Renewable and Sustainable Energy Reviews 88 (2018) 109–122

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Glycerol from biodiesel production: Technological paths for sustainability T

a,⁎ b c
Marcos Roberto Monteiro , Cristie Luis Kugelmeier , Rafael Sanaiotte Pinheiro ,
Mario Otávio Batalhad, Aldara da Silva Césare
a
Department of Mechanical Engineering, Federal University of São Carlos, Rod. Washington Luis, km 235, São Carlos 13565-905, SP, Brazil
b
Department of Materials Engineering, Federal University of São Carlos, Rod. Washington Luis, km 235, São Carlos 13565-905, SP, Brazil
c
Production Engineering, Campus Três Lagoas, Federal University of Mato Grosso do Sul, Av. Ranulpho Marque Leal, 3484, Três Lagoas 79620-080, MS, Brazil
d
GEPAI, Department of Production Engineering, Federal University of São Carlos, Rod. Washington Luis, km 235, São Carlos 13565-905, SP, Brazil
e
GASA, Department of Agribusiness Engineering, Fluminense Federal University, Av. dos Trabalhadores, 420 - Vila Santa Cecília, Volta Redonda, RJ, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Increases in biodiesel production have led to a surplus of crude glycerol, which represents a major bottleneck in
Biodiesel the biodiesel production chain and has created new challenges to its sustainable use. Although there is a wide
Glycerol range of potential uses for crude glycerol, they are limited by its degree of purity, which affects its physical,
Sustainability chemical and biological properties. This paper presents a review and analysis of patents related to the use of
Innovation
glycerol in the period from 1993 to 2015, showing the quantity and diversity of work related to the search for
alternatives to add value to glycerol. It was found that 85.7% of the filed patents fell into four categories of
applications: 1) manufacture of chemical products; 2) production of polymer compounds; 3) production of
biofuels and biogas; and 4) purification and use of glycerol. In this regard, the development of new technologies
for the use of glycerol, without the need for traditional purification steps, are fundamental. This paper portrays
the efforts that have been made in this direction and the obstacles that still have to be overcome.

1. Introduction A downside to this promising scenario is that biodiesel production

The use of biodiesel as a renewable fuel that is an alternative to
petrodiesel has been seen as an important transition strategy in the
search for new energy sources. Biodiesel can be produced from many
renewable sources. These include the following types of plant oil: ba-
bassu, canola, crambe, palm, oilseed radish, sunflower, jatropha, lu-
pine, soybean, peanut [1], castor bean [2,3], and macaúba [4,5]. It can
also be made from animal fat [6], waste cooking oil [7,8] and photo-
synthetic algae [9–11].
Global biodiesel production has been growing in recent years. In
2016 more than 30.8 million m3 (Mm3) were produced, 7.5% more than
in 2015. The main producing countries in 2016 were the United States
(5.5 Mm3), Brazil (3.8 Mm3), Germany (3.0 Mm3), Indonesia (3.0 Mm3)
and Argentina (3.0 Mm3). The countries of the European Union pro-
duced 10.7 Mm3, i.e. the equivalent of 34.7% of global biodiesel pro-
duction, in 2016 [12].
It is estimated that in the future, biodiesel production will grow by
around 4.5% annually, reaching 41 Mm3 in 2022. It is expected that the
European Union will remain the main producer and consumer of bio-
diesel, and that countries such as Argentina, the United States, Brazil,
Thailand and Indonesia will continue to lead the biodiesel market [13].
costs are not competitive when compared to the costs of fuels derived
from fossil fuels [14–16]. Government policies, fiscal incentives and
emissions laws have been deployed in order to encourage the devel-
opment of the global biodiesel market and assist in overcoming the
effect of production costs. However, rapid growth in the biodiesel in-
dustry has raised concerns related to ethical issues [17]. In addition,
advanced production technologies utilizing the ideal feedstock for
biodiesel have had limited success, and glycerol – the main byproduct
in this process – is still a major bottleneck in the biodiesel production
chain [18,19]. Therefore, finding new uses for glycerol is very im-
portant in order to ensure the sustainability of global production of
biodiesel. Otherwise, glycerol could become a barrier to increased
biodiesel production and threaten the environmental gains from re-
placing fossil fuels with renewable resources.
Regarding the amounts of glycerol produced in the biodiesel sector,
the transesterification reaction produces biodiesel and glycerol at a
volumetric ratio of 10:1, that is, for every 1 m3 of biodiesel, 0.1 of crude
glycerol is produced [20]. In 2015, global production was almost 30
Mm3, and it is estimated that more than 300,000 m3 of glycerol were
produced. The boom in the biodiesel industry means an increase in
surplus production of glycerol.

⁎
Corresponding author.
E-mail address: marcosmonts@gmail.com (M.R. Monteiro).

