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TUTORIAL REVIEW

Ethyl lactate as a solvent: Properties, applications and production processes a review

Carla S. M. Pereira, Viviana M. T. M. Silva* and Al rio E. Rodrigues
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Received 6th May 2011, Accepted 11th July 2011 DOI: 10.1039/c1gc15523g Ethyl lactate is an environmentally benign solvent with effectiveness comparable to petroleum-based solvents. The worldwide solvent market is about 30 million pounds per year, where ethyl lactate can have an important share. It is considered a chemical commodity and has attracted much attention in recent years, since it is formed by the esterication reaction of ethanol and lactic acid, which can be generated from biomass raw materials through fermentation. In this work, an overview regarding the main properties and applications of ethyl lactate, as well as its synthesis and production processes, with a particular emphasis on reactive/separation processes, is presented.

1.

Introduction

Organic esters are a very important class of chemicals having applications in a variety of areas in the chemical industry, such as perfumes, avours, pharmaceuticals, plasticizers, solvents and intermediates.1 Ethyl lactate is an important monobasic ester, also known as lactic acid ethyl ester (IUPAC name: Ethyl (S)2-hydroxypropanoate), with molecular formula C5 H10 O3 (see Fig. 1). It is a clear to slightly yellow liquid, and it is found naturally in small quantities in a wide variety of foods, including wine, chicken, and some fruits. Ethyl lactate can be either in the levo (S) or dextro (R) forms, and it is industrially produced as a racemic mixture through a reversible reaction between ethanol and lactic acid, wherein water is a by-product. Lactic acid itself is a very important chemical with applications in the food, pharmaceutical and cosmetic industries. It is also used as a monomer for the manufacture of biodegradable polymers, as substitutes for traditional petrochemical polymers. Lactic acid has been produced through both chemical synthesis or fermentation routes. This last process is the most common,2 however, lactic acid derived from fermentation broths requires extensive purication processes that should be inexpensive and environmentally friendly. Ethyl lactate hydrolysis is one of the methods used to obtain pure lactic acid.3,4 Ethyl lactate has attracted much attention in recent years, which is reected in the number of articles published, as shown in Fig. 2. This is probably due to the environmental movement that emerged in the 1970s (United Nations Conference on the Human Environment at Stockholm in 1972). Chemical legisla-

Fig. 1

The molecular structure of ethyl lactate.

Laboratory of Separation and Reaction Engineering (LSRE), Associate Laboratory LSRE/LCM, Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr Roberto Frias s/n, 4200-465, Porto, Portugal. E-mail: viviana.silva@fe.up.pt; Fax: +351 225081674; Tel: +351 225081489

tion and environmental regulation were mainly nation based, until the 1980s. Since then, with the increase of international chemical trade and the knowledge of the impact of global trade on the environment, international environmental treaties, directives, and conventions have emerged.5 Moreover, it was in the 1980s that environmental protection was connected with economic development, leading to dissemination of sustainable development as a means to encourage the integration of policies across sectors (Rio Declaration on Environment and Development and Johannesburg Declaration on Sustainable Development, informally known as Earth Summit 1992 and 2002, respectively). Furthermore, with the Yom Kippur War (1973) and the subsequent Arab Oil Embargo, the Iranian Revolution (between November 1978 and June 1979), and the IraqIran War (1980), crude oil production declined, and, consequently, the crude oil price increased drastically, from 3 USD per barrel in 1972 up to 35 USD in 1981. More recently, the PDVSA strike (Venezuela, 20022003) and the Iraq War This journal is The Royal Society of Chemistry 2011

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Carla Pereira was born in 1980 in Coimbra, Portugal. She obtained her Ph.D. degree in Chemical and Biological Engineering from Porto University (FEUP) in 2009 working on process intensication for the sustainable production of ethyl lactate based on membrane and chromatographic reactors under the supervision of Professor Al rio Rodrigues and Dr Viviana Silva. This work was developed in the Laboratory of Separation and Reaction Engineering, where she is currently working as a post-doctoral fellow. Her research interests focus on integrated reaction and separation processes, particularly, simulated moving bed reactor and pervaporation membrane reactors, for diesel additives and green solvents production. Viviana Silva (1974) received her Ph.D. in Chemical Engineering from University of Porto (Portugal) in 2003. In 2001, she was Assistant Professor at Instituto Polit ecnico de Braganc a (Portugal) and, in 2006, she joined Fluidinova (Portugal) as Group Leader. In November 2007, she returned to the Associated Laboratory LSRE/LCM (University of Porto) as Assistant Researcher. Her primary interest is the process intensication of green fuels and solvents, being awarded with the 1st prize IChemE Awards for Innovation & Excellence 2008, in the category ABB Global Consulting Award for Sustainable Technology. Since 2006, she is also developing continuous processes for the production of nanoparticles and microcapsules based on the NETmix R technology. Al rio E. Rodrigues is Professor of Chemical Engineering at the University of Porto (Portugal). He graduated in Chemical Engineering from the University of Porto in 1968 and received his Dr-Ing degree at the University of Nancy (France) in 1973. He is Director of the Associate Laboratory LSRE/LCM (http://lsre.fe.up.pt). His main research interests are in cyclic separation/reaction processes (simulated moving bed, pressure swing adsorption, and parametric pumping), chemical reaction engineering and product engineering (perfume engineering and microencapsulation).

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From left to right: Viviana Silva, Al rio E. Rodrigues, Carla Pereira

Fig. 2 Publications related to ethyl lactate since 1980 using all databases. Total number of publications with ethyl lactate in the topic = 1566. Total number of publications with ethyl lactate in the title = 304. Total number of publications with ethyl lactate + synthesis = 51. Data were obtained from ISI Web of Knowledge on 5th of July 2011.

