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Ethyl lactate as a solvent: Properties, applications and production
processes – a review
Carla S. M. Pereira, Viviana M. T. M. Silva* and Alı́rio E. Rodrigues
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

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 esterification reaction of ethanol and lactic
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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, flavours, 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
Fig. 1 The molecular structure of ethyl lactate.
cosmetic industries. It is also used as a monomer for the manu-
facture of biodegradable polymers, as substitutes for traditional
tion and environmental regulation were mainly nation based,
petrochemical polymers. Lactic acid has been produced through
until the 1980s. Since then, with the increase of international
both chemical synthesis or fermentation routes. This last pro-
chemical trade and the knowledge of the impact of global
cess is the most common,2 however, lactic acid derived from
trade on the environment, international environmental treaties,
fermentation broths requires extensive purification processes
directives, and conventions have emerged.5 Moreover, it was in
that should be inexpensive and environmentally friendly. Ethyl
the 1980s that environmental protection was connected with
lactate hydrolysis is one of the methods used to obtain pure lactic
economic development, leading to dissemination of “sustainable
acid.3,4
development” as a means to encourage the integration of
Ethyl lactate has attracted much attention in recent years,
policies across sectors (Rio Declaration on Environment and
which is reflected in the number of articles published, as shown
Development and Johannesburg Declaration on Sustainable
in Fig. 2. This is probably due to the environmental movement
Development, informally known as Earth Summit 1992 and
that emerged in the 1970s (United Nations Conference on the
2002, respectively). Furthermore, with the Yom Kippur War
Human Environment at Stockholm in 1972). Chemical legisla-
(1973) and the subsequent Arab Oil Embargo, the Iranian
Revolution (between November 1978 and June 1979), and
Laboratory of Separation and Reaction Engineering (LSRE), Associate the Iraq–Iran War (1980), crude oil production declined, and,
Laboratory LSRE/LCM, Department of Chemical Engineering, Faculty consequently, the crude oil price increased drastically, from 3
of Engineering, University of Porto, Rua Dr Roberto Frias s/n, USD per barrel in 1972 up to 35 USD in 1981. More recently,
4200-465, Porto, Portugal. E-mail: viviana.silva@fe.up.pt; Fax: +351
225081674; Tel: +351 225081489 the PDVSA strike (Venezuela, 2002–2003) and the Iraq War

2658 | Green Chem., 2011, 13, 2658–2671 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 intensification for the sustainable production of ethyl lactate based on membrane
and chromatographic reactors under the supervision of Professor Alı́rio 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 Politécnico de Bragança (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 intensification 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
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

the production of nanoparticles and microcapsules based on the NETmix R technology.

Alı́rio 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, Alı́rio E. Rodrigues, Carla Pereira

the crude oil price reached a new maximum of 126 USD per
barrel in June 2008, followed by a drastic drop due to the
financial 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 implementa-
tion of completely green products and processes. There is no
systematic and reliable method to ensure that the chemistry
Fig. 2 Publications related to ethyl lactate since 1980 using all implemented is green, since the number of chemical synthesis
databases. Total number of publications with “ethyl lactate” in the pathways is vast, and in general it is only possible to verify
topic = 1566. Total number of publications with “ethyl lactate” in if a proposed manufacturing process is “greener” than other
the title = 304. Total number of publications with “ethyl lactate” + alternatives. Anastas and Warner have developed the “Twelve
“synthesis” = 51. Data were obtained from ISI Web of Knowledge on Principles of Green Chemistry”, which are a list of suggestions
5th of July 2011. on how to design a greener process and/or a greener product,9
which are:
(2003), together with a weak dollar and the continued rapid 1. It is better to prevent waste than to treat or clean up waste
growth in Asian economies and their petroleum consumption, after it is formed.

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2. Synthetic methods should be designed to maximize the avoids the use of corrosive catalysts and, thus, eliminates a
incorporation of all materials used in the process into the final further step of their neutralization: 1st and 9th principles.
product. 4) Ethyl lactate can be produced by using hybrid technologies
3. Wherever practicable, synthetic methodologies should be where reaction and separation of at least one product take place
designed to use and generate substances that possess little or no in a single unity eliminating the use of solvents, reducing the
toxicity to human health and the environment. capital cost (less separation units are needed) and requiring less
4. Chemical products should be designed to preserve efficacy energy consumption: 5th and 6th principles.
of function while reducing toxicity. In summary, as shown in Fig. 3, ethyl lactate can be easily
5. The use of auxiliary substances (e.g. solvents, separation obtained by carbohydrate feedstocks, since it is produced from
agents, etc.) should be made unnecessary whenever possible and, ethanol and lactic acid that are obtained by fermentation of
innocuous when used. biomass, as corn starch crops; and it is a biodegradable com-
6. Energy requirements should be recognized for their en- pound with good properties to be applied as a green solvent in
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