https://doi.org/10.1016/j.rser.2018.02.019
Received 3 November 2016; Received in revised form 16 November 2017; Accepted 20 February 2018
1364-0321/ © 2018 Elsevier Ltd. All rights reserved.
M.R. Monteiro et al.
Fig. 1. Traditional applications of glycerol in industry. Adapted from Cornejo et al. [23].
In 2011, it was estimated that 2 million tons (or just 40%) of a total
of 5.1 million tons of glycerol were used, the remaining 3 million tons
was surplus. Among European Commission directives is a goal of in-
creasing the proportion of biofuels in use, which has led to estimates
that global production of glycerol will reach 7.66 million tons in 2020
[18].
Between 2008 and 2012, world production of glycerol increased by
9.3% per year, driven mainly by increased biodiesel production. It is
estimated that by 2025 this growth will be 3.5% per year. In 2012, in
the global market for oleochemicals, glycerol accounted for about 26%
of the volume sold in the segment of chemicals derived from oils and
fats of animal and vegetable origin [21].
Glycerol is a versatile renewable raw material used mainly in the
chemical industry. It can be used as a humectant in sweets, cakes, meats
and cheeses, and also as a solvent, sweetener and preservative in bev-
erages and foods, giving flavor and color to foods and soft drinks [22].
This wide range of industrial applications, coupled with the in-
creased availability of biodiesel, has boosted the world market for
glycerol and encouraged the search for new applications, since the
traditional uses of glycerol, as shown in Fig. 1, are not able to absorb
growing production. Therefore, it is necessary to investigate new al-
ternatives for enhancing its use and avoid market saturation [23]. In
recent years, a number of studies of the use of glycerol have been de-
veloped [24–30].
The present article is a review of the literature related to innova-
tions in the applications of glycerol from the biodiesel production
process. The review included scientific articles present in the Scopus
[31] and Web of Science [32] databases and analysis of patents filed
with the Brazilian National Institute of Industrial Property (INPI) [33],
the Patent and Trademark Office (USPTO) of the U.S. Department of
Commerce [34], the European Patent Office (EPO) [35], the World
Intellectual Property Organization (WIPO) [36] and the Derwent World
Patents Index [37] related to the application of glycerol in new products
and processes.
Table 1
Databases searched, terms used and search scope (1993–2015).
Patent Database
National Institute of Industrial Property – INPI [33]
Patent and Trademark Office of the U.S. Department of Commerce (USPTO) [34]
European Patent Office (EPO) [35]
World Intellectual Property Organization. This is a global patent organization that collects data
from national patent offices (Africa, America, Asia and Europe) (WIPO) [36]
Derwent World Patents Index. This is a patent database belonging to the Web of Science
(Thomson Reuters) (DERWENT) [37]
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Renewable and Sustainable Energy Reviews 88 (2018) 109–122
The objective was to gather information on the main advances that
allow the use of glycerol as a raw material providing added value in the
production of goods. The paper is structured as follows. Section 2
presents the method used to collect the data. Section 3 highlights the
most common chemical reactions used to obtain glycerol, various ap-
plications in industry, and the main chemical reactions used with gly-
cerol to obtain intermediates and / or chemicals. Section 4 presents
some of the applications of crude glycerol derived from biodiesel in the
production of chemical products, polymer compounds and biofuels,
such as hydrogen. Section 5 presents final considerations.
2. Methodology
This review presents a systematic documentary analysis based on
the identification of the main work dealing with the use of glycerol
from biodiesel production. The search for alternatives to the use of
glycerol from new applications was based on a patent search in the
following databases: the Brazilian National Institute of Industrial
Property (INPI) [33]; the Patent and Trademark Office (USPTO) of the
U.S. Department of Commerce [34]; the European Patent Office (EPO)
[35]; the World Intellectual Property Organization (WIPO) [36]; and
the Derwent World Patents Index [37]. Also included were published
scientific articles related to the terms biodiesel, glycerin and glycerol.
Patent filings from 1993 to 2015 were included in the review (Table 1).
In addition to the patent analysis, a literature review was conducted
to identify articles published on the theme in a specific period. Since the
beginning of the use of biodiesel as fuel, many works on the use of
glycerol have appeared, especially related to its chemical transforma-
tion. A search was conducted in the Web of Science and Scopus, using
the string (glycerol or glycerine or glycerin) and (biodiesel), covering
the period from January 1993 to September 2017. The total numbers of
articles found were 3555 in the Web of Science and 3960 in the Scopus
database. Fig. 2 shows the results, organized by year.
The data clearly show a constant increase in the number of scientific
articles in this area and a sustained increase in the interest of re-
searchers in this subject. Between 2008 and 2016, the number of arti-
cles increased by about 3.5 times in the Web of Science and practically
doubled in Scopus.
The data also indicate that a large number of articles have been
published in the last 10 years, mainly in the following areas: chemistry,
chemical engineering, engineering, energy fuels, environmental science
and biotechnology (Figs. 3 and 4). In both databases, the energy area,
where a large proportion of articles on biodiesel are located, includes
much of the major research relating to aspects of the production and
use of glycerol obtained from biodiesel.
3. Overview of the production chain from biodiesel to glycerol
The terms glycerol (1,2,3-propanetriol), glycerin, and glycerine tend
to be used in the literature. However the term glycerol generally applies
to the pure substance (Fig. 5), while the expression glycerin applies to
commercial products of solutions of glycerol in water, usually
Terms used Scope
Biodiesel, glycerin and glycerol Entire database
Biodiesel, glycerin, glycerol, Issued patents (USPTO-IP) and patent
byproduct and coproduct applications (USPTO-PA)
Biodiesel, glycerin, glycerol, Entire database
byproduct and coproduct
Biodiesel, glycerin, glycerol, Databases for Africa, Asia, and Europe
byproduct and coproduct
Biodiesel, glycerin, glycerol, Entire database
byproduct and coproduct
M.R. Monteiro et al.
Fig. 2. Number of publications in the Web of Science and Scopus databases using the
string (glycerol or glycerine or glycerin) and (biodiesel) (1993–2017).
containing more than 95% glycerol [20]. These products differ in
content of glycerol, color, odor and traces of impurities.
Crude glycerol is commonly used to designate glycerin from the
biodiesel production process, which contains about 70–80% glycerol,
along with water, catalysts, fatty acids and dissolved salts [20,38,39].
Among the most common routes for glycerol synthesis are hydro-
lysis (Fig. 6A), saponification (Fig. 6B), or as a byproduct of the
transesterification reaction (Fig. 6C) of vegetable oils and animal fats.
[23,40,41].
Although there are other methods, such as fermentation or hydro-
genolysis of carbohydrates, they are not used industrially [22]. The
main route used in the biodiesel industry is obtaining the alkyl esters
from the transesterification reaction (Fig. 8) of vegetable oils and an-
imal fats with ethanol or methanol, mainly using basic catalysis. As a
byproduct of the reaction, one molecule of glycerol is formed for every
three molecules of methyl or ethyl esters, which are the basis of bio-
diesel [42,43].
Glycerol has a wide variety of applications (Fig. 7), mainly as a raw
material for pharmaceutical, cosmetic and food products [25,39]. Ac-
cording to the Glycerine & Oleochemical Division of SDA, there are over
1500 applications for glycerol, which include dozens of categories
ranging from food to foams [22]. However, possibilities of use are
limited by degree of purity.
This wide diversity of applications is due to the wide variety of
chemical reactions that can be used with glycerol to convert it into
