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[1] - Ethyl lactate as a solvent Properties, applications and production processes – a review

[1] - Ethyl lactate as a solvent Properties, applications and production processes – a review

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Green Chemistry 
Green Chem.
, 2011,
13
, 2658www.rsc.org/greenchem
TUTORIALREVIEW
Ethyl lactate as a solvent: Properties, applications and productionprocesses – a review
Carla S. M. Pereira, Viviana M. T. M. Silva* and Al´ırio E. Rodrigues
Received 6th May 2011, Accepted 11th July 2011
DOI: 10.1039/c1gc15523g
Ethyl lactate is an environmentally benign solvent with effectiveness comparable topetroleum-based solvents. The worldwide solvent market is about 30 million pounds per year, whereethyl lactate can have an important share. It is considered a chemical commodity and has attractedmuch attention in recent years, since it is formed by the esterification reaction of ethanol and lacticacid, which can be generated from biomass raw materials through fermentation. In this work, anoverview regarding the main properties and applications of ethyl lactate, as well as its synthesis andproduction processes, with a particular emphasis on reactive/separation processes, is presented.
1. Introduction
Organic esters are a very important class of chemicals havingapplications in a variety of areas in the chemical industry, suchasperfumes,flavours,pharmaceuticals,plasticizers,solventsandintermediates.
1
Ethyl lactate is an important monobasic ester,also known as lactic acid ethyl ester (IUPAC name: Ethyl (
)-2-hydroxypropanoate), with molecular formula C
5
H
10
O
3
(seeFig. 1). It is a clear to slightly yellow liquid, and it is foundnaturallyinsmallquantitiesinawidevarietyoffoods,includingwine, chicken, and some fruits.Ethyl lactate can be either in the levo (
) or dextro (
R
) forms,and it is industrially produced as a racemic mixture througha reversible reaction between ethanol and lactic acid, whereinwater is a by-product. Lactic acid itself is a very importantchemical with applications in the food, pharmaceutical andcosmetic industries. It is also used as a monomer for the manu-facture of biodegradable polymers, as substitutes for traditionalpetrochemical polymers. Lactic acid has been produced throughboth chemical synthesis or fermentation routes. This last pro-cess is the most common,
2
however, lactic acid derived fromfermentation broths requires extensive purification processesthat should be inexpensive and environmentally friendly. Ethyllactatehydrolysisisoneofthemethodsusedtoobtainpurelacticacid.
3,4
Ethyl lactate has attracted much attention in recent years,which is reflected in the number of articles published, as shownin Fig. 2. This is probably due to the environmental movementthat emerged in the 1970s (United Nations Conference on theHuman Environment at Stockholm in 1972). Chemical legisla-
Laboratory of Separation and Reaction Engineering (LSRE), AssociateLaboratory LSRE/LCM, Department of Chemical Engineering, Facultyof Engineering, University of Porto, Rua Dr Roberto Frias s/n,4200-465, Porto, Portugal. E-mail: viviana.silva@fe.up.pt; Fax: +351225081674; Tel: +351 225081489
Fig. 1
The molecular structure of ethyl lactate.
tion and environmental regulation were mainly nation based,until the 1980s. Since then, with the increase of internationalchemical trade and the knowledge of the impact of globaltrade on the environment, international environmental treaties,directives, and conventions have emerged.
5
Moreover, it was inthe 1980s that environmental protection was connected witheconomicdevelopment,leadingtodisseminationof“sustainabledevelopmentas a means to encourage the integration of policies across sectors (Rio Declaration on Environment andDevelopment and Johannesburg Declaration on SustainableDevelopment, informally known as Earth Summit 1992 and2002, respectively). Furthermore, with the Yom Kippur War(1973) and the subsequent Arab Oil Embargo, the IranianRevolution (between November 1978 and June 1979), andthe Iraq–Iran War (1980), crude oil production declined, and,consequently, the crude oil price increased drastically, from 3USD per barrel in 1972 up to 35 USD in 1981. More recently,the PDVSA strike (Venezuela, 2002–2003) and the Iraq War
2658
|
GreenChem.
