation, the choice of suitable organisms de-
pends on the way of starch hydrolysis: If α- and β-amylases (barley malt) are
used, the resulting carbon source will be mainly maltose. Organisms capable
of fermenting maltose are L. delbrueckii ssp. lactis and some strains of L.
delbrueckii ssp. delbrueckii (Teuber, 1993). In the case of saccharification
with α-amylases and glucoamylases, resulting in the production of mainly
glucose and glucose oligosaccharides, suitable strains will be those already
described. One exception should be mentioned: Lactobacillus amylophilus
(Nakamura and Crowell, 1979) and Lactobacillus amylovorus (Nakamura,
1981) have been described to actively ferment starch, and this has led to
alternative processes of industrial lactic acid production (Cheng et al., 1991;
Zhang and Cheryan, 1994). Irrespective of the raw material used, it is de-
sirable to select strains with high rates of productivity. Since productivity is
strongly dependent on the hydrogen concentration of the fermentation broth,
it might be expected that adaptation to higher concentrations of lactic acid
would increase the performance of a given strain. Increased yields have, in
fact, been claimed following this procedure (U.S. Patent 4,794,080, 1988).
Application of chemical mutagens (e.g., ethyl methane sulfonate) has been
reported to yield mutant of L. delbrueckii (ATCC 9649) with improved tol-
erance to higher acid concentrations and higher productivities (Demirci and
Pometto, 1992).
In recent years, research efforts in microbiology have concentrated on
the development of improved microorganisms for the production of lactic
acid. The targets are increased growth rates, improved pH resistance, and
increased yields of lactic acid. These targets are partially achieved by ef-
forts through genetic engineering, control of metabolic activity by appro-
priate culturing techniques, and development of acid resistant mutants. A
notable patent (U.S. Patent 6,660,515, 2003) in this regard provides meth-
ods of enhancing the growth rate and/or controlling the metabolic activity
of lactic acid bacteria, which are defective in their pyruvate metabolism.
There are also starter culture compositions comprising such defective lac-
tic acid bacteria as helper organisms and lactic acid bacterial starter culture
strains. Useful helper organisms are Lactococcus strains, which are defec-
tive with respect to pyruvate formate-lyase (Pfl) and/or lactate dehydroge-
nase (Ldh) activity. The helper organisms may overexpress a gene coding
for an NAD+ -regenerating enzyme such as NADH oxidase, encoded the by
nox gene. Accordingly, invention relates in a first aspect to a method of
enhancing the growth rate and/or controlling the metabolic activity of a
lactic acid bacterial strain, comprising cultivating the strain in association
with a lactic acid bacterial helper organism that is defective in its pyruvate
metabolism.
In another recent patent (U.S. Patent 6,645,754, 2003), mutants of lac-
tic acid bacteria including Lactococcus lactis that are defective in pyru-
vate formate-lyase production and/or in their lactate dehydrogenase (Ldh)
production and methods of isolating such mutants or variants are pro-
vided. The mutants are useful in the production of food products or in
the manufacturing of compounds such as diacetyl, acetoin, and acetalde-
hyde and as components of food starter cultures, in particular Lactococ-
cus lactis DN223 deposited under accession number DSM 11036. Accord-
ingly, the invention provides a method of isolating a pyruvate formate-
lyase (Pfl) defective lactic acid bacterium, with the method comprising the
steps of
1. Providing a wild-type lactic acid bacterial strain that under aerobic con-
ditions is not capable of growth in the absence of acetate in a medium
not containing lipoic acid, but that is capable of growth is such medium
under anaerobic conditions.
2. Selecting from said wild-type strain a mutant that under said conditions
essentially does not grow in the absence of acetate.
In U.S. Patent 6,475,759 (2002), a process for producing lactic acid,

which includes incubating the acid-tolerant homolactic bacteria in nutrient
medium to produce a fermentation broth with high levels of free lactic acid,
is provided. An isolate of the acid-tolerant homolactic bacteria capable of
producing high levels of free lactic acid is also provided. The invention by
Sato and his coworkers (U.S. Patent 5,597,716, 1997) relates to a process
for producing D-lactic acid and L-lactamide, comprising a culture broth of

a microorganism capable of asymmetric hydrolysis of DL-lactamide belong-
ing to the genus Alcaligenes, Pseudomonas, Agrobacterium, Brevibacterium,
Acinetobacter, Corynebacterium, Enterobacter, Micrococcus, or Rhodococ-
cus, a material obtained therefrom or an immobilized material thereof to act
on DL-lactamide, and recovering the resulting D-lactic acid and the remaining
L-lactamide. This invention enables sufficient production of D-lactic acid and
L-lactamide by the microorganism used in the study. (U.S. Patent 5,597,716,
1997).
3. ORGANISMS OTHER THAN LACTIC ACID BACTERIA
A limited number of other microorganisms are capable to produce larger

amounts of lactic acid from common carbon sources. The best known is
Rhizopus. Foster (1949) has recommended the use of Rhizopus for commer-
cial lactic acid production (U.S. Patent 2,132,712, 1938; Prescott and Dunn,
1959) because this organism is able to convert several sugars with apprecia-
ble yields into synthetic fermentation media. Thus, downstream processing
was considered to be easier than fermentation by the more fastidious lactic
acid bacteria. So far, although the process is patented (U.S. Patent 3,125,494,
1964); commercial use of this potential technique has not been accomplished.
Recently, a process has been patented in which conversion of starch by Rhi-
zopus oryzae in single-step fermentation process with high lactic acid yields
is claimed (U.S. Patent 4,963,486 A, 1990). Several reports have been pub-
lished on a group of spore-forming bacteria, which have long been known
as lactic acid producers:
r Sporolactobacillus inulinus culture produces D-(−)-lactic acid (U.S. Patent

3,262,862, 1966; Japan Patent 61058588 A2, 1986; European Patent 190770
A2, 1986; Kobayashi and Tanaka, 1988).
r Bacillus coagulans (10 strains listed) and lactic acid production by this or-
ganism (Blumenstock, 1984) have been patented (German Patent 4000942
A1, 1990).
Owing to their common properties, both organisms have been studied

extensively, especially with regard to their phylogenetic relationships (Suzuki
and Yamasato, 1994). Crabtree negative organisms such as Kluyveromyces,
Pichia, Hansenula, and Candida are used to produce selected organic prod-
ucts such as lactic acid. The organisms are cultured in a first culture medium
that includes glucose, under conditions that promote cellular respiration. The
organisms are then cultured under a second set of conditions that promote
production of the selected organic product. The organisms preferably contain
an exogenous lactate dehydrogenase gene (U.S. Patent 6,485,947, 2002).
4. BIOCHEMISTRY OF LACTIC ACID PRODUCTION
Review of the literature on fermentative production of lactic acid reveals

that, whatever the starting material, ultimately lactic acid is produced from
dextrose through pyruvic acid, and the reaction is
bacteria
−→ CH3 COCOOH −→ CH3 CHOHCOOH (5)
Pyruvic acid Latic acid
If polysaccharides are to be used as raw material, then they have to be

hydrolyzed to mono- or disaccharide, as mentioned earlier.
The various fermentation reactions involved can be expressed as
Hydrolysis Bacteria
Starch −→ n(C6 H12 O6 ) −→ 2nCH3 CHOHCOOH (6)
Dextrose Lactic acid
Starch → n(C22 H22 O11 ) → 4nCH3 CHOHCOOH (7)

