Production and Recovery of Lactic Acid For Polylactide

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Critical Reviews in Environmental Science and Technology

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Production and Recovery of Lactic Acid for PolylactideAn Overview

A. N. Vaidya a; R. A. Pandey a; S. Mudliar a; M. Suresh Kumar a; T. Chakrabarti a; S. Devotta a a National Environmental Engineering Research Institute, Nehru Marg Nagpur, India Online Publication Date: 01 September 2005
To cite this Article Vaidya, A. N., Pandey, R. A., Mudliar, S., Kumar, M. Suresh, Chakrabarti, T. and Devotta, S.(2005)'Production and
Recovery of Lactic Acid for PolylactideAn Overview',Critical Reviews in Environmental Science and Technology,35:5,429 467
To link to this Article: DOI: 10.1080/10643380590966181 URL: http://dx.doi.org/10.1080/10643380590966181
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Critical Reviews in Environmental Science and Technology, 35:429467, 2005 Copyright Taylor & Francis Inc. ISSN: 1064-3389 print / 1547-6537 online DOI: 10.1080/10643380590966181
Production and Recovery of Lactic Acid for PolylactideAn 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
Downloaded By: [Canadian Research Knowledge Network] At: 19:52 19 October 2009
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 ultimate disposability, resource utilization, and conservation. Traditionally, all plastics have been manufactured from nonrenewable petroleum resources, and these plastics are nonbiodegradable. Conventional disposal methods include incineration and secured landll, which are associated with many environmental problems, such as production of dioxins. The continued depletion of landll 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 production 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 production 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
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I. INTRODUCTION
Growing environmental concerns, regulations, and social demands throughout 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 utilization, 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 realized for shifting the policies toward minimizing the resource consumption, and employing alternative renewable resources for fuels and chemicals including synthetic plastics. As a result, research in the recent past is directed toward the development of alternative processes for the production of plastics utilizing renewable raw material sources and thereby conserving nonrenewable 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 degradable. The existing disposal methods, therefore, include secured landll and incineration. The disposal of plastic materials by incineration generates air pollutants/wastes of environmental concern, namely, dioxins, toxic hydrocarbons, and so on. The continued depletion of landll space is posing severe restriction on the secured landll 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 production 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 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 nonrenewable resource base.
Production and Recovery of Lactic Acid for Polylactide
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history of development of PLA: types of raw materials used for production of PLA via lactic acid, production and recovery processes available, environmental benets derived from the use of PLA, and probable impacts 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 scientic interest only, and very few have been commercialized. These reactions can be classied broadly in six categories:
r r r r r r
Hydrolysis of lactic acid derivatives, for example, esters or nitriles. Hydrolysis of other 2-substituted propionic acids. Decarboxylation of certain derivatives of 2-methylmalonic acid. Reduction. Oxidation. Rearrangement and disproportionation.
TABLE 1. Properties of Lactic Acid 50-21-5, 79-33-4 (L), 10326-41-7 (D) 200-018-0 CH3 CH(OH)COOH 90.08 2918.11 Oral rat LD50: 3543 mg/kg 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 Specic gravity 1.2 Solubility in water Miscible NFPA ratings Health 3, Flammability 1, Reactivity 1 Flash point 112 C Stability Stable under ordinary conditions Product identication CAS no. EINECS no. Formula Mol. wt. H.S. code Toxicity Synonyms
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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 treatment, however, there is no practical advantage, as lactic acid is the raw material for these derivatives. Lactonitrile and lactic acid nitrate are the important 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: CH3 CHO + HCN CH3 CHOH CN
Acetaldehyde
HCl
(1)
lactonitrile
CH3 CHOH CN + 2H2 O CH3 CHOH COONH4