vironmental and economic impacts and should be minimized. several applications, such as organic synthesis, pharmaceutical
Synthetic methods should be conducted at ambient temperature preparations, fragrances, for inks and coatings industries, and
and pressure. food additives.
7. A raw material or feedstock should be renewable rather than
depleting whenever technically and economically practical.
8. Unnecessary derivatization (blocking group, protec-
tion/deprotection, and temporary modification of physi-
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cal/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
fires.
The 2nd principle can be quantitatively evaluated through
Sheldon’s E-factor, which is a very simple green chemistry
metric, defined 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 Fig. 3 The life cycle of ethyl lactate.
(production, use, and disposal) should be quantified using, for
example, the life cycle assessment (LCA) methodology.12 For Following these four topics, this review will address: (i) the use
those who do not have the data and/or the skills required to do a of renewable resources, where the concept of a biorefinery will
proper LCA of a solvent, Jessop13 suggests a simple methodology be briefly introduced and the platform of the chemicals involved
to do a quick “green-ness test”, that involves the analysis of in the ethyl lactate synthesis will be presented; (ii) ethyl lactate’s
the solvent’s synthesis tree. In that work it is reported that the main properties and applications; (iii) its synthesis through the
ethyl lactate synthesis involves more chemical steps than the esterification reaction between ethanol and lactic acid; and (iv)
synthesis of hexane or methanol, but has significantly fewer steps ethyl lactate production processes with particular emphasis on
than some ionic liquids, such as 1-butyl-3-methyli-midazolium process intensification.
acetate ([Bmim]OAc).
Anyway, ethyl lactate is in accordance with at least eight of
2. Renewable resources
the “Twelve Principles of Green Chemistry”:
1) Ethyl lactate can be produced from renewable raw materials In recent years, an increasing demand for using biorenewable
that can be a more environmentally friendly alternative to materials instead of petroleum based feedstocks for chemicals
petrochemical solvent: 7th principle. production, driven by environmental concerns and by the
2) Ethyl lactate is 100% biodegradable, easy to recycle, non- concept of sustainability, has been noticed. Biobased products
corrosive, non-carcinogenic and non-ozone depleting.14 Indeed, are one of the main pillars of a sustainable economy. Nature
it is so benign that the U.S. Food and Drug Administration produces 170 billion tons of biomass per year by photosynthesis,
approved its use in food products: 3rd , 4th and 10th principles. 75% of which belong to the class of carbohydrates; however, just
3) Ethyl lactate can be produced through heterogeneous 3–4% of these compounds are used by humans for food and non-
catalysis without using an excess of any of the reactants; the food purposes.15 Carbohydrates are very abundant renewable
elimination of homogenous catalysts (usually mineral acids) resources and they are currently considered as an important

2660 | Green Chem., 2011, 13, 2658–2671 This journal is © The Royal Society of Chemistry 2011
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Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

Fig. 4 A schematic diagram of a biorefinery for precursor-contained biomass.19–20


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feedstock for the Green Chemistry of the future.16–18 Industrial


plants, called biorefineries, have been proposed, where biomass
is converted economically and ecologically, into chemicals,
materials, fuels and energy (see Fig. 4). Biorefineries could
be the basis of the new bioindustry. Its concept is similar to
the petroleum refinery; the difference is that the biorefinery
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), Fig. 5 The percent change in greenhouse gas emissions.24
or cellulosic feedstocks (e.g., wood, grasses and agricultural
Lactic acid platform
residues). Ethanol production from starch crops involves, as
the main steps: liquefaction and saccharification (conversion Lactic acid (2-hydroxypropionic acid) is an important chemical
to sugar), milling, pressing, fermentation and distillation. The platform for the biorenewable economy. It is an a-hydroxy acid
production from cellulosic feedstocks is similar; however, it containing a hydroxyl group adjacent to the carboxylic acid
is significantly more difficult and costly to convert cellulose functional group; a review on lactic acid chemistry can be found
and hemicellulose into their component sugars (glucose and in the literature.26
xylose, respectively) than is the case for starches.21 In 2006, Lactic acid can be produced through chemical synthesis or
about 37 billion liters of ethanol were produced worldwide through the fermentation of different carbohydrates, such as,
from starch and sugar crops.22 In 2008, the cellulosic ethanol glucose (from starch), maltose (produced by specific enzymatic
industry developed some new commercial-scale plants: in the starch conversion), sucrose (from syrups, juices, and molasses),
United States, plants with a 12 million liter capacity per year or lactose (from whey).27,28 Alternative feedstocks, particularly
were operational, and an additional 80 million liters per year of from wastes, are being sought. In recent years, lactic acid
capacity (26 new plants) were under construction; in Canada, fermentation and separation from fresh grass juice have also
a capacity of 6 million liters per year was operational; in been investigated.29–31 In Brandenburg, Germany, a pilot plant
Europe, several plants were operational in Germany, Spain, is being operated to ferment fresh grass juice in combination
and Sweden, and a capacity of 10 million liters per year was with hydrolyzed cereals to lactic acid.32 In Utzenaich, Austria,
under construction.23 Ethanol derived from cellulosic crops is a pilot scale biorefinery was implemented in 2008, which
appealing since it broadens the scope of potential feedstocks separates lactic acid and amino acids from grass silage press
beyond starch and sugar-based food crops. Moreover, cellulosic juice.29 Currently, lactic acid is commercially produced by
ethanol can be more effective and promising as an alternative fermentation of glucose. One of the most important steps
renewable biofuel than corn ethanol because it reduces the net in lactic acid production is the recovery from fermentation
greenhouse gas (GHG) emissions even more when compared broths. The separation and purification stages represent about
with the petroleum fuel24,25 (see Fig. 5). 50% of the total production cost. However, current advances