Maltose Lactic acid
(8)
(9)
It is interesting to note that dextrose can also be chemically broken down

to lactic acid in the presence of KOH at high temperature, according to the
following reaction:
(10)
At present, lactic acid production from fermentation of starch is com-

monly used for commercial purpose. Dairy wastes contain lactose and sugar,
and beverage industry wastes contain sucrose. Therefore, if proper fermen-
tation processes are developed to produce lactic acid from waste sucrose or
lactose, a twofold objective of rendering wastes into a resource and minimiz-
ing environmental problems can be achieved.
III. DOWNSTREAM PROCESSING OF LACTIC ACID
Downstream processing of lactic acid broth is extremely complicated and

involves a number of steps. Different methods for purification of lactic acid
have been mentioned in the literature and patents. Review of this literature
clearly reveals the fact that no single method could be referred to as a stan-
dard method. However, the recovery and purification of the lactic acid can
be broadly classified in to the following steps. Each step can have multiple
alternatives and combinations thereof.
r Separation of biomass and other solids from the broth.
r Acidification of broth with strong acid to liberate the lactic acid.
r Removal of salt from the lactic acid solution or removal of lactic acid from
the broth or splitting of lactate salt. The general alternatives are:
r Precipitation of salt of cation with strong acid.
r Liquid–liquid extraction with simultaneous lactate salt formation with
strong base and back-extraction of lactic acid with water.
r Simultaneous acidification and esterification with alcohol followed by
back-extraction with water.
r Direct removal of lactic acid from broth by advanced separation methods
such as adsorption, membrane separations, and ion exchange.
r Concentration of lactic acid.
Separation of biomass and other solids can be achieved by any conven-

tional method. Acidification of broth is necessary to break the lactate into
lactic acid and cation. This can be achieved below a pH of 3.86 as the pK a
value for lactic acid is 3.86 and above this pH lactate is virtually present as
a salt. If calcium is used as the cation for maintaining the pH during fermen-
tation, then acidification with sulfuric acid results in precipitation of calcium
sulfate. Likewise, a number of processes can be used to remove cations.
For example, if sodium is used as the cation in fermentation, then it can
be removed by ion exchange. Removal of lactic acid can also be effected by
esterification of lactic acid with alcohols, by liquid–liquid extraction, or by ad-
sorption. Membrane processes, distillation, evaporation, crystallization, and
so on can achieve the concentration of the separated lactic acid. Separation
and purification can also be achieved by chromatography and ion exchange.
A. Precipitation of Salt of Cation With Strong Acid

The general trend in lactic acid production practices is to use bases of alkaline
earth metals to control the pH, and in such cases precipitation of metal cation
by strong mineral acid is the most common downstream processing option.
Rauch et al. (1960) have described product recovery and purification in such
cases. Accordingly, the fermentation liquid is heated to dissolve all calcium
lactate and treated with stoichiometric amounts of sulfuric acid. The resulting
calcium sulfate is separated by filtration with thorough washing of the filter
cake. The combined liquids are vacuum evaporated. Residual amounts of
gypsum precipitating in the concentrated lactic acid solution are filtered off
together with coloring substances, which may be adsorbed onto activated
carbon. Further purification is achieved by passing the solution through ion-
exchange columns and by treatment with hydrogen peroxide or potassium
permanganate. The resulting solution yields rather pure lactic acid (food
quality) with a concentration of 80%. Improvements have been reported us-
ing zinc lactate or magnesium lactate instead. Purifications with magnesium
lactate have been recommended in fermentations using crude carbohydrate
sources such as molasses because of improved crystallization properties (U.S.
Patent 3,429,777, 1969). In another approach to obtain high-purity lactic acid,
as described in European Patent (EP) 849252 (1988), multiple crystallizations
are generally carried out, first of the calcium lactates in order to remove the
soluble impurities from the fermentation medium, and then of the calcium
sulfates liberated after treatment with sulfuric acid. The first disadvantage of
this method is the high sulfuric acid consumption and above all the produc-
tion of large amounts of gypsum, which poses serious problems in terms of
waste treatment. The second disadvantage is the complexity and the high
number of steps required to obtain high-purity lactic acid. Other methods
have therefore been proposed, leading to the crystallization of salts of lac-
tic acid. For example, U.S. Patent 5,641,406 (1997) describes, after the step
involving the precipitation of calcium lactate with sulfuric acid and the treat-
ment with ferrocyanide or hexaferrocyanide salts to remove the copper and
iron ions, the depolarization of the “crude” lactic acid thus obtained with
activated charcoal, and after the subsequent purification steps to remove all
the residual salts, concentration by evaporation, and hence crystallization of
the lactates. Here again, this process suffers due to a large number of purifi-
cation steps and the handling of toxic chemicals. The latest patented process
for the preparation of high-purity lactic acid from an aqueous solution con-
taining lactic acid in the form of salt(s) is characterized in that the aqueous
solution is treated with a strong acid in order to liberate lactic acid in the free
form, and to produce corresponding salts of the strong acid, the salts of the
strong acid are crystallized by evaporative crystallization and the lactic acid
is recovered in the free form in solution (U.S. Patent 6,384,276, 2002).
A general schematic for all such processes is shown in Figure 1.
FIGURE 1. Schematic for recovery of lactic acid from lactate.

B. Liquid–Liquid Extraction With Simultaneous Lactate Salt Formation

With Strong Base and Back-Extraction of Lactic Acid With Water
Solvent extraction of lactic acid has been proposed as an effective down-
stream process in many patents and publications. Liquid–liquid extraction of
lactic acid involves addition of suitable solvent to the dilute aqueous solu-
tion of acid, resulting in distribution of lactic acid in the solvent phase and
aqueous phase. The fundamental requirement of a good extractive solvent is
a high distribution coefficient, which is the ratio of the lactic acid concentra-
tions in solvent phase to aqueous phase. Other important requirements are
high selectivity for lactic acid, low viscosity, low miscibility with water, higher
density difference between aqueous and solvent phase, thermal stability, and
low toxicity to microorganisms in fermentation broth.
Three major types of extractant solvents have been suggested. These are:
1. Conventional oxygen-bearing hydrocarbons, such as octanol and methyl