Ammonium lactate
HCl
(2)
CH3 CHOHCOOH
lactic acid
Unreacted or waste lactonitrile may be used as a raw material. In 1963, Monsanto Chemical Company installed the rst commercial the plant in United States that produced technical-grade lactic acid (55 to 85% w/w). In another route, propene is converted into -nitropropionic acid by nitric acid in the presence of oxygen. -Nitropropionic is further hydrolyzed to lactic acid. Reactions involved can be expressed as: CH3 CH2 CH3 + HNO3 + O2 CH3 CH (NO2 ) COOH -Nitropropionic acid CH3 CH (NO2 ) COOH + H2 O CH3 CHOHCOOH
Lactic acid
(3) (4)
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.
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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 fermentation 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, unreacted materials, nutrients, microorganisms, and so on. Such a fermentation broth cannot be utilized for the further use, and therefore additional processing steps are required to obtain pure lactic acid. The recent research work in lactic acid production comprises mainly downstream processing, and various 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 requirements besides being available at reasonable prices, since these are critical for the further purication of the produced lactic acid. The choice of raw materials largely depends on the intended application and the respective costs of product purication. Various readily available mono- and disaccharide materials are traditional substrates for lactic acid manufacturing. These are
r Glucose (dextrose) and glucose syrups of varying qualities as end products r Maltose as a product of specic enzymatic starch conversion applying r Sucrose as end product, intermediate products (syrups, juices), and byr 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 common lactic acid bacteria, except Lactobacillus amylophilus and L. amylovorus. Starch hydrolysis can be performed by either chemical or enzymatic methods, with chemical methods being abandoned for some time. Since maltose is the main product of enzymatic hydrolysis, only a limited number of organisms are suitable of the fermentation process. Starch liquefaction and product (molasses) of beet and cane sugar production. amylases and -amylases from barley malt or other sources. of starch conversion processes applying enzymes such as glucoamylases.
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saccharication are achieved, at present by the combined action of different -amylases of bacterial origin and of fungal glucoamylases. Sucrose-derived raw materials are also suitable as raw materials for lactic 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 purication procedures have impeded the successful utilization of whey. The fact that whey represents a considerable environment load has stimulated the development of modern technologies of whey concentration and fractionation, such as ultraltration and electrodialysis. These, in turn, have exerted a strong stimulus on fermentation research laboratories, as may be seen from the recent 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 glucose 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 respective 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 optimal growth of mesophilic lactic acid bacteria is from 28 to 45 C and that of thermophilic lactic acid bacteria is 4562 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. According 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).
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Lactic acid bacteria have complex nutrient requirements. These comprise 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 Lactobacillus delbrueckii, now designated as Lactobacillus delbrueckii ssp. Delbrueckii (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. Bulgaricus 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 depends on the way of starch hydrolysis: If - and -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 saccharication with -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 desirable 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 tolerance 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
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acid. The targets are increased growth rates, improved pH resistance, and increased yields of lactic acid. These targets are partially achieved by efforts through genetic engineering, control of metabolic activity by appropriate culturing techniques, and development of acid resistant mutants. A notable patent (U.S. Patent 6,660,515, 2003) in this regard provides methods 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 lactic acid bacteria as helper organisms and lactic acid bacterial starter culture strains. Useful helper organisms are Lactococcus strains, which are defective with respect to pyruvate formate-lyase (P) and/or lactate dehydrogenase (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 rst 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 lactic acid bacteria including Lactococcus lactis that are defective in pyruvate formate-lyase production and/or in their lactate dehydrogenase (Ldh) production and methods of isolating such mutants or variants are provided. The mutants are useful in the production of food products or in the manufacturing of compounds such as diacetyl, acetoin, and acetaldehyde and as components of food starter cultures, in particular Lactococcus lactis DN223 deposited under accession number DSM 11036. Accordingly, the invention provides a method of isolating a pyruvate formatelyase (P) defective lactic acid bacterium, with the method comprising the steps of 1. Providing a wild-type lactic acid bacterial strain that under aerobic conditions 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
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for producing D-lactic acid and L-lactamide, comprising a culture broth of a microorganism capable of asymmetric hydrolysis of DL-lactamide belonging to the genus Alcaligenes, Pseudomonas, Agrobacterium, Brevibacterium, Acinetobacter, Corynebacterium, Enterobacter, Micrococcus, or Rhodococcus, 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 sufcient 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 commercial lactic acid production (U.S. Patent 2,132,712, 1938; Prescott and Dunn, 1959) because this organism is able to convert several sugars with appreciable 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 Rhizopus 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 published 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 organism (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 products such as lactic acid. The organisms are cultured in a rst 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).
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A. N. Vaidya et al. BIOCHEMISTRY OF LACTIC ACID PRODUCTION
4.
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 Pyruvic acid Latic acid
(5)
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 Starch n(C6 H12 O6 ) 2nCH3 CHOHCOOH
Dextrose Lactic acid Hydrolysis Bacteria
(6)
Starch n(C22 H22 O11 ) 4nCH3 CHOHCOOH