(2003), together with a weak dollar and the continued rapid growth in Asian economies and their petroleum consumption, This journal is The Royal Society of Chemistry 2011

the crude oil price reached a new maximum of 126 USD per barrel in June 2008, followed by a drastic drop due to the nancial crisis, being currently at about 94 USD.6 Considering both the environmental regulations, as well as the increase in crude oil prices, the search for greener chemicals obtained from renewable sources is imperative for sustainable development. The most popular green solvents are water (aqueous biphasic), supercritical carbon dioxide and ionic liquids.7 In spite of the increasing interest, less attention is being given to bio-based solvents, such as the lactate ester family solvents,8 in which ethyl lactate is the most important member. Currently, a great challenge is the design and implementation of completely green products and processes. There is no systematic and reliable method to ensure that the chemistry implemented is green, since the number of chemical synthesis pathways is vast, and in general it is only possible to verify if a proposed manufacturing process is greener than other alternatives. Anastas and Warner have developed the Twelve Principles of Green Chemistry, which are a list of suggestions on how to design a greener process and/or a greener product,9 which are: 1. It is better to prevent waste than to treat or clean up waste after it is formed. Green Chem., 2011, 13, 26582671 | 2659

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2. Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the nal product. 3. Wherever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment. 4. Chemical products should be designed to preserve efcacy of function while reducing toxicity. 5. The use of auxiliary substances (e.g. solvents, separation agents, etc.) should be made unnecessary whenever possible and, innocuous when used. 6. Energy requirements should be recognized for their environmental and economic impacts and should be minimized. Synthetic methods should be conducted at ambient temperature and pressure. 7. A raw material or feedstock should be renewable rather than depleting whenever technically and economically practical. 8. Unnecessary derivatization (blocking group, protection/deprotection, and temporary modication of physical/chemical processes) should be avoided whenever possible. 9. Catalytic reagents (as selective as possible) are superior to stoichiometric reagents. 10. Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products. 11. Analytical methodologies need to be further developed to allow for real-time in-process monitoring and control prior to the formation of hazardous substances. 12. Substances and the form of a substance used in a chemical process should be chosen so as to minimize the potential for chemical accidents, including releases, explosions, and res. The 2nd principle can be quantitatively evaluated through Sheldons E-factor, which is a very simple green chemistry metric, dened by the ratio of the mass of waste per unit of desired product.10,11 To evaluate how green a product is, the environmental impact associated with all the stages of its life (production, use, and disposal) should be quantied using, for example, the life cycle assessment (LCA) methodology.12 For those who do not have the data and/or the skills required to do a proper LCA of a solvent, Jessop13 suggests a simple methodology to do a quick green-ness test, that involves the analysis of the solvents synthesis tree. In that work it is reported that the ethyl lactate synthesis involves more chemical steps than the synthesis of hexane or methanol, but has signicantly fewer steps than some ionic liquids, such as 1-butyl-3-methyli-midazolium acetate ([Bmim]OAc). Anyway, ethyl lactate is in accordance with at least eight of the Twelve Principles of Green Chemistry: 1) Ethyl lactate can be produced from renewable raw materials that can be a more environmentally friendly alternative to petrochemical solvent: 7th principle. 2) Ethyl lactate is 100% biodegradable, easy to recycle, noncorrosive, non-carcinogenic and non-ozone depleting.14 Indeed, it is so benign that the U.S. Food and Drug Administration approved its use in food products: 3rd , 4th and 10th principles. 3) Ethyl lactate can be produced through heterogeneous catalysis without using an excess of any of the reactants; the elimination of homogenous catalysts (usually mineral acids)
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avoids the use of corrosive catalysts and, thus, eliminates a further step of their neutralization: 1st and 9th principles. 4) Ethyl lactate can be produced by using hybrid technologies where reaction and separation of at least one product take place in a single unity eliminating the use of solvents, reducing the capital cost (less separation units are needed) and requiring less energy consumption: 5th and 6th principles. In summary, as shown in Fig. 3, ethyl lactate can be easily obtained by carbohydrate feedstocks, since it is produced from ethanol and lactic acid that are obtained by fermentation of biomass, as corn starch crops; and it is a biodegradable compound with good properties to be applied as a green solvent in several applications, such as organic synthesis, pharmaceutical preparations, fragrances, for inks and coatings industries, and food additives.

Fig. 3

The life cycle of ethyl lactate.

Following these four topics, this review will address: (i) the use of renewable resources, where the concept of a biorenery will be briey introduced and the platform of the chemicals involved in the ethyl lactate synthesis will be presented; (ii) ethyl lactates main properties and applications; (iii) its synthesis through the esterication reaction between ethanol and lactic acid; and (iv) ethyl lactate production processes with particular emphasis on process intensication.

2. Renewable resources
In recent years, an increasing demand for using biorenewable materials instead of petroleum based feedstocks for chemicals production, driven by environmental concerns and by the concept of sustainability, has been noticed. Biobased products are one of the main pillars of a sustainable economy. Nature produces 170 billion tons of biomass per year by photosynthesis, 75% of which belong to the class of carbohydrates; however, just 34% of these compounds are used by humans for food and nonfood purposes.15 Carbohydrates are very abundant renewable resources and they are currently considered as an important This journal is The Royal Society of Chemistry 2011