Fig. 3. Main subject areas in the Web of Science database with publications on glycerol or glycerine or glycerin and biodiesel (1993–2017).
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Renewable and Sustainable Energy Reviews 88 (2018) 109–122
synthetic precursors and/or materials with higher added value and
possibility of insertion in several areas. Fig. 8 shows some of the major
chemical reactions used in glycerol transformation.
Glycerol obtained from the synthesis of biodiesel, known as crude
glycerol, presents dark coloration, water content, catalysts, free fatty
acids, mono-, di- and triacylglycerols, salts, alcohol (usually methanol)
and biodiesel. These impurities can vary from 20% to 60%, depending
on the raw material, the efficiency of the catalytic process, and the
stages of preparation and purification of biodiesel (Schwengber et al.
[44]).
An important aspect of the production chain of glycerol is its direct
relationship with the biodiesel production chain; the growth of bio-
diesel production has led to a large surplus of glycerol, affecting its
market value. The market price for crude glycerol (80% purity) is be-
tween US $0.09 and US $0.20 per kg. However, for pure glycerol, that
figure is between US $0.60 and US $0.91 per kg. Projections show that
in 2020, world production of glycerol will be approximately 41.9 bil-
lion liters. The 2012 data on the Brazilian market for glycerol showed
that the value of a ton of glycerol with purity of 99.7% was five times
greater than that of a ton of crude glycerol [45].
Biodiesel plants usually use crude glycerol to generate energy or sell
the product without any treatment. Combustion of crude glycerol as an
alternative to energy generation is one of its main applications; how-
ever its high viscosity hinders flow spraying, pumping and flame sta-
bility [44]. In addition, uncontrolled burning promotes the formation of
acrolein (2-propenal), an unsaturated aldehyde that causes severe risks
to human health [46].
The glycerol produced by saponification and hydrolysis presents
higher purity and higher percentages of glycerol compared to that re-
sulting from the transesterification reaction. Previously, the glycerol
market was directly related to trends in demand in the pharmaceutical,
food, cosmetic, polymer and oleochemical markets. However, emer-
gence of the biodiesel industry led to a significant increase in the global
supply of glycerol, which change the dynamics of its market. Currently,
the transesterification process used to obtain biodiesel is the main
mechanism responsible for global production of crude glycerol.
In a study of the agents of the glycerol and biodiesel production
chains, Pinheiro [47] cited the emergence of two consumer markets for
glycerol. The first was the already-existing market, which demanded a
product of higher purity, depending on the quality specifications of the
markets, mainly food, pharmaceutical and cosmetic. The second was
the use of crude glycerol from biodiesel in the transformation of pro-
ducts or chemical intermediates. This market is characterized by con-
sumption of high volumes of the product, lower requirements for
quality, and lower prices.
Biodiesel-producing industries are focused on the technological
M.R. Monteiro et al.
Fig. 4. Main subject areas of the Scopus database with publications on glycerol or glycerine or glycerin and biodiesel (1993–2017).
Fig. 5. Chemical structure of glycerol.
challenges of production processes and storage of biodiesel, treating
crude glycerol as industrial waste. This means that the development of
new applications to allow added value and the exploitation of new
markets do not have high priority in the business strategies of
Fig. 6. Hydrolysis (A), Saponification (B) and Transesterification (C) of triacylglycerols.
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Renewable and Sustainable Energy Reviews 88 (2018) 109–122
companies. This reality does not favor technological innovation by
biodiesel production companies in relation to the byproduct the crude
glycerol. However, there is a trend for companies not belonging to the
biodiesel production chain to engage in a search for technological so-
lutions for the use of crude glycerol as a raw material for other products
[47]. The relationship between the production chains of glycerol and
biodiesel is shown in Fig. 9.
The possibility of using glycerol for different applications is based
on its physical and chemical properties, which include: low volatility,
hygroscopicity, plasticizing effect, promotion of softness and flexibility,
solvent power and solubility, high miscibility, compatibility with a
wide range of materials, stability, high viscosity, antifreeze properties,
nontoxicity, and being an emollient, bodying, and sweetening agent
[22].
Despite the wide range of possible applications, the use of crude
glycerol is limited by its degree of purity, because impurities affect its
M.R. Monteiro et al.
Fig. 7. Various applications of glycerol. Adapted from Mota et al. [39].
Fig. 8. Pathways for possible glycerol derivatives. Adapted from Mota et al. [39].
physical, chemical and biological properties. The search for alternative
uses of glycerol is evident when one looks at the growth in the number
of new applications filed in patent databases between 2002 and 2015 in
the INPI, USPTO-IP, USPTO-PA, EPO, Derwent and WIPO databases
(Fig. 10). Prior to this period, from 1993 to 2001, no records were
found.
Note that most of the patents related to glycerol were filed during
the last seven years of the period (Table 2). WIPO and the USPTO
yielded 19.9% and 56.7% of the total patents, respectively. Although
Brazil is one of the world's largest producers of biodiesel, the number of
Brazilian patents was low compared to other countries. In the period
from 2002 to 2015, only 70 patents were registered in the INPI, 4.1% in
relation to the global total. In general, it is evident that the scientific
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Renewable and Sustainable Energy Reviews 88 (2018) 109–122
community is interested in seeking new opportunities for the use of
glycerol, mainly that derived from the production of biodiesel.
Table 3 presents a detailed analysis of the studies. Among the 1716
patents examined, 827 (48.2%) were related to the use of glycerol in
the development and manufacture of other chemical compounds.
As shown in Table 3, 85.7% of the patents fell into four categories of
applications: 1) manufacture of chemical products; 2) production of
polymer compounds; 3) biofuel and biogas production; and 4) pur-
ification and utilization of crude glycerol. This last category is of great
importance for the use of this byproduct, since the main problem of
glycerol generated through the biodiesel production process is its de-
gree of purity.
4. Applications of crude glycerol derived from biodiesel
Due to the increasing supply of glycerol, many studies have sought
chemical routes for different industrial processes to transform it into
derivatives, as can be seen by the growing number of patents filed and
in the documents published by researchers and scholars in the area.
Glycerol was initially viewed as just being a residue of the biodiesel
production chain, after purification processes. However, it has come to
be seen as a valuable byproduct and a raw material for the production
of products with higher added value in various industrial sectors. In
addition to being used in the creation of several synthetic inter-
mediates, it is a product that comes from a process that uses renewable
resources, mainly vegetable oils and animal fat.
4.1. Chemical products
In patents involving the manufacture of chemicals, some compo-
nents stand out for the quantity presented. The case of 1,3-propanediol
production is highlighted by the synthesis of residual glycerol; this was
present in a total of 31 patents in the various databases analyzed. This
compound is an important chemical with several applications in med-
icine, polymers, cosmetics, food, adhesives, lubricants, solvents, and
others [48].
The synthesis of 1,3-propanediol involves environmental issues. The
use of microorganisms is preferred, especially in biomedical, cosmetic
and tissue applications. Among the microorganisms that are known to
M.R. Monteiro et al. Renewable and Sustainable Energy Reviews 88 (2018) 109–122