This journal is © The Royal Society of Chemistry 2011 Green Chem., 2011, 13, 2658–2671 | 2661
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in membrane-based separation and purification technologies,


particularly in microfiltration, ultrafiltration 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
12–15%.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, super-
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

absorbent materials, among others;34 and polylactic acid used in


packaging, agricultural products and disposable material, and
Fig. 7 Solvent demand by market segment.40
with great potential for applications in medicine, surgery, and
pharmaceuticals.35 Another product that can be derived from processing advances could drive the price as low as $0.85 to
lactic acid is propylene glycol; however, at the present time, $1.00 per pound, enabling ethyl lactate to compete directly with
lactic acid prices (€1.2–€1.5/kg) are of the same order as that of the petroleum-derived solvents currently used.38,39 Moreover, the
petrochemical based propylene glycol.36 Nevertheless, with the crude oil prices have risen sharply, making ethyl lactate as a
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increase of crude oil prices and with the further technological green solvent more commercially attractive, and due to the rising
development of lactic acid production, it is expected that this environmental consciousness, some consumers are willing to pay
compound will become cheap enough in order to offer a more for products that are less detrimental to the environment.
biomass-based route to produce propylene glycol. Weis and Visco,41 developed a study using computer-aided
molecular design to identify potential new environmentally
friendly solvents as a supplement to GlaxoSmithKline’s 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 graffiti
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.
Fig. 6 Some potential derivatives of lactic acid.28,35
Other applications of ethyl lactate are as a cleaning agent
for the polyurethane industry and for metal surfaces, efficiently
Ethyl lactate properties and applications removing greases, oils, adhesives and solid fuels. Recently, it
also been shown to be effective on the removal of copper from
Ethyl lactate can be used as a food additive, in perfumery, contaminated soils.45 Ethyl lactate can also be applied in the
as flavour chemicals and solvent, which can dissolve acetic pharmaceutical industry as a dissolving/dispersing excipient for
acid cellulose and many resins.37 Its main application is as a various biologically active compounds without destroying the
solvent, being particularly attractive for the coatings industry pharmacological activity of the active ingredient. It is a very
as a result of its high solvency power, high boiling point, low effective agent for solubilising biologically active compounds
vapour pressure and low surface tension. Some physical and that are difficult to solubilise in usual excipients.46,47 Ethyl lactate
thermodynamic properties of ethyl lactate as well of the species can also be used as a more environmentally friendly alternative
involved in its synthesis are presented in the Appendix.
Almost all manufacturing and processing industries depend
Table 1 The solvating properties of ethyl lactate and N-methyl
on the use of solvents (see Fig. 7). Some industry experts suggest pyrrolidone
that ethyl lactate could replace the traditional solvents in more
than 80% of their applications.38 However, this is probably N-Methyl
Ethyl lactate pyrrolidone
highly inflated, since ethyl lactate is a high boiling polar protic
Kauri Butanol(KB) Value >1000 350
solvent13 and there are applications where non-polar, aprotic
and/or lower boiling point solvents are required. Annually, just Solubility Hildebrand parameter 21.3 23.1
in the U.S.A, the solvents demand is about 10 billion pounds parameters
Disperse Hansen parameter 7.8 8.8
at prices from $0.90 to $1.70 per pound. Selling prices for
Polar Hansen parameter 3.7 6.0
ethyl lactate have ranged from $1.50 to $2.00 per pound, but

2662 | Green Chem., 2011, 13, 2658–2671 This journal is © The Royal Society of Chemistry 2011
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Table 2 The major advantages of ethyl lactate The self-esterification degree increases with increasing acid
concentration. This makes the use of lactic acid difficult as
Ethyl Lactate Benefits
a reactant for ethyl lactate synthesis, since the use of a high
100% Biodegradable Renewable – made from corn and lactic acid concentration implies the presence of lactic acid
other carbohydrates oligomers during the esterification, which will be converted into
FDA approved as a flavour EPA approved SNAP solvent the corresponding esters that simultaneously undergo hydrolysis
additive
Non carcinogenic Non corrosive
and transesterification, leading to a mixture of acid and ester
Great penetration Stable in solvent formulations until monomer and oligomers:
characteristics exposed to water
Rinses easily with water High solvency power for resins, 2La1 ¤ La2 + W (lactic acid dimer formation)
polymers and dyes
High boiling point Easy and inexpensive to recycle
Low VOC Not an ozone depleting chemical
La1 + La2 ¤ La3 + W (lactic acid trimer formation)
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