Maltose Lactic acid
(7)
(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:
439
(10)
At present, lactic acid production from fermentation of starch is commonly used for commercial purpose. Dairy wastes contain lactose and sugar, and beverage industry wastes contain sucrose. Therefore, if proper fermentation processes are developed to produce lactic acid from waste sucrose or lactose, a twofold objective of rendering wastes into a resource and minimizing 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 purication 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 standard method. However, the recovery and purication of the lactic acid can be broadly classied 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 Acidication 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 Liquidliquid extraction with simultaneous lactate salt formation with r Simultaneous acidication and esterication with alcohol followed by r Direct removal of lactic acid from broth by advanced separation methods
such as adsorption, membrane separations, and ion exchange. back-extraction with water. strong base and back-extraction of lactic acid with water.
r Concentration of lactic acid.

Separation of biomass and other solids can be achieved by any conventional method. Acidication of broth is necessary to break the lactate into
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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 fermentation, then acidication 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 esterication of lactic acid with alcohols, by liquidliquid extraction, or by adsorption. Membrane processes, distillation, evaporation, crystallization, and so on can achieve the concentration of the separated lactic acid. Separation and purication 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 purication 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 ltration with thorough washing of the lter cake. The combined liquids are vacuum evaporated. Residual amounts of gypsum precipitating in the concentrated lactic acid solution are ltered off together with coloring substances, which may be adsorbed onto activated carbon. Further purication is achieved by passing the solution through ionexchange 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 using zinc lactate or magnesium lactate instead. Purications 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, rst 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 rst disadvantage of this method is the high sulfuric acid consumption and above all the production 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 lactic 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 treatment with ferrocyanide or hexaferrocyanide salts to remove the copper and
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iron ions, the depolarization of the crude lactic acid thus obtained with activated charcoal, and after the subsequent purication 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 purication steps and the handling of toxic chemicals. The latest patented process for the preparation of high-purity lactic acid from an aqueous solution containing 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.
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B. LiquidLiquid 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 downstream process in many patents and publications. Liquidliquid extraction of lactic acid involves addition of suitable solvent to the dilute aqueous solution 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 coefcient, which is the ratio of the lactic acid concentrations 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 coefcients for the rst type of extractants are very low, while those for the second type extractants are not high enough to extract lactic acid efciently. Extractants from the third type, high-molecular-weight amines, are the most effective ones. The high basicity of amines results in reactive extraction of lactic acid, which increases the extraction efciency substantially. Any solvent that has a high enough capacity 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, extraction alone does not economically produce lactic acid of high enough purity. Several extractants such as isopropyl ether (U.S. Patent 1,906,068, 1931) , -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 membranes 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 longchain trialkyl amine of low basicity, such as tridodecylamine, using various tridodecylamine solutions in n-dodecanol. It was found that extraction of lactic 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
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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 911. 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 signicantly 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
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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 byproduct 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 efciency of the amine, and are usually referred to as enhancers. Alkanols provide very efcient 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 Acidication and Esterication With Alcohol Followed by Back-Extraction With Water
Another method of lactic acid purication is esterication 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 lactate salts exist in the broth. Therefore, substantially complete recovery and purication of lactic acid require acidulation with a strong acid that releases lactic acid from its salt to react with alcohol. Esterication is performed in countercurrent operation with concomitant separation of the volatile ester and subsequent de-esterication with water in a second stage to yield free lactic acid and alcohol to be reintroduced into the system. This method is
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FIGURE 2. General schematic for liquidliquid 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 uid with higher contents of inorganic compounds.
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In lactic acid purication, 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 acidication of an aqueous solution containing ammonium lactate in the presence of an alcohol, having four to ve carbon atoms, being used as a diluent, with sulfuric acid (or any other strong acid), removal of water from the acidied 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 difculty 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 ve carbon atoms (namely, n-butanol in this case) in order to obtain sufciently coarse ammonium sulfate crystals to facilitate their separation by simple ltration 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 1butyl lactate by dehydrating 70% lactic acid with excess 1-butanol at 117 C, followed by the addition of HCl catalyst, and reuxing and esterication 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 acidied crude fermentation broth with 1-butanol, followed by esterication of the extract phase. BASF (EP 159-285) considers the production of isobutyl lactate by extraction of an acidied crude fermentation broth with isobutanol, followed by esterication of the extract phase, which was then distilled in vacuum to give puried 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 alcohol, and a concentrated fermentation broth that contains mainly basic salts of lactic acid, which react to form a crystal precipitate comprising of the basic
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salts of the strong acid and an impure lactate ester of the alcohol; (2) removing 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 esterication suffer in practice from succession of numerous and cumbersome steps that make the purication of lactic acid from an aqueous solution containing lactic acid in the form of salt(s) long and tedious. A general ow diagram for lactic acid recovery by esterication is shown in Figure 3.
FIGURE 3. Schematic for recovery of lactic acid by esterication.
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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 purication steps, has been proposed for primary separation of lactic acid from fermentation 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 possible 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 rst 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 extraction has been developed by Eyal et al. (U.S. Patent 6,320,077, 2001) for the recovery of puried 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 anion exchanger to form a substantially water-immiscible phase comprising of an anion exchangerlactic acid adduct; (2) effecting a condensation reaction 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 lactic 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 adsorption 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 purication of lactic acid. Currently this process has two disadvantages: high cost and a product of intermediate purity. Other methods used for recovery and purication of lactic acids are membrane processes. Membrane processes may include microltration, ultraltration, nanoltration or reverse osmosis or combinations thereof (U.S.
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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 unsatised need for a simpler and cheaper process that permits the separation, concentration, and purication of a high-purity lactic acid with an excellent yield from an aqueous solution containing lactic acid in the form of salt(s).
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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 manufacturing lactic acid in a classical way is described in Figure 6.
FIGURE 6. Block diagram for calcium lactate process.
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The raw material (glucose, sucrose) is brought to a sugar concentration of 120180 g L1 . 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 concentrations between 1 and 10 g L1 , 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 uid by soluble compounds (heavy metals etc.) that would complicate the further purication steps. In the current industrial scenario, suitably lined concrete or stainlesssteel vessels are preferred. Conventional stirrers perform gentle agitation. As the fermentation is conducted at temperatures greater than 40 C, heating has to be provided in the rst stages, and cooling as soon as the heat is generated by the fermentation itself. Maintaining relatively high temperatures of upto 50 C for L. delbrueckii or similar strains reduces the probability of contaminations by, for example, butyric acid forming anaerobic bacteria. Sterile calcium carbonate, preferably as powdered chalk, is added either 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 26 days, depending on the concentration of the used carbon source. In calcium lactate fermentations, the upper limits of sugar concentration 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 L1 ) 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 sugars 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 +
Lactic acid
CaCO3 (CH3 CHOHCOO)2 Ca + H2 O + CO2 Calcium lactate Calcium carbonate (11) (12)
(CH3 CHOHCOO)2 Ca + H2 SO4 2CH3 CHOHCOOH + CaSO4