Fig. 9. Representation of the relationships between the production chains of biodiesel and glycerol. Adapted from Pinheiro [47].

Table 2
Distribution of patents related to applications of glycerol in the period from 2002 to 2015.

Year INPI USPTO-IP USPTO-PA EPO Derwent WIPO Total

2002 0 2 0 0 0 0 2
2003 0 1 3 0 1 1 6
2004 0 4 1 0 0 0 5
2005 3 2 8 1 5 3 22
2006 2 5 6 5 15 1 34
2007 10 2 20 5 28 0 65
2008 8 4 38 11 30 18 109
2009 17 7 54 14 45 26 163
2010 9 26 108 16 33 14 206
2011 7 45 107 21 52 18 250
2012 6 51 72 27 37 19 212
2013 6 82 78 34 41 28 269
2014 2 89 68 18 35 24 236
2015 0 47 43 3 20 24 137
Total 70 367 606 155 342 176 1716

Fig. 10. Patents related to glycerol applications in the period from 2002 to 2015.
produce 1,3-propanediol, species of the family Lactobacillaceae offer
great potential for production from glycerol, reaching concentration of
85 g/L [49].
The global production of 1,3-propanediol is constantly growing,
having already reached approximately 45,300 t annually. This increase
is due to its extensive use in the production of value-added products,
since it is an important chemical intermediary in the manufacture of
polyester and polyurethane. It is estimated that by 2019, global demand
for 1,3-propanediol will be 150,000 t per year, with estimates that its
price will increase from US $157 million in 2012 to US $560 million in
2019 [27,50].
Another compound mentioned was 1,2-propanediol, shown in 27
patents. This is an important chemical that presents medium value and
has an annual production of about 1 million tons in the United States
[51]. Its production by hydrogenolysis of glycerol is of great interest
because of the renewable nature of this chemical route, which employs
a catalyst base of noble metals such as platinum, ruthenium, palladium
and rhodium or a catalyst base of transition metals like copper, nickel
or cobalt. Without the use of glycerol, 1,2-propanediol is obtained by
the hydration of ethylene oxide or propylene oxide. This chemical has
applications in unsaturated polyester resins, such as antifreeze and
deicing agents, pharmaceuticals, food, cosmetics, liquid detergents,
flavorings, personal care products and paint [52].
Glycerol can also give rise to other products through the

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Table 3
Applications for glycerol.

Applications INPI EPO Derwent WIPO USPTO - IP USPTO - PA Total

Manufacture of chemical products 22 79 90 199 172 265 827

Production of polymer compounds 10 32 11 44 62 136 295
Production of biofuels and biogas 8 12 24 16 45 70 175
Purification and production of glycerol with higher purity 14 11 17 42 46 44 174
Industrial control and reuse (Power sources, air filters, dust control, antifreeze) 3 6 9 16 21 36 91
Agricultural supply (Composting, pesticides, feed) 3 6 16 14 10 42 91
Pelletizing agents (Pelletizing of iron ore, cement, paving, organic compounds) 2 2 5 5 5 8 27
Surface protection 4 7 3 6 3 3 26
Rheological agents (Extraction of petroleum, various fluids) 4 0 1 0 3 2 10
Total 70 155 176 342 367 606 1716

bioconversion process, in which the use of specific microorganisms with
crude glycerol produces ethanol. Although conversion to ethanol is still
small in volume, this process, when refined, can be considered a po-
tential option for biorefineries that are based on a variety of raw ma-
terials [53].
present a unique combination of characteristics such as colorless
transparency, easy adhesion, elasticity and light stability. Acrylic acid
produced from propylene obtained from non-renewable resources cur-
rently has a market of more than 3 million tons/year and presents in-
creasing demand for the monomer and its derivatives [61].

4.2. Polymer compounds 4.3. Production of biofuels

Two terms appear more frequently in the patent databases for
production of these compounds: polyols, with 22 patents; and acrylic or
propenoic acid, with 14 patents. Both compounds are polymerized for
the production of polymers such as polyester, polyurethane and acrylic
[54].
The use of glycerol for the production of biodegradable plastics,
mentioned in 5 patents, is highlighted. Of the 5 patents analyzed, 3
referred to the production of propene from crude glycerol. Propylene,
one of the most important olefinic monomers for the polymer manu-
facturing industry, is the raw material for polypropylene, a thermo-
plastic substance used in food packaging, hygiene and cleaning pro-
ducts, toys, hospital supplies, car parts, carpets, fabrics, furniture, etc.
Propene also is used in the production of acrylic derivatives for paints,
adhesives, fibers and superabsorbent polymer for disposable diapers
[55].
Propene is obtained from fossil resources; for example, steam re-
formation of naphtha is one of the main chemical processes used.
However, it is already possible to rely on a technological route to obtain
this product using the selective hydrogenolysis reaction supported on
commercial catalysts based on ruthenium, and palladium and mo-
lybdenum (Zn / Mo, Cu / Mo and Fe / Mo) [56]. With the use of new
chemical routes that do not harm the environment, propene has begun
to be called "green propene.” This allows new perspectives on obtaining
products and plastic packaging, as well as replacing the renewable re-
source propene, which enables the development of a market that uses
the surplus of glycerol from biodiesel production.
Acrolein can be obtained as an oxidation product of dehydration of
glycerol. It is an important chemical intermediate for the production of
acrylic acid, widely used for the synthesis of adhesives, paints, plastics
and rubbers [57], and is also used in the production of superabsorbent
polymers and butyl acrylate, one of the raw materials most used in the
manufacture of paints, adhesives and mortars.
Acrylates are widely used in water-based coatings, paints, leather
finishing, and paper coatings, and in the manufacture of plastics, fab-
rics, chemical intermediates, etc. [58]. Obtaining acrolein represents a
competitive alternative in the production of propylene [59], and as
discussed by Zhao et al. [60], represents a versatile intermediate for use
in the synthesis of several products, appearing as an alternative to the
conventional petrochemical process.
The glycerol oxidation reaction presents potential for transforming
glycerol into value-added products, improving the economics of bio-
diesel production, and providing industry with new alternative sources
of chemicals. That is because the resulting acrylic acid and its esters
4.3.1. Hydrogen production
Glycerol can be used in the production of fuels from renewable
sources, called biofuels, such as ethanol and biodiesel [42]. Further-
more, hydrogen production is gaining prominence; among other uses, it
can also meet energy demand from the transportation sector, which
year after year invests in the development and production of vehicles
powered by alternative sources of energy. This is gradually contributing
to reducing dependence on fossil fuels and the reduction of greenhouse
gas emissions. Interest in this topic can be measured by the number of
patents filed: of the 1716 patents analyzed, 175 (10.2%) cited tech-
nologies for the production of biofuels from glycerol.
Hydrogen gas represents a clean option when used to generate en-
ergy. However, environmental gains from hydrogen use are directly
related to the type of raw material used for its generation, which can be
from renewable and non-renewable resources [62]. Hydrogen use has
been notable in the generation of electric energy and in the transpor-
tation sector, through the use of fuel cells or internal combustion en-
gines [63,64]. Although its use eliminates the serious problems caused
by the emission of gases from burning traditional fuels, hydrogen gas
production faces major challenges. These include the development of
technologies with greater economic viability, establishment of dis-
tribution infrastructures, final consumption, and government support.
The use of hydrogen gas has value in industry due to a wide variety
of applications as a chemical and energy input. Its use in the chemical
and petrochemical industries stands out, especially in the following
areas: oil processing for sulfur removal (hydrodesulphurisation); hy-
drocracking for the production of fuels and fertilizers; the pharmaceu-
tical industry for the production of vitamins, surfactants and adhesives;
the food industry for hydrogenation of oils and fats; in metallurgical
processes as a reducing agent for metallic ores; the electronics industry
in semiconductor manufacturing processes; and, more recently, gen-
eration of energy as a fuel cell input. Although it presents a wide variety
of applications, the demand for hydrogen is higher in the oil refining
and fertilizer industries [63,65,66]. In a review study, Sarma et al. [67]
described the use of crude glycerol as a raw material for the production
of hydrogen from microbial processes, and they concluded that the
microorganism Enterobacter aerogenes produced the highest amount of
hydrogen, a rate of 80 mmol L−1 h−1.
Currently, various technologies are applied to the production of
hydrogen from glycerol. Although the processes for obtaining glycerol
designated for hydrogen production involve high costs, the use of raw
material from a renewable resource and decentralized production could
make these technologies more accessible and competitive. In order for