isobutyl ketone (MIBK).
2. Phosphorus-bonded oxygen-bearing solvents, such as tributyl phosphate.
3. High-molecular-weight aliphatic amines, such as dodecyl amine.
It has been reported that distribution coefficients for the first type of
extractants are very low, while those for the second type extractants are not
high enough to extract lactic acid efficiently. Extractants from the third type,
high-molecular-weight amines, are the most effective ones. The high basic-
ity of amines results in reactive extraction of lactic acid, which increases the
extraction efficiency substantially. Any solvent that has a high enough capac-
ity for lactic acid to be economic, such as amyl alcohol or a tertiary amine,
will also coextract some water, salts, and other organic acids. Thus, extrac-
tion alone does not economically produce lactic acid of high enough pu-
rity. Several extractants such as isopropyl ether (U.S. Patent 1,906,068, 1931)
α, ω-diamino-oligoethers (Miesiac et al., 1992), isobutanol (German Patent
3415141, 1985), and trialkyl tertiary amines in an organic solvent (U.S. Patent
4698303, such as) di-n-octylamine and n-hexane (Hano et al., 1993), have
been described. As a novel improvement, the application of liquid mem-
branes should be mentioned (Chaudhari and Pyle, 1992a, 1992b; Scholler
et al., 1993; Lazarova and Peeva, 1994). Bar and Geiner (1987) studied the
feasibility of extracting lactic acid from aqueous solution by means of a long-
chain trialkyl amine of low basicity, such as tridodecylamine, using various
tridodecylamine solutions in n-dodecanol. It was found that extraction of lac-
tic acid with a long-chain trialkyl amine such as tridodecylamine was effective
only at a pH that is lower than the pK a of lactic acid, which is 3.86. At such
a low pH, however, the lactic acid-fermenting microorganisms such as, for
example, Lactobacillus delbrueckii or Lactobacillus acidophilus are severely
inhibited. In addition, the extraction of lactic acid with amines produces the
salt of lactic acid with amine, and not pure lactic acid. Obviously, lactic acid
and amine should be recovered back from the salt, and several methods
are suggested for this salt splitting. These methods include back-extraction
with water, back-extraction with another amine, thermal splitting, and inert
gas-induced splitting. Applying these methods, pure lactic acid is obtained
and the recovered amine is recycled back to extraction. In effect, extraction
of lactic acid with amines becomes at least two or many times a multistep
downstream process.
U.S. Patent 5,132,456, 1992, describes a process for recovering carboxylic
acid from a carboxylic acid-containing aqueous feed stream having a pH close
to or above the pK a level of the acid. The recovery process involves what
may be described as a cascade-type acid withdrawal operation, in which the
basicity of the extractant is increased stepwise. In the second stage, carboxylic
acid is back-extracted either by ammonia or low-molecular-weight tertiary
amine, referred to as secondary extractant, which results in formation of
lactate salt with ammonia or tertiary amine. This salt is then thermally split to
yield back pure acid and secondary extractant. Applying this process to lactic
acid involves the formation of salts of lactic acid with strong bases having
a pK a value of about 9–11. Thus, the decomposition of these salts into free
lactic acid is energy-intensive. The patent also mentions the use of Alamine
336 (tricaprylylamine) for the extraction of, among others, lactic acid from an
aqueous solution, but no yields are mentioned. With the extraction of even
small quantities of lactic acid from a fermentation broth, the pH of the broth
rises rapidly to above 7, while the pK a of an extractant based on Alamine
336 is less than 6. As shown in the patent, the uptake of carboxylic acids
from aqueous solutions drops rapidly with an increase of pH. It is therefore
inherent that the lactic acid uptake, if any, is negligible. It is further noted that
upon heat treatment and concentration of an ammonium lactate, crystalline
lactic acid does not precipitate; instead, the viscosity of the solutions increases
steadily as a result of self-association of the acid. Baniel et al. (U.S. Patent
4,275,234, 1981), found that the extracted acid can be recovered from the
acid comprising extractant by back-extraction with water. They have also
found that if the back-extraction is conducted at a temperature higher than
that of the extraction, the concentration of the acid in the back-extract (the
aqueous product of the back-extraction) could be significantly higher than
that of the aqueous feed to the process. Yet if the concentration of the acid
in the feed is very low, the concentration of the back-extract could still be
too low. That is particularly true when the feed consists mainly of the salt
of the acid rather than the free acid. Acidulating neutral fermentation liquors
by the addition of acids for recovery via ester formation or other methods
results in the formation of by-product salts, such as gypsum in the case of
calcium lactate acidulation with sulfuric acid or sodium, or ammonium sulfate
in others. Reagents are consumed, and disposal of undesired by-products is
required. Efforts have recently been made to recover the lactic acid from
fermentation liquors without formation of by-product salts. Such a process

is like salt splitting processes. In some recently published patents, extraction
is applied to salt splitting. Thus, in U.S. Patent (5,132,456, 1992), a strongly
basic extractant extracts part of the lactic acid from the neutral solution,
which results in a lactic acid-loaded extractant and a basic solution. This
basic solution, which still comprises most of the lactic acid values, could
be recycled as a neutralizing medium to the fermentation. In U.S. Patent
5,510,526 (1996) the extraction of the acid is conducted under CO2 pressure,
so that bicarbonate is formed. The latter can be used as a neutralizing agent in
the fermentation. In order to limit the CO2 pressure to an economic one and
still achieve high yields, the extractant used should be quite strong. In fact,
any extraction-based salt splitting process that avoids the production of by-
product salts would require a strongly basic extractant. These extractants are
usually composed of an amine as the main active component. The preferred
amines are chosen from the group of primary, secondary or tertiary amines,
with a total number of at least 18 carbon atoms. Mostly preferred are tertiary
amines. A diluent is usually used to achieve the required physical properties.
The basicity of the extractant is easily adjusted by adding a polar solvent
to the extractant. Such polar solvents enhance the extraction efficiency of
the amine, and are usually referred to as enhancers. Alkanols provide very
efficient enhancers. The basicity of the extractant is thus adjusted by the
amount of the enhancer in the extractant, or, more precisely, by the enhancer
to amine molar ratio. In the strongly basic extractants used in salt splitting
processes, the enhancer to amine molar ratio is usually at least 1:1, and in
many cases is higher than that.
A general schematic for liquid-liquid extraction is shown in Figure 2.
C. Simultaneous Acidification and Esterification With Alcohol

Followed by Back-Extraction With Water
Another method of lactic acid purification is esterification with alcohol, and
distillation of the volatile ester as a most effective separation step to yield
pure products (U.S. Patent 2,350.370, 1943; British Patent 90322, 1962; Czech
Patent 104398, 1962). Forming lactic acid ester with alcohol, purifying the
ester by distillation or extraction, and then converting the ester back to lactic
acid can produce high purity lactic acid. Since the pK a of lactic acid is 3.86,
which is much lower than the near-neutral pH of fermentation, mostly lac-
tate salts exist in the broth. Therefore, substantially complete recovery and
purification of lactic acid require acidulation with a strong acid that releases
lactic acid from its salt to react with alcohol. Esterification is performed in
countercurrent operation with concomitant separation of the volatile ester
and subsequent de-esterification with water in a second stage to yield free
lactic acid and alcohol to be reintroduced into the system. This method is
FIGURE 2. General schematic for liquid–liquid extraction.
said to yield lactic acid of optimum purity without any waste product to
be disposed of. Disadvantages of this method are the expensive equipment
and technical problems in handling a fluid with higher contents of inorganic
compounds.
In lactic acid purification, it is known that lactic acid can be reacted