Low vapor pressure Not a hazardous air pollutant

route to produce 1,2-propanediol, which is normally produced ...


by the hydration of propylene oxide derived from petrochemical
resources.48
A significant amount of solvents are used in pharmaceutical La1 + Lan-1 ¤ Lan + W (lactic acid oligomer formation)
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manufacturing processes; indeed, it was estimated that around with n ≥ 2


80% of the total mass of chemicals involved in the pharmaceuti-
cal manufacture comprises solvents.49 The redesign of synthetic La1 + Eth ¤ EL1 + W (ethyl lactate formation)
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 La2 + Eth ¤ EL2 + W (ethyl lactate dimer formation)
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 La3 + Eth ¤ EL3 + W (ethyl lactate trimer formation)
aldimines,50 synparvolide B,51 varitriol,52 among others. It was
also used as a green solvent to extract phytosterols from wet corn
fiber, 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 Lan + Eth ¤ ELn + W (ethyl lactate oligomer formation)
The major advantages of ethyl lactate are summarized in
Table 2. where:

4. Synthesis of ethyl lactate


The conventional way to produce ethyl lactate is the esterification
of lactic acid with ethanol catalyzed by an acid catalyst,
according to the reaction:
+
Ethanol ( Eth ) + Lactic A cid ( La) ←⎯⎯
H

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 esterification in aqueous solutions above 20 wt%
to form a linear dimer, and higher oligomer acids.55,56 An 88 Some of the kinetic studies regarding ethyl lactate syn-
wt% lactic acid solution comprises 43.5 mol% of monomer thesis are performed using a 20 wt% lactic acid solution in
(La1 ), 9.2 mol% of dimer (La2 ), 1.8 mol% of trimer (La3 ) and order to avoid the formation of oligomers, but even when
about 45 mol% of water. On the other hand a 20 wt% aqueous higher lactic acid concentrations are used, the presence of
solution of lactic acid is constituted only by monomer and oligomers is normally neglected. Just two works take into
water, with a monomer molar percentage of about 5.6 mol%.57 account the oligomers; however, their amount is less than 5%

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Table 3 Summary of the kinetic studies of the esterification reaction between ethanol and lactic acid

Lactic acid Activation


Temperature solution Oligomers Expression of Energy
Refs. Catalyst range (wt.%) presence Kinetic model the components (kJ mol-1 )

Troupe and DiMilla, 195761 Sulfuric acid 25–100 ◦ C 85; 44 neglected empirical equation concentrations 62.47
Tanaka et al., 200237 Amberlyst 15 90–92 ◦ C 91 considered simple nth-order concentrations 47.00c
reversible rate
expressions
Benedict et al., 200362 Without catalyst 95 ◦ C 88 neglected homogeneous concentrations —
Amberlyst XN-1010 75–95 ◦ C 88 neglected based on single-site concentrations 30.54
mechanisms
Engin et al., 200363 Heteropoly acid 70 ◦ C 92 neglected simple nth-order concentrations —
supported on reversible rate
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

Lewatit
R S100 expressions
Zhang et al., 200464 002 60–88 ◦ C 20 neglected Langmuir– activitiesa 51.58
Hinshelwood
NKC Langmuir– activitiesa 52.26
Hinshelwood
57 ◦
Asthana et al., 2006 Amberlyst 15 62–90 C 20; 50; 88 considered simple nth-order concentrations 48.00c
reversible rate
expressions
Delgado et al., 200760 Amberlyst 15 55–86 ◦ C 20 neglected Langmuir– activitiesb 52.29
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Hinshelwood

Without catalyst 55–85 C 20 neglected homogeneous activitiesb 62.50
Pereira et al., 200858 Amberlyst 15 50–90 ◦ C 88 neglected Langmuir– activitiesb 49.98
Hinshelwood
Bamoharram et al., 201065 Preyssler acid 70–85 ◦ C 20 neglected simple nth-order concentrations 47.11
reversible rate
expressions
a
activity coefficients calculated by the UNIFAC model. b activity coefficients calculated by the UNIQUAC model. c activation energy of the lactic
acid monomer esterification.

