Production of Green Surfactants Market Prospects

Electronic Journal of Biotechnology 51 (2021) 28–39
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Electronic Journal of Biotechnology

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Review
Production of green surfactants: Market prospects q

Charles Bronzo B. Farias a,b,c, Fabíola C.G. Almeida a,c, Ivison A. Silva a,b,c, Thais C. Souza c,
Hugo M. Meira a,c, Rita de Cássia F. Soares da Silva a,c, Juliana M. Luna a,c,
Valdemir A. Santos a,c, Attilio Converti c,d, Ibrahim M. Banat c,e, Leonie A. Sarubbo a,b,c,⇑
a
Universidade Católica de Pernambuco (UNICAP), Rua do Príncipe, n. 526, Boa Vista, Recife, Pernambuco CEP 50050-900, Brazil
b
Rede Nordeste de Biotecnologia (RENORBIO), Universidade Federal Rural de Pernambuco (UFRPE), Rua Dom Manuel de Medeiros, s/n, Dois Irmãos, CEP: 52171-900 Recife, PE, Brazil
c
Instituto Avançado de Tecnologia e Inovação (IATI), Rua Potyra, 31 - Prado, Recife, Pernambuco CEP: 50751-310, Brazil
d
Università degli Studi di Genova (UNIGE), Dipartimento di Ingegneria Civile, Chimica e Ambientale (DICCA), Via Opera Pia, n. 15, 1-16145 Genova, Italy
e
Faculty of Life and Health Sciences, School of Biomedical Sciences, University of Ulster, BT52 1SA Northern Ireland, UK
a r t i c l e i n f o a b s t r a c t
Article history: Science has greatly contributed to the advancement of technology and to the innovation of production
Received 8 September 2020 processes and their applications. Cleaning products have become indispensable in today’s world, as per-
Accepted 23 February 2021 sonal and environmental hygiene is important to all societies worldwide. Such products are used in the
Available online 11 March 2021
home, in most work environments and in the industrial sectors. Most of the detergents on the market are
synthesised from petrochemical products. However, the interest in reducing the use of products harmful
Keywords: to human health and the environment has led to the search for detergents formulated with natural,
Biosurfactants
biodegradable surfactant components of biological (plant or microbiological) origin or chemically synthe-
Cleaning product
Detergents
sised from natural raw materials usually referred to as green surfactants. This review addresses the dif-
Green surfactants ferent types, properties, and uses of surfactants, with a focus on green surfactants, and describes the
Surfactant market current scenario as well as the projections for the future market economy related to the production of
Surfactants the different types of green surfactants marketed in the world.
How to cite: Farias CBB, Almeida FCG, Silva IA, et al. Production of green surfactants: Market prospects.
Electron J Biotechnol 2021;51. https://doi.org/10.1016/j.ejbt.2021.02.002
Ó 2021 Pontificia Universidad Católica de Valparaíso. Production and hosting by Elsevier B.V. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
2. Detergents and soaps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3. Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.1. Synthetic surfactants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.1.1. Main reactions for producing synthetic surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.2. Green surfactants (biosurfactants) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.2.1. Biosurfactants of microbial origin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.2.2. Biosurfactants of plant origin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.2.3. Economy and global market of green surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
3.2.4. Green surfactants manufacturing industries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Financial support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Peer review under responsibility of Pontificia Universidad Católica de Valparaíso

⇑ Corresponding author.
E-mail address: leonie.sarubbo@unicap.br (L.A. Sarubbo).
https://doi.org/10.1016/j.ejbt.2021.02.002
0717-3458/Ó 2021 Pontificia Universidad Católica de Valparaíso. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Charles Bronzo B. Farias, Fabíola C.G. Almeida, I.A. Silva et al. Electronic Journal of Biotechnology 51 (2021) 28–39
1. Introduction practices and more efficient products to do household chores.