Sulfuric acid Lactic acid gypsum
Usually, conversion yields of 8595% (calculated on the basis of sugars) 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
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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 applies 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 esterication 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
Lactic acid Ammonia Ammonium lactate
(13) (14)
CH3 CHOHCOOONH4 + H2 SO4 CH3 CHOHCOOH + NH3
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 ow rates, productivities reached up to about 50 g L1 h1 (Richter et al., 1987). Such high productivities, of course, were considered to be interesting for the conversion of whey, especially in places with high accumulation 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 processes 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
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factors is very small. Often the costs of nutrients are more than the sugar feedstock. 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 production 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 glucose, 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 nal polymer product. In addition, these processes were developed to yield small quantities of polymers with high costs, with less emphasis given to cost and yield. However, viable and competitive processes for the continuous manufacture of puried 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 molecular weight of the polymer was attributed to the competing depolymerization reaction in which the cyclic dimer of lactic acid, referred to as lactide, is generated. The rate of polymerization reaction gradually reduces as the polymer
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chain length increases, and ultimately it equals the rate of depolymerization, which effectively limits the molecular weight of the polymer. It was also observed 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 proportion. 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 inuence on the properties of the polymer. The chiral purity of the polymer controls the ability of the polymer to crystallize. In some instances, polymers with controlled amounts of crystallinity are desired in order to get polymer properties that are advantageous in an industrial applicationfor 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 bers, nonwoven fabrics, lms, 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 purication of lactide prior to polymerization. The purication of lactide could be carried out using solvent extraction 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 commercialization of these processes. The real breakthrough in lactide polymerization was achieved in the 1990s, when P. Gruber developed a continuous process for lactide preparation, purication, 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 bers (e.g., carpet bers), spinning bers in woven applications to replace (or in blends with) cotton, wool, and polyesters, extruded lms 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
Production and Recovery of Lactic Acid for Polylactide TABLE 2. Polylactic Acid Development Researcher/institution/industry, international status Carothers Year 1932 Salient development
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Bonsigore P.V. et al. University of Tennessee, Knoxville Kanebo (Japan)

