Perspective

Is there a future in glycerol

as a feedstock in the production
of biofuels and biochemicals?
Fredric Bauer and Christan Hulteberg, Lund University, Sweden
Received July 10, 2012; revised August 17, 2012; accepted September 11, 2012
View online November 26, 2012 at Wiley Online Library (wileyonlinelibrary.com); DOI: 10.1002/bbb.1370;
Biofuels, Bioprod. Bioref. 7:4351 (2013)
Abstract: Glycerine is a chemical with a wide variety of uses. There are over 2000 known applications in cosmetics, foodstuffs, fine chemicals, and other industries. With the recent boom for liquid
biofuels however, glycerine which is a by-product mainly of biodiesel production has become
abundant. New uses for the chemical are being researched, but little attention has been paid to
the production and supply of glycerine. This perspective shows that the development of liquid
biofuels is a key point for the future glycerine market. Glycerine could become available in large
volumes from the production not only of biodiesel but also bioethanol. Second-generation biofuels,
cellulose-based bioethanol, and algal biodiesel will continue to produce large quantities of glycerine.
However, new technology pathways such as glycerine-to-methanol and glycerine-to-ethanol could
rapidly change the market situation. Instead of viewing glycerine as a waste, biofuel producers may
come to view the by-product as a valuable resource for their own production processes. This could
rapidly change the market situation for other industries which now rely on the glycerine supply
from the biofuels industry. 2012 Society of Chemical Industry and John Wiley & Sons, Ltd
Keywords: biofuels; glycerine; biodiesel; bioethanol; market projection

Glycerine a promising resource

ollowing the liquid biofuel boom, biodiesel in
particular, glycerine (alt. glycerin or glycerol) has
become abundant on the world market as a byproduct from the biodiesel production process, in which
the oils are reacted with an alcohol to produce biodiesel
via transesterication. Glycerine production has historically been dominated by the production of soap, a process in which glycerine is also formed as a by-product,
together with synthesis from petroleum-based feedstocks
(propylene-based). Glycerine is used in a wide variety of
applications, ranging from pharmaceuticals to foodstus

and explosives.1,2 Over the last decade, however, production has come to outnumber the demand by several times,
the price has plummeted, and the interest in nding new
applications for the versatile chemical has increased substantially. At the same time, production facilities have
seen their prot margins disappear; some have had to shut
down or convert production into other end-products in
later years.3
Several research reviews on new and emerging usage of
glycerine show a large interest into the chemical. Pagliaro
et al. published a rst review in 2007,4 later expanding the
topic into a book,5 which presents numerous industrial
examples on glycerine conversion and applications for

Correspondence to: Fredric Bauer, Lund University, Dep. of Chemical Engineering, P.O. Box 124 Lund SE-221 00, Sweden.
E-mail: fredric.bauer@chemeng.lth.se

2012 Society of Chemical Industry and John Wiley & Sons, Ltd

43

F Bauer and C Hulteberg

downstream products. Other reviews published thereafter

include the works by Johnson and Taconi,6 da Silva
etal.,7 Fan and Burton8 and Stelmachowski,9 presenting
the possibilities for both thermochemical and biological
conversion of glycerine to valuable fuels and chemicals.
The long list of products that can be produced from glycerine includes 1,3-propanediol, dierent butyl ethers,
-carotene, propionic acid, epichlorohydrin, ethanol,
methane, syngas, and hydrogen. Proposed production
paths for these compounds include bacterial and yeast
fermentation, steam reforming, liquid phase reforming,
pyrolysis, and gasication.48 There is obviously a large
interest in glycerine and developing technologies which
enable the ecient utilization of this renewable resource.
Research focusing on how the glycerine market will continue to develop and analyzing possible obstacles for new
glycerine-based technologies is however absent in the literature. This perspective aims to give an in-depth analysis
on the development of glycerine production and demand
until today, the probable development in the near future,
and prospects for the long-term future. The market situation changed drastically when biodiesel production started
increasing a decade ago. Thus, this perspective will focus
on the link between the development of liquid biofuels and
glycerine production.