at equilibrium.37,57 The extent of oligomer formation depends equilibrium constant defined as function of the species liquid
on the water concentration, but also on the ethanol contents; activities, described by the following expression: ln(K) = 2.9625
for example, for a lactic acid solution of 88 w.%, the oligomers - 515.13/T(K).58 There is another work regarding the vapour–
composition at equilibrium is 2.4 molar% when using a molar liquid reactive equilibrium for the ethyl lactate synthesis,59 where
ratio between ethanol and lactic acid of 1 and of 0.4 molar% the thermodynamic equilibrium constant is also determined,
when using an ethanol : lactic acid molar ratio of 3.58 but the values predicted by the proposed equilibrium constant
Esterifications are self-catalyzed reactions, since the H+ cation expression present high deviations from the experimental ones.
released from the partial dissociation of the carboxylic acid As mentioned previously, the hydrolysis of ethyl lactate is also
used as a reactant catalyses the reaction. However, the use of an important reaction since it can be used to obtain highly pure
a catalyst is favourable for the reaction rate as the kinetics of the lactic acid. However, just one work presents a study regarding
self-catalyzed reaction are extremely slow, since its rate depends this subject.60
on the autoprotolysis of the carboxylic acid. For example, the
lactic acid acidity constant is pK a = 3.86 at 25 ◦ C, and therefore
5. Production processes
an aqueous solution with 85% of lactic acid (about 10.8 M)
has a pH = 1.4. Typically, the catalytic production of lactates There are a considerable number of patented processes for ethyl
is performed with homogeneous catalysts using acids, such lactate production; in most of them, the esterification reaction
as sulphuric acid, phosphoric acid and anhydrous hydrogen between ethanol and lactic acid is carried out until equilibrium
chloride. However, the use of a heterogeneous catalyst (as for and then the ethyl lactate is separated from the reaction mixture
example, zeolites, ion-echange resins like Amberlyst 15-wet, by distillation. In order to overcome the equilibrium limitation,
Nafion NR50, among others) has clear advantages, i.e.: easy an excess of ethanol is applied and a strong acid is used as
to separate from the reaction mixture; long life time; higher a catalyst, the most common being sulphuric acid.66–69 There
purity of products (side reactions can be eliminated or are are similar processes, but using ammonium lactate instead of
less significant); and elimination of the corrosive environment lactic acid.70–75 A recent work76 presents the synthesis of ethyl
caused by the discharge of acid containing waste. A summary lactate from ammonium lactate solution by the coupling of
of the kinetic studies performed for lactic acid esterification solvent extraction with esterification. Dimethyl sulfoxide, N-
with ethanol is presented in Table 3. As can be seen, the kinetic methyl pyrrolidine and triethyl phosphate were evaluated as
model is usually expressed in terms of species concentration; solvents, but the last proved to be the most efficient.
few authors take into account the non-ideality of the reaction Arkema (France) has two patented processes related to
mixture using activities instead of concentration. There are a continuous ethyl lactate production from the esterification
reasonable number of kinetic studies for this system available reaction between lactic acid and ethanol using sulphuric acid
in the literature; however, only one presents the thermodynamic as catalyst. One consists of extracting a mixture comprising

2664 | Green Chem., 2011, 13, 2658–2671 This journal is © The Royal Society of Chemistry 2011
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ethyl lactate, ethanol, water and different heavy products from this is followed by separation of the reaction mixture in two
the reaction medium at partial lactic acid conversion rate consecutive distillation columns or, alternatively, by several
and, then, feeding the mixture to a reduced-pressure flash pervaporation steps (see Fig. 8).81 It is reported that a lactic
separation, producing an overhead stream containing a mixture acid conversion of 99% and an ethyl lactate purity of 76% was
of ethyl lactate, ethanol and water, that is subjected to a obtained, for an initial ethanol/lactic acid molar ratio of 2 : 1, a
fractional distillation column.77,78 The other is characterized by reaction mixture temperature of 95 ◦ C, a permeate-side vacuum
the continuous extraction of a near-azeotropic water/ethanol pressure less than 0.5 mbar and, as the catalyst, an ion-exchange
gas mixture from the reaction medium, followed by dehydration resin, Amberlyst XN-1010, at 10% of lactic acid weight.
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
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

the first process (initial ethanol/lactic acid molar ratio equal to


2.5; esterification carried out at 80 ◦ C; flash 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 separa-
tion units in order to recover the ethyl lactate, to remove the
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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 efficient are preferable for ethyl lactate production.
Fig. 8 A schematic representation of ethyl lactate production using a
reactor coupled with a pervaporation membrane unit and followed by:
5.1 Process intensification 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 The ethyl lactate synthesis on pervaporation and vapour-
a by-product, thus its production is improved using multifunc- permeation membrane reactors was also studied by other
tional reactors, where reaction and separation are integrated into authors. Three different configurations were adopted (Fig. 9):
a single unit, since at least one of the products is continuously (i) batch reactor, where the esterification reaction takes place,
removed from the reaction mixture to lead to depletion of the followed by a membrane for water removal, and reflux of the
limiting reactant, increasing the ethyl lactate yield and purity. retentate to the reactor;62,81–85 (ii) membrane inside a batch
Some reactive separation processes have already been studied reactor37,86,87 and (iii) continuous integrated membrane reactor,
for ethyl lactate production, as membrane reactors, reactive that consists of a tubular membrane packed with a heteroge-
distillation and chromatographic reactors. These studies are neous catalyst (Amberlyst 15-wet).88 The type of hydrophilic
presented next. membranes tested were polymeric,62,81,82 ceramic88 and organic–
inorganic hybrid membranes84,87 for pervaporation and zeolites
5.1.1. Membrane based processes. The Argonne National for vapour permeation.37,86 A summary of the results obtained
Laboratory patented a process that consists of a reactor coupled for ethyl lactate synthesis by means of membrane reactors is
with a pervaporation membrane unit for water removal and presented in Table 4.