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Fig. 4 A schematic diagram of a biorenery for precursor-contained biomass.1920

feedstock for the Green Chemistry of the future.1618 Industrial plants, called bioreneries, have been proposed, where biomass is converted economically and ecologically, into chemicals, materials, fuels and energy (see Fig. 4). Bioreneries could be the basis of the new bioindustry. Its concept is similar to the petroleum renery; the difference is that the biorenery is based on conversion of biomass feedstocks instead of crude oil. Ethanol platform Ethanol, an important raw material in the chemical industry and also used as transportation fuel, can be produced from a variety of biomass crops, including sugar crops (e.g., sugar cane and sugar beet), starch crops (e.g., corn and cassava), or cellulosic feedstocks (e.g., wood, grasses and agricultural residues). Ethanol production from starch crops involves, as the main steps: liquefaction and saccharication (conversion to sugar), milling, pressing, fermentation and distillation. The production from cellulosic feedstocks is similar; however, it is signicantly more difcult and costly to convert cellulose and hemicellulose into their component sugars (glucose and xylose, respectively) than is the case for starches.21 In 2006, about 37 billion liters of ethanol were produced worldwide from starch and sugar crops.22 In 2008, the cellulosic ethanol industry developed some new commercial-scale plants: in the United States, plants with a 12 million liter capacity per year were operational, and an additional 80 million liters per year of capacity (26 new plants) were under construction; in Canada, a capacity of 6 million liters per year was operational; in Europe, several plants were operational in Germany, Spain, and Sweden, and a capacity of 10 million liters per year was under construction.23 Ethanol derived from cellulosic crops is appealing since it broadens the scope of potential feedstocks beyond starch and sugar-based food crops. Moreover, cellulosic ethanol can be more effective and promising as an alternative renewable biofuel than corn ethanol because it reduces the net greenhouse gas (GHG) emissions even more when compared with the petroleum fuel24,25 (see Fig. 5). This journal is The Royal Society of Chemistry 2011

Fig. 5 The percent change in greenhouse gas emissions.24

Lactic acid platform Lactic acid (2-hydroxypropionic acid) is an important chemical platform for the biorenewable economy. It is an a-hydroxy acid containing a hydroxyl group adjacent to the carboxylic acid functional group; a review on lactic acid chemistry can be found in the literature.26 Lactic acid can be produced through chemical synthesis or through the fermentation of different carbohydrates, such as, glucose (from starch), maltose (produced by specic enzymatic starch conversion), sucrose (from syrups, juices, and molasses), or lactose (from whey).27,28 Alternative feedstocks, particularly from wastes, are being sought. In recent years, lactic acid fermentation and separation from fresh grass juice have also been investigated.2931 In Brandenburg, Germany, a pilot plant is being operated to ferment fresh grass juice in combination with hydrolyzed cereals to lactic acid.32 In Utzenaich, Austria, a pilot scale biorenery was implemented in 2008, which separates lactic acid and amino acids from grass silage press juice.29 Currently, lactic acid is commercially produced by fermentation of glucose. One of the most important steps in lactic acid production is the recovery from fermentation broths. The separation and purication stages represent about 50% of the total production cost. However, current advances Green Chem., 2011, 13, 26582671 | 2661

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in membrane-based separation and purication technologies, particularly in microltration, ultraltration and electrodialysis, have originated new processes that should reduce lactic acid production costs.33 Lactic acid production is around 350 000 tons per year and the predicted worldwide growth per year is 1215%.33 Many products are derived from lactic acid; some of them are new chemical products and others are just biobased routes to chemicals currently produced from petroleum; the most important ones are shown in Fig. 6. Among these, perhaps the most interesting are: acrylic acid used as a raw material for the production of polymeric products applied in surface coatings, textiles, adhesives, paper treatment, detergents, superabsorbent materials, among others;34 and polylactic acid used in packaging, agricultural products and disposable material, and with great potential for applications in medicine, surgery, and pharmaceuticals.35 Another product that can be derived from lactic acid is propylene glycol; however, at the present time, lactic acid prices (1.21.5/kg) are of the same order as that of petrochemical based propylene glycol.36 Nevertheless, with the increase of crude oil prices and with the further technological development of lactic acid production, it is expected that this compound will become cheap enough in order to offer a biomass-based route to produce propylene glycol.

Fig. 7 Solvent demand by market segment.40

Fig. 6 Some potential derivatives of lactic acid.28,35

Ethyl lactate properties and applications

Ethyl lactate can be used as a food additive, in perfumery, as avour chemicals and solvent, which can dissolve acetic acid cellulose and many resins.37 Its main application is as a solvent, being particularly attractive for the coatings industry as a result of its high solvency power, high boiling point, low vapour pressure and low surface tension. Some physical and thermodynamic properties of ethyl lactate as well of the species involved in its synthesis are presented in the Appendix. Almost all manufacturing and processing industries depend on the use of solvents (see Fig. 7). Some industry experts suggest that ethyl lactate could replace the traditional solvents in more than 80% of their applications.38 However, this is probably highly inated, since ethyl lactate is a high boiling polar protic solvent13 and there are applications where non-polar, aprotic and/or lower boiling point solvents are required. Annually, just in the U.S.A, the solvents demand is about 10 billion pounds at prices from $0.90 to $1.70 per pound. Selling prices for ethyl lactate have ranged from $1.50 to $2.00 per pound, but
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processing advances could drive the price as low as $0.85 to $1.00 per pound, enabling ethyl lactate to compete directly with the petroleum-derived solvents currently used.38,39 Moreover, the crude oil prices have risen sharply, making ethyl lactate as a green solvent more commercially attractive, and due to the rising environmental consciousness, some consumers are willing to pay more for products that are less detrimental to the environment. Weis and Visco,41 developed a study using computer-aided molecular design to identify potential new environmentally friendly solvents as a supplement to GlaxoSmithKlines solvent selection guide,42 and ethyl lactate was presented as one of the potential solvents. This evidence is supported by many references documenting ethyl lactate applications as an environmentally friendly solvent, presented below. Ethyl lactate is a desirable coating for wood, polystyrene and metals and also acts as a very effective paint stripper and grafti remover. It can also be used in magnetic tape coatings replacing the hazardous air pollutants (MEK, MIBK and toluene).43 Ethyl lactate is replacing solvents, such as N -methyl pyrrolidone (NMP),44 toluene, acetone and xylene, which has resulted in a safer workplace. In Table 1, the solvating properties of ethyl lactate and NMP are presented. Other applications of ethyl lactate are as a cleaning agent for the polyurethane industry and for metal surfaces, efciently removing greases, oils, adhesives and solid fuels. Recently, it also been shown to be effective on the removal of copper from contaminated soils.45 Ethyl lactate can also be applied in the pharmaceutical industry as a dissolving/dispersing excipient for various biologically active compounds without destroying the pharmacological activity of the active ingredient. It is a very effective agent for solubilising biologically active compounds that are difcult to solubilise in usual excipients.46,47 Ethyl lactate can also be used as a more environmentally friendly alternative
Table 1 The solvating properties of ethyl lactate and N -methyl pyrrolidone N -Methyl Ethyl lactate pyrrolidone >1000 350 21.3 7.8 3.7 23.1 8.8 6.0