Early developments
Industrial glycerine production has completed a full circle
with respect to feedstock technology. Historically, glycerine was derived from fats and oils, mainly as a by-product
in the soap industry in which the fats and oils are boiled
with caustic soda to form soap and glycerine.2 This was
also the main glycerine production pathway for quite some
time. Fermentation of sugars to glycerine has been known
since the mid-nineteenth century and was used industrially during World War I as the demand for glycerine
peaked due to the expanding production of explosives.10
The fermentative production route has not been important
since however, although a revival of this technology was
viable only a decade ago as glycerine prices peaked before
starting to fall rapidly.5,10,11
In the middle of the twentieth century, production of
synthetic glycerine increased quickly and accounted for
about half the market in the 1960s and 1970s. Synthesis
of glycerine from propene follows three main paths. The
rst process, developed in the 1940s, uses allyl chloride as
an intermediary, which is then converted into epichlorohydrin using hypochlorite. Hydrolysis of the epichlorohydrin nally gives glycerine. A second path was developed

44

Perspective: The future of glycerine

in the 1950s and eliminates the use of chlorine; instead

propene is oxidized to acrolein. The acrolein is converted
into allyl alcohol and then glycidol which can be hydrolyzed to glycerine. The third alternative path converts
propene to propylene oxide in its rst step. Th is is then
isomerized to allyl alcohol, which via glycidol is converted
to glycerine.1,2
In 1990, this fossil-fuel-based production accounted
for 30% of the glycerine production, but as of today this
capacity has been shut down or converted to other endproducts. In fact, the process has now been reversed and
glycerine is used to produce the former intermediary
epichlorohydrin in some plants.5 Turning from synthesized product to feedstock shows just how drastic the
change has been on the glycerine market in recent years.
The traditional demand of glycerine comprises about
750 000 tonnes over many dierent industries. Glycerine
is used in a number of products, including toothpaste,
drugs, cosmetics, and tobacco. In tobacco, glycerine is
used as an additive for casing the tobacco leaves to stop
them from curling during processing. In cosmetics, it is
used in creams and lotions as a skin softener. In the food
industry it is used as a heat-transfer medium in direct
contact with foods in quick freezing and as a lubricant
in machinery used for food processing. It is also used to
sweeten food-products substituting other polyols such as
sorbitol. The many applications for glycerine (over 2000)
are a consequence of its many characteristic properties;
glycerine is water soluble, sweet, odorless, non-toxic,
colorless, biodegradable, plasticizing, and water absorbing.1,2 In Fig. 1, the traditional market distribution is
depicted.

Present situation and near future

development
Today, the glycerine supply is dominated by glycerine from
biodiesel production. However, there is also a possibility
of extracting glycerine co-produced in ethanol fermentation processes that has not been as well described earlier.
The interest in liquid biofuels has increased dramatically
as awareness of climate change has spread across the
globe. Although many problems with liquid biofuels have
been reported and debated in academic literature as in
other media, the production of liquid biofuels is increasing. The debated problems include eects of direct and
indirect land-use change, the working conditions in the
agricultural sector, and the eects biofuel production may
have on food prices. However, the use of liquid biofuels
will likely continue to increase, due to policies such as the

2012 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:4351 (2013); DOI: 10.1002/bbb

Perspective: The future of glycerine

F Bauer and C Hulteberg

Pharmaceuticals
13%

Miscellaneuos
11%

Tobacco
8%

Plastics
14%

Resins
6%

Cellophane
2%
Explosives
1%

Cosmetics
20%
Food
25%

Figure 1. Market shares for glycerine demand in traditional industrial applications.1

180000
160000

Million litres per annum

140000
120000
100000
80000
60000
40000
20000
0
2009

2010

2011

Ethanol OECD-FAO

2012

2013

2014

Biodiesel OECD-FAO

2015

2016

2017

Ethanol IEA

2018

2019

2020

Biodiesel IEA

Figure 2. Recent statistics and projections for the production of liquid biofuels.13,14

European directive stating that all vehicle fuels should

contain a minimum percentage of renewable fuel.12 Recent
production statistics and projections on the development
of liquid biofuels show that bioethanol production will
continue to grow faster than biodiesel, but that both will
steadily increase over the next ve to ten years. Recent

projections have been presented by OECD and FAO in

their common report Agricultural Outlook 2011-202013 and
the forecast presented by IEA in the Medium-term Oil &
Gas Markets,14 reports which project similar developments
over the next few years. These forecasts are both presented
in Fig. 2.