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hydrogen to become a truly sustainable energy source, its production
from renewable resources must be promoted; however more than 95%
of the hydrogen produced today comes from raw materials from non-
renewable resources [44].
The production of hydrogen by use of glycerol is important for the
biodiesel industry, since it adds value to the production chain [68].
Shao et al. [69] studied the production of hydrogen by steam reforming
of glycerol using Ni-based catalysts, which features good activity in the
cleavage process of C-C, O-H and C-H bonds; these metals are cheaper
and more available compared to noble metals. In these catalysts, the
high content of cerium in the Ni/CeZrO catalyst, up to 77.3%, allows an
increase in glycerol conversion and selectivity to hydrogen. A favorable
aspect of the use of steam reforming of glycerol is that this reaction is
highly endothermic and, at low pressure, favors selectivity for hy-
drogen.
Schwengber et al. [44] presented a review of the catalytic reform
process of glycerol for the production of hydrogen using the following
processes: steam reforming (SR), partial oxidation reforming (POR),
aqueous phase reforming (APR), autothermal reforming (ATR) super-
critical water reforming (SWR) and liquid phase reforming (LPR).
Steam Reforming is the process most commonly used by the che-
mical industry to obtain hydrogen from natural gas. It is becoming a
promising alternative for the use of glycerol, since the processing of
glycerol by catalytic reform requires few changes in the industrial
processes currently in place for production of hydrogen.
Partial oxidation reforming consists of a reaction of glycerol that
occurs under atmospheric pressure, where the oxygen amounts are
below the ideal stoichiometry for complete combustion. This is an
exothermic process whose efficiency depends directly on the control of
the amount of oxygen entering the mixture. In addition, this process
offers the potential to be efficient in terms of energy and also allows the
production of synthetic gases according to the different amounts of
oxygen added.
These two reform processes (SR and POR) are inserted into the
process called autothermal reforming (ATR), characterized by energy
self-sufficiency, where the SR process is endothermic and the POR
process is exothermic. The reactor itself provides the energy to generate
the products. At this early stage, the addition of oxygen leads to in-
creased oxygen production, which makes the use of glycerol attractive
in the reform process attractive.
The aqueous phase reforming process is generally performed at high
pressures (59 atm) and moderate temperatures (270 °C). Through a
continuous flow, glycerol is converted to the aqueous phase without
pre-vaporization. The cleavage of C-H bonds leads to the formation of
products of interest, among them hydrogen and carbon dioxide.
Another process consists of so-called supercritical water reforming,
consisting which is another route option for the production of hydrogen
using glycerol. This process is characterized as operating at high pres-
sure and low temperature (218 atm, 374 °C). This provides interesting
properties such as low viscosity and high diffusivity, besides attracting
increasing interest due to its high efficiency and selectivity in the
production of hydrogen.
All these reform processes use catalysts that act as agents of re-
duction of activation energy, favoring the kinetics of the reaction.
However, these catalysts must be highly active and stable, generate the
smallest possible amounts of coke, be sintering-resistant, and not fa-
cilitate undesirable parallel reactions such as methanation or
Fischer–Tropsch synthesis [44].
Carbon monoxide, carbon dioxide and hydrogen are the major
compounds in the process of thermal decomposition of glycerol. The gas
mixture resulting from the process has minority fractions that may
contain methane and short-chain alcohols such as methanol, ethanol,
ethylene, acetaldehyde, acetic acid, acetone, and acrolein. The main
glycerol reforming processes involve fixed bed reactors and catalysts at
temperatures in the range 300–900 °C [44].
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Renewable and Sustainable Energy Reviews 88 (2018) 109–122
4.3.2. Biogas production
In the processes of co-digestion and co-gasification, glycerol also
presents possibilities for use as a low-cost raw material, mainly for the
generation of biogas with applications such as fuel for heat-generator
boilers [70]. The anaerobic co-digestion of crude glycerol can be per-
formed using waste water containing specific microorganisms that
promote its biodegradation. The main resulting gaseous products are
methane [71] and hydrogen [72]. In addition, the solid fraction consists
in an organic matter containing considerable amounts of residual or-
ganic carbon, which can be released into the soil as fertilizer. [73].
An example of an application is mixing crude glycerol and pig
manure, which presents some advantages. These include: high water
content in the manure that acts as a solvent for glycerol; the presence of
a wide range of macro- and micronutrients that are necessary for the
development of microorganisms; and the fact that glycerol is a biode-
gradable product [74].
In a study by Astals, Nolla-Ardèvol and Mata-Alvarez [75], glycerol
was used as a co-substrate mixed with pig manure. The results showed
that the thermophilic anaerobic co-digestion (above 35 °C) of pig
manure with 3% (w/w) of glycerol allowed production of biogas at a
rate 180% higher when compared with manure-only digestion. Al-
though the percentage of crude glycerol used was small, the study
showed that there is great potential for using this process as a way to
expand biogas production.
In another study using glycerol with pig manure, Astals, Nolla-
Ardèvol and Mata-Alvarez [73] found that the co-digestion of a small
percentage (4% w/w) of crude glycerol in pig manure allowed an in-
crease of 400% in the production of biogas in mesophilic conditions (up
to 35 °C).
The addition of glycerol can be part of co-digestion, not only in pig
manure, but also in other residues, such as fruit and vegetable residues
[76], organic solid waste [77], and sewage sludge [78] among others.
This increases the possibilities of using glycerol with the specific re-
sidues that occur in certain regions.
In addition to the production of biogas and organic matter, anae-
robic co-digestion also produces hydrogen (biohydrogen) [72]. Ac-
cording to Silva et al. [79], hydrogen can be produced under mesophilic
conditions by combining food waste with crude glycerol itself. In this
study, they obtained a maximum yield of 180 mL H2/gVS (mL H2 per
gram of volatile compounds) at a concentration of 5% crude glycerol.
4.4. Additives
In the area of fuel additives, Izquierdo et al. [80] stated that the
etherification reaction of glycerol with liquid-phase light olefins, cata-
lyzed by acidified macroporous ion exchange resins, allows a larger
volume of diesel oil to be mixed with light olefins, improving product
properties, also allowing their use as additives in biodiesel.
Oxygenated additives, mainly those derived from biomass, such as
ethanol, biodiesel derivatives, and some derivatives of glycerol such as
diethyleneglycol, propylene glycol and dimethyl ether, have been stu-
died because they lead to remarkable improvement in the combustion
process and engine performance. One of the alternatives is the chemical
transformation of glycerol into derivatives with energy potential that
can compete with those produced from petroleum, such as tertiary alkyl
ethers.
Additionally, some additives generated from glycerol (by ester-
ification routes with glycerol acetylation and by etherification routes)
lead to the improvement of the viscosity of liquid fuels in octane and /
or cetane number according to the type of engine used, in addition to
making it possible to reduce emissions of pollutants [81].
The catalytic etherification of glycerol, as described by
Viswanadham and Saxena [82] and Melero et al. [83], is a chemical
route that allows for obtaining additives as oxygenated blends for use
with diesel oil, making the fuel exhibit lower viscosity and better cold
properties, improving both yield and quality.
M.R. Monteiro et al.
Some ethers, acetals and acetis of glycerol have been identified as