Therefore, the focus of detergents has changed, with greater
The development of industrialisation in most economic markets emphasis on practicality, efficiency, and shorter application time.
has received considerable support from the advances achieved As a result, detergents became a commercial success of chemistry
through the uninterrupted encouragement of science, with innova- in the Twentieth Century and, together with soaps, they currently
tive research projects and the proper use of technology over time account for 85% of the world’s consumption of cleaning materials.
[1,2]. Investigations and explorations of natural resources, such Detergents clean in the same way as soaps (through fat solubilisa-
as fossil fuels, and the use of hydrocarbons, such as crude oil, have tion), but they can have both negative and positive charges [16].
had a positive impact on today’s economy and society through the Detergents are synthetic products derived from petroleum that
parallel advancement of science. However, pollutants produced by are produced by chemical means and leave residues that can pol-
these exploration activities and their harmful by-products, such as lute rivers and other environments. Over the years, there has been
heavy metals and inorganic substances or recalcitrant organic an increase in the use of biodegradable detergents, which do not
compounds that end up in ecosystems, soils, rivers, and oceans, have these shortcomings and are made up of linear chain (un-
are harmful to terrestrial and marine flora and fauna [3,4]. branched) organic compounds that allow organisms to degrade
Petroleum is in demand in various industrial sectors and is part them effectively. Therefore, the need to develop clean products
of the world energy matrix due to its high energy value and its and technologies has led to the use of different techniques to opti-
importance for the chemical industry. The discovery of petroleum mise production systems as well as the creation of tools aimed at
has led to huge changes in the economic development of interna- sustainability. However, this implementation continues to be a
tional markets and the consequent improvement in technologies challenge for the consumer goods industry [17].
in the modern world of the past century [5,6,7,8,9]. The detergent Detergents and soaps reach numerous markets for use in homes
industry deserves particular attention, as the raw materials of as well as commercial businesses and large companies. Different
these products are often derived from petroleum. Cleaning prod- versions of detergents are used for household cleaning, the food
ucts have become indispensable, as hygiene has become important industry and heavy cleaning in industrial settings [18].
to mankind worldwide and is used in homes, different work envi-
ronments and most industrial sectors. 3. Surfactants
The detergent market includes products for different applica-
tions such as cleaning products for homes, personal hygiene and Surfactants are tensioactive agents responsible for the cleaning
industrial cleaning of heavy oils. MarketsandMarketsTM data pre- property of detergents and can be of a synthetic or natural origin
dicted that the global cleaning products industry will achieve a [8,19,20]. Surfactants are amphipathic compounds with hydrophi-
growth rate of $ 46.8 billion in 2019, with estimates of $ 58.3 bil- lic and hydrophobic portions that preferably partition at the inter-
lion by 2024 and an annual growth rate of 4.5% [10]. This perspec- face between liquid phases with different degrees of polarity, such
tive is based on factors such as the growing awareness of as oil/water or air/water interfaces [19], as illustrated in Fig. 1. This
populations around the world on the issues of health, hygiene, characteristic reduces the surface tension of liquids through speci-
and cleanliness [11,12]. The detergent industry has also shown a fic, preferential interactions at surfaces and interfaces due to the
growing interest in developing environmentally friendly products, presence of hydrophilic and hydrophobic portions in the same
which each year account for a larger share of the market, particu- molecule [21,22]. The non-polar portion of a surfactant is often a
larly through the growth of biotech industries. This need for sus- hydrocarbon chain, whereas the polar portion (hydrophilic head
tainability is causing a shift in the detergent industry that is group) may be ionic (cationic or anionic), non-ionic, or amphoteric
potentially moving away from synthetic surfactants to replace [9]. The dynamics of the surfactant market are determined at a fun-
them with more sustainable alternatives. One way to achieve this damental level by the cost, variety, and availability of hydrophobes
has been the potential utilization of green surfactants [5,8,9]. as well as the cost and complexity of attaching or creating hydro-
This paper offers a description of biotechnological advances philic head groups [16].
involving natural surfactants of microbial or plant origin and the The efficiency of a surfactant is determined by its ability to
use of biodegradable synthetic surfactants, as well as a market reduce surface tension, which is the mechanical energy required
analysis of the biosurfactant industry and the expected changes to create a unit new area of a liquid surface. Surfactants increase
in the detergent market in the near future. the aqueous solubility of hydrophobic molecules, reducing the sur-
face/interfacial tension of air/water and oil/water surfaces/inter-
2. Detergents and soaps faces. Good surfactants can reduce the surface tension of water
from 72 mN/m to 35 mN/m and the interfacial tension (tension
Records of soaps and cleaning agents date back to ancient civil- between polar and non-polar liquids) of water and n-hexadecane
isations, with products made by Sumerians, Egyptians, Babyloni- from 40 mN/m to 1 mN/m [23,24].
ans, Jews, and many other people. The first soaps and detergents, Surface tension decreases with the increase in surfactant con-
which were made with clay, animal fat, plants that contained sapo- centration in the aqueous medium up to the formation of micelles,
nin, and essential oils, were used for hygienic and medicinal pur- which are aggregated structures with the hydrophilic portion posi-
poses. Over time, products have been prepared for different uses, tioned towards outside of the molecule and the hydrophobic por-
with the addition of specific materials suitable for each application, tion positioned towards the inside. The critical micelle
such as detergents for cleaning metal surfaces, degreasers, soap concentration (CMC) is the concentration that corresponds to the
powder, dish detergent and soap for personal hygiene. All these point at which the surfactant achieves the lowest stable surface
products were born according to customer needs and have been tension, i.e., the minimum concentration of surfactant necessary
adapted to the context of each era [13,14,15]. for the maximum reduction in the surface tension. Micelles are
Detergents began to be industrially produced during the Second usually formed when the CMC is reached [25].
World War due to the scarcity of oils and fats for the manufacture
of soaps, and in the United States the consumption of detergents 3.1. Synthetic surfactants
surpassed that of soaps by 1953. Another example of product adap-
tation occurred in the mid Twentieth Century, when women were Most surfactants of synthetic origin can be obtained from five
finding jobs in the labour market and needed less time-consuming simple reactions, which are described in more detail below. Among
29
Fig. 1. Surfactant molecule at interface (A). When adsorbed, the surfactant is oriented at the oil/water interface so that its hydrophobic portion is directed towards the oil,
while the hydrophilic portion is directed towards the water (B).
these processes, basically two types of reactions are responsible for