with high excesses of methanol to produce methyl lactate, with methanol and
water being drawn overhead to drive the reaction. An alternate method, using
methanol as the esterifying alcohol, involves removing the ester continuously
from the top to drive the reaction. The scheme involves bubbling excess
hot alcohol, such as methanol vapor, through the lactic acid solution at a
temperature above the boiling point of alcohol, whereby the produced lactate
ester is removed with the alcohol vapors and water. Approximately 9 moles of
methanol are required to remove 1 mole of lactic acid from an 82% solution.
Dramatically larger quantities of methanol are required for more dilute lactic
acid feed solutions. This may be acceptable if a highly concentrated pure
lactic acid feed solution is used. However, the disadvantage of this method is
that there is little liquid alcohol or liquid ester present in the reaction broth,
leaving behind a thick residue of impurities and partially reacted material,
with limited yield in a given cycle. A solution to these problems was given in
U.S. Patent 5,210,296 (1993) by the use of a process consisting of continuous
acidification of an aqueous solution containing ammonium lactate in the
presence of an alcohol, having four to five carbon atoms, being used as a
diluent, with sulfuric acid (or any other strong acid), removal of water from
the acidified mixture by distillation of the water/alcohol azeotrope, and, in
a simultaneous or sequential manner, removal of the produced ammonium
sulfate crystals (or salts of strong acid produced), distillation, and hydrolysis
of the liberated lactic acid ester to produce a free lactic acid having a purity
of more than 99.5% (U.S. Patent 5,210,296, 1993). However, the difficulty of
this process lies in particular in the need to remove the ammonium sulfate. It
is mentioned that it is imperative to use alcohols having four to five carbon
atoms (namely, n-butanol in this case) in order to obtain sufficiently coarse
ammonium sulfate crystals to facilitate their separation by simple filtration of
the reaction medium. Gabriel et al. (U.S. Patent 1,668,806, 1928) disclose the
composition of matter of 1-butyl lactate and its preparation. They prepared 1-
butyl lactate by dehydrating 70% lactic acid with excess 1-butanol at 117◦ C,
followed by the addition of HCl catalyst, and refluxing and esterification
with addition of excess 1-butanol and drawing a 1-butanol water azeotrope
overhead. Nakanishi and Tsuda (Japanese Patent 46/30176, 1971) studied the
production of 1-butyl lactate by extraction of an acidified crude fermentation
broth with 1-butanol, followed by esterification of the extract phase. BASF
(EP 159-285) considers the production of isobutyl lactate by extraction of an
acidified crude fermentation broth with isobutanol, followed by esterification
of the extract phase, which was then distilled in vacuum to give purified
isobutyl lactate.
In WO 93/00440, assigned to DuPont Corporation, a process is described
that comprises the steps of: (1) simultaneously mixing a strong acid, an alco-
hol, and a concentrated fermentation broth that contains mainly basic salts of
lactic acid, which react to form a crystal precipitate comprising of the basic
salts of the strong acid and an impure lactate ester of the alcohol; (2) re-
moving water from the mixture as a water/alcohol azeotrope, which can be
accomplished either sequentially or substantially simultaneously with step 1;
(3) removing the crystal precipitate from the mixture; (4) distilling the impure
lactate ester to remove the impurities; and (5) recovering the high-purity ester.
It can be seen that the processes of the esterification suffer in practice
from succession of numerous and cumbersome steps that make the purifica-
tion of lactic acid from an aqueous solution containing lactic acid in the form
of salt(s) long and tedious. A general flow diagram for lactic acid recovery
by esterification is shown in Figure 3.
FIGURE 3. Schematic for recovery of lactic acid by esterification.

D. Direct Removal of Lactic Acid from Broth by Advanced Separation

Methods Such as Membranes, and Ion Exchange
More recently, ion exchange, hitherto only used in later purification steps,
has been proposed for primary separation of lactic acid from fermenta-
tion broths (German Patent 4000942 A1, 1990; Japanese Patent 01091788,
1989; U.S. Patent 5,068,418, 1991; European Patent 517242 A2, 1992; Japan
Patent 04320691 A2, 1992; Evangelista et al., 1994). It is claimed that this
method makes the production of food-grade, heat-stable lactic acid possi-
ble without the problem of waste disposal as in the calcium and sulfuric
acid procedure. Ion-exchange methods normally involve exchange of cation
that has been used for the maintenance of pH during fermentation (U.S.
Patent 6,280,985, 2001). A process involving ion exchange has been referred
to for extracting pure lactic acid from fermentation broth by ion-exchange
chromatography on a strongly acidic cation exchanger, preferably in H+
form. In a first step, the ammonium lactate coming from the fermentation
is converted into the free acid by genuine ion exchange. This conversion is
preferably affected on a weakly acidic cation exchanger in H+ form (U.S.
Patent 5,641,406, 1997). A process combining ion exchange and solvent ex-
traction has been developed by Eyal et al. (U.S. Patent 6,320,077, 2001) for
the recovery of purified lactic acid values from an aqueous feed solution
containing lactic acid, lactic acid salt, or mixtures thereof. It includes: (1)
bringing said feed solution into contact with a substantially immiscible an-
ion exchanger to form a substantially water-immiscible phase comprising of
an anion exchanger–lactic acid adduct; (2) effecting a condensation reac-
tion in the said substantially water-immiscible phase between a carboxylic
moiety of said lactic acid adduct and a moiety selected from a hydroxyl
moiety and a primary or secondary amine moiety to respectively form a lac-
tic acid ester or amine product; and (3) separating the formed lactic acid
product from the anion exchanger. (U.S. Patent 6,160,173, 2000). Similar
logic is applied for the processes wherein adsorption is used instead of
ion exchange. Schematics for lactic acid recovery by ion exchange and ad-
sorption are given in Figures 4. The commercially available ion-exchange
resins such as Reillex 425 and Reillex HP (Reilly Industries, Inc., USA),
Dowex MWA-1 and Dowex 66 (Dow Chemical Company, Midland, MI), and
Duolite A561 and AmberliteIRA-67 (Rohm and Hass Corp., USA) are generally
used.
Recently, electrodialysis has been proposed for purification of lactic acid.
Currently this process has two disadvantages: high cost and a product of
intermediate purity.
Other methods used for recovery and purification of lactic acids are
membrane processes. Membrane processes may include microfiltration, ul-
trafiltration, nanofiltration or reverse osmosis or combinations thereof (U.S.
FIGURE 4. General schematic of lactic acid separation by ion exchange.
Patent 5,250,182, 1993). Overall application of membrane processes in lactic

acid recovery is schematically represented in Figure 5.
It is evident from the preceding discussion that there is an unsatisfied
need for a simpler and cheaper process that permits the separation, concen-
tration, and purification of a high-purity lactic acid with an excellent yield
from an aqueous solution containing lactic acid in the form of salt(s).
FIGURE 5. General schematic for lactic acid separation by membranes.
IV. COMMERCIAL PROCESSES FOR LACTIC ACID PRODUCTION

A. Classical Calcium Lactate Process
Considering most of the information just described, a basic protocol for man-
ufacturing lactic acid in a classical way is described in Figure 6.
FIGURE 6. Block diagram for calcium lactate process.