Table 4 Ethyl lactate production by means of membrane reactors

Membrane water Eth/La molar La


Refs. Membrane Temperature flux (kg m-2 h-1 )a Catalyst ratio Conversion EL Purity

Rathin and GFT PerVap 1005 95 ◦ C 1.20 Amberlyst XN-1010 2.0 99% 76%
Shih-Perng,
199881
Jafar et al., 200286 zeolite A 70 ◦ C 0.18 p-toluene sulphonic acid 2.0 95% —
Tanaka et al., zeolite T 120 ◦ C 0.33 Amberlyst 15 2.4 99% —
200237
Benedict et al. GFT PerVap 1005 95 ◦ C — Amberlyst XN-1010 1.2 71%d —
2003, 200662,82
Budd, et al., zeolite/polyelectrolyte 100 ◦ C 0.60b p-toluenesulfonic acid 2.0 90% —
200487 multilayer
c
0.19
Ma et al., 200984 chitosan–TEOS 80 ◦ C 0.27 Amberlyst 15 3.0 80%e —
Pereira et al., Microporous silica 70 ◦ C 2.55 Amberlyst 15 1 98% 96%
201088
a
for water/ethanol liquid mixture (ª10/90 wt%); b sheet membrane (70 ◦ C); c tube membrane (70 ◦ C); d after 8 h; e after 9 h.

This journal is © The Royal Society of Chemistry 2011 Green Chem., 2011, 13, 2658–2671 | 2665
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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.

5.1.2 Reactive distillation. The reactive distillation (RD)


technology was successfully implemented by Asthana and
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

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
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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

from an economic point of view, than a traditional batch or a


continuous process, for an intermediate range of ethyl lactate
Fig. 10 A schematic representation of a reactive distillation unit for production, however, for high production rates, the continuous
the production of ethyl lactate. process remains the most suitable.
5.1.4 Chromatographic reactors. The application of a sim-
5.1.3 Distillation and membrane based process. A novel ulated moving bed reactor (SMBR) for ethyl lactate production
semicontinuous distillation (SD) process was proposed by was studied by Pereira et al.,92 where it is reported an ethyl lactate
Adams and Seider,91 where a distillation column interacting with productivity of 18.06 kgEL /(Lads .day)), a desorbent consumption
a middle vessel, a continuous stirred tank reactor (CSTR) and of 4.75 LEth /kgEL and an ethyl lactate purity of 95% (without
a pervaporation unit are used. The reaction takes place in the ethanol), when using this technology at 50 ◦ C, ethanol as
CSTR until equilibrium is reached, then the reaction mixture is a desorbent and Amberlyst-15 wet resin as a catalyst and
moved to the middle vessel that is integrated with the distillation selective adsorbent for water (see Fig. 12). The maximum ethyl
column, and the CSTR is recharged. The middle vessel feeds a lactate productivity attained was 31.7 kgEL /(Lads .day)), but it was
reaction mixture to the distillation column, which recycles back accompanied by a high consumption of ethanol (7.6 LEth /kgEL ).
a side stream. During the cycle, ethanol and water are collected When using SMBR technology, two diluted streams are ob-
in the distillate and are separated in a pervaporation unit using tained: the extract and the raffinate (Fig. 12), requiring two
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 flow rates, eventually approaching zero flow, 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, Fig. 12 A schematic diagram of the SMBR unit the with configuration
the middle vessel contains highly concentrated ethyl lactate (see 3-3-4-2 applied to ethyl lactate synthesis. Each box represents a SMBR
Fig. 11). It was shown that the SD process is more feasible, column packed with the resin Amberlyst-15 wet.

2666 | Green Chem., 2011, 13, 2658–2671 This journal is © The Royal Society of Chemistry 2011
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Table 5 Basic properties of lactic acid, ethanol, ethyl lactate and water95

Properties Lactic Acid Ethanol Ethyl Lactate Water

Molecular weight – M/g mol-1 90.079 46.069 118.133 18.015


Density – r/g cm-3 1.209 0.789 1.031 1.027
Melting temperature – T f (K) 289.95–291.15 159.15 248.25 273.15
Normal boiling temperature – T b (K) 395.15 351.45 426.15–427.15 373.15
Critical temperature – T c (K) 616.00 516.25 588.00 647.13
Critical pressure – Pc (bar) 59.65 63.84 38.60 221.20
Critical volume – V c (cm3 mol-1 ) 216.9 166.9 354.0 57.1
Acentric factor – w 1.035 0.637 0.793 0.344

additional separation steps. In order to achieve high ethyl lactate lactate productivity, but with the penalty of the consumption
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

