Green Surfactants
Green Surfactants
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                                                                                     Res. J. Chem. Environ.
and classification of green surfactants, technological                 compared to other biosurfactants. However, cost-
developments, global scenario and path forward.                        competitiveness is one of the major factors holding
                                                                       rhamnolipids back from becoming the champions of their
Classification of green surfactants                                    field.
On the basis of the origin, the green surfactants can be
classified in two categories:                                          Sophorolipids: Sophorolipid is surface-active glycolipid
                                                                       compound composed of carbohydrate head and lipid tail5.
 Biologically derived (biosurfactants) green surfactants              This is a class of microbial biosurfactants which consists of
                                                                       a hydrophobic fatty acid tail of 16 or 18 carbon atoms and a
 Chemically derived green surfactants                                 hydrophilic carbohydrate head, sophorose.
The classification of green surfactants is depicted in fig. 1.
                                                                       They have gained increased attention as potential bio-
                                                                       surfactants due to their biodegradability and low eco-toxicity
Biologically derived (biosurfactants) green surfactants:
                                                                       and renewable raw material based production. Today
Surfactants produced by biologically route are called as
                                                                       sophorolipids are considered promising bio-surfactants34.
biosurfactants. They are produced by yeast or bacteria from
various substrates including sugars, oils, alkanes and wastes.
                                                                       Surfactin: Surfactin is a lipopeptide-type biosurfactant that
Biosurfactants are categorized as glycolipids, lipopeptides,
                                                                       is generated by the gram-positive, endospore-producing,
phospholipids, fatty acids, neutral lipids, polymeric and
                                                                       microorganism Bacillus subtilis. Surfactin consists of a
particulate compounds26. The hydrophobic part of these
                                                                       peptide loop of seven amino acids (aspragine, L-leucine,
surfactants is based on long chain fatty acids and the
                                                                       glutamic acid, L-leucine, L-valine and two D-leucines)40.
hydrophilic part can be carbohydrate, amino acid, cyclic
                                                                       The potential applications of surfactin are therapeutic
peptide, phosphate, carboxylic acid or alcohol.
                                                                       applications and environmental applications.
The examples of main biosurfactants are rhamnolipids,
                                                                       Lecithin: Lecithin is a multi-purpose food ingredient that
sophorolipids, surfactin and lecithin etc. Rhamnolipids are
                                                                       primarily functions as an emulsifier and dispersing agent15.
well-characterized and scientifically proven biosurfactants
                                                                       Lecithins are a complex mixture of glycolipids,
which are slowly and steadily becoming highly sought
                                                                       phospholipids, triglycerides and carbohydrates. As such,
biomolecules.
                                                                       lecithin interacts well with other substances in foods such as
                                                                       proteins, lipids and carbohydrates.
Rhamnolipids: Rhamnolipid is composed of β-hydroxy
fatty acid connected by the carboxyl end to a rhamnose sugar
                                                                       Lecithin is prepared by extracting and purifying
molecule.     Rhamnolipid      provides     non-toxic    and
                                                                       phospholipids from naturally occurring products such as
environmentally friendly biosurfactant applications and
                                                                       soybeans, eggs, sunflower and canola seeds.
innovative technologies to various industries including
agricultural and environmental11. Rhamnolipids have the
                                                                       The structure and applications of biosurfactants are
highest number of patents and research publications as
                                                                       summarized in table 1.
Green Surfactants
             Glycolipids                                                         Alkylpolyglycosides
             Lipopeptides                                                        Fatty acid methyl ester
             Phospholipids                                                       Methyl ester sulfonate
             Fatty acids                                                         Fatty alcohols
             Neutral lipids                                                      Fatty acid sulfates
             Polymeric and particulate compounds                                 Sucrose esters
                                                                                  Sorbitan esters
                                                                                  Betains
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                                                                                     Res. J. Chem. Environ.