high-value additives capable of replacing those whose raw materials are
of fossil origin. These additives are products with great potential for use
in both diesel and biodiesel blends [84]. Glycerol acetals are easily
synthesized and used in alternative fuels or fossil fuels, or in mixtures of
alternative fuels [85].
The use of acetals reduces the emission of harmful substances
during the burning of fuel in engines. One promising additive is 2,2-
dimethyl-4-hydroxymethyl-1,3-dioxolane (known as solketal). When
added to gasoline, it causes an increase in the octane number of the fuel
and contributes to a reduction in the formation of gum. In the case of
diesel, biodiesel, and their mixtures, this additive acts to reduce emis-
sions of gases such as oxides of nitrogen, carbon monoxide, hydro-
carbons, aldehydes and particulate matter [85].
4.5. Production and purification of glycerol of higher purity
One of the major difficulties in the reuse of glycerol derived from
biodiesel is its high impurity content; variations in the purity level
make commercialization difficult. The food, pharmaceutical and cos-
metics industries, which are currently among the largest consumer
markets, require high-purity glycerol. The U.S. Pharmacopeia (USP)
indicates that glycerin is commonly available commercially at anhy-
drous glycerol content levels of 96.0%, 99.0% and 99.5%. The
European equivalent of the USP is the Pharmacopoeia Europaea
(Ph.Eur.), in which listings are commonly followed by a percentage
indicating glycerol content (e.g., Ph.Eur. 99.5%) [22].
The degree of purity of crude glycerol and the needs of the market
justify the large number of patents filed (174) on purification processes.
Purification can make use of processes such as vacuum distillation,
which avoids degradation of glycerol by maintaining controlled pH,
pressure and temperature, which may allow for obtaining glycerol with
high purity. This process utilizes already-established technology, can be
applied in both small-scale and large-scale industries, uses low-cost
chemicals, and is adaptable to different qualities of raw material. Also
worth mentioning is the use of the ion exchange adsorption process,
which removes impurities such as fatty acids, inorganic salts and free
ions [86].
A similar process was carried out by Dhabhai et al. [87], through
sequential physicochemical treatment (saponification, acidification,
phase separation and extraction), membrane filtration, and treatment
with activated carbon. This sequence of treatments was shown to be
promising for the purification of crude glycerol, with a maximum yield
of 97.5% of high-purity glycerol.
4.6. Other alternatives for the use of glycerol
With the phenomenal growth in biodiesel production, the increase
in the availability of glycerol in the market represents a source of cheap
raw material for the production of chemical intermediates of greater
added value, and stands out as an alternative to burning in boilers.
Glycerol can be used in catalytic reactions (Fig. 8) for oxidation, de-
hydration, acetylation, esterification, reforming, and etherification,
among others, which allow for obtaining products with different ap-
plications for the food, chemical, pharmaceutical and automotive in-
dustries [88,89].
Tomaszewska et al. [90] evaluated the use of a Yarrowia lipolytica
microorganism strain to obtain erythritol with glycerol as the substrate.
Erythritol, a polyol, is a natural component of the human diet, found in
fruit, fermented food, honey, seaweed and mushrooms. It is also used in
the chemical, cosmetics, food and pharmaceutical industries. It has
health benefits because of its low caloric value and does not affect in-
sulin levels in the blood. Obtaining it by chemical processes involves
high costs and low production. Hence the search to obtain it through
biotechnological processes, making use of glycerol as a low-cost and
unconventional substrate.
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Renewable and Sustainable Energy Reviews 88 (2018) 109–122
A study by Tomaszewska et al. [90] pointed to the viability of in-
dustrial production of erythritol from glycerol. The final product con-
centration (201.2 kg/m3) was obtained by a batch process using
325 kg/m3 glycerol after seven days of cultivation. This result was
comparable to, or even better than, that obtained using another sub-
strate (glucose) and osmotic microorganisms. Another advantage of this
process is the low amount of byproducts formed, and the remaining
matter (biomass) can be used as animal feed.
Another important product is mannitol, another polyol. It is present
in fruit, vegetables and mushrooms; it has a sweet taste and low caloric
value [91]. It is used as a valuable additive by the food and pharma-
ceutical industries, besides serving as raw material in the production of
bioethanol [92,93].
However, the commercial production of mannitol occurs through a
hydrogenation reaction of a glucose/fructose mixture at high tem-
perature and pressure, and is associated with problems such as low
catalyst selectivity, difficulty in separating the product and byproducts,
and high cost. Yoshikawa et al. [91] reported that the production of
mannitol by the biotechnological route represents an attractive alter-
native. In their study, glycerol was used in its crude form, together with
a strain NBRC 10406 of the yeast Candida azyma from the NITE Bio-
logical Resource Center (NBRC); this proved to be efficient in the pro-
duction of 25% mannitol (m/v) in glycerol.
Another alternative for the use of glycerol is in the preparation of
polyglycerol. It is highly branched, light-colored, viscous, highly so-
luble in water and other organic polar solvents such as methanol, and
essentially non-volatile at room temperature. It is available commer-
cially for different applications, ranging from cosmetics to controlled
drug release. One of the processes for obtaining it is to link individual
glycerol monomers to polyglycerol, a route that can be used to physi-
cally enhance the structure of glycerol [89].
Obtaining new products with added value allows the surplus of
glycerol to be used as a source of raw material in the biorefinery in-
dustry itself. Zakaria et al. [94] evaluated the use of catalyst screening
to convert glycerol to light olefins, oil derivatives obtained by thermal
cracking of natural gas and crude oil, which are widely used in the
production of plastics and chemical intermediates and in the solvent
industry. The authors investigated the catalytic performance of the
conversion of glycerol to olefins, using as catalysts zeolites impregnated
with metals such as lithium, magnesium, chromium and copper, in
order to improve the activity of acidic sites on the surface of these
catalysts. It was observed in the catalytic tests that the highest pro-
duction of ethylene in terms of gas selectivity was obtained with the
Cu/ZSM-5 catalyst (18.62%), followed by the Cr/ZSM-5 catalyst
(15.20%).
Sun et al. [95] studied the production of propylene by catalytic
conversion in the vapor phase of glycerol using over Cu/Al2O3 and acid-
loaded Cu / Al2O3 catalysts at ambient H2 pressure. A high propylene
yield of 84.8% was obtained by double bed catalysts at 242 °C.
Glycerol is also used in the co-gasification and co-liquefaction pro-
cesses of biomass and organic waste to obtain products with higher
added value. Given that hydrogen production represents one of the
main green energy sources of the future [96] and is used in the pro-
duction of second-generation chemicals, the literature shows [97,98]
that the process known as co-gasification of biomass and organic re-
sidues allows the production of a synthesis gas (syngas) that presents
important energy characteristics, which may complement or replace the
use of petroleum derivatives.
The use of co-gasification requires additional study to identify
which residues are best-suited for application with glycerol and to
quantify the proportions of the constituents. These studies are im-
portant because of the need to describe how the products of interest can
be effectively obtained, since this influences the process, along with
other components of the composition of the raw material [99].
The co-gasification process consists of thermochemical conversion
of the carbon present in the raw material. In this case, crude glycerol is
 M.R. Monteiro et al.