Kauri Butanol(KB) Value Solubility Hildebrand parameter parameters Disperse Hansen parameter Polar Hansen parameter

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Table 2 The major advantages of ethyl lactate Ethyl Lactate Benets 100% Biodegradable FDA approved as a avour additive Non carcinogenic Great penetration characteristics Rinses easily with water High boiling point Low VOC Low vapor pressure Renewable made from corn and other carbohydrates EPA approved SNAP solvent Non corrosive Stable in solvent formulations until exposed to water High solvency power for resins, polymers and dyes Easy and inexpensive to recycle Not an ozone depleting chemical Not a hazardous air pollutant

The self-esterication degree increases with increasing acid concentration. This makes the use of lactic acid difcult as a reactant for ethyl lactate synthesis, since the use of a high lactic acid concentration implies the presence of lactic acid oligomers during the esterication, which will be converted into the corresponding esters that simultaneously undergo hydrolysis and transesterication, leading to a mixture of acid and ester monomer and oligomers: 2La1 La2 + W (lactic acid dimer formation)

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La1 + La2 La3 + W (lactic acid trimer formation)

route to produce 1,2-propanediol, which is normally produced by the hydration of propylene oxide derived from petrochemical resources.48 A signicant amount of solvents are used in pharmaceutical manufacturing processes; indeed, it was estimated that around 80% of the total mass of chemicals involved in the pharmaceutical manufacture comprises solvents.49 The redesign of synthetic processes in order to reduce the amount of solvent applied and the use of nontoxic and nonhazardous solvents that are easy to recover and re-use are of major importance. From this perspective, ethyl lactate is currently being advertised as an environmentally attractive solvent for chemical reactions.7,11 Ethyl lactate has been used in the greener synthesis of aryl aldimines,50 synparvolide B,51 varitriol,52 among others. It was also used as a green solvent to extract phytosterols from wet corn ber, which provides an oil product with free phytosterols and free fatty acids,53 and to extract carotenoid, an effective solvent for both the cis and trans lycopene isomers from dried tomato powder.54 The major advantages of ethyl lactate are summarized in Table 2.

...

La1 + Lan-1 Lan + W (lactic acid oligomer formation) with n 2 La1 + Eth EL1 + W (ethyl lactate formation)

La2 + Eth EL2 + W (ethyl lactate dimer formation)

La3 + Eth EL3 + W (ethyl lactate trimer formation)

...

Lan + Eth ELn + W (ethyl lactate oligomer formation) where:

4.

Synthesis of ethyl lactate

The conventional way to produce ethyl lactate is the esterication of lactic acid with ethanol catalyzed by an acid catalyst, according to the reaction:
H Ethanol ( Eth ) + Lactic A cid ( La) Ethyl Lactate ( EL ) +W ater (W ) +

The use of lactic acid and ethanol as reactants for the ethyl lactate synthesis has the advantage of both being produced from renewable resources (by glucose or sugar fermentation processes). Lactic acid has a bifunctional nature (contains a hydroxyl group adjacent to the carboxylic acid) and thus it undergoes intermolecular esterication in aqueous solutions above 20 wt% to form a linear dimer, and higher oligomer acids.55,56 An 88 wt% lactic acid solution comprises 43.5 mol% of monomer (La1 ), 9.2 mol% of dimer (La2 ), 1.8 mol% of trimer (La3 ) and about 45 mol% of water. On the other hand a 20 wt% aqueous solution of lactic acid is constituted only by monomer and water, with a monomer molar percentage of about 5.6 mol%.57 This journal is The Royal Society of Chemistry 2011

Some of the kinetic studies regarding ethyl lactate synthesis are performed using a 20 wt% lactic acid solution in order to avoid the formation of oligomers, but even when higher lactic acid concentrations are used, the presence of oligomers is normally neglected. Just two works take into account the oligomers; however, their amount is less than 5% Green Chem., 2011, 13, 26582671 | 2663

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Table 3 Summary of the kinetic studies of the esterication reaction between ethanol and lactic acid Lactic acid solution Oligomers (wt.%) presence Kinetic model 85; 44 91 88 88 92 20 neglected empirical equation considered simple nth-order reversible rate expressions neglected homogeneous neglected based on single-site mechanisms neglected simple nth-order reversible rate expressions neglected Langmuir Hinshelwood Langmuir Hinshelwood considered simple nth-order reversible rate expressions neglected Langmuir Hinshelwood neglected homogeneous neglected Langmuir Hinshelwood neglected simple nth-order reversible rate expressions Activation Energy (kJ mol-1 ) 62.47 47.00c 30.54 51.58 52.26 48.00c 52.29 62.50 49.98 47.11

Refs. Troupe and DiMilla, 195761 Tanaka et al., 200237 Benedict et al., 200362 Engin et al., 200363