more than half of the industrial production of surfactants, as most
of the surfactants produced are either anionic (negatively charged)
or non-ionic (neutral) [26]. The preference for these types of sur-
factants is due to their low toxicity and higher biodegradability
compared to cationic and amphoteric surfactants [27].
The two major classes of inputs used in the production of sur-
factants are petrochemical and renewable sources [3,28]. The
development of petrochemical processing, especially petroleum
cracking, resulting in unsaturated, short-chain hydrocarbons,
enabled the acquisition of hydrophobic structures of surfactant
molecules through polymerization of these alkenes, such as ethy-
lene or propylene, giving rise to surfactants with C9 to C18 carbon
chains. Although ethylene has been employed as a carbon chain
building block, its increased applicability in the industrial surfac-
tant production has resulted from the production of an intermedi-
ate or precursor known as ethylene oxide, which is a key
component of ethoxylation [29].
Surfactants of a natural origin are normally obtained from veg-
etable oils or animal fat, which appear in the form of triglycerides
[16]. Prior to petrochemical processing, much of the surfactant
industry was essentially directed to the saponification of oils and
fats, yielding soluble salts of fatty acids, which can be subjected
to the same reactions as their non-renewable counterparts. Such
reactions allow modifying the chemical and physical properties
of compounds to meet the needs of industrial segments working
with product formulation and development [16,29].
3.1.1. Main reactions for producing synthetic surfactants Fig. 2. Reaction between dodecyl benzene and sulfur trioxide to form anionic
surfactant dodecylbenzenesulfonic acid (A). Reaction between dodecanol and sulfur
The most common sulfonation reaction employed in the surfac-
trioxide forming the surfactant hydrogen dodecyl sulfate (B). Generic ethoxylation
tant industry occurs between an alkylbenzene and sulfur trioxide, reaction between ethylene oxide and alcohol function (C). Generic esterification
forming alkylbenzene sulfonates, as illustrated in Fig. 2A. The main reaction between a carboxylic acid and alcohol, forming ester and water (D).
feature of this type of compounds is a direct bond between carbon Reaction of a secondary amine with halide, forming tertiary amine (E).
and sulfur. Due to their acidic characteristics, these types of surfac-
tants are normally neutralised as sodium salts as the final product.
Although it appears similar, the sulfation reaction has crucial dif- The creation of these chains occurs by reaction between ethylene
ferences that lead to a less stable product, an ester of a mineral acid oxide and an alcohol (Fig. 2C), which is generally a fatty alcohol
(generally sulfuric acid), which is susceptible to hydrolysis if not in the case of surfactants [30]. The surfactants produced in this
neutralized. The formation of these compounds occurs through a way, known as ethoxylated fatty alcohols, are very numerous, since
reaction between aliphatic or aromatic alcohols and sulfur trioxide the length of their chain (described by the subscript ‘‘n” in Fig. 2C)
through the carbon–oxygen bond (Fig. 2B). Although most reac- can vary from one to 10 carbon atoms. Ethoxylation reactions are
tions occur with the use of sulfuric acid or its anhydrous form (sul- generally combined with other reactions described in the produc-
fur trioxide), it is possible to obtain similar compounds using tion of synthetic surfactants [16].
phosphoric acid [16]. Esterification is one of the simplest reactions employed in the
Ethoxylation is one of the most important reactions in indus- production of surfactants, whose practicality also lies in the wide
tries that produce synthetic surfactants, given the possibility of availability of reagents involved, such as fatty acids found in oils
creating numerous tensioactive molecules with different hydro- and fats and a compound with alcoholic functions like glycerol or
philic–lipophilic balances. This reaction consists in the creation one of the many types of sugars. In general, the esterification pro-
of ether groups whose chain terminations normally have alcohol cess consists of the reaction between an acid (generally carboxylic
functions responsible for the hydrophilic portion of the molecule. acid) and an alcohol, as illustrated in Fig. 2D. Monoglycerides are
30
examples of surfactants produced by this type of reaction, which hydrophobic portion consisting of a hydrocarbon chain or one or
are widely used in the food industry as emulsifying agents. Many more fatty acids, which can be saturated, unsaturated, hydroxy-
of these surfactants are classified as non-ionic and have low toxic- lated, or branched, linked to a hydrophilic portion, which can be
ity and high biodegradability, especially if derived from renewable an ester, hydroxyl group, phosphate, carboxylate, carbohydrate,
sources. Therefore, the cosmetic and food industries often employ amino acid, or peptide. Most biosurfactants have neutral or anio-
them in commercial formulations [31]. nic polar groups ranging from small fatty acids to large polymers
Alkylation, which consists of the transfer of an alkyl group from [40,41].
one structure of the molecule to another, can be performed in dif- As mentioned above, biosurfactants are of paramount impor-
ferent ways. This reaction is mainly employed in the petroleum tance in the current scenario, as these compounds are considered
industry to increase the size of the carbon chains of the molecules, ecologically sound products due to their low (or absent) toxicity
as mentioned above. However, some of these processes end up and high biodegradability. Compared to their synthetic counter-
producing branched types of carbon chains, which later proved parts, biosurfactants are more efficient at reducing surface and
extremely harmful to the environment [16]; therefore, new types interfacial tensions and are tolerant to high temperatures as well
of alkylation have been developed to create linear chains that could as extreme values of pH and ionic strength [34,42]. They are also
be more easily degraded. The creation of longer carbon chains is considered versatile compounds thanks to their broad applicability