productivity without the penalty on the consumption of ethanol, of desorbent, which should be further separated and recycled
a new technology was recently developed: the simulated moving in the SMBR unit, two subsequent separation units being
bed membrane reactor (PermSMBR), which comprises the necessary. PermSMBR seems the most promising technology
integration of hydrophilic membranes into the SMBR columns93 for ethyl lactate production, since it operates at moderate
(Fig. 13). These membranes enhance the water removal, allowing temperatures (70 ◦ C), and results in high ethyl lactate production
the elimination of the extract stream and leading to a better rates, low desorbent consumption and just one additional
performance for ethyl lactate production, as shown in the work separation step to separate ethyl lactate from ethanol. However,
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of Silva and collaborators.94 For ethyl lactate synthesis, the RD it requires vacuum costs and the limitations associated with the
and SMBR processes require more than 152% and 165% of membranes’ stability/durability are also an issue. Moreover, the
the ethanol consumption, respectively, of the new PermSMBR proof-of-concept of this technology has not yet been performed.
technology. 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 efficient 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
(configuration 3-3-4-2) for ethyl lactate synthesis. Each box represents Density and molar volume
a PermSMBR column that consists of a set of membranes packed with
The modified form of the Rackett equation was selected for
the Amberlyst 15-wet resin.
the correlation of saturated liquid density as a function of
temperature,
6. Conclusions T n
−(1− )
(A.1)
A literature survey regarding ethyl lactate production processes rL = A B Tc

was presented in this review with special focus on reac-


tive/separation processes, since they provide the most feasible with rL (g cm-3 ) and T/K. The constants used are presented in
engineering solution to the sustainable synthesis of ethyl lactate, Table 6.
as at least one of the products is continuously removed from the The molar volumes for all components were estimated with
reaction mixture, leading to depletion of the limiting reactant. the Gunn–Yamada method:96
Membrane reactors, reactive distillation and chromatographic f (T )
V (T ) = VR (A.2)
reactors, namely, SMBR and PermSMBR technologies, have f (T R )
been successfully implemented for ethyl lactate synthesis. In
all these processes, it was possible to attain nearly complete
where
lactic acid conversion and high ethyl lactate purity (≥95%),
although under different operating conditions. The RD process f (T) = H 1 (1 - wH 2 ) (A.3)
is the one that requires more heat supply, since it operates at
high temperatures (128 ◦ C bottom temperature); however, the H 1 = 0.33593 - 0.33953T r + 1.51941T 2r - 2.02512T 3r +
(A.4)
capital costs are lower and it is a more industrially consolidated 1.11422T 4r
technology. The membrane reactor requires more moderate
temperatures (around 70 ◦ C) and an extra separation step is H 2 = 0.29607 - 0.9045T r - 0.04842T 2r (A.5)
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 T TR
Tr = or (A.6)
costs. Using the SMBR it is possible to attain high ethyl Tc Tc

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Table 6 Constants used for density calculation95 Table 9 Ethyl lactate viscosity for different temperatures at atmo-
spheric pressure
Constants Lactic Acid Ethanol Water Ethyl Lactate
h (cP) 278.15 K 298.15 K 318.15 K
A 0.39816 0.26570 0.34710 0.33372
B 0.26350 0.26395 0.27400 0.21190 Estimated by Eq. A.7 (Ref. 95) 4.55 2.21 1.26
n 0.28570 0.23670 0.28571 0.45530 Experimental (Ref. 97) — 2.40 —
T min (K) 291.15 159.05 273.16 247.15 Experimental (Ref. 98,99) 4.75 2.53 1.6
T max (K) Tc Tc Tc Tc

Table 10 Viscosity of lactic acid


Table 7 Molar volumes at the reference temperature
T/K 293.15 323.15
VR (cm3 mol-1 ) h (cP) 53.67 13.99
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

Reference Temperature
TR (K) Lactic Acid Ethanol Ethyl Lactate Water
Table 11 Constants used for vapour pressure calculation95
293.15 74.640 58.174 113.986 18.082
Constants Lactic Acid Ethanol Water Ethyl Lactate

V R is the molar volume at the reference temperature T R A -27.0836 23.8442 29.8605 32.0863
B -3.9661 ¥ 103 -2.8642 ¥ 103 -3.1522 ¥ 103 -2.9164 ¥ 103
(cm3 mol-1 ), w is the acentric factor and T c is the critical T/K.
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C 2.0233 ¥ 101 -5.0474 -7.3037 -9.5666


The Gunn–Yamada method could be used just in the case D -4.2176 ¥ 10-2 3.7448 ¥ 10-11 2.4247 ¥ 10-9 6.5114 ¥ 10-3
when the liquid molar volume is known at some temperature E 2.0310 ¥ 10-5 2.7361 ¥ 10-7 1.8090 ¥ 10-6 4.5645 ¥ 10-13
T min (K) 291.15 159.05 273.16 247.15
(reference temperature). The reference molar volumes are pre-
T max (K) Tc Tc Tc Tc
sented at Table 7.