The raw material (glucose, sucrose) is brought to a sugar concentration

of 120–180 g L−1 . Complex nitrogen sources such as mixture of inorganic
N-compounds such as ammonia and ammonium phosphates with complex
organic materials such as corn steep liquor, yeast extracts, peptones and
other protein digests, malt sprouts, and so on, yielding nitrogen concen-
trations between 1 and 10 g L−1 , are added. Fermentation is carried out
in reactor volumes of even more than 100 m3 . One important factor is the
material of construction, since lactic acid is known to be highly corrosive.
Corrosion of the vessels has to be prevented not only to protect the reactor
but also to avoid contamination of the fermentation fluid by soluble com-
pounds (heavy metals etc.) that would complicate the further purification
steps. In the current industrial scenario, suitably lined concrete or stainless-
steel vessels are preferred. Conventional stirrers perform gentle agitation.
As the fermentation is conducted at temperatures greater than 40◦ C, heat-
ing has to be provided in the first stages, and cooling as soon as the heat
is generated by the fermentation itself. Maintaining relatively high temper-
atures of upto 50◦ C for L. delbrueckii or similar strains reduces the prob-
ability of contaminations by, for example, butyric acid forming anaerobic
bacteria.
Sterile calcium carbonate, preferably as powdered chalk, is added ei-
ther at the beginning or in increments during the fermentation to keep the
concentration of free lactic acid as low as possible. As mentioned earlier,
pH values should be maintained between 5.5 and 6.0. Active fermentation is
completed after 2–6 days, depending on the concentration of the used car-
bon source. In calcium lactate fermentations, the upper limits of sugar con-
centration are determined by the solubility of the resulting calcium lactate,
which at higher concentrations tends to precipitate from the fermentation
broth. It has been claimed, however, that the application of higher sugar
concentrations (e.g., 260 g L−1 ) would be feasible in fermentation with a
certain CaO dosage to adjust the pH to 6.3, causing continuous precipitation
of calcium lactate. This would shift the equilibrium of the reaction to the
direction of product formation. A 99.6% conversion based on reducible sug-
ars over 3 days was reported with this protocol (Poland Patent 144390 B2,
1985).
The reactions involved in calcium lactate process are as follows:
2CH3 CHOHCOOH + CaCO3 → (CH3 CHOHCOO)2 Ca + H2 O + CO2

Lactic acid Calcium carbonate Calcium lactate
(11)
(CH3 CHOHCOO)2 Ca + H2 SO4 → 2CH3 CHOHCOOH + CaSO4 (12)
Sulfuric acid Lactic acid gypsum
Usually, conversion yields of 85–95% (calculated on the basis of sug-

ars) of the theoretical accessible values are reported. Amounts of up to 2%
of acetic acid and propionic acid as by-products may be due to temporary
switches to heterolactic phases of fermentation by deviations from optimum

conditions of pH or substrate concentrations due to incomplete mixing.
The protocol is not limited to the use of calcium carbonate but also ap-
plies to use of hydroxides and carbonates of other alkali or alkaline earth
metals.
B. Ammonium Lactate Proces

Several workers have tried the usage of ammonia as a neutralizing agent in
the fermentative production of lactic acid. Ammonia reacts with lactic acid to
form ammonium lactate and thereby reduces the acidity of the fermentation
broth. The industrial fermentations are carried out using ammonia liquor, and
the rest of the process steps are similar to those of the calcium lactate process.
Recovery of lactic acid from ammonium lactate is effected by acidulation with
sulfuric acid and subsequent crystallization of ammonium sulfate salt, or by
esterification of free lactic acid by alcohol and subsequent back-recovery by
water.
The involved reactions are expressed as follows:
CH3 CHOHCOOH + NH4 OH → CH3 CHOHCOONH4 (13)

Lactic acid Ammonia Ammonium lactate
CH3 CHOHCOOONH4 + H2 SO4 → CH3 CHOHCOOH + NH3 (14)
C. Continuous Fermentation Process

In continuous fermentation processes, considerably higher productivities are
achieved, and thus they have been performed in various forms. Early studies
comprised experiments using cell suspensions (Childs and Welsby, 1966),
eventually with cell recycling (Vick et al., 1983). In fermenter systems with
high flow rates, productivities reached up to about 50 g L−1 h−1 (Richter
et al., 1987). Such high productivities, of course, were considered to be in-
teresting for the conversion of whey, especially in places with high accumu-
lation of whey. Several authors have reported continuous fermentations of
whey permeates with high productivities (Boyaval et al., 1987; Mehaia and
Cheryan, 1987a; Aeschlimann and Von Stockar, 1990; Krischke et al., 1991;
Kulozik et al., 1992; Boergardts et al., 1994). Some aspects of integrated pro-
cesses have been discussed in a textbook published recently (Chmiel and
Paulsen, 1991). Combinations of these processes with electrodialysis have
also been described (Hongo et al., 1986; Czytko et al., 1987; Yao and Toda,
1990).
In all these methods, the lactic acid production is strongly dependent
on the growth of the bacterial population. Lactic acid bacteria are known to
require a rich medium for growth, as their capacity to synthesize the growth
factors is very small. Often the costs of nutrients are more than the sugar feed-
stock. In addition, part of the nutrients not bound to the growing biomass
remain in the product, thus lowering its purity. It has been recently reported
that in the preparation of lactic acid, the actual fermentation reaction and
the culturing of producer organisms can be separated into discrete produc-
tion and refreshing cycles. In the culturing stage, that is, refreshing cycle, the
rich nutrient medium is passed through the bioreactor for a few hours. After
the culturing stage, pure feedstock solution that reacts into lactic acid can
be passed through the bioreactor. A carbohydrate, such as starch, or other
polysaccharide, such as polydextrose or inulin, or sucrose, lactose, or glu-
cose, or other mono-, di-, or oligosaccharides or a mixture of these may be
used as feedstock (U.S. Patent 5,932,455, 1999, U.S. Patent 4698303, 1987).
D. Application of Immobilized Cells

An appreciable amount of work has been devoted to studies of lactic acid
production with immobilized cell systems (Linko et al., 1984; Mehaia and
Cheryan, 1987b; Boyaval and Goulet, 1988; Bassi et al., 1991), but industrial
applications have not been realized so far (Venkatesh et al., 1993).
V. BRIEF HISTORY OF DEVELOPMENT OF POLYLACTIC ACID