only one of the possible applications of alkylation in the production in the petroleum, chemical, food, pharmaceutical, textile, and agri-
of surfactants. Other classes of surfactants that benefit from this cultural industries [43,44,45,46].
type of reaction are cationic and amphoteric surfactants, as an
amine can react with a haloalkane to form a substituted alky-
lamine and the respective halogen acid (Fig. 2E) [32]. 3.2.1. Biosurfactants of microbial origin
Although the hydrophilic head groups of surfactants usually fall Microbial surfactants are a structurally diverse group of com-
into one of the four categories described above, there are a number pounds ranging from simple molecules, such as phospholipids
of exotic hydrophobic ‘‘tail” groups, both synthetic and natural, and fatty acids, to glycolipids, lipopeptides and high molecular
which confer unique surface-active properties to all classes of sur- weight polymers, such as lipopolysaccharides. The hydrophilic por-
factants, such as achieving extraordinarily low air/water and inter- tion can be composed of a carbohydrate, amino acid, cyclic peptide,
facial tensions and improving consumer and industrial product phosphate, carboxylic acid, or alcohol, while the hydrophobic one
performance at surprisingly low usage levels [33]. Similarly, natu- can be composed of long-chain fatty acids, hydroxylated fatty
rally derived surfactants extracted from fermentation broths or acids, or other structures [34,35]. Microbial surfactants are mainly
prepared by partial hydrolysis of natural extracts, the so-called classified into two categories: low molecular weight tensioactive
biosurfactants, have unique structural features that cause them agents (biosurfactants) and high molecular weight tensioactive
to deposit on chemically similar surfaces and modify the surface agents (bioemulsifiers) [47,48].
energy even at very low concentrations [19,20]. According to Zoller A variety of microorganisms, such as bacteria, yeasts, and fila-
[16], the emergence of biotechnology in the 21st century will drive mentous fungi, are capable of producing biosurfactants with differ-
the development of new surfactants and improve the commercial ent molecular structures. The main species investigated for this
feasibility of known surfactants from such processes, as we will purpose are Bacillus subtilis, Pseudomonas aeruginosa, Acinetobacter
discuss in the following sections. calcoaceticus, Candida lipolytica, and Starmerella (Candida) bombicola
[23,38,49].
3.2. Green surfactants (biosurfactants) Some microorganisms produce biosurfactants when grown on
different substrates. The use of different carbon sources alters
Advances in sustainable technologies have driven the search for the structure of the biosurfactant produced and, consequently,
natural, biodegradable compounds to remediate sites contami- its emulsifying properties. These changes can be beneficial when
nated with hydrocarbons [5,34]. Environmental legislation and specific properties are desired for a given application [23,35].
governmental restrictions related to the use of toxic detergents Most biosurfactants are glycolipids, i.e. carbohydrates linked
in products have also contributed to the development and use of to aliphatic or hydro-aliphatic long-chain fatty acids via an ester
biosurfactants as possible alternatives to synthetic surfactants bond, the best known of which are rhamnolipids and sophoroli-
[35]. Due to their compatibility with the environment and low tox- pids. Rhamnolipids are extracellular metabolites produced
icity as well as numerous other advantages, the replacement of mainly by the opportunistic pathogenic bacterium P. aeruginosa
chemical surfactants with these natural compounds has been stud- on a variety of substrates, which allow to achieve surface ten-
ied [36]. Indeed, biosurfactants or ‘‘green surfactants” are consid- sion values around 29 mN/m [50,51,52]. Sophorolipids are pro-
ered the next generation of industrial surfactants, as these duced by yeasts and consist of a dimeric carbohydrate called
compounds meet most of the requirements for low environmental sophorose linked to a long-chain hydroxylated fatty acid via a
impact industrial projects [8,35,37]. glycosidic bond [53]. Although Starmerella (Candida) bombicola
Although for a long time the concept of biosurfactant was stands out among the different types of yeast used to produce
restricted only to microbial surfactants, the current classification these biosurfactants [54], a survey of the literature also identi-
divides biosurfactants, based on their origin, into first-generation fied the potential of other species of the genus Candida as gly-
and second-generation compounds [3,38]. First-generation biosur- colipid producers, such as Candida sphaerica [55], C. lipolytica
factants are those extracted and purified from plant-based and [56,57,58], Candida utilis [59,60], and Candida tropicalis
animal-based raw materials or entirely produced from renewable [61,62,63]. These biomolecules achieve surface tension values
resources through chemical synthesis, including, for example, of about 30 mN/m.
saponins, sugar esters, alkyl polyglucosides and alkanolamines Among the lipopeptides, surfactin, which is mainly produced by
[39]. Main examples of second-generation biosurfactants, which the bacterium B. subtilis is considered one of the most powerful
are instead produced entirely from renewable resources or by a biosurfactants ever reported in literature, as it is capable of reduc-
biological process (biocatalysis or fermentation), are microbial sur- ing the surface tension of water from 72 mN/m to 27 mN/m [64].
factants such as glycolipids and lipopeptides [35]. Table 1 displays the main classes of biosurfactants and their
The physicochemical properties and classification of biosurfac- respective microbial sources, while Fig. 3 illustrates the structure
tants are based on their structural characteristics, with a of some of the main types of biosurfactants produced.
31
Table 1 Table 2
Main classes/subclasses of microbial biosurfactants. Use and functions of phospholipids (adapted from Dorsa [89]).
Class Subclass Microbial source Reference Industry Products Functions