Viscosity
Table 12 Constants used for heat capacity calculation95
The correlation for liquid viscosity as a function of temperature
Constants Ethanola Watera Ethyl Lactate Lactic acida
is given by eqn (A.7) (see constants in Table 8).
A 1.0264 ¥ 105 2.7637 ¥ 105 -46.239 6.1082 ¥ 104
B
log10 hL = A + + CT + DT 2 (A.7) B -1.3963 ¥ 102 -2.0901 ¥ 103 2.1823 5.0343 ¥ 102
T C -3.0341 ¥ 10-2 8.1250 -5.9832 ¥ 10-3 —
D 2.0386 ¥ 10-3 -1.4116 ¥ 10-2 6.8683 ¥ 10-6 —
with hL (cP) and T/K. E — 9.3701 ¥ 10-6 — —
Ethyl lactate viscosity data are very scarce in the literature. T min (K) 159.05 273.16 248.00 289.90
T max (K) 390.00 533.15 529.00 675.00
Some works just present the viscosity of this compound at a Error <3% <1% — <10%
single temperature.97 However, in the works of Aparicio and
a
Alcalde the values of ethyl lactate viscosity for a wide range parameters taken from ref. 100.
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 Table 13 Constants used for heat vaporization calculation100
presented. As can be seen, the correlation estimates smaller
Constants Ethanol Water Ethyl Lactate Lactic acid
viscosity values than the ones obtained experimentally. At
278.15 K, the correlation leads to a value 4% smaller than the A 5.5789 ¥ 107 5.2053 ¥ 107 8.0260E ¥ 107 1.0436 ¥ 108
value reported in Aparicio and Alcalde.98,99 B 3.1245 ¥ 10-1 3.1990 ¥ 10-1 4.0930 ¥ 10-1 3.8548 ¥ 10-1
The lactic acid viscosity might be estimated by the following C — -2.1200 ¥ 10-1 — —
D — 2.5795 ¥ 10-1 — —
expression:100 T min (K) 159.05 273.16 247.15 289.90
T max (K) 514.00 647.13 588.00 675.00
⎛ 4097.9 ⎞
hLA = exp ⎜⎜−14.403 + − 0.4407 × ln(T )⎟⎟⎟ (A.8) Error <1% <1% <10% <25%
⎜⎝ T ⎠

Table 8 Constants used for viscosity calculation95


with hLA (Pa s)and T/K. The lactic acid viscosity at two
temperatures is presented in Table 10.
Constants Ethanol Water Ethyl Lactate
Vapour pressure
A -6.4406 -10.2158 -20.0105
B 1.1176 ¥ 103 1.7925 ¥ 103 3.2123 ¥ 103 The Antoine-type equation with extended term was selected for
C 1.3721 ¥ 10-2 1.7730 ¥ 10-2 4.1891 ¥ 10-2 correlation of vapour pressure as a function of temperature:
D -1.5465 ¥ 10-5 -1.2631 ¥ 10-5 -3.2733 ¥ 10-5
T min (K) 240 273 247 B
T max (K) Tc 643 Tc log10 Pvp = A + + C log10 T + DT + ET 2 (A.9)
T

2668 | Green Chem., 2011, 13, 2658–2671 This journal is © The Royal Society of Chemistry 2011
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Table 14 Constants used for thermal conductivity calculation100

Constants Ethanol Water Ethyl Lactate Lactic acid

A 2.4680 ¥ 10-1 -4.3200 ¥ 10-1 2.8358 ¥ 10-1 3.4850 ¥ 10-1


B -2.6400 ¥ 5.7255 ¥ 10-3 -3.5110 ¥ 10-4 -3.7085 ¥ 10-4
10-4
C — -8.0780 ¥ 10-6 — —
D — 1.8610 ¥ 10-9 — —
T min (K) 159.05 273.16 247.15 289.90
T max (K) 353.15 633.15 427.65 490.00
Error <5% <1% <25% <10%

with Pvp (mmHg) and T/K.95 The constants used in the vapour
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G

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.
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Fig. 14 Variation of the vapour pressure of the compounds with the Fig. 16 Variation of the heat of vaporization of the different species
temperature. with the temperature.

Thermal conductivity
Liquid heat capacity
The thermal conductivity was calculated by eqn (A.12) using the
The correlation for the heat capacity of a liquid is a series
constants presented in Table 14.100
expansion in temperature, given by eqn (A.10).
l = A + BT + CT 2 + DT 3 + ET 4 (A.12)
C p = A + BT + CT 2 + DT 3 + ET 4 (A.10)
-1 -1
with l (W m K ) and T/K.
with C p (J kmol-1 K-1 ) and T/K, with exception for the ethyl The coefficients for each chemical compound for all the cor-
lactate species where C p is given in J mol-1 K-1 . relations presented in this appendix were based on appropriate
The liquid heat capacity as a function of temperature was experimental data available in the literature, with the exception
estimated by the above equation (Fig. 15), using the constants of the Gunn–Yamada method to estimate the molar volume,
presented in Table 12. since this is based on the corresponding-states principle.

Heat of vaporization
Acknowledgements
The correlation selected for the calculation of the heat of
The authors acknowledge financial support provided by
vaporization as a function of temperature is given by eqn
Fundação para a Ciência e a Tecnologia (Portugal) through
(A.11).100
the project PPCDT/EQU/61580/2004 and post-doctoral grant
SFRH/BPD/71358/2010 of C.S.M. Pereira.
DH V = A ⎡⎣1−T r ⎤⎦(B +CT r +DT r )
2
(A.11)

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