(PLA)—A BIODEGRADABLE PLASTIC
The use of lactic acid and lactide to manufacture biodegradable polymers is

well known in the medical industry. Such polymers have been used in the
making of biodegradable sutures, clamps, bone plates, and biologically active
controlled-release devices. The processes developed for the manufacture of
the polymers to be used in medical industry included techniques appropriate
to the need for high purity and biocompatibility in the final polymer product.
In addition, these processes were developed to yield small quantities of poly-
mers with high costs, with less emphasis given to cost and yield. However,
viable and competitive processes for the continuous manufacture of puri-
fied lactide and lactide polymers from lactic acid, having physical properties
suitable for replacing the present petrochemical-based plastics used in non
medical applications, were not developed till the 1990s. It is a well-known
fact that lactic acid undergoes a condensation reaction to form polylactic
acid when water is removed by evaporation or other means. However, the
resulting polylactic acid was found to be a low-molecular-weight polymer
with very limited application based on physical properties. The low molecu-
lar weight of the polymer was attributed to the competing depolymerization
reaction in which the cyclic dimer of lactic acid, referred to as lactide, is gen-
erated. The rate of polymerization reaction gradually reduces as the polymer
chain length increases, and ultimately it equals the rate of depolymerization,

which effectively limits the molecular weight of the polymer. It was also ob-
served that high-molecular-weight polymer could be manufactured from the
lactide that is generated by the depolymerization of lactic acid. Lactic acid
exists in two optically active isomers, L and D. It also exists as a recemic
mixture where D-lactic acid and L-lactic acid are present in equal propor-
tion. Depending on the type of lactic acid, L- or D- or LD-actide is generated.
The chiral purity of the lactic acid is important with respect to the needs of
industrial applications. For polylactic acid applications, the chiral purity of
the lactic acid has a strong influence on the properties of the polymer. The
chiral purity of the polymer controls the ability of the polymer to crystal-
lize. In some instances, polymers with controlled amounts of crystallinity are
desired in order to get polymer properties that are advantageous in an indus-
trial application—for example, to raise the heat distortion temperature of the
polymer. Other advantages of controlled polymer crystallinity relate to the
storage, transfer, and processing of polylactic acid resins into fibers, nonwo-
ven fabrics, films, and other end products. Lactic acid currently used in food
applications has chiral purity requirements greater than 95%, generally with
a preference for the L form. The chiral purity of lactic acid is also important
for end products such as pharmaceuticals and other medical devices where
lactic acid is a starting material. The term “95% chiral purity” means 95% of
the lactic acid/lactate content is one the of two possible enantiomers. It was
soon recognized that high-molecular-weight polylactide of desired physical
properties could be manufactured by purification of lactide prior to polymer-
ization. The purification of lactide could be carried out using solvent extrac-
tion and recrystallization of lactide. However, these processes were known
to have poor yields and were associated with substantial loss of material in
recrystallization steps. These facts imposed limitations on the commercial-
ization of these processes. The real breakthrough in lactide polymerization
was achieved in the 1990s, when P. Gruber developed a continuous pro-
cess for lactide preparation, purification, and subsequent polymerization to
polylactide (U.S. Patents 6,326,458, 2001; and 5,357,035, 1994). Cargill, Inc.,
(Minneapolis), USA, has commercialized the process . In recent years many
multinationals are in the process of commercialization of PLA production. A
chronological account of polylactide development on an international level
is presented in Table 2.
Polylactic acid is a multifunctional thermoplastic that can be processed
into staple fibers (e.g., carpet fibers), spinning fibers in woven applications
to replace (or in blends with) cotton, wool, and polyesters, extruded films
for wrappings, injection and thermo-molded products such as polyethylene,
propylene, and styrene foam products, and thermo-formed plastics such as
eating utensils, coatings, and others. Polylactic acid is completely recyclable
and is the only major polymer that slowly but totally biodegrades during
composting. The use of polylactic acid as a mass polymer, until now, has been
TABLE 2. Polylactic Acid Development
Researcher/institution/industry,
international status Year Salient development
Carothers 1932 Polymerization of lactic acid in

solvent under high vacuum
produced polymer with too low
melting point
Bonsigore P.V. et al. 1992 PLA as alternative binder for
cellulosic nonwovens
University of Tennessee, 1993 Spun-laid and melt-blown
Knoxville nonwoven based on PLA
Kanebo (Japan) 1994 and 1998 Poly-L-lactide Lactron
R fiber and
spun-laid nonwoven (2000 tpa to

3000 tpa)
BBA France 1997 Disclosed non woven webs and
laminates made of 100% PLA
Galactic Laboratories (Belgium) 1999 Excellent overview of polylactic acid
polymers concluding that there
would be 3,90,000 tonnes of PLA
polymers production by 2008 at a
price of $2/kg
Cargill Dow Polymers LLC 2000, 2003 Production of 4000 tpa of PLA
polymer–Eco PLATM (now Nature
worksTM ), 140,000 MT/annum
NKK (Japan), Kuraray (Japan), 2001 LACEATM , HaibonTM , Lactron R -PLA
Dai-Nippan, Ink Polymers, based polymers

Showa Polymers, Shimadzu
Corp., and Mitsui Totasue,
Shinawa (Japan)
limited due to the high costs associated with its production, primarily energy
costs, making it uncompetitive with similar nonbiodegradable petroleum-
based polymers and polyesters.
VI. PRODUCTION PROCESSES FOR POLYLACTIDE POLYMER
The diagrammatic representation of PLA production in general is depicted

in Figure 7. There are two major routes of producing polylactic acid directly
from the lactic acid monomer. The first route involves the removal of water
of condensation by using a solvent under high vacuum and temperature.
This approach is currently used, for example, by Mitsui Toatsu Chemicals
to produce a low- to intermediate-molecular-weight polymer. In an alterna-
tive route, which is considered to be the classical approach of producing
polylactic acid, water is removed under milder conditions directly from lactic
acid, without using a solvent, to produce a cyclic (ring closing) intermediate
dimer referred to as “dilactic acid.” This dimer is then purified under vacuum
distillation and then “ring-opening” polymerization is accomplished using
FIGURE 7. Block diagram for the production of polylactic acid (PLA), a green polymer.
heat, without solvent, to produce the polylactic acid. This “ring-opening”

method of producing polylactic acid is currently used worldwide and is the
subject of many patents and other literature. This process, however, suffers
from long reaction times and high temperatures and the formation of a num-
ber of side reactions and by-products. It usually results in a low chemical
yield of 50% to 55% for the polylactic acid polymer (on the basis of lactic
acid).
Recently a third route of producing polylactic acid has been patented
and is now being commercially practiced by Cargill. This process relies
on the initial production of an impure and low-molecular-weight polylac-
tic acid/polylactide polymer (sometimes referred as oligomer) as a feedstock
in the production of polylactic acid. This impure polymer must then be de-
polymerized using additional energy steps in order to achieve a more pure
polylactic acid/polylactide polymer. These steps are also energy-intensive
FIGURE 8. Production of polylactide (PLA) polymer from lactic acid.
and therefore result in a high production cost associated with producing

polylactic acid. The diagrammatic representation of this process is shown in
Figure 8.
Yet another process of producing dilactic acids or dimers and subse-
quently producing polylactic acid avoids such energy-intensive steps as de-
scribed in the Cargill process. This particular method uses aminium lactate
salt (crystal) instead of an impure polylactic acid as a starting material for the
production of dilactic acids or dimers. It describes the use of organic amines