Glycolipids Rhamnolipids Pseudomonas [65,66] Food Baked goods Modification of baking properties,
aeruginosa emulsifier, antioxidant
Pseudomonas cepacia [52] Chocolate Reduction in viscosity, antioxidant
Lysinibacillus [67] Margarine Emulsifier, waterproofing, antioxidant
sphaerica Dietetic Nutritive supplement
Trehalose Rhodococcus sp. [68] products
lipids Nocardia farcinica [69] Solubles Humectant, dispersant, emulsifier
Sophorolipids Candida bombicola [70,71] Substitute in Emulsifier, humectant, dispersant
Starmerella bombicola [72] milk
Candida sphaerica [55,73]
Chemistry Insecticides Emulsifier, dispersant
Candida magnolia [74]
Paints Dispersant, stabiliser
Torulopsis [74]
petrophilum Textiles Fabrics Softener, lubricant
Torulopsis apicola [74] Leather Softening agent, penetrating oil
Lipopeptides Surfactin Bacillus subtilis [75] Cosmetics Hair Foam stabiliser, emollient
Kocuria marina [76] Skin Emulsifier, emollient, humectant
Lichenysin Bacillus licheniformis [77] Pharmaceuticals Parental Emulsifier
Phospholipids Pseudomonas putida [78] nutrition
Thiobacillus [79] Suppositories Attenuating agent
thiooxidans Creams, Emulsifier
lotions
Polymeric Rufisan Candida lipolytica [80,79]
biosurfactants Liposan
Emulsan Acinetobacter [79]
Biodispersan calcoceticus
Alasan pharmaceutical, detergent, paint, and cosmetic industries
[82,83,84,85,86].
Lecithin is currently one of the most widely used phospholipids
3.2.2. Biosurfactants of plant origin in the world market thanks to its surfactant properties and wide
Plant-based surfactants are widely distributed throughout the availability, as it is produced through the degumming of soybean,
planet, being present in different parts of plants, such as the roots, rice, canola, cottonseed, palm, corn, and sunflower oils. It is esti-
stems, seeds, fruit, and leaves. They are amphiphilic compounds mated that 95% of commercially available lecithin is produced
(hydrophobic and hydrophilic) that constitute a diverse group of from soy [84,87].
compounds characterized by a structure of phospholipids, proteins The technological bases used in processes for the production of
or protein hydrolysates and saponins [81]. lecithin are diverse and normally involve extraction and purifica-
Phospholipids, such as phosphatidylcholine, phos- tion with solvents or a membrane. Production methods have been
phatidylethanolamine, and phosphatidylinositol, are surfactants continually adapted over the past decades to meet the demands of
with structures comprising a molecule of phosphoric acid bound internal and external markets and it has become necessary to find
to nitrogenous bases (primary or secondary amines) and alcohols. new low-cost sources of lecithin with a high degree of purity. Thus,
Lecithin is a commercial blend containing various compounds of industries are employing used soybean oil, formerly previously
this class, whose hydrophilic/hydrophobic nature causes it to be considered a waste product, as a rich, low-cost substrate to
classified as a natural emulsifier that also offers stabilizing, thick- increase production [88]. A detailed description of the industrial
ening, and lubricating properties, with applications in the food, use of different types of phospholipids and their qualitative charac-
teristics is shown in Table 2.
Proteins have larger molar masses and contain various quanti-
ties of hydrophilic and hydrophobic groups randomly distributed
throughout the structure. Proteins are emulsifiers that generate
more stable emulsions and foams and do not reduce surface ten-
sion as much. However, in protein hydrolysates their structure is
modified by chemical, thermal, or enzymatic treatments that alter
their composition and size and improve their functional properties,
such as emulsification and foaming. The main applications of pro-
teins and protein hydrolysates are in the food and cosmetic indus-
tries [86].
Saponins are part of a group of tensioactive compounds synthe-
sised through the acetate mevalonate pathway, which lead to a sig-
nificant reduction in surface tension and abundant foaming
[23,90,91]. Foam is one of the consequences of the amphiphilic
structure of saponins that ensures their surfactant property. They
are stable even in the presence of diluted mineral acids, unlike
common soaps [39,84,92]. These biosurfactants are classified,
based on the type of aglycone structure, as steroids or triterpenes,
which have a high molecular mass (known as sapogenins) bound
to long glycidic chains. Steroidal aglycones are less common than
triterpene aglycones, but both types may be present in the same
Fig. 3. Chemical structure of most studied microbiological surfactants: (A) rham-
plant, as occurs in Avena sp. and Lysimachia paridiformis (Fig. 4)
nolipid; (B) sophorolipid, and (C) surfactin. [93,94,95,96].
32
based surfactants [102,103]. Zhou et al. [104], comparing the abil-