2012 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:4351 (2013); DOI: 10.1002/bbb

45

F Bauer and C Hulteberg

Crude glycerine can be divided into two major classes:

hydrolysis crude glycerine is derived from triglyceride
hydrolysis and contains low amounts of inorganic salts
whereas salt crude is the residual, salt-containing glycerine
fraction from the soap industry and biodiesel industry.15
Either of these qualities can be upgraded to food-grade
or pharmaceutical-grade glycerine. Crude glycerine from
biofuel production is especially interesting as a feedstock
for environmentally concerned producers in Europe as it
is credited with zero carbon dioxide emissions up to the
process of collection by a decision of the EU.16

Glycerine and biodiesel

With the large-scale introduction of liquid biofuels to
the market, glycerine is now available at a level exceeding
demand by several times. Th is is mainly due to the fact
that glycerine is an inevitable by-product in the production of rst-generation biodiesel, which has increased from
almost nothing to 20 billion liters per annum in just over
a decade.13 In the biodiesel production process, triglycerides vegetable oils such as palm oil or rapeseed oil are
transesteried with an alcohol, usually methanol, to form
fatty acid esters, the biodiesel. Glycerine, which constitutes the backbone of the triglycerides, is co-produced in
the process and later separated from the biodiesel product
by splitting the chemicals into two phases: one oily phase
containing the fatty acid esters and one polar phase containing glycerine (5060%), methanol (1030%), catalyst
salts (820%), water (<5%), and some soap, free fatty acids
and other components split from the feedstock. The glycerine phase is then processed to recover as much of the
methanol as possible and the catalyst salts are neutralized by addition of an acid such as sulfuric acid.3 After
post-processing, neutralization, and washing, the crude
glycerine from biodiesel production contains about 80%
glycerine, 10% water, 7% ash, and less than 1% methanol.17
The glycerine amounts to approximately 10% (w/w) of the
biodiesel produced.5
Biodiesel is conventionally produced with a homogeneous alkaline catalyst such as KOH or NaOH, but acid
catalysts are also used in some industrial processes.
Enzyme catalysts with higher tolerance for water have
been researched, but are yet not economically feasible
industrially.18 To reduce the contamination of the glycerine produced in the process, using heterogeneous catalysts
is an important improvement, which also reduces the
need for the continuous addition of catalyst to the process. Research on heterogeneously catalyzed processes for
biodiesel production is ongoing and has been reviewed
recently18,19 and although complete process designs

46

Perspective: The future of glycerine

using this type of process are available,20 the traditional

approach is still the most common. That said, there are
several plants in operation using heterogeneous catalysts.
Biodiesel production has peaked globally in the last few
years, according to statistics. Europe was the rst large
market for production and consumption of biodiesel, but
recently the Americas have started and expanded production, and Asia is following. Projections from OECD-FAO13
and IEA14 show an increase in biodiesel production over
the coming years, indicating increased glycerine production as well. Figure 3 shows the projection for the production of biodiesel. Although biodiesel production does not
increase as much as bioethanol, production is still likely
to double by 2020 according to this forecast. This would
mean that crude glycerine from biodiesel production
would also double.