Catalyst Sulfuric acid Amberlyst 15 Without catalyst Amberlyst XN-1010 Heteropoly acid supported on Lewatit R S100 002 NKC

Temperature range 25100 C 9092 C 95 C 7595 C 70 C 6088 C

Expression of the components concentrations concentrations concentrations concentrations concentrations activitiesa activitiesa concentrations activitiesb activitiesb activitiesb concentrations

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Zhang et al., 200464

Asthana et al., 2006

57

Amberlyst 15 Amberlyst 15 Without catalyst Amberlyst 15 Preyssler acid

6290 C 5586 C 5585 C 5090 C 7085 C

20; 50; 88 20 20 88 20

Delgado et al., 200760 Pereira et al., 200858 Bamoharram et al., 201065

activity coefcients calculated by the UNIFAC model. b activity coefcients calculated by the UNIQUAC model. c activation energy of the lactic acid monomer esterication.

at equilibrium.37,57 The extent of oligomer formation depends on the water concentration, but also on the ethanol contents; for example, for a lactic acid solution of 88 w.%, the oligomers composition at equilibrium is 2.4 molar% when using a molar ratio between ethanol and lactic acid of 1 and of 0.4 molar% when using an ethanol : lactic acid molar ratio of 3.58 Esterications are self-catalyzed reactions, since the H+ cation released from the partial dissociation of the carboxylic acid used as a reactant catalyses the reaction. However, the use of a catalyst is favourable for the reaction rate as the kinetics of the self-catalyzed reaction are extremely slow, since its rate depends on the autoprotolysis of the carboxylic acid. For example, the lactic acid acidity constant is pK a = 3.86 at 25 C, and therefore an aqueous solution with 85% of lactic acid (about 10.8 M) has a pH = 1.4. Typically, the catalytic production of lactates is performed with homogeneous catalysts using acids, such as sulphuric acid, phosphoric acid and anhydrous hydrogen chloride. However, the use of a heterogeneous catalyst (as for example, zeolites, ion-echange resins like Amberlyst 15-wet, Naon NR50, among others) has clear advantages, i.e.: easy to separate from the reaction mixture; long life time; higher purity of products (side reactions can be eliminated or are less signicant); and elimination of the corrosive environment caused by the discharge of acid containing waste. A summary of the kinetic studies performed for lactic acid esterication with ethanol is presented in Table 3. As can be seen, the kinetic model is usually expressed in terms of species concentration; few authors take into account the non-ideality of the reaction mixture using activities instead of concentration. There are a reasonable number of kinetic studies for this system available in the literature; however, only one presents the thermodynamic
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equilibrium constant dened as function of the species liquid activities, described by the following expression: ln(K ) = 2.9625 - 515.13/T (K ).58 There is another work regarding the vapour liquid reactive equilibrium for the ethyl lactate synthesis,59 where the thermodynamic equilibrium constant is also determined, but the values predicted by the proposed equilibrium constant expression present high deviations from the experimental ones. As mentioned previously, the hydrolysis of ethyl lactate is also an important reaction since it can be used to obtain highly pure lactic acid. However, just one work presents a study regarding this subject.60

5. Production processes
There are a considerable number of patented processes for ethyl lactate production; in most of them, the esterication reaction between ethanol and lactic acid is carried out until equilibrium and then the ethyl lactate is separated from the reaction mixture by distillation. In order to overcome the equilibrium limitation, an excess of ethanol is applied and a strong acid is used as a catalyst, the most common being sulphuric acid.6669 There are similar processes, but using ammonium lactate instead of lactic acid.7075 A recent work76 presents the synthesis of ethyl lactate from ammonium lactate solution by the coupling of solvent extraction with esterication. Dimethyl sulfoxide, N methyl pyrrolidine and triethyl phosphate were evaluated as solvents, but the last proved to be the most efcient. Arkema (France) has two patented processes related to continuous ethyl lactate production from the esterication reaction between lactic acid and ethanol using sulphuric acid as catalyst. One consists of extracting a mixture comprising This journal is The Royal Society of Chemistry 2011

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ethyl lactate, ethanol, water and different heavy products from the reaction medium at partial lactic acid conversion rate and, then, feeding the mixture to a reduced-pressure ash separation, producing an overhead stream containing a mixture of ethyl lactate, ethanol and water, that is subjected to a fractional distillation column.77,78 The other is characterized by the continuous extraction of a near-azeotropic water/ethanol gas mixture from the reaction medium, followed by dehydration of this mixture using molecular sieves, where two streams are obtained: an ethanol gas stream that is recycled to the reaction medium; and a water/ethanol stream that is fed to a distillation column.79,80 An ethyl lactate purity higher than 95% is reported in the rst process (initial ethanol/lactic acid molar ratio equal to 2.5; esterication carried out at 80 C; ash separation at 85 C and 50 mbar, and fractional distillation at a column bottom temperature of 155 C and top temperature of 77.2 C), while for the second an ethyl lactate purity higher than 97% is claimed. The use of this kind of process (reactor followed by separation units in order to recover the ethyl lactate, to remove the by-product (water) and to recycle the unconverted reactants to the reactor) represents high costs, either capital or operating, and the use of equipment and techniques that are more compact and energy efcient are preferable for ethyl lactate production. 5.1 Process intensication

this is followed by separation of the reaction mixture in two consecutive distillation columns or, alternatively, by several pervaporation steps (see Fig. 8).81 It is reported that a lactic acid conversion of 99% and an ethyl lactate purity of 76% was obtained, for an initial ethanol/lactic acid molar ratio of 2 : 1, a reaction mixture temperature of 95 C, a permeate-side vacuum pressure less than 0.5 mbar and, as the catalyst, an ion-exchange resin, Amberlyst XN-1010, at 10% of lactic acid weight.