                                                           Table 1
                                          Structure and applications of biosurfactants
   Bio-surfactants          Type                          Chemical Structure                                Applications
    Rhamnolipids         Glycolipids                                                                  Personal care applications
                                                                                                    Bioremediation of organic and
                                                                                                            heavy metal
Chemically derived green surfactants: Surfactants derived               Alkyl Polyglycosides: Alkyl polyglycosides (APGs) are
by synthetic route using natural and renewable resourcesare             non-ionic surfactants derived from sugars, mainly glucose or
environment friendly are called chemically derived green                its derivatives and fatty alcohols42. For industrial
surfactants. Chemically green surfactants are classified as             manufacturing of APGs, the raw materials are starch and fat.
alkyl polyglycosides, methyl ester ethoxylate, methyl ester             Alkyl polyglycosides are nontoxic, renewable, green
sulfonate, fatty alcohols, fatty acid sulfates, sucrose esters,         surfactants which are environment friendly and used in such
sorbitan esters and betaines.                                           industries as food, beverages, pharmaceuticals, cosmetics or
                                                                        detergents. They are used as foaming agent in detergents for
Renewable sources of hydrophilic groups include                         cleansing applications.
carbohydrates, proteins, amino acids and lactic acid and
sources of the hydrophobic moiety as steroids,                          Methyl ester ethoxylate: Methyl ester ehoxylates (MEE)
monoterpenes, rosin acids, fatty acids and long chain alkyl             are a type of renewable surfactant derived by ethoxylation of
groups as well as aromatic compounds. Chemically derived                fatty acid methyl ester (FAME) (Fig. 2)20. Fatty acid methyl
green surfactants have been synthesized using renewable                 ester are synthesized (Fig. 3) by the reaction of fats with
resources such as amino acids, sugars and organic acids and             methanol in the presence of base such as sodium hydroxide,
they have been used in human life because of their low                  sodium methoxide or potassium hydroxide7.
toxicity and high biodegradability.
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                                                                                     Res. J. Chem. Environ.
                                 O                    O                    O
                                                                                                      O
                                               Kolb's catalyst
                         R            O                           R                 O
                                                                                                           n
                                     Fig. 2: Ethoxylation of fatty acid methyl ester (FAME)
R1 O
       O                                                                                        CH3
                                                                                                                 OH
                   O             O                                                        O
                                                                               R1
                                                                                    O
                                              +     3CH3OH                                      CH3   +                   OH
                                       R2
                             O
                                                                                          O
                                                                               R2
                                                                                    O
                                                                                                                    OH
                                                                                                CH3
                    O
                                                                                          O
                                                                               R3
        O
                       R3
                Triglyceride                        Methanol               Fatty acid methyl ester             Glycerol
                           Fig. 3: Trans-esterification of triglycerides into fatty acid methyl ester
                                                                                        COOMe
            R           COOMe             Sulphonation
                                                                       R                          +        MeOSO3Na
                                             Base
                                                                                        COOMe
        Fatty acid methyl ester                                  Methyl ester sulfonate Sodium methyl sulfate
                       Fig. 4: Sulfonation of fatty acid methyl ester into methyl ester sulfonate
Methyl ester sulfonate: Methyl ester sulfonates (MES) are             Sorbiton Esters: Sorbitan esters are nonionic surfactants
anionic surfactants that can be made by sulfonation of                used as emulsifiers in the preparation of emulsions, creams
saturated fatty acid methyl esters derived from natural fats          and ointments for pharmaceutical and cosmetic use. Sorbitan
and oils10 (Fig. 4). Because of these properties and because          esters are well known emulsifiers and produce stable water-
of the perceived potential for cheap availability of the              in-oil emulsions with a variety of textures and
feedstocks, interest has grown in using MES in combination            consistencies14. Sorbitan esters are synthesised from 1,4-
with other anionic surfactants in laundry powders and                 anhydro-sorbitol and fatty acids. Ethoxylated derivatives of
soaps35.                                                              sorbitan esters can also be prepared by the reaction of
                                                                      various moles of ethylene oxide to the sorbitan
Fatty Alcohols: Fatty alcohols (or long-chain alcohols) are           monoglycerol ester and on the basis of various ethylene
usually high-molecular-weight, straight-chain primary                 oxide (EO) moles, they have a wide range of HLB18.
alcohols, but can also range from as few as 4–6 carbons to
as many as 22–26 derived from natural fats and oils. The              Betains: Betaine is one class of amphoteric surfactants.
precise chain length varies with the source. The main sources         Because of its structure, it can exist in only two ionic forms,
and large-scale feedstock of fatty alcohols are various               zwitterionic and cationic. Amphoteric surfactants are a class
vegetable oils. They find use as co-emulsifiers, emollients           of compounds that have both a positive (+) and negative (-)
and thickeners in cosmetics and food industry13.                      charge in the same molecule. The structure shown is a
                                                                      zwitterionic form, having both positive and negative charges
Sucrose Esters: Sucrose esters are a group of surfactants             present in the same molecule.
chemically synthesized from esterification of sucrose and
fatty acids. These are biodegradable surfactants that can be          As the pH is decreased, the carboxyl group is protonated and
manufactured in various hydrophilic-lipophilic balances               a compound with a positive (+) charge develops. Due to this
(HLB) through the use of different fatty acids and they have          behavior, betaines provide better conditioning in low-pH
the ability to bind both water and oil simultaneously and act         systems. Since the nitrogen is surrounded by carbon atoms,
as emulsifiers 38.                                                    it cannot lose its positive (+) charge by pH alteration28.
