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Green Surfactants

This document discusses green surfactants, which are surface active molecules synthesized from natural resources that are environmentally friendly. It begins by providing background on conventional surfactants and their negative environmental impacts. It then describes various types of green surfactants, including those derived biologically from microorganisms (biosurfactants) and those derived chemically from renewable resources. Specific biologically derived biosurfactants discussed include rhamnolipids, sophorolipids, and surfactin. The document concludes by stating that green surfactants have promising properties and meet eco-friendly criteria, and that more attention is being given to developing them as sustainable alternatives to conventional surfactants.
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0% found this document useful (0 votes)
228 views9 pages

Green Surfactants

This document discusses green surfactants, which are surface active molecules synthesized from natural resources that are environmentally friendly. It begins by providing background on conventional surfactants and their negative environmental impacts. It then describes various types of green surfactants, including those derived biologically from microorganisms (biosurfactants) and those derived chemically from renewable resources. Specific biologically derived biosurfactants discussed include rhamnolipids, sophorolipids, and surfactin. The document concludes by stating that green surfactants have promising properties and meet eco-friendly criteria, and that more attention is being given to developing them as sustainable alternatives to conventional surfactants.
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Research Journal of Chemistry and Environment_______________________________________Vol.

25 (6) June (2021)


Res. J. Chem. Environ.
Review Paper:
Green Surfactants: Technological Innovations
and Path Forward
Arora Pinklesh* and Kaicker Praveen Kumar
Material Science Division, Shriram Institute for Industrial Research, 19, University Road, Delhi-110007, INDIA
*pinklesh@shriraminstitute.org

Abstract aqueous solutions (cationic, anionic) or remain un-ionised


Surfactants are surface active agents that reduce (non-ionic). Major types of synthetic surfactants include
surface tension in water and other liquids. Surfactants linear alkyl benzene sulphonates, alcohol sulphates, alcohol
are composed of both hydrophilic (lipopohbic) and ether sulphates, alcohol glyceryl ether sulphonates, alcohol
ethoxylates and alkyl phenol ethoxylates etc.41
hydrophobic (lipophilic) groups. The discharge of
surfactants in water bodies has serious effects on the Surfactants have been widely used in personal care and
ecosystem if they persist long, leading to the cleansing applications. The major part of the surfactants
accumulation of potentially toxic and harmful reaches the environment after their use and residual
substances. To overcome these drawbacks of the surfactants are discharged into sewage systems or directly
surfactants, there is a great need of new alternate into surface waters and most of them end up dispersed in
chemicals, effective and compatible with the different environmental compartments such as soil and
environment. Green surfactants are surface active water.
molecules synthesized using wide variety of natural
resources. Their hydrophilic part contains Industries worldwide discharge a wide range of surfactants
to their waste water treatment facilities. The discharge of
polysaccharide, amino acids, peptide or protein,
surfactants in water bodies has serious effects on the
whereas the hydrophobic part is composed of saturated ecosystem if they persist long leading to the accumulation of
or unsaturated fatty acids, hydroxy fatty acids or fatty potentially toxic and harmful substances17.
alcohols.
Most of the surfactants are petroleum derived synthetic
The development of surfactants based on natural compounds and are toxic to health and ecosystems and
renewable resources is a concept of green chemistry resistant to complete degradation. Water pollution caused by
that is gaining recognition in detergents and cosmetics. synthetic surfactants has been increasing during the past few
In this study, attempts have been made to describe the years due to their extensive use in household, agriculture and
type and classification, technological developments, other cleaning operations. Certain classes of surfactants are
global scenario of green surfactants followed by path present in sufficient concentrations to constitute toxicity
problems to aquatic organisms.
forward.
To overcome these drawbacks of the surfactants, there is a
Keywords: Surfactants, green chemistry, bio-surfactants,
great need of new alternate chemicals, effective and
environment-friendly.
compatible with the environment. The demand for green
surfactants is increasing. Green surfactants have promising
Introduction properties and fulfill the eco-friendly criteria.
Surfactants (also called surface active agents or wetting
agents) are organic compounds. The most common The surface active agents that are produced from renewable
applications of surfactants are as soaps, laundry detergents, resources that are environment friendly, are considered to be
dish washing liquids and shampoos. Other important uses of green surfactants31. These molecules can be used in various
surfactants are in many industrial applications such as fields as multifunctional materials for new era. Green
lubricants, emulsion polymerisation, textile processing, surfactants are surface active molecules synthesized by wide
mining flocculates, petroleum recovery, wastewater variety of natural sources. Their hydrophilic part contains
treatment and agriculture etc 12. Surfactants are compounds polysaccharide, amino acids, peptide or protein whereas the
composed of both hydrophilic or lipophobic and hydrophobic part is composed of saturated or unsaturated
hydrophobic or lipophilic groups. The hydrophobic part of a fatty acids, hydroxy fatty acids or fatty alcohols.
surfactant is generally derived from a hydrocarbon
containing 8 to 20 carbon atoms (e.g. fatty acids, paraffins, Green surfactants have recently received much more
olefins, alkylbenzenes) and hydrophilic parts are generally attention in concern with the protection of environment,
sulfates, sulfonates and ethoxylates etc. making them “green” chemicals, primarily because of their
inherent good biodegradability and low toxicity. In the
Surfactants are classified as cationic, anionic, zwitterionic present study, an attempt has been made to review the types
and non-ionic. The hydrophilic portion may ionise in

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Research Journal of Chemistry and Environment_______________________________________Vol. 25 (6) June (2021)
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

Biologically Derived Chemically derived

 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

Fig. 1: Classification of Green Surfactants

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Research Journal of Chemistry and Environment_______________________________________Vol. 25 (6) June (2021)
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

Sophorolipids Glycolipid Antimicrobial agents


Foaming agents
Cleaning applications
Personal care applications
Emulsifiers

Lactone form Acid form

Surfactin Cyclic Antibacterial, antiviral and


lipopeptide anti-inflammatory applications
Anti-adhesive applications

Lecithin Phospholipid Pharmaceuticals


Animal feed and food additive
Paint industries
Release agent Anti-gumming
agent, Emulsifier, spreading
agent and antioxidant

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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Research Journal of Chemistry and Environment_______________________________________Vol. 25 (6) June (2021)
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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Research Journal of Chemistry and Environment_______________________________________Vol. 25 (6) June (2021)
Res. J. Chem. Environ.
Table 2
Structure and applications of chemically derived green surfactants
Green Chemical Structure Applications
surfactants
Alkyl Cosmetic, household and
polyglycoside industrial applications

Methyl ester O Cleansing and detergent


ethoxylate applications
O
R O
n
Methyl ester Laundry Detergent powders &
sulfonete detergent cakes

Fatty alcohol Emulsifiers, thickeners in food


H3C OH and cosmetic industry
n
Sucrose ester Cosmetics, food preservatives,
food additives

Sorbitan Ester Emulsifiers in pharmaceuticals


and food industries

Betaines Foaming booster in cleansing


applications, emulsifying agents,
thickener

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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Research Journal of Chemistry and Environment_______________________________________Vol. 25 (6) June (2021)
Res. J. Chem. Environ.
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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Research Journal of Chemistry and Environment_______________________________________Vol. 25 (6) June (2021)
Res. J. Chem. Environ.
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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