Glycerine and bioethanol

Another opportunity for readily available crude-glycerine
is within the bioethanol industry. When fermenting sugars to ethanol, glycerol is simultaneously produced by the
yeast. This glycerine is important in wine production21
but an unwanted by-product in industrial production of
bioethanol for fuel purposes. Earlier research shows that
production levels of glycerine compared to ethanol can
vary in the range of 515% (w/w), depending on feedstock
and process conditions.22 This glycerine, however, is not
as easily recovered as the glycerine from biodiesel production; it is but one component in the residual stream from
the fermentation process. This stream also contains other
chemical compounds, which possibly could be of interest in a future integrated ethanol and biorenery process
such as acetic acid, succinic acid, and other organic acids
and higher alcohols.23 Extraction of glycerine from this
residual stream is not economically feasible today, but
studies show that it would be possible to increase glycerine
production in ethanol fermentation to give glycerine yields
suitable for extraction.24 This, however, would implicate
a transition for fermentation plants from solely focusing
on maximized ethanol production to improving the total
yield of extractable compounds.
According to the projections, production of bioethanol
is expected to increase substantially over the coming decade. Most of the bioethanol will continue to be produced
by the major actors the USA and Brazil while China
and the EU-27 will also increase the production as shown
in Fig. 4.13 When looking at the transition from rst- to
second-generation bioethanol, this does not necessarily
mean either an increase or a decrease in the opportunity
for extraction of glycerine. As the glycerine is produced to

2012 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:4351 (2013); DOI: 10.1002/bbb

Perspective: The future of glycerine

F Bauer and C Hulteberg

45000
40000

Million litres per annum

35000
30000
25000
20000
15000
10000
5000
0
2009

2010

2011

European Union-27

2012

2013

2014

United States

2015

2016

Argentina

2017
Brazil

2018

2019

Canada

2020
World

Figure 3. Forecast of global biodiesel production by region.13

180000
160000

Million litres per annum

140000
120000
100000
80000
60000
40000
20000
0
2009

2010

2011

European Union-27

2012

2013

United States

2014

2015

2016

Brazil

2017

China

2018

2019

Canada

2020
World

Figure 4. Forecast of global bioethanol production by region.13

regulate important cellular functions,10,11 fermentation of

cellulose instead of starch or sugar is not likely to drastically change the production of glycerine.
Estimating the glycerine that could be extracted from
bioethanol industries conservatively to 3% (w/w) of the

ethanol produced the glycerine produced by the bio-ethanol industry turns out to be a very large quantity globally
it is actually much larger than the glycerine from global
biodiesel production as seen in Fig. 5. Should a larger
share of the glycerine be extractable from the ethanol

2012 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:4351 (2013); DOI: 10.1002/bbb

47

F Bauer and C Hulteberg

Perspective: The future of glycerine

140000

120000

Tonnes per annum

100000

80000

60000

40000

20000

0
2009

2010

2011

2012

2013

2014

2015

2016

2017

2018

2019

2020

Glycerine from ethanol production (High)

Glycerine from ethanol production (Medium)

Glycerine from ethanol production (Low)

Glycerine from biodiesel production (Low)

Figure 5. Estimation of global production of glycerine from liquid biofuel production processes.13

fermentation process (6 or even 10%), the potential supply

from this source is vast. However, it is also questionable
if this resource will become available, as new research
shows that glycerine is a suitable feedstock for ethanol
production. Microbial fermentation of glycerine to ethanol has been studied by several researchers with positive
results.17,2528 Turning in-house waste streams to product
will, of course, be very interesting for ethanol producers if
a process for this, viable at industrial scale, is developed.
Otherwise, a new vast stream of glycerine may become
available to the market and applications specialized in
turning glycerine into new products.