1992 1993 1994 and 1998 1997 1999
BBA France Galactic Laboratories (Belgium)
Cargill Dow Polymers LLC NKK (Japan), Kuraray (Japan), Dai-Nippan, Ink Polymers, Showa Polymers, Shimadzu Corp., and Mitsui Totasue, Shinawa (Japan)
2000, 2003 2001
Polymerization of lactic acid in solvent under high vacuum produced polymer with too low melting point PLA as alternative binder for cellulosic nonwovens Spun-laid and melt-blown nonwoven based on PLA Poly-L-lactide Lactron R ber and spun-laid nonwoven (2000 tpa to 3000 tpa) Disclosed non woven webs and laminates made of 100% PLA 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 Production of 4000 tpa of PLA polymerEco PLATM (now Nature worksTM ), 140,000 MT/annum LACEATM , HaibonTM , Lactron R -PLA based polymers
limited due to the high costs associated with its production, primarily energy costs, making it uncompetitive with similar nonbiodegradable petroleumbased 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 rst 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 alternative 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 puried under vacuum distillation and then ring-opening polymerization is accomplished using
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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 number 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 polylactic acid/polylactide polymer (sometimes referred as oligomer) as a feedstock in the production of polylactic acid. This impure polymer must then be depolymerized using additional energy steps in order to achieve a more pure polylactic acid/polylactide polymer. These steps are also energy-intensive
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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 subsequently producing polylactic acid avoids such energy-intensive steps as described in the Cargill process. This particular method uses aminium lactate salt (crystal) instead of an impure polylactic acid as a starting material for the
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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 specically, other salts such as ammonium 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 rst produce impure polylactic acid polymers as the feedstock in order to produce such dilactic acids. In this process, however, ultraltration and electrocoagulation are used to concentrate 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 ultraltration 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 4585% 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 (4585%), 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 process 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 major 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
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cost of production and processing of PLA for commercial use. The commercial items made from PLA include packaging materials, computer cases, paper coatings, bers, 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.
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r Establishment of balance between production of green plastic and ecosystem 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 plantbased 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 signicant portion of fossil resource into the nal product. Burning of more fossil fuels will cause global climatic problems by increasing greenhouse gases such as CO2 . Naturally, the level of emission associated 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 benet of producing plastic from renewable resources 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, its 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.
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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 feedstock 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 greenhouse 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 specic and desirable properties and derived from petrochemical feedstock are nonbiodegradable. This results in the disturbance of the ecosystem through accumulation in the environment, 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 disposal, 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
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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 sufciently for it to fragment. Complete biodegradation to CO2 occurs over the next 3040 days (http://www.Nonwore.co.uk). Cargil Dow pledges to support the development 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 efcient composting system for the green plastic materials prior to switching over from conventional 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.
463
The conventional plastics are not biodegradable, but they have broader range of material properties when compared to PLA. Biodegradability, helps to relieve the problem of solid-waste disposal, but degradation gives off greenhouse gases, thereby compromising air quality. Although PLA production uses fewer fossil resources than its petrochemical counterparts, it still requires more energy and emits more greenhouse gases during manufacture.
IX. DISCUSSION
The production of green plastics, energy requirement for production, conservation of resources, and the environment are very complex issues. The choice will ultimately depend on how to prioritize the depletion of fossil resources, emissions of greenhouse gases, land use, solid-waste disposal, and protabilityall 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 signicant impact on the environment. In light of this fact, it is proposed that any scheme to produce plastics should not only reduce greenhouse gas emissions but should also go a step beyond that, to reverse the ux of carbon into the atmosphere. Accomplishing this goal will require nding ways to produce nondegradable plastic from resources that absorb carbon dioxide from the atmosphere, sequestering the carbon in the ground instead of returning it to the atmosphere. Some biodegradable plastics may also end up sequestering carbon, because landlls, 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 difcult due to constraints of funds and infrastructure facilities. Therefore, it is very difcult 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 production processes, especially in lactic acid recovery and purication 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.
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r Development of processes, especially membrane processes, for the conr Development of bioreactor systems for fermentation, specically then
xed lm systems or immobilized culture systems, to enhance the tolerance of microorganisms to acid shock loads. r Development of the recovery and purication processes that include minimum numbers of steps and consume minimum energy. r Minimizing the wastes in order to make PLA truly eco-friendly. tinuous removal of lactic acid from fermentation broths.
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Production and Recovery of Lactic Acid For Polylactide - An Overview