(technically called heterocyclic amines, for example, Piperazine) within the
lactic acid fermentation broth to produce aminium lactate (salts). Though
aminium lactate salts are referred to specifically, other salts such as ammo-
nium lactate salts may also be produced and used in such a process. Lactate
salts have lower melting points, from 80 to 150◦ C, and can dissociate in the
presence of catalysts (acetonitrile, dioxan, ethylene glycol monoethylether,
dimethyl sulfoxide-d6 ) and low heat to form dilactic acids or dimers. This
process completely avoids the need to first produce impure polylactic acid
polymers as the feedstock in order to produce such dilactic acids. In this
process, however, ultrafiltration and electrocoagulation are used to concen-
trate and extract the lactic acids and lactate salts. The fallacy of this process,
for large-scale processing, lies in the use of the organic amines within the
fermentation broth and the use of ultrafiltration membranes that require high
pressures to remove and separate out the cell mass from the lactic acid salt.
Once the lactic acid is separated from the cell mass, electrocoagulation is
then used to bring about the separation or breakdown of the lactic acid from
the amine salt in order to concentrate it to a minimum of a 45–85% pure lactic
acid. The purer lactic acid is then recontacted with the organic amine once
again, for example, Piperazine, to form the Piperazine salt once again. The
Kamm process, as described, requires unnecessary steps of forming the salt
from the lactic acid in order to achieve a higher concentration of the lactic
acid (45–85%), which then must be recrystallized to form the salt that must
be restructured to form the dilactic acid or dimmer. This process results in the
production of impure dilactic acids and lactate salts (as an interim step), and
the impurities in the lactic acid produced during fermentation within this pro-
cess limit the achievable polymer length. It has recently been reported that
the lactate salts of the Kamm process can, under certain conditions, become
a low-cost and low-energy starting material for the production of polylactic
acid (U.S. Patents 6,667,385 [2003], 6,569,989 [2003], 6,277,951 [2001]).
VII. INTERNATIONAL STATUS
Most of the developed countries have gone for production of PLA on a

commercial scale. Cargill (USA), Minneapolis, MN, Ecochem, Wilmington,
DE, Kanebo (Japan), BBA (France), Di-Nippon (Japan), and Ink Chemical,
Showa Polymers, Shimadzu Corporation, and Mitsui Toatsu (Japan) are ma-
jor international corporate bodies that have gone into the production of PLA.
The other industries in these countries process the produced PLA to different
commercial items. Thus, the production of PLA is in an advanced phase of
commercialization. However, the cost of the produced items based on PLA
is 10- to 12-fold more than for plastic items produced by the conventional
petrochemical-based polymers. The efforts are now directed to minimize the
cost of production and processing of PLA for commercial use. The com-
mercial items made from PLA include packaging materials, computer cases,
paper coatings, fibers, garbage bags, and automobile parts.
VIII. PLA AND THE ENVIRONMENT
PLA is a green plastic that is produced from renewable resource such as plant
starch. It is biodegradable and is likely to minimize the disposal problems.
Thus it can be viewed as an environmentally friendly plastic. The life cycle
of PLA is shown in Figure 9. However, its real impact on the environment
should be assessed in detail with regard to:
r Energy requirement for production and processing of green plastics.

r Substitution of nonrenewable resource base with renewable resource base.
FIGURE 9. Life cycle of PLA polymer.

r Establishment of balance between production of green plastic and ecosys-

tem through the principle of “cradle to grave” without affecting the
environment.
A. Energy Requirement for Production and Processing of PLA

The energy requirement for producing plant-derived plastics gives rise to
a considerable environmental concern, as the process consumes 19 times
more electricity, 22% more steam, and 7 times more water than the chemical
method of manufacturing polystyrene. Fossil crude oil is the main resource
for conventional plastic production, but making plastics from plant material
depends mainly on coal and gas, which are used to power the corn farming
and corn processing industries for production of PLA. Any kind of plant-
based method, therefore, involves switching from a less abundant fuel (oil)
to more abundant one (coal). Such a shift is considered to be a step toward
sustainability. Major concern in this context is that all fossil fuels used to
make PLA from renewable raw materials (corn) are combusted to generate
energy, whereas the petrochemical-based processes incorporate a significant
portion of fossil resource into the final product.
Burning of more fossil fuels will cause global climatic problems by in-
creasing greenhouse gases such as CO2 . Naturally, the level of emission asso-
ciated with the combustion of fossil fuel such as sulfur dioxide is also likely
to be enhanced. This gas contributes to acid rain and therefore is of concern.
Thus, switching from conventional plastics to green plastics requires special
attention to improve air quality and to curtail global warming by reducing
carbon dioxide and other gases in the atmosphere.
The environmental benefit of producing plastic from renewable re-
sources is overshadowed by increase in the energy consumption and gas
emissions. PLA seems to be the only plant-based plastic that has a chance
of becoming competitive in this regard. In spite of the advantages of
PLA over other plant-based green polymers, it’s production is likely to
emit more greenhouse gases than by petrochemical-based conventional
plastics.
In analyzing the energy requirement for production of green plastics
using the route of PLA production and processing, one can depend on the
renewable energy source that can be derived from burning of plant material
or biomass. This may supply and act as an additional source of energy for
the processing of PLA. Emissions generated in this way may be viewed more
favorably than CO2 released by fossil fuels. Burning the carbon content in
the corn stalks would not increase net CO2 in the atmosphere because new
plants growing in the following seasons would absorb an equal amount of
CO2 gas. This is the reason why plant-based plastics do not increase the CO2
level and dioxins when they are incinerated, as in the case of conventional
plastics.
Monsanto and Cargill Dow, USA, have formulated strategies for deriving
energy from biomass. Monsanto proposes to burn all the corm stover that
remains after extraction of plastic, to generate electricity. Thus, it seems that
utilization of biomass-derived electricity is possible and more than enough
to meet the power requirement of PLA extraction.
B. Substitution of Nonrenewable Resource Base With Renewable

Resource Base for Maintaining the Ecological Balance
The PLA polymers are derived from the plant-based materials. Therefore, it is
certain that one conserves the petroleum crude by using the plants, which are
abundant in starch/sugar. However, the conservation of nonrenewable feed-
stock and energy source with renewable is totally dependent on the extent
of fuel energy input and improvement in the production process of PLA with
minimum input of energy that is associated with lesser generation of green-
house gases without disturbing the existing ecological balance. This requires
extensive research and development (R&D) for improving the production
process of PLA and plastics using these polymers. Thus, it is certain that the
conservation of nonrenewable resources is possible only if production of PLA
is achieved through economically and environmentally sound processes, by
adopting appropriate balance strategies for minimizing the consumption of
fossil fuel sources.
C. Establishment of a Balance Between Production of Green Plastics

and Ecosystem by Adoption the Principle of “Cradle to Grave”
Complex polymeric plastic materials with specific and desirable properties
and derived from petrochemical feedstock are nonbiodegradable. This results
in the disturbance of the ecosystem through accumulation in the environ-
ment, and therefore the need for green plastics was realized. The elemental
constituents of green plastics, especially carbon, are processed by the carbon
cycles of the ecosystem without getting accumulated. Carbon in the form of
atmospheric CO2 and compost and manure aris taken up by the plants and
reduced to carbohydrates through photosynthesis. In the case of ultimate dis-
posal, carbohydrate/starch/sugar is recycled back for the production of green
plastics. This process of recycling and reuse in the ecosystem is called the
principle of “cradle to grave” (Figure 10). The PLA even can be fermented to
lactic acid, and the rate for conversion of polylactide with maximum recycle
and reuse can be followed. However, the number of times of recycling of
PLA for reproduction of green polymers is yet to be studied in detail. Thus,
after some time of recycling, the PLA-based items have been processed for
biodegradability. The preliminary studies have indicated that PLA is largely
resistant to attack by microorganisms until and unless it is hydrolyzed at
elevated temperature to reduce the molecular weight before biodegradation
FIGURE 10. “Cradle to grave” concept for PLA.
commences. Claims of biodegradability can therefore only be made where