Table 4
Some glycerol applications.

Product Reaction Use Researchers and year Ref.

Hydrogen Glycerol steam reforming by Ni/CeZrO catalysts Alternative energy to the use of fossil fuels. Power generation. Shao et al., 2014 [69]
Glycerol supercritical water reforming and autothermal Galera and Gutiérrez Ortiz, 2015 [112]
supercritical water reforming
Glycerol fermentation by Escherichia coli Trchouniana, Sargssyana and [113]
Trchounian, 2014
Ethanol Glycerol fermentation by Escherichia coli and by mixed Constituent of alcoholic beverages. Vikromvarasiria et al., 2014 [114]
culture of microorganism Used as fuel and fuel additive.
1,3-propanediol Glycerol fermentation by microorganisms and by catalytic Important chemical intermediary in the manufacture of polyethers, polyesters and Lee et al., 2015 [50]
hydrogenolysis process polyurethanes.
It has many applications such as fragrances, paints, coatings, adhesives, laminates,
laboratory chemicals and personal care products.
Butanol Glycerol fermentation by Clostridium pasteurianum Potential drop-in liquid biofuel for mixing in gasoline, diesel and aviation kerosene, Khanna, Goyal and Moholkar, [115]
without the need for engine changes. 2013
Excellent solvent for the production of antibiotics, vitamins, hormones and paints.