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                                                          Table 2
                            Structure and applications of chemically derived green surfactants
              Green                           Chemical Structure                                Applications
            surfactants
               Alkyl                                                                      Cosmetic, household and
           polyglycoside                                                                   industrial applications
The structure and applications of chemically derived green              a hydrophobic fatty acid chain. The sugar at the hydrophilic
surfactants are summarized in table 2.                                  end is sophorose in the sophorolipids, rhamnose in the
                                                                        rhamnolipids and mannose and erythritol in MELS22. The
Technological Developments                                              sophorolipids are produced by yeasts of the genus Candida
The development of surfactants based on natural renewable               comprising usually 8 major and 15 minor components. The
resources is a concept that is gaining recognition in personal          fatty acid chain typically has 16 or 18 carbon atoms with
care and detergent industries. This new class of                        different degrees of saturation39.
biodegradable and biocompatible surfactants is a response to
the increasing consumer demand for products that are                    Rhamnolipid surfactant has been produced by the bacterium
greener and more efficient. In order to achieve these                   Pseudomonas aeruginosa using C10 and C12 fatty acyl
objectives, it is necessary to use renewable low cost                   chains by fermentation process9. MELs are produced by
materials that are available in large quantities and to develop         basidiomycetous yeasts of the genus Pseudozyma with
new green surfactants that show improved performance in                 medium chain length of fatty acyl esters2. Low cost
terms of lower eco-toxicity and reduced environmental                   fermentative medium using molasses and cheese whey was
impact4.                                                                developed for biosurfactant production by L. Lactis 53 and
                                                                        S. thermophilus A.36 Trehalose lipids synthesized by
Microbially produced glycolipid biosurfactants / green                  Rhodococcus erythropolis are typical compounds in which
surfactants comprise a hydrophilic carbohydrate section and             the fatty acid moiety depends on the carbon chain length
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whereas the hydrophilic moiety is not affected by the                 to petroleum feedstock. Personal care and homecare
carbonsubstrates16.                                                   companies are looking at alternatives to synthetic surfactants
                                                                      and emulsifiers to use sustainable materials. The move
In the enzymatic reaction, the fatty acid is esterified to            towards green surfactants is due to consumer demands for
trehalose-6-phosphate which is subsequently subjected to              sustainable products as well as industry pressure to adopt
dephosphorylation and further modification8. A pea protein            renewable feedstock.
isolate was hydrolyzed by enzyme treatment to obtain
peptide sequences used as raw materials to synthesize                 Global scenario of green surfactants
lipopeptides-based surfactants. Pea protein hydrolysates              With increasing demand for green products with favorable
were synthesized using the enzymes such as Alcalase and               regulatory outlook in developed countries, the global green
Flavourzyme.                                                          surfactant market is growing. Due to increasing consumer
                                                                      awareness and need for ecologically safe products, bio-
The effect of the process parameters was studied to optimize          surfactants is one of the alternatives. But the existing and
the proteolytic degradation of hydrolysis. The average                potential demand for surfactants is very high and it cannot
peptide chain lengths were obtained at 3–5 amino acid units           be catered by biosurfactants alone.
after a hydrolysis of 30 min with the mixture of enzymes3.
Green surfactants based on mannuronate moieties derived               At the commercial level, green surfactants have been
from alginates (cell-wall polyuronic acids from brown                 available since more than a decade now. Green surfactants
seaweeds) and fatty hydrocarbon chains were derived from              are mainly used in personal care and cleansing applications
vegetable resources. Controlled chemical and/or enzymatic             due to mildness and low toxicity. Recent survey by
depolymerizations of the algal polysaccharides give                   transparency research market has revealed that the
saturated and/or unsaturated functional oligomannuronates.            worldwide biosurfactants market volume is expected to be
An amino based surfactant was prepared by the reaction of             476,512.2 tons by 2018. The global market value of
cysteine    with      N-cetyl-N,N-dimethyl-N-ß-aminoethyl             biosurfactants was US$ 1735.5 million in 2011 and it is
ammonium chloride25.                                                  expected to grow at a rate of 3.5% annually and reach US$
                                                                      2210.5 million by year 20186.