composting infrastructure facility exists. The data from Cargill Dow, USA,
shows that composting at 60◦ C causes hydrolytic degradation of PLA, which
over 10 days depolymerizes and embrittles the polymer sufficiently for it to
fragment. Complete biodegradation to CO2 occurs over the next 30–40 days
(http://www.Nonwore.co.uk). Cargil Dow pledges to support the develop-
ment of composting infrastructure in those countries that do not have one.
This requires extra expenditure before adopting the process for production
of green plastics. Otherwise, this will create a solid waste disposal problem.
Therefore, the need exists for designing a suitable and efficient composting
system for the green plastic materials prior to switching over from conven-
tional plastics to green ones.
Unfortunately, no single strategy can overcome all the environmental,
technical, and economic limitations of the various manufacturing approaches.
Conventional plastics require fossil fuels as a raw material, but PLA does not.
The conventional plastics are not biodegradable, but they have broader range
of material properties when compared to PLA. Biodegradability, helps to re-
lieve the problem of solid-waste disposal, but degradation gives off green-
house gases, thereby compromising air quality. Although PLA production
uses fewer fossil resources than its petrochemical counterparts, it still re-
quires more energy and emits more greenhouse gases during manufacture.
IX. DISCUSSION
The production of green plastics, energy requirement for production, con-

servation of resources, and the environment are very complex issues. The
choice will ultimately depend on how to prioritize the depletion of fossil re-
sources, emissions of greenhouse gases, land use, solid-waste disposal, and
profitability—all of which are subject to their own interpretation, political
constituencies, and value systems. Regardless of the particular approach to
making plastics, energy use and the resulting emissions constitute the most
significant impact on the environment.
In light of this fact, it is proposed that any scheme to produce plas-
tics should not only reduce greenhouse gas emissions but should also go a
step beyond that, to reverse the flux of carbon into the atmosphere. Accom-
plishing this goal will require finding ways to produce nondegradable plastic
from resources that absorb carbon dioxide from the atmosphere, sequester-
ing the carbon in the ground instead of returning it to the atmosphere. Some
biodegradable plastics may also end up sequestering carbon, because land-
fills, where many plastic products end up, typically do not have the proper
conditions to initiate rapid biodegradation.
If things are viewed in the context of a developing country like India,
the energy crisis is very deep and the shift from conventional fossil energy
sources to renewable energy is very difficult due to constraints of funds and
infrastructure facilities. Therefore, it is very difficult to adopt these processes
for production and use of green plastic-based materials for conservation of
nonrenewable resources by adopting the principle of “cradle to grave.”
X. RESEARCH NEEDS
It is quite evident from this article that production of PLA on a commercial

scale, although fairly established, needs substantial improvements in produc-
tion processes, especially in lactic acid recovery and purification stages, to
make it competitive with petrochemical-based plastics. The areas that warrant
special research attention are:
r Development of acid resistant microbial strains to enhance the lactic acid
yields and to minimize the chemical consumption.
r Development of processes, especially membrane processes, for the con-

tinuous removal of lactic acid from fermentation broths.
r Development of bioreactor systems for fermentation, specifically then
fixed film systems or immobilized culture systems, to enhance the tol-
erance of microorganisms to acid shock loads.
r Development of the recovery and purification processes that include min-
imum numbers of steps and consume minimum energy.
r Minimizing the wastes in order to make PLA truly eco-friendly.
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Production and Recovery of Lactic Acid for Polylactide—An

Article in Critical Reviews In Environmental Science and Technology · September 2005

Atul Vaidya Ram Avtar Pandey

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M Suresh Kumar Tapan Chakrabarti

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Production and Recovery of Lactic Acid

A. N. VAIDYA, R. A. PANDEY, S. MUDLIAR, M. SURESH KUMAR,

In the recent past the ultimate disposability of synthetic plastics has

KEY WORDS: biodegradable plastic, fermentation, lactic acid, life

Address correspondence to A. N. Vaidya, National Environmental Engineering Research

Growing environmental concerns, regulations, and social demands through-

r Utilization of renewable resources that leads to conservation of the

history of development of PLA: types of raw materials used for produc-

II. PROCESSES FOR PRODUCTION OF LACTIC ACID

r Hydrolysis of lactic acid derivatives, for example, esters or nitriles.

TABLE 1. Properties of Lactic Acid

Unreacted or waste lactonitrile may be used as a raw material. In 1963,

CH3 CH2 CH3 + HNO3 + O2 → CH3 CH (NO2 ) COOH (3)

CH3 CH (NO2 ) COOH + H2 O → CH3 CHOHCOOH (4)

The commercial details of these reactions are not available.

B. Fermentation Processes for Lactic Acid Production

r Actual production of lactic acid by fermentation of a carbohydrate source.

Several microorganisms have been isolated and used in the production

I. RAW MATERIALS FOR LACTIC ACID PRODUCTION

r Glucose (dextrose) and glucose syrups of varying qualities as end products

Starch-based raw materials can be obtained from corn (maize), potatoes,

saccharification are achieved, at present by the combined action of different

2. MICROORGANISMS USED IN LACTIC ACID PRODUCTION

Substantial information related to the genetics of lactic acid bacteria and

Lactic acid bacteria have complex nutrient requirements. These com-

In U.S. Patent 6,475,759 (2002), a process for producing lactic acid,

for producing D-lactic acid and L-lactamide, comprising a culture broth of

3. ORGANISMS OTHER THAN LACTIC ACID BACTERIA

A limited number of other microorganisms are capable to produce larger

r Sporolactobacillus inulinus culture produces D-(−)-lactic acid (U.S. Patent

Owing to their common properties, both organisms have been studied

4. BIOCHEMISTRY OF LACTIC ACID PRODUCTION

Review of the literature on fermentative production of lactic acid reveals

If polysaccharides are to be used as raw material, then they have to be

Starch → n(C22 H22 O11 ) → 4nCH3 CHOHCOOH (7)

It is interesting to note that dextrose can also be chemically broken down

At present, lactic acid production from fermentation of starch is com-

III. DOWNSTREAM PROCESSING OF LACTIC ACID

Downstream processing of lactic acid broth is extremely complicated and

Separation of biomass and other solids can be achieved by any conven-

A. Precipitation of Salt of Cation With Strong Acid

FIGURE 1. Schematic for recovery of lactic acid from lactate.

B. Liquid–Liquid Extraction With Simultaneous Lactate Salt Formation

1. Conventional oxygen-bearing hydrocarbons, such as octanol and methyl

fermentation liquors without formation of by-product salts. Such a process

C. Simultaneous Acidification and Esterification With Alcohol

FIGURE 2. General schematic for liquid–liquid extraction.

In lactic acid purification, it is known that lactic acid can be reacted

FIGURE 3. Schematic for recovery of lactic acid by esterification.

D. Direct Removal of Lactic Acid from Broth by Advanced Separation

FIGURE 4. General schematic of lactic acid separation by ion exchange.