ity of saponin from the pericarp of Sapindus mukorossi to mobilize
phenanthrene from contaminated soil compared to the synthetic
surfactant Tween 80, demonstrated that the plant-based surfactant
promoted a linear increase in the solubilisation of the pollutant.
Saponins are quite effective in the biodegradation of hydrocar-
bons, although their concentration does not have significant influ-
ence on cellular hydrophobicity [105]. Smułek et al. [106] reported
that the addition of S. mukorossi extract can be a useful tool to
Fig. 4. Representative structure of steroidal (A) and triterpenic (B) saponins. enhance the microbial degradation of hydrocarbons by strains pre-
sent in contaminated soil environments. Davin et al. [103], who
Saponins are found nearly exclusively in plants, although there investigated the potential of saponins as intensifiers of the biore-
are reports of these compounds in some marine animals such as mediation of soils contaminated by polycyclic aromatic hydrocar-
starfish and sea cucumbers [82,97]. A variety of raw materials bons, observed that the saponin solution (4 g.L 1) led to an
can be used to obtain saponins, which are widely reported in the increase in the removal of acenaphthylene, fluorene, phenan-
literature. The main sources of steroidal saponins are distributed threne, anthracene, and pyrene compared to the control (water)
among the families Agavaceae, Alliaceae, Asparagaceae, Costaceae, after 28 d.
Dioscoreaceae, Liliaceae, Ruscaceae, and Solanaceae as well as the
species Aspilia montevidensis (Asteraceae), Balanites aegyptiaca
(Balanitaceae), Trigonella foenum-graecum (Leguminosae), and 3.2.3. Economy and global market of green surfactants
Tribulus terrestris (Zygophyllaceae). Triterpene saponins are found The growing interest of consumers in eco-friendly products is a
in a number of dicotyledons [98,99]. factor that has increasingly influenced the cleaning products mar-
Saponins have been widely studied and are available commer- ket. This demand has prompted the search for natural or derived
cially as natural surfactants [39,84]. Studies have shown that the biodegradable raw materials with fewer preservatives and petro-
surfactant power of saponins from the genus Quillaja is similar to chemicals. Biosurfactants and plant-based compounds are exam-
that of the commercial tensioactive agent Tween 80, suggesting ples of materials that have been gaining more prominence in
that these compounds have the potential to replace commercial attempts to create or transform products, making them more eco-
surfactants in food and beverage formulations [97]. Other biologi- logically sustainable [8].
cal effects have been attributed to saponins such as immunostim- Recent studies have shown that the global market believes in
ulating, anticarcinogenic, antimicrobial, antifungal, anti- new initiatives and is looking for biological replacements for syn-
inflammatory, antiviral, antiallergic, and antioxidant properties thetic surfactants, whose sales reached approximately $ 1.74 bil-
[100,101]. Therefore, these compounds are widely used in the food, lion in 2011. In 2013, the world production of biosurfactants was
pharmaceutical, cosmetic, agricultural, and environmental sectors, estimated at approximately 344 thousand tonnes, and in 2016 bio-
mainly as foaming agents and to reduce surface tension [23]. surfactant sales surpassed $ 1.8 billion. Estimates for 2018 were $
Table 3 provides examples of plant species from which saponins 2.21 billion and approximately 442 thousand tonnes, with projec-
are obtained. tions for 2020 of $ 2.31 billion and annual production of about 462
Other studies report the effect of saponins on the biodegrada- thousand tonnes. The expected annual growth rate for this market
tion of hydrocarbons, the removal of organic compounds, and the was 4.3% between 2014 and 2020 [5,127,128]. Sales of biosurfac-
hydrophobicity of cells resulting from the use of these plant- tants are likely to reach 2.6 billion in 2023, with sophorolipids
Table 3
Distribution of saponins in some plant species and applications.
Industry Family Surfactant Applications Reference

Pharmaceutical Quillaja (Family Triterpenic Adjuvants in oral and injectable vaccines [91]
Quillajaceae) Saponin
Hedera (Family Araliaceae) Triterpenic Phytotherapy [107,108,109]

Aesculus (Family Sapindaceae) Saponin
Calendula officinalis (Family Asteraceae)
Camellia sinensis, Camellia oleifera (Family Theaceae) Triterpenic
Saponin Anti-protozoan [97,110]
Cosmetics Calendula officinalis (Family Asteraceae) Triterpenic Lipstick and shampoos [98,111,112]
Camellia japonica (Family Theaceae) Saponin
Argania spinosa (Family Sapotaceae)
Camellia oleifera, Triterpenic Antioxidant [113,114,115]
Camellia sasanqua (Family Theaceae) Saponin
Agricultural Tribulus terrestris (Zygophyllaceae) Steroidal Saponin Additives in animal feed (pet, bird and swine lines) [116,117]
Clematis tangutica Triterpenic Antifungal [92,118,119]
Saponin
Camellia Oleifera (Family Theaceae) Triterpenic Insecticide [120,121,122,123]
Saponin
Food Quillaja saponaria (Family Triterpenic Dentifrices and beverages (sodas, beer, sauces) [99,124]
Quillajaceae) Saponin
Solanum melongena (Family Solanaceae) Steroidal Saponin Fermented vegetables and sauces [94,125]
Avena (Family Poaceae) Triterpenic Sauces and beverages [126]
Saponin
and
Steroidal Saponin
33
and rhamnolipids expected to achieve 8% in sales growth. Another have a variety of applications, which differ in the different purity
market research predicted that the global biosurfactant market required as well as the specific structure of the compound used.
will exceed $ 5.52 billion by 2022, with a Compound Annual Hence, utilization of raw product without expensive purification
Growth Rate (CAGR) of 5.6% from 2017 to 2022 [129]. processes would greatly contribute to lowering the overall produc-
However, one of the biggest obstacles to the widespread use of tion cost. This would be particularly profitable in case of environ-
biosurfactants in industries is their high cost. While the average mental applications, where the use of the crude product would
price of synthetic surfactants, such as sodium dodecyl sulfate and be equally effective [41].
plant-based amino acid surfactants, is one to four dollars per kilo- Other compounds, such as chemical surfactants derived from
gram, the average price of sophorolipids, which are the most viable vegetable oils and glycerol, are also sustainable alternatives con-
microbial biosurfactants, is $ 34 per kilogram. The higher price of a sidered by industries when creating formulations and products to
biosurfactant is due to production factors, such as lower yields, satisfy consumers concerned with environmental sustainability
longer times, higher downstream processing costs, energy require- [134,135,136]. Once a product is established in the market, it is
ments for sterilisation, and maintenance of biological culture, possible to focus on strategies to increase profit through marketing
among others [130]. Studies, however, have been seeking to reduce strategies, improving consumer contact with the product, or
costs using agro-industrial waste products as substrate for fermen- through the appeal of safety and innovation with the proposal of
tation processes, increasing yields and reducing downstream pro- a sustainable detergent. The success of a new environmentally
cessing costs [41,131,132]. Indeed, the choice of a low-cost friendly product is linked to market planning and the recognition
substrate is important for the economy of the process, as the sub- that natural resources are renewable.
strate represents for up to 50% of the final manufacturing cost. The Fig. 5 illustrates the representativeness of the expected con-
argument of using industrial wastes, however, cannot be limited to sumption of some types of synthetic and natural surfactants
the cost of the raw materials alone, since the availability, stability between 2012 and 2020. Some regions, such as China, Africa,
and variability of each component are also critical factors to con- and Latin America, contribute to this estimate. Analysing Brazil,
sider. Moreover, the amount to be used, form (solid or liquid), par- the estimated sales were $ 2.1 billion for the year 2018 [137].
ticle size, texture, packaging, transportation, storage, stability and However, the European market was the largest consumer of bio-
purity all play a fundamental role in final selection and formulation surfactants, reaching 178.9 thousand tonnes in 2013, which repre-
of any substrate for biosurfactant production [41]. sented more than 50% of global consumption. North America was
In recent years, various strategies have been used to establish the second largest consumer of biosurfactants in the same year,
biosurfactants as economical commercial compounds [41]. accounting for more than a quarter of the global market. The
Response Surface Methodology (RSM) and statistical methods have Asia-Pacific block had a relatively small consumer market in
been applied to optimize the composition of culture media for bio- 2013, although significant projections were indicated for this mar-
surfactant production. The use of nanoparticles (NPs) is another ket up to the end of 2019 due to the presence of large industries in
upcoming approach for enhanced biosurfactant production. Bio- the region [5]. The main biosurfactant-producing companies in the
surfactant production is significantly affected by many metal salts, world market are Jeneil Biotechnology, Ecover, Soliance, Saraya,
especially of Fe. Hence, an upcoming potential strategy for MG Intobio, and AGAE Technologies (Table 5), which together
enhanced biosurfactant production is the use of low concentra- share the target markets of North America, Europe, and Asia-
tions of Fe-NPs. Coproduction of biosurfactants with another eco- Pacific [138].
nomically important product in a single bioprocess would allow The study of the production costs of a biotechnological product
the entire production chain to become more profitable. One such is fundamental for the development of an economically sustainable
compound used extensively in various industries is the enzyme fermentation process, which allows the estimation of global profit
lipase. Another strategy that could play an important role in study- margins and ensures the continuity of the product in the market.
ing and enhancing the large-scale yield of biosurfactants is the use Initial cost analyses are critical to optimizing production opera-
of microbioreactors for optimization studies [133]. Biosurfactants tions and minimizing expenses [9].
Fig. 5. Global positioning in production of synthetic surfactants over time [137].
34
Table 4
Industrial applications of biosurfactants.
Industries Properties References

Detergents Emulsifiers Demulsifiers Wetting Dispersants Foaming Corrosion Antistatic, Antimicrobial
agents agents inhibition Antiadhesive agents
agents agents
Petroleum [3,8,9,141]
Industrial cleaning [8,142]
Food [25]
Cosmetic [23,143,144]
Pharmaceutical [145,146]
Medical [147]
Agriculture [35,148]
Mining (metals), [20,142]
construction
Nanotechnology [3]
Table 5
Green surfactant-producing companies with different industrial applications.
Company site Tensioactive Application Reference

Fraunhofer IGB – Germany https://www.igb.fraunhofer.de/ Glycolipid and cellobiose Cleaning products, dishwashing liquids, [3,150]
lipid biosurfactants pharmaceutical products (bioactive properties)
AGAE Technologies – USA https://www.agaetech.com/ Rhamnolipid Pharmaceuticals, cosmetics, personal care [3,150]
biosurfactants products, bioremediation (in situ and ex situ),
enhanced oil recovery (EOR)
TeeGene Biotech – UK http://www.teegene.co.uk/ Rhamnolipids and Pharmaceutical products, cosmetics, [3,150]
lipopeptides antimicrobials and anticarcinogen ingredients
Jeneil Biosurfactant – USA http://www.jeneilbiotech.com/ Rhamnolipid Cleaning and oil recovery from storage tanks, [3,150]
biosurfactants EOR
Allied Carbon Solutions (ACS) https://www.allied-c-s.co.jp/english- Sophorolipids Agricultural products, ecological research [150]
Ltd – Japan site
Rhamnolipid Companies – USA http://rhamnolipid.com/ Rhamnolipid Agricultura, cosmetics, EOR, bioremediation, [3,150]
biosurfactants food products, pharmaceutical products
Saraya Co. Ltd. – Japan http://worldwide.saraya.com/ Sophorolipid Cleaning products, hygiene products [3,150]
biosurfactants
BioFuture – Ireland https://biofuture.ie/ Rhamnolipid Washing of fuel tanks [3,150]
biosurfactants
TensioGreen – USA http://www.tensiogreen.com/index. Rhamnolipid Petroleum industry, cleaning, and oil recovery [150]
php biosurfactants from storage tanks, EOR
EcoChem Organics Company – http://www.biochemica.co.uk/ Rhamnolipid Dispersant of insoluble hydrocarbons in water [150]
Canada biosurfactants
Logos Technologies – USA https://www.natsurfact.com/ Rhamnolipid Petroleum industry, cleaning, and oil recovery [3,150]
biosurfactants from storage tanks, EOR
Synthezyme – USA http://www.synthezyme.com/index. Sophorolipid Emulsification of crude oil, petroleum, and gas [3,150]
html biosurfactants
EnzymeTechnologies – USA Bacterial biosurfactant Oil removal; oil recovery and processing, EOR [3,150]
(unknown)
Ecover Eco-Surfactant – Belgium https://www.ecover.com/ ACS-Sophor/Sophorolipid Oil recovery and processing, EOR; biofilm [3,8]
removing agent, biofilm growth inhibitor;
detergent action
Cognis (BASF) – Germany, USA http://saifuusa.com/portfolio-item/ Green surfactant alkyl Shampoo, body wash; facial wash; liquid hand [3]
mildsurfactants/ polyglucoside (APG) – soap; moistened towelettes, laundry, hard
0810-65 surface cleaning
Cognis (BASF) – Germany, USA http://saifuusa.com/portfolio-item/ Green surfactant alkyl Industrial and institutional surface cleaning [3]
mildsurfactants/ polyglucoside (APG) –
0810H-70N
Cognis (BASF) – Germany, USA http://saifuusa.com/portfolio-item/ Green surfactant alkyl Hard surface cleaning [3]
mildsurfactants/ polyglucoside (APG) –
0810-70DK
Paradigm Biomedical Inc – USA http://www.akama.com/company/ Rhamnolipid biosurfactant Pharmaceutical products [3]
Paradigm_Biomedical_Inc_
a7bcb2680775.html
Kaneka Corporation – Japan https://www.kaneka.co.jp/en/ Sodium surfactin Cosmetics –
business/qualityoflife/nbd_002.html
Sabo S.p.A. – Italy www.sabo.com/sabo/home.php. Sodium surfactin Cosmetics –
Groupe Soliance – France http://www.soliance.com/dtproduit. Sopholiance S Cosmetics and pharmaceuticals [3]
php?id = 42 (Sophorolipid)
The vast structural diversity that characterizes biosurfactants number of patent applications [138]. Most of the patents relating
and the wide range of properties exhibited by this group of to biosurfactants concern acquisition processes involving microor-
molecules have increasingly attracted the scientific interest of ganisms, mainly belonging to the genera Pseudomonas, Bacillus,
researchers and companies, which has led to an increase in the Acinetobacter, and Candida, which include an infinity of industrial
35
applications [139,140]. These appear to be effective strategies for processes, as the concern with the planet’s environmental future
overcoming the competitiveness of synthetic products. Therefore, has become an emerging trend among companies and consumers.
efforts towards the development of biosurfactant production tech- One of the notable advantages of companies in the biotech sector
nologies will enable access to innovative products in a field that over competitors is the biodegradable, non-toxic nature of these
has been little explored in one country [5]. products and the potential for using industrial waste products or
The market for biosurfactants in Brazil is quite promising, given sustainably produced substrate as part of their manufacturing pro-
the existence of companies specialized in the production of these cess. Another important point that needs to be considered is that
products. Although the biosurfactant industry has shown notable the long-term global supply of fossil fuel-derived resources is
growth in recent decades, the large-scale production of these bio- expected to decline, and price of petroleum to increase, as will
molecules continues to pose an economic challenge mainly due to short-term market volatility. Furthermore, fossil fuel supply
the huge differences between the necessary financial investment depends upon stability in the socio-political scenario, which is
and industrial production. Therefore, for biosurfactant production never guaranteed. In this scenario, the interest in green surfactants
to become truly viable, the main criteria that should be considered will increase in the years to come, and the biosurfactant market is
are the type of raw materials, type of microorganisms, proper expected to overtake the synthetic surfactant market in the long
design of industrial bioreactors, target market, purification pro- term.
cesses, properties of the biosurfactant, production conditions, and
time required for adequate fermentation and achievable produc- Conflict of interest
tion yields, as discussed above [19].
The target market is also of fundamental importance for the The authors declare no competing interests.
installation of an industrial biosurfactant production project. For
cosmetic, medicinal and food products, production is more viable
Financial support
on a small scale, as the methods required to separate the com-
pounds are not cheap on a large scale. Thus, the use of raw fermen-
The authors are grateful for the funding of this study by the
tation broths could be a viable solution, especially if the
Research and Development Programme of the Agência Nacional de
application is in an environmental context, as biosurfactants in
Energia Elétrica (ANEEL [National Electrical Energy Agency]) and
such cases do not have to be pure and can be synthesized using
the companies Centrais Elétricas da Paraíba (EPASA [State of Paraíba
a blend of inexpensive carbon sources, which would enable the
Electrical Centers]), Centrais Elétricas de Pernambuco SA (EPESA
creation of an economically and environmentally sustainable tech-
[State of Pernambuco Electrical Centers]), and Termocabo SA,
nology for bioremediation processes [19].
Brazil. The authors are also grateful to the Brazilian fostering agen-
cies Fundação de Amparo à Ciência e Tecnologia do Estado de Pernam-
3.2.4. Green surfactants manufacturing industries buco (FACEPE [State of Pernambuco Assistance to Science and
Biosurfactants, besides being biodegradable, offer the advan- Technology Foundation]), Coordenação de Aperfeiçoamento de Pes-
tages of a low environmental impact and the possibility of in situ soal de Nível Superior (CAPES [Coordination for the Advancement
production using renewable and cheap substrates. These biomole- of Higher Education Personnel] finance code 0001), and the
cules have many interesting properties that make them suitable for Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq
application in various industrial processes, such as emulsification [National Council of Scientific and Technological Development]).
and de-emulsification activities and dispersion, wetting and foam-
ing capacities. They have also been found to possess several prop- Acknowledgments
erties of therapeutic and biomedical importance [19,20,23,25].
Various applications for biosurfactants in industry are shown in The authors are grateful for laboratory support from Instituto
Table 4. Avançado de Tecnologia e Inovação (IATI [Advanced Institute of
Manufacturing industries are staking money on biosurfactants Technology and Innovation]), the labs of the Centre for Sciences
due to their potential and prospective characteristics and proper- and Technology of the Catholic University of Pernambuco (UNI-
ties. With the use of microorganisms with high production capac- CAP), Brazil, and the Faculty of Life and Health Sciences, School
ities and inexpensive renewable substrates as raw material, of Biomedical Sciences, University of Ulster, Northern Ireland, UK.
production has been improved on an industrial scale. Regardless
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Production of Green Surfactants Market Prospects

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Electronic Journal of Biotechnology 51 (2021) 28–39

Contents lists available at ScienceDirect

Electronic Journal of Biotechnology

Production of green surfactants: Market prospects q

Peer review under responsibility of Pontificia Universidad Católica de Valparaíso

1. Introduction practices and more efficient products to do household chores.

these processes, basically two types of reactions are responsible for

Class Subclass Microbial source Reference Industry Products Functions

based surfactants [102,103]. Zhou et al. [104], comparing the abil-

Industry Family Surfactant Applications Reference

Hedera (Family Araliaceae) Triterpenic Phytotherapy [107,108,109]

Fig. 5. Global positioning in production of synthetic surfactants over time [137].

Industries Properties References

Company site Tensioactive Application Reference

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