Fig. 8 A schematic representation of ethyl lactate production using a reactor coupled with a pervaporation membrane unit and followed by: a) pervaporation unit; b) two distillation columns.

Ethyl lactate is formed through a thermodynamic equilibrium limited reaction between lactic acid and ethanol with water as a by-product, thus its production is improved using multifunctional reactors, where reaction and separation are integrated into a single unit, since at least one of the products is continuously removed from the reaction mixture to lead to depletion of the limiting reactant, increasing the ethyl lactate yield and purity. Some reactive separation processes have already been studied for ethyl lactate production, as membrane reactors, reactive distillation and chromatographic reactors. These studies are presented next. 5.1.1. Membrane based processes. The Argonne National Laboratory patented a process that consists of a reactor coupled with a pervaporation membrane unit for water removal and
Table 4 Ethyl lactate production by means of membrane reactors

The ethyl lactate synthesis on pervaporation and vapourpermeation membrane reactors was also studied by other authors. Three different congurations were adopted (Fig. 9): (i) batch reactor, where the esterication reaction takes place, followed by a membrane for water removal, and reux of the retentate to the reactor;62,8185 (ii) membrane inside a batch reactor37,86,87 and (iii) continuous integrated membrane reactor, that consists of a tubular membrane packed with a heterogeneous catalyst (Amberlyst 15-wet).88 The type of hydrophilic membranes tested were polymeric,62,81,82 ceramic88 and organic inorganic hybrid membranes84,87 for pervaporation and zeolites for vapour permeation.37,86 A summary of the results obtained for ethyl lactate synthesis by means of membrane reactors is presented in Table 4.

Refs. Rathin and Shih-Perng, 199881 Jafar et al., 200286 Tanaka et al., 200237 Benedict et al. 2003, 200662,82 Budd, et al., 200487 Ma et al., 200984 Pereira et al., 201088
a

Membrane GFT PerVap 1005 zeolite A zeolite T GFT PerVap 1005

Temperature 95 C 70 C 120 C 95 C

Membrane water ux (kg m-2 h-1 )a 1.20 0.18 0.33 0.60b 0.19 0.27 2.55
c

Catalyst Amberlyst XN-1010 p-toluene sulphonic acid Amberlyst 15 Amberlyst XN-1010 p-toluenesulfonic acid Amberlyst 15 Amberlyst 15

Eth/La molar La ratio Conversion EL Purity 2.0 2.0 2.4 1.2 2.0 3.0 1 99% 95% 99% 71%d 90% 80%e 98% 76% 96%

zeolite/polyelectrolyte 100 C multilayer chitosanTEOS Microporous silica 80 C 70 C

for water/ethanol liquid mixture (10/90 wt%); b sheet membrane (70 C); c tube membrane (70 C); d after 8 h; e after 9 h.

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Fig. 9 The layout of a pervaporation membrane reactor: (i) batch reactor with an external pervaporation unit; (ii) membrane and reactor in the same unit; (iii) continuous integrated membrane reactor.

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5.1.2 Reactive distillation. The reactive distillation (RD) technology was successfully implemented by Asthana and collaborators,89 where a lactic acid conversion of 95% and an ethyl lactate purity of 95% were obtained, when a mixture of ethanol and 88 wt% lactic acid solution (ethanol/lactic acid molar ratio of 3.6) was fed and using a bottom temperature of 128 C. A schematic representation of the RD unit is shown in Fig. 10. This process was also studied by Gao and co-workers,90 where an ethyl lactate yield of just 53% is reported, using a bottom temperature of about 115 C and a feed ratio of ethanol to lactic acid of 4 : 1.

Fig. 11 The semicontinuous process for the ethyl lactate production.91

Fig. 10 A schematic representation of a reactive distillation unit for the production of ethyl lactate.

from an economic point of view, than a traditional batch or a continuous process, for an intermediate range of ethyl lactate production, however, for high production rates, the continuous process remains the most suitable. 5.1.4 Chromatographic reactors. The application of a simulated moving bed reactor (SMBR) for ethyl lactate production was studied by Pereira et al.,92 where it is reported an ethyl lactate productivity of 18.06 kgEL /(Lads .day)), a desorbent consumption of 4.75 LEth /kgEL and an ethyl lactate purity of 95% (without ethanol), when using this technology at 50 C, ethanol as a desorbent and Amberlyst-15 wet resin as a catalyst and selective adsorbent for water (see Fig. 12). The maximum ethyl lactate productivity attained was 31.7 kgEL /(Lads .day)), but it was accompanied by a high consumption of ethanol (7.6 LEth /kgEL ). When using SMBR technology, two diluted streams are obtained: the extract and the rafnate (Fig. 12), requiring two

5.1.3 Distillation and membrane based process. A novel semicontinuous distillation (SD) process was proposed by Adams and Seider,91 where a distillation column interacting with a middle vessel, a continuous stirred tank reactor (CSTR) and a pervaporation unit are used. The reaction takes place in the CSTR until equilibrium is reached, then the reaction mixture is moved to the middle vessel that is integrated with the distillation column, and the CSTR is recharged. The middle vessel feeds a reaction mixture to the distillation column, which recycles back a side stream. During the cycle, ethanol and water are collected in the distillate and are separated in a pervaporation unit using a hydrophilic membrane, which allows the breaking of the ethanol/water azeotrope. The retentate stream rich in ethanol is recycled back to the CSTR. Lactic acid is collected at the bottom of the distillation column and it is also recycled to the CSTR at decreasing ow rates, eventually approaching zero ow, since it is being consumed in the reaction. During this process water, ethanol, and lactic acid are removed from the middle vessel, and, therefore, at the end of the cycle, when the products are collected, the middle vessel contains highly concentrated ethyl lactate (see Fig. 11). It was shown that the SD process is more feasible,
2666 | Green Chem., 2011, 13, 26582671

Fig. 12 A schematic diagram of the SMBR unit the with conguration 3-3-4-2 applied to ethyl lactate synthesis. Each box represents a SMBR column packed with the resin Amberlyst-15 wet.