Surfactants containing the sugar moiety as a hydrophilic
group have been synthesized by many researchers and used              Europe and North America are the mainproducers and
as detergents, emulsifiers and cosmetics36. The syntheses             consumers of green surfactants. Asia Pacific has high
and properties of anionic, cationic and amphoteric                    potential for production and consumption of bio-based green
surfactants containing amino acid moieties such as arginine           surfactants due to more strict regulations about toxicity. Key
24,30, tryptophan29, lysine37, cysteine43, glutamate and
                                                                      players operating in the Green surfactants market include
aspartate1 have also been reported. Polycarboxylate based             Tate and Lyle Plc, ADM, Cargill Inc., Du Pont, DSM,
surfactants with either sulfide- (S-) or imino- (N-) linkages         Ingredion Incorporated, Roquette Freres and Südzucker AG
were produced by addition reaction of fatty mercaptan or              Company 32.
fatty amine with unsaturated polycarboxylic acids such as
maleic, fumaric, aconitic, anditaconic acids. They exhibited          Jencil Biosurfactants, USA has become a renowned
surfactant properties and excellent biodegradabilities27.             company in this field. AGAE Technologies LLC, USA and
                                                                      Rhamnolipid Inc, USA are main manufacturers of
Green surfactants have been synthesized using renewable               rhamnolipids. Fraunhofer IGB, Germany is invoved in
and sustainable resources as raw materials i.e. amino acids,          production     of    mannosylerythritol    lipids.    Other
sugars and organic acids etc. due to their low toxicity and           manufacturers of biosurfactants are Ecochem Ltd., Canada,
high biodegradability. Several families of surfactants were           Sigma Aldrich Co., USA, Saraya, Japan, Intobio, South
prepared using environment friendly processes using by-               Korea, Solience, France and Allied Carbon Solutions, Japan.
products of sugar and oleochemical industries, glycins and            Evonik, Germany is main producer of biosurfactant
betains with attractive surface tension, good foaming and             sophorolipid32.
emulsifying capabilities with potential applications in
detergency and cosmetic industry19.                                   India’s Biosurfactants Market is expected to demonstrate
                                                                      moderate growth over the coming years owing to the
Semi-natural, eco-friendly and biodegradable surfactant was           increasing demand for green substitutes of synthetic and
developed using starch and some synthetic surfactants with            conventional surfactants in the country. The increasing
good emulsifying efficiency and surfactant performance                applications in polymer, oilfields, construction chemicals,
properties and analyzed by FT-IR, XRD and SEM23. Alkyl                cosmetics and many other industries are probing the
polyglucoside is a type of non-ionic green surfactant.                consumption of biosurfactants in the country. In India the
Dodecyl polyglucoside was synthesized by glucose and                  major manufacturers of biosurfactants are– Evonik India
dodecanol using P-toluenesulfonic acid as catalyst by one             Pvt. Ltd., Mitsubishi India, Vetline and Galaxy Surfactants
step process21. Green surfactants from waste biomass and              Ltd., India etc.33
agricultural raw materials are gaining attention as compared
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Total Indian surfactant market earned revenues of $2278                  recovery, green surfactants are not yet widely used in
million in 2013 and was expected to reach $3748 million in               industry compared to synthetic surfactants. Hence to
2017 approximately. India constitutes about 9% of total                  overcome these drawbacks, it is needed to do research using
global    surfactants   consumption        (volume     basis).           cheap renewable resources such as natural waste and to
Multifunctional surfactants are gaining acceptance in Indian             enhance product recovery so that the cost of green
consumer segment37. Green Catalyst Processes for the                     surfactants is reduced and these can because approachable
manufacture of Amino Acid Surfactants (including,                        for surfactant consumers in diversified applications.
Glycinates, Sarcosinates, Taurates and Glutamates) were
developed by Galaxy Surfactants43. In India, although some               Acknowledgement
manufacturers are manufacturing the bio-surfactants but the              The authors wish to express their sincere thanks to
research on green surfactant in India is in preliminary stage.           Management of Shriram Institute for Industrial Research,
                                                                         Delhi, India, for their encouragement and support.
Path Forward
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