, 2011,
13
, 2658–2671This journal is
©
The Royal Society of Chemistry 2011
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View Online / Journal Homepage / Table of Contents for this issue
 
Carla Pereira was born in 1980 in Coimbra, Portugal. She obtained her Ph.D. degree in Chemical and Biological Engineering fromPorto University (FEUP) in 2009 working on process intensification for the sustainable production of ethyl lactate based on membraneand chromatographic reactors under the supervision of Professor Al ´ ırio Rodrigues and Dr Viviana Silva. This work was developed inthe 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.VivianaSilva(1974)receivedherPh.D.inChemicalEngineeringfromUniversityofPorto(Portugal)in2003.In2001,shewasAssistantProfessor at Instituto Polit´ ecnico de Braganc¸a (Portugal) and, in 2006, she joined Fluidinova (Portugal) as Group Leader. In November2007, 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 forthe production of nanoparticles and microcapsules based on the NETmix
R
technology.Al ´ ırio 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).
From left to right: Viviana Silva, Al´ırio E. Rodrigues, Carla Pereira
Fig. 2
Publications related to ethyl lactate since 1980 using alldatabases. Total number of publications with “ethyl lactate” in thetopic
=
1566. Total number of publications with “ethyl lactate” inthe title
=
304. Total number of publications with “ethyl lactate” +“synthesis”
=
51. Data were obtained from ISI Web of Knowledge on5th of July 2011.
(2003), together with a weak dollar and the continued rapidgrowth in Asian economies and their petroleum consumption,the crude oil price reached a new maximum of 126 USD perbarrel in June 2008, followed by a drastic drop due to thefinancial crisis, being currently at about 94 USD.
6
Consideringboth the environmental regulations, as well as the increase incrude oil prices, the search for greener chemicals obtained fromrenewable 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 theincreasing interest, less attention is being given to bio-basedsolvents, such as the lactate ester family solvents,
8
in which ethyllactate is the most important member.Currently, a great challenge is the design and implementa-tion of completely green products and processes. There is nosystematic and reliable method to ensure that the chemistryimplemented is green, since the number of chemical synthesispathways is vast, and in general it is only possible to verifyif a proposed manufacturing process is “greener” than otheralternatives. Anastas and Warner have developed the “TwelvePrinciples of Green Chemistry”, which are a list of suggestionson 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 wasteafter it is formed.
 This journal is
©
The Royal Society of Chemistry 2011
GreenChem.
, 2011,
13
, 2658–2671 |
2659
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View Online
 
2. Synthetic methods should be designed to maximize theincorporation of all materials used in the process into the finalproduct.3. Wherever practicable, synthetic methodologies should bedesigned to use and generate substances that possess little or notoxicity to human health and the environment.4. Chemical products should be designed to preserve efficacyof function while reducing toxicity.5. The use of auxiliary substances (
e.g.
solvents, separationagents,
etc.
)shouldbemadeunnecessarywheneverpossibleand,innocuous when used.6. Energy requirements should be recognized for their en-vironmental and economic impacts and should be minimized.Synthetic methodsshouldbe conducted at ambient temperatureand pressure.7.Arawmaterialorfeedstockshouldberenewableratherthandepleting whenever technically and economically practical.8. Unnecessary derivatization (blocking group, protec-tion/deprotection, and temporary modification of physi-cal/chemical processes) should be avoided whenever possible.9. Catalytic reagents (as selective as possible) are superior tostoichiometric reagents.10.Chemicalproductsshouldbedesignedsothatattheendof their function they do not persist in the environment and breakdown into innocuous degradation products.11. Analytical methodologies need to be further developed toallow for real-time in-process monitoring and control prior tothe formation of hazardous substances.12. Substances and the formof a substance usedin a chemicalprocess should be chosen so as to minimize the potentialfor chemical accidents, including releases, explosions, andfires.The 2nd principle can be quantitatively evaluated throughSheldon’s E-factor, which is a very simple green chemistrymetric, defined by the ratio of the mass of waste per unit of desired product.