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Table 5 Basic properties of lactic acid, ethanol, ethyl lactate and water95 Properties Molecular weight M /g mol-1 Density r/g cm-3 Melting temperature T f (K) Normal boiling temperature T b (K) Critical temperature T c (K) Critical pressure Pc (bar) Critical volume V c (cm3 mol-1 ) Acentric factor w Lactic Acid 90.079 1.209 289.95291.15 395.15 616.00 59.65 216.9 1.035 Ethanol 46.069 0.789 159.15 351.45 516.25 63.84 166.9 0.637 Ethyl Lactate 118.133 1.031 248.25 426.15427.15 588.00 38.60 354.0 0.793 Water 18.015 1.027 273.15 373.15 647.13 221.20 57.1 0.344

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additional separation steps. In order to achieve high ethyl lactate productivity without the penalty on the consumption of ethanol, a new technology was recently developed: the simulated moving bed membrane reactor (PermSMBR), which comprises the integration of hydrophilic membranes into the SMBR columns93 (Fig. 13). These membranes enhance the water removal, allowing the elimination of the extract stream and leading to a better performance for ethyl lactate production, as shown in the work of Silva and collaborators.94 For ethyl lactate synthesis, the RD and SMBR processes require more than 152% and 165% of the ethanol consumption, respectively, of the new PermSMBR technology.

lactate productivity, but with the penalty of the consumption of desorbent, which should be further separated and recycled in the SMBR unit, two subsequent separation units being necessary. PermSMBR seems the most promising technology for ethyl lactate production, since it operates at moderate temperatures (70 C), and results in high ethyl lactate production rates, low desorbent consumption and just one additional separation step to separate ethyl lactate from ethanol. However, it requires vacuum costs and the limitations associated with the membranes stability/durability are also an issue. Moreover, the proof-of-concept of this technology has not yet been performed. A fair comparison of technologies must be done in terms of economic and environmental impact assessment, in order to determine the most viable process for the efcient production of ethyl lactate.

Appendix: Physical and Thermodynamic Properties

In Table 5 some physical and thermodynamic properties of lactic acid, ethanol, ethyl lactate and water are presented.95
Fig. 13 A schematic diagram of a PermSMBR unit with 4 sections (conguration 3-3-4-2) for ethyl lactate synthesis. Each box represents a PermSMBR column that consists of a set of membranes packed with the Amberlyst 15-wet resin.

Density and molar volume The modied form of the Rackett equation was selected for the correlation of saturated liquid density as a function of temperature,

6.

Conclusions
rL = A B

(1

A literature survey regarding ethyl lactate production processes was presented in this review with special focus on reactive/separation processes, since they provide the most feasible engineering solution to the sustainable synthesis of ethyl lactate, as at least one of the products is continuously removed from the reaction mixture, leading to depletion of the limiting reactant. Membrane reactors, reactive distillation and chromatographic reactors, namely, SMBR and PermSMBR technologies, have been successfully implemented for ethyl lactate synthesis. In all these processes, it was possible to attain nearly complete lactic acid conversion and high ethyl lactate purity (95%), although under different operating conditions. The RD process is the one that requires more heat supply, since it operates at high temperatures (128 C bottom temperature); however, the capital costs are lower and it is a more industrially consolidated technology. The membrane reactor requires more moderate temperatures (around 70 C) and an extra separation step is not necessary; however, ethyl lactate productivity is low, the membranes durability and/or stability under acidic conditions might be a problem and it has the additional associated vacuum costs. Using the SMBR it is possible to attain high ethyl This journal is The Royal Society of Chemistry 2011

T n ) Tc

(A.1)

with rL (g cm-3 ) and T /K. The constants used are presented in Table 6. The molar volumes for all components were estimated with the GunnYamada method:96

V (T ) =
where

f (T R )

f (T )

VR

(A.2)

f (T ) = H 1 (1 - w H 2 )
3 H 1 = 0.33593 - 0.33953T r + 1.51941T 2 r - 2.02512T r + 4 1.11422T r

(A.3) (A.4) (A.5)

H 2 = 0.29607 - 0.9045T r - 0.04842T 2 r

Tr =

T TR or Tc Tc

(A.6)

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Table 6 Constants used for density calculation95 Constants A B n T min (K) T max (K) Lactic Acid 0.39816 0.26350 0.28570 291.15 Tc Ethanol 0.26570 0.26395 0.23670 159.05 Tc Water 0.34710 0.27400 0.28571 273.16 Tc Ethyl Lactate

Table 9 Ethyl lactate viscosity for different temperatures at atmospheric pressure h (cP) 0.33372 0.21190 0.45530 247.15 Tc Estimated by Eq. A.7 (Ref. 95) Experimental (Ref. 97) Experimental (Ref. 98,99) 278.15 K 4.55 4.75 298.15 K 2.21 2.40 2.53 318.15 K 1.26 1.6

Table 7 Molar volumes at the reference temperature

Table 10 Viscosity of lactic acid T /K h (cP) Water 18.082 Table 11 Constants used for vapour pressure calculation95 Constants Lactic Acid Ethanol 23.8442 -2.8642 103 -5.0474 3.7448 10-11 2.7361 10-7 159.05 Tc Water 29.8605 -3.1522 103 -7.3037 2.4247 10-9 1.8090 10-6 273.16 Tc Ethyl Lactate 32.0863 -2.9164 103 -9.5666 6.5114 10-3 4.5645 10-13 247.15 Tc 293.15 53.67 323.15 13.99

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VR (cm3 mol-1 ) Reference Temperature TR (K) Lactic Acid Ethanol Ethyl Lactate 293.15 74.640 58.174 113.986

V R is the molar volume at the reference temperature T R (cm3 mol-1 ), w is the acentric factor and T c is the critical T /K. The GunnYamada method could be used just in the case when the liquid molar volume is known at some temperature (reference temperature). The reference molar volumes are presented at Table 7. Viscosity The correlation for liquid viscosity as a function of temperature is given by eqn (A.7) (see constants in Table 8).