Prospects for the long-term future

In the longer perspective, there are several opportunities
for a stable supply of glycerine, should the technologies
for turning glycerine into valuable products be implemented on a large scale. A promising source for renewable chemicals and fuels are microalgae, which have been
studied intensively for dierent applications, although oils
for biodiesel production attract a large share of the interest.2933 The possibilities and obstacles to produce biofuels
using microalgae have been discussed in-depth earlier.34
Although microalgae have received much attention in
recent years as they have a high productivity and can be
grown without competing with food crops for arable land,
the market is yet awaiting the large-scale introduction of

48

algal oils. Important stakeholders, such as the US Navy

and the large shipping company Maersk have engaged in
full-scale testing of algal fuels.35 Large-scale production of
algal fuels will give rise to large amounts of glycerine; how
much and how far into the future are dicult to estimate
at the time of writing.
Another method would be to use algae to produce the
desired glycerine directly, without the triglyceride addition. This can be done using an algae from the Dunaliella
group.36 These algae have the advantage of not only producing glycerine in high yields and quantities, but also
surviving and being productive in very high saline concentrations. The use of these high saline concentrations
eectively avoids contamination from other living organisms and thus ensures an ecient production process. The
possible contribution to the global glycerine supply of this
kind of production is dicult to estimate. However, it is
plausible that in conjunction with fuel or chemical production from the glycerine, it may be economically feasible
to perform.
Yet another promising source for biodiesel production
is jatropha, a drought-resistant tree which produces seeds
that are very rich in oil and can be used to produce biodiesel.3740 Research shows that the oil can be used without
problems in biodiesel production but cultivation seems
to be the problem. As jatropha can be grown on marginal
soils and is poisonous it would not compete with food production, but other problems such as harvesting diculties

2012 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:4351 (2013); DOI: 10.1002/bbb

Perspective: The future of glycerine

F Bauer and C Hulteberg

have yet prohibited the introduction of jatropha biodiesel.

It still seems to be a promising alternative to food-grade
vegetable oils as it can develop rural areas, mitigate greenhouse gas emissions, and create jobs in a new agricultural
sector if grown and produced sustainably.41 As jatropha oil
is a vegetable oil, glycerine of the same quality would be
produced in jatropha biodiesel as when using other ordinary feedstock oils.

Different valorization strategy

options
As this perspective focuses on the general aspects of the
development for the future glycerine market, specic technologies for conversion and valorization of glycerine will
not be discussed; this has been done extensively earlier by
researchers presented in the introduction. However, when
studying the macro strategies for the valorization processes of glycerine, three dierent options can be identied.
These strategies relate to the product that is the goal of the
valorization process and is determined by the price and
the market volume of the product, which can be described
as high, mid or low. The possibility for success and economic feasibility for these strategies is of course also
related to the feedstock streams that are available and the
quality of feedstock needed for the specic valorization
process. These product types and processes and illustrated
in Fig. 6.
Type I products can be described as aiming at chemicals
with a very high specic value but strictly limited market
volume. Although the high prices for these chemicals are
a good motivation to develop a process in which glycerine
is converted into these chemicals, one must acknowledge
the imminent risk of a market collapse. The case of glycerine is a good example; a chemical previously synthesized and sold at a rather high price seemed to be a good
source of income as a by-product for the early biodiesel
Type I product
high price
low volume

High quality
glycerine
Valorization
process
Low quality
glycerine

Type II product
mid price
mid volume
Type III product
low price
high volume

Figure 6. Schematics of glycerine valorization.