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Production and Recovery of Lactic Acid for PolylactideAn Overview

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Production and Recovery of Lactic Acid for PolylactideAn Overview

CH3 CHOH CN + 2H2 O CH3 CHOH COONH4

The commercial details of these reactions are not available.

B. Fermentation Processes for Lactic Acid Production

Production and Recovery of Lactic Acid for Polylactide

RAW MATERIALS FOR LACTIC ACID PRODUCTION

MICROORGANISMS USED IN LACTIC ACID PRODUCTION

Production and Recovery of Lactic Acid for Polylactide

Production and Recovery of Lactic Acid for Polylactide

ORGANISMS OTHER THAN LACTIC ACID BACTERIA

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

A. N. Vaidya et al. BIOCHEMISTRY OF LACTIC ACID PRODUCTION

CH3 COCOOH CH3 CHOHCOOH Pyruvic acid Latic acid

Starch n(C22 H22 O11 ) 4nCH3 CHOHCOOH

Production and Recovery of Lactic Acid for Polylactide

III. DOWNSTREAM PROCESSING OF LACTIC ACID

r Concentration of lactic acid.

A. Precipitation of Salt of Cation With Strong Acid

Production and Recovery of Lactic Acid for Polylactide

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

Production and Recovery of Lactic Acid for Polylactide

Production and Recovery of Lactic Acid for Polylactide

FIGURE 2. General schematic for liquidliquid extraction.

Production and Recovery of Lactic Acid for Polylactide

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

Production and Recovery of Lactic Acid for Polylactide

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

FIGURE 5. General schematic for lactic acid separation by membranes.

FIGURE 6. Block diagram for calcium lactate process.

Production and Recovery of Lactic Acid for Polylactide

(CH3 CHOHCOO)2 Ca + H2 SO4 2CH3 CHOHCOOH + CaSO4

B. Ammonium Lactate Proces

CH3 CHOHCOOONH4 + H2 SO4 CH3 CHOHCOOH + NH3

C. Continuous Fermentation Process

Production and Recovery of Lactic Acid for Polylactide

D. Application of Immobilized Cells

V. BRIEF HISTORY OF DEVELOPMENT OF POLYLACTIC ACID (PLA)A BIODEGRADABLE PLASTIC

Bonsigore P.V. et al. University of Tennessee, Knoxville Kanebo (Japan)

1992 1993 1994 and 1998 1997 1999

BBA France Galactic Laboratories (Belgium)

2000, 2003 2001

VI. PRODUCTION PROCESSES FOR POLYLACTIDE POLYMER

Production and Recovery of Lactic Acid for Polylactide

FIGURE 8. Production of polylactide (PLA) polymer from lactic acid.

VII. INTERNATIONAL STATUS

Production and Recovery of Lactic Acid for Polylactide

VIII. PLA AND THE ENVIRONMENT

FIGURE 9. Life cycle of PLA polymer.

A. Energy Requirement for Production and Processing of PLA

Production and Recovery of Lactic Acid for Polylactide

FIGURE 10. Cradle to grave concept for PLA.

Production and Recovery of Lactic Acid for Polylactide

r Development of acid resistant microbial strains to enhance the lactic acid

Production and Recovery of Lactic Acid for Polylactide

Production and Recovery of Lactic Acid for Polylactide

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