A B C D E T min (K) T max (K)

-27.0836 -3.9661 103 2.0233 101 -4.2176 10-2 2.0310 10-5 291.15 Tc

Table 12 Constants used for heat capacity calculation95 Constants Ethanola A B C D E T min (K) T max (K) Error
a

Watera 2.7637 105 -2.0901 103 8.1250 -1.4116 10-2 9.3701 10-6 273.16 533.15 <1%

Ethyl Lactate Lactic acida -46.239 2.1823 -5.9832 10-3 6.8683 10-6 248.00 529.00 6.1082 104 5.0343 102 289.90 675.00 <10%

log10 hL = A +

B + CT + DT 2 T

(A.7)

with hL (cP) and T /K. Ethyl lactate viscosity data are very scarce in the literature. Some works just present the viscosity of this compound at a single temperature.97 However, in the works of Aparicio and Alcalde the values of ethyl lactate viscosity for a wide range of pressures and temperatures are reported.98,99 In Table 9, the viscosities of ethyl lactate estimated by the correlation mentioned above (eqn (A.7)) and experimentally measured are presented. As can be seen, the correlation estimates smaller viscosity values than the ones obtained experimentally. At 278.15 K, the correlation leads to a value 4% smaller than the value reported in Aparicio and Alcalde.98,99 The lactic acid viscosity might be estimated by the following expression:100

1.0264 105 -1.3963 102 -3.0341 10-2 2.0386 10-3 159.05 390.00 <3%

parameters taken from ref. 100.

Table 13 Constants used for heat vaporization calculation100 Constants Ethanol A B C D T min (K) T max (K) Error 5.5789 107 3.1245 10-1 159.05 514.00 <1% Water 5.2053 107 3.1990 10-1 -2.1200 10-1 2.5795 10-1 273.16 647.13 <1% Ethyl Lactate Lactic acid 8.0260E 107 4.0930 10-1 247.15 588.00 <10% 1.0436 108 3.8548 10-1 289.90 675.00 <25%

4097.9 hLA = exp 14.403 + 0.4407 ln(T ) T

Table 8 Constants used for viscosity calculation95 Constants A B C D T min (K) T max (K) Ethanol -6.4406 1.1176 103 1.3721 10-2 -1.5465 10-5 240 Tc Water -10.2158 1.7925 103 1.7730 10-2 -1.2631 10-5 273 643

(A.8)

with hLA (Pa s)and T /K. The lactic acid viscosity at two temperatures is presented in Table 10.
Ethyl Lactate -20.0105 3.2123 103 4.1891 10-2 -3.2733 10-5 247 Tc

Vapour pressure The Antoine-type equation with extended term was selected for correlation of vapour pressure as a function of temperature:

log10 Pvp = A +

B + C log10 T + DT + ET 2 T

(A.9)

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Table 14 Constants used for thermal conductivity calculation100 Constants Ethanol A B C D T min (K) T max (K) Error 2.4680 10-1 -2.6400 10-4 159.05 353.15 <5% Water Ethyl Lactate Lactic acid

-4.3200 10-1 2.8358 10-1 3.4850 10-1 5.7255 10-3 -3.5110 10-4 -3.7085 10-4 -8.0780 10-6 1.8610 10-9 273.16 633.15 <1% 247.15 427.65 <25% 289.90 490.00 <10%

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with Pvp (mmHg) and T /K.95 The constants used in the vapour pressure calculations are presented in Table 11 and its graphical representation as a function of temperature is shown in Fig. 14.

Fig. 15 Variation of the liquid heat capacity of the different species with the temperature.

Fig. 14 Variation of the vapour pressure of the compounds with the temperature.

Fig. 16 Variation of the heat of vaporization of the different species with the temperature.

Liquid heat capacity The correlation for the heat capacity of a liquid is a series expansion in temperature, given by eqn (A.10). C p = A + BT + CT 2 + DT 3 + ET 4 (A.10)

Thermal conductivity The thermal conductivity was calculated by eqn (A.12) using the constants presented in Table 14.100 l = A + BT + CT 2 + DT 3 + ET 4
-1 -1

(A.12)

with C p (J kmol-1 K-1 ) and T /K, with exception for the ethyl lactate species where C p is given in J mol-1 K-1 . The liquid heat capacity as a function of temperature was estimated by the above equation (Fig. 15), using the constants presented in Table 12. Heat of vaporization The correlation selected for the calculation of the heat of vaporization as a function of temperature is given by eqn (A.11).100

with l (W m K ) and T /K. The coefcients for each chemical compound for all the correlations presented in this appendix were based on appropriate experimental data available in the literature, with the exception of the GunnYamada method to estimate the molar volume, since this is based on the corresponding-states principle.

Acknowledgements
The authors acknowledge nancial support provided by o para a Ci Fundac a encia e a Tecnologia (Portugal) through the project PPCDT/EQU/61580/2004 and post-doctoral grant SFRH/BPD/71358/2010 of C.S.M. Pereira.

DH V = A 1T r (B +CT r +DT r

(A.11)

with T r = T /T c and DH V in J K-1 mol-1 . The heat of vaporization was estimated by the correlation given by eqn (A.11) (see Fig. 16) using the constants presented in Table 13. This journal is The Royal Society of Chemistry 2011

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