manufacturers, but the new cheap products stream made

the whole market collapse. The same may happen to other
chemicals in this market fraction, i.e. developing a production process from glycerine cheap enough to compete
with current production methods can make todays promising prots shrink quickly. Thus, developing and investing in new processes aiming for a very limited market
segment constitutes a high risk even if the prot initially
is projected to be high. Type I products include very ne
specialty chemicals or compounds used in pharmaceutical
industries and functional foods.
Type II products constitute another market segment of
chemicals with more moderate prices but higher market
volumes. Thus, the resilience for these chemical markets
may be greater, for example, if they are used in many different applications or used in bulk quantities in some
industries. The need for process optimization may be
larger in this valorization strategy, but the future revenues
are probable to cover the initial expenses. Balancing the
need for feedstock upgrading for this type of relatively ne
chemical against production process costs and product
purity will probably be one of the cornerstones in implementing successful processes of this kind. Possible product
categories within this type could be monomers for bioplastics and other bio-based polymers, materials for which the
interest is increasing steadily.
Type III products, nally, are products which require little or cheap upgrading from the feedstock, making products available at low cost and in high volumes. The prots
per specic quantity are necessarily lower for these products, but integration of the valorization process into existing infrastructure and the high volumes makes success for
this strategy probable. The main product type in this strategy is naturally fuels, typically vehicle fuels, but could also
include other bulk-traded chemicals and products. The key
here is identied to be the adaptability for the valorization
process to low-quality feedstocks, such as crude glycerine
with high salt content or carboxylic acids, and using existing resources and infrastructure for producing and osetting the products.
The choice of strategy could be crucial for the valorization of glycerine. A strategy focusing on niche markets
described by Type I products seems to come with a high
risk as the valorization processes are likely to require high
investments and only low product volumes are expected.
When strategizing and choosing between Type II and
Type III products important factors to consider are those
of the industrial and infrastructural context. Type II products are more likely to require new processes and industrial infrastructure to be implemented on a larger scale in

2012 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:4351 (2013); DOI: 10.1002/bbb

49

F Bauer and C Hulteberg

the next step of valorization, whereas Type III products

may be easier to integrate into existing facilities, processes
and infrastructure, for example petroreneries already
producing vehicle fuels. Thus downstream integration
may be a breaking point for the successful development
and large-scale introduction of new processes for conversion of glycerine into new chemical products and fuels.
Local tax incentives may also favor the production of fuels
instead of chemicals or other products from renewable
resources; these eects are further developed in the following discussion.

Discussion and conclusions

As has been shown, a variety of technologies for the ecient utilization of bioglycerine is being developed. Some
of these technologies need to extract rather high-quality
glycerine from the biofuel industries; today this is mainly
from biodiesel production facilities. Thus, technologies
adapted to using the lowest quality of available glycerine
will have an advantage and possibly gain a large share of
the market if they are able to add a value to their product
higher than the cost of re ning the glycerine to grades
needed for other applications. According to standard economic theory, the process able to add the most value to
the feedstock at the lowest cost will dominate the market.
However, there are always transaction costs and other phenomena that disturb the ideal market. Taxes are market
disturbances, which today focus more on renewable fuels
than renewable chemicals and products. Thus, using the
glycerine for fuel production seems to be a very promising alternative. As mentioned, several alternative ways
to process glycerine into fuels are being researched, but
one must ask if any of them will at all be feasible for new
market actors. As the largest suppliers of glycerine will be
the producers of biodiesel and bioethanol, the possibility
for these facilities to incorporate a glycerine-based process
may come to determine the feasibility of all other glycerine-based processes. The biodiesel facilities could have the
chance of closing the circle and producing methanol from
the glycerine, eliminating the need for natural-gas-based
methanol and turning the biodiesel completely renewable.
The bioethanol industry on the other hand could increase
the ethanol production by fermenting the glycerine to
ethanol in a new fermentation process.
The possibilities for large-scale use of glycerine from the
bioethanol industry rely heavily on the possibility of costecient extraction of this stream. Today, it is not feasible
to extract the glycerine from the fermentation process.
Increased production of glycerine in ethanol fermentation

50

Perspective: The future of glycerine

processes together with new separation technologies such

as chromatographic separation could increase the global
glycerine supply drastically, especially in the USA and
Brazil. Thus, glycerine will probably continue to be available at a low cost for the foreseeable future, which encourages continued research in using this resource for new
innovative applications. A breakthrough in the technology
for conversion of glycerine to liquid fuels could however
possibly disrupt the glycerine market as these products
can be sold in almost unlimited volumes. Thus, when
developing technologies based on cheap glycerine, the possibility of competing with the biofuels industry should be
carefully considered.

Acknowledgement
The funding received from the Swedish Knowledge
Centre for Renewable Transportation Fuels (f3) is greatly
acknowledged.
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Fredric Bauer
Fredric Bauer is a junior researcher at
the Department of Chemical Engineering at Lund University. He holds an
MSc in Sustainable Energy Systems