10,11
To evaluate how green a product is, theenvironmental impact associated with all the stages of its life(production, use, and disposal) should be quantified using, forexample, the life cycle assessment (LCA) methodology.
12
Forthosewhodonothavethedataand/ortheskillsrequiredtodoaproperLCAofasolvent,Jessop
13
suggestsasimplemethodologyto do a quick “green-ness test”, that involves the analysis of the solvent’s synthesis tree. In that work it is reported that theethyl lactate synthesis involves more chemical steps than thesynthesisofhexaneormethanol,buthassignificantlyfewerstepsthan some ionic liquids, such as 1-butyl-3-methyli-midazoliumacetate ([Bmim]OAc).Anyway, ethyl lactate is in accordance with at least eight of the “Twelve Principles of Green Chemistry”:1)Ethyllactatecanbeproducedfromrenewablerawmaterialsthat can be a more environmentally friendly alternative topetrochemical solvent:
7
th
principle
.2) Ethyl lactate is 100% biodegradable, easy to recycle, non-corrosive, non-carcinogenic and non-ozone depleting.
14
Indeed,it is so benign that the U.S. Food and Drug Administrationapproved its use in food products:
3
rd
, 4
th
and 10
th
principles
.3) Ethyl lactate can be produced through heterogeneouscatalysis without using an excess of any of the reactants; theelimination of homogenous catalysts (usually mineral acids)avoids the use of corrosive catalysts and, thus, eliminates afurther step of their neutralization:
1
st
and 9
th
principles
.4) Ethyl lactate can be produced by using hybrid technologieswhere reaction and separation of at least one product take placein a single unity eliminating the use of solvents, reducing thecapital cost (less separation units are needed) and requiring lessenergy consumption:
5
th
and 6
th
principles
.In summary, as shown in Fig. 3, ethyl lactate can be easilyobtained by carbohydrate feedstocks, since it is produced fromethanol and lactic acid that are obtained by fermentation of biomass, as corn starch crops; and it is a biodegradable com-pound with good properties to be applied as a green solvent inseveral applications, such as organic synthesis, pharmaceuticalpreparations, fragrances, for inks and coatings industries, andfood additives.
Fig. 3
The life cycle of ethyl lactate.
Followingthesefourtopics,thisreviewwilladdress:(i)theuseof renewable resources, where the concept of a biorefinery willbe briefly introduced and the platform of the chemicals involvedin the ethyl lactate synthesis will be presented; (ii) ethyl lactate’smain properties and applications; (iii) its synthesis through theesterification reaction between ethanol and lactic acid; and (iv)ethyl lactate production processes with particular emphasis onprocess intensification.
2. Renewable resources
In recent years, an increasing demand for using biorenewablematerials instead of petroleum based feedstocks for chemicalsproduction, driven by environmental concerns and by theconcept of sustainability, has been noticed. Biobased productsare one of the main pillars of a sustainable economy. Natureproduces170billiontonsofbiomassperyearbyphotosynthesis,75% of which belong to the class of carbohydrates; however, just3–4%ofthesecompoundsareusedbyhumansforfoodandnon-food purposes.
15
Carbohydrates are very abundant renewableresources and they are currently considered as an important
2660
|
GreenChem.
, 2011,
13
, 2658–2671This journal is
©
The Royal Society of Chemistry 2011
   D  o  w  n   l  o  a   d  e   d   b  y   I  n  s   t   i   t  u   t  o   M   i   l   i   t  a  r   d  e   E  n  g  e  n   h  a  r   i  a  o  n   2   5   F  e   b  r  u  a  r  y   2   0   1   2   P  u   b   l   i  s   h  e   d  o  n   1   5   A  u  g  u  s   t   2   0   1   1  o  n   h   t   t  p  :   /   /  p  u   b  s .  r  s  c .  o  r  g   |   d  o   i  :   1   0 .   1   0   3   9   /   C   1   G   C   1   5   5   2   3   G
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