118
Also used as raw material for the production of methacrylate and butyl acrylate, the
starting materials for the production of various polymers.
Acrolein Glycerol dehydration by catalysts Production of acrylic acid that originates sodium polyacrylate, a super absorbent Talebian-Kiakalaieh, Amin and [59]
polymer used in hygiene products such as diapers and detergents. Production of DL- Hezaveh, 2014
Methionine (used for animal growth and meat production).
Glycerol carbonate (4-hydroxymethyl- Glycerol with carbonyl sources like CO, CO2, urea or Applications such as high boiling polar solvent, emulsifier for cosmetics, lithium Lanjekar and Rathod, 2013 [116]
1,3-dioxolan- 2-one) dimethyl carbonate battery additives, source of new polymeric materials for the production of
polycarbonates and polyurethanes, gas separation membrane component, and as a
surfactant component.
Valuable intermediary for the production of glycidol, used in resins, plastics and in
the pharmaceutical and cosmetic industries.
Glycerol triacetate (triacetin) Obtained by interesterification reaction of triglycerides with Anti-knock additive when used with biodiesel in diesel, improves engine Calero et al., 2015 [117]
methyl acetate in the presence of strong acid catalysts performance and reduces gas emissions.
Propionic acid Glycerol fermentation by Propionibacterium acidipropionici Chemical product widely used in cellulose plastics, herbicides and perfumes. Clomburg and Gonzalez, 2013 [118]
Succinic acid Glycerol fermentation by Anaerobiospirillum Succiniproducens Used in the agricultural sector and in the food and pharmaceutical industries. Clomburg and Gonzalez, 2013 [118]
Erythritol Glycerol fermentation by Yarrowialipolytica Used in the chemical, cosmetic, food and pharmaceutical industries. Tomaszewska, Rywinska and [90]
Rymowicz, 2014
Mannitol Glycerol fermentation by Candida azyma Applications in the food and pharmaceutical industries. Yoshikawa et al., 2014 [91]
Renewable and Sustainable Energy Reviews 88 (2018) 109–122
M.R. Monteiro et al.
used as one of the reactants, in a gas with a fuel characteristic. This
leads to a change in the chemical structure of the fuel particles due to
the high temperatures (above 700 °C) required for the conversion pro-
cess [100,101]. As described by Couto et al. [102], the main sequence
of events that occur in the co-gasification process are: 1) pyrolysis /
devolatilization at low temperature, with thermal cracking reactions,
producing liquid and gaseous fractions; 2) decomposition of these
products by the additional supply of heat, which creates a gaseous
mixture of molecules of smaller size; and 3) char gasification, which
results in syngas (composed of CO, CO2, H2 and light hydrocarbons), a
product with higher added value.
Skoulou and Zabaniotou [103] evaluated co-gasification of glycerol
with olive kernels in a fixed-bed reactor at 750–850 °C at three different
mixing levels (24 wt%, 32 wt% and 49 wt% of crude glycerol in olive
kernels) in an effort to maximize the generation of hydrogen from the
gas obtained in the gasification process. The results showed that the co-
gasification process of crude glycerol with olive kernels was favorable
in obtaining gas, from 0.4 to 1.2 Nm3/kg in the mixed condition of 49%
by weight of crude glycerol with the biomass.
These results encourage production even on a small scale, especially
in rural areas where there is availability of lignocellulosic biomass, a
renewable and abundant resource that can be used in the sustainable
production of chemical products and transportation fuels [104].
A similar study was carried out by Wei et al. [105] on co-gasifica-
tion of hardwood chips with crude glycerol at various pilot scale load
levels using a pilot scale fixed-bed downdraft gasifier. To obtain syngas,
hardwood chips were mixed with 5%, 10% and 20% crude glycerol by
weight, remaining stored in sealed containers. After one week of rest,
the material was ready for the co-gasification process.
The results showed that the co-gasification of hardwood chips with
up to 20% (by weight) crude glycerol allowed for obtaining syngas with
concentrations of impurities (such as tar) within the limits considered
tolerable in comparison with the same limits used for internal com-
bustion engines. In addition, the use of glycerol also allows for a de-
crease in the percentage of lignocellulosic biomass used in the gasifi-
cation process, without affecting the yield of the process and the quality
of the products. Thus, after the filtration process, syngas is free of im-
purities and can be used in both the production of electricity and as a
raw material in biofuels or other chemical products [105].
Another process that allows the use of crude glycerol is the so-called
co-liquefaction process, where residual organic matter can be converted
into a liquid, similar to heavy fuel oil [106–108]. This makes it possible
to improve the production of so-called bio-oil, which is a viscous oil
with physicochemical characteristics similar to petroleum, considered
as a fuel of the future [108]. The use of this process also represents a
viable alternative to the use of glycerol regarding the waste generated.
It can be observed that, according to the literature, this process has
more applications for the use of crude glycerol with swine manure,
since liquid products are more favorable for the use of co-liquefaction to
obtain bio-oil [107,109], which is another advantage of co-liquefaction.
Ye et al. [106] proposed that reaction pathways for conversion of swine
manure and crude glycerol to bio-oil involve an esterification reaction,
which occurs not only because of the methanol present in crude gly-
cerol, but also because of the presence of methanol produced by the
hydrothermal reactions of glycerol.
Glycerol may also be used as feedstock in animal feed; however, due
to the presence of impurities, treatment steps are required prior to this
use. One way to overcome this situation is to carry out fermentation of
glycerol by the use of food-grade fungi, such as Rhizopus microsporus
var. oligosporus. This appears to be an alternative that can be integrated
into the biodiesel producing industries, since it requires minimal al-
teration of operational processes and does not require that glycerol be
purified.
The protein obtained from fungi show great potential for inclusion
of glycerol as an ingredient in the formulation of rations for ruminants,
producing a balanced profile of amino acids that, together with crude
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Renewable and Sustainable Energy Reviews 88 (2018) 109–122
protein and lipid content similar that of proteins in high-quality feed
(such as fishmeal and soybean meal), make glycerol a possible alter-
native raw material for animal feed [110].
Eiras et al. [111] studied the effect of glycerol as a partial re-
placement of corn on feed intake, digestion, feed efficiency and animal
performance of young bulls in confinement for 240 days, with diets
containing glycerol in amounts of 60, 120 and 178 g/kg of dry matter
and diets without glycerol. It was verified that the apparent digestibility
of nutrients increased with the increase of glycerol in the diet, allowing
a 33% increase in feed conversion efficiency when it was included in
the amount of 120 g/kg of dry matter.
Glycerol has great chemical potential for the development of new
products and raw materials with higher added value. The structural
characteristics of its molecule allow a wide variation of strategies for
the development of new products, processes and applications. Table 4
summarizes some uses of glycerol and different procedures for ob-
taining products with specific applications.
5. Final considerations
The increase in the world production of biodiesel has led to the
generation of increasing amounts of glycerol. It is vital that alternative
sustainable technologies be found for the use of glycerol, so that diffi-
culties in using and disposing of this substance do not inhibit biodiesel
production.
Glycerol also represents an important alternative in the sustain-
ability of biodiesel production. Flexibility in the use of glycerol enables
it to be used as a raw material for the manufacturing of chemical in-
termediates or products in several industrial segments.
The chemical, food, polymer, fuel additive, hydrogen production,
and energy generation industries, in addition to those related to the co-
gasification, co-liquefaction and co-digestion of organic residues, are
important potential destinations for the supply of glycerol resulting
from biodiesel.
With the objective of broadening this discussion, the present study
described the main technological innovations associated with the use of
glycerol resulting from the production of biodiesel. Of the 1716 patents
filed between 2002 and 2015, 1471 (85.7%) were grouped into four
categories of applications: 1) manufacture of chemical products; 2)
production of polymer compounds; 3) production of biofuels and
biogas; and 4) purification and use of glycerol.
The possibilities of utilization of glycerol resulting from biodiesel
production in a wide variety of products has garnered the interest of
researchers from public and private companies. This can be demon-
strated by the number and diversity of patents and scientific studies
cited in this article, all of which are related to the search for alternatives
that can add value to the products in the biodiesel production chain.
From this perspective, studies related to the reformulation of ap-
plication, feasibility, and production models still have room for the
development of more efficient methods, with the aim of obtaining
products with higher added value that also meet conditions for sus-
tainability of the production chain.
The present article reports on efforts to consolidate innovations that
could be applied in glycerol worldwide. Future research should con-
sider the economic viability of the selected processes and the appro-
priateness of the technologies, considering the infrastructure, synthetic
routes, and industrial technology employed in the countries that are the
main producers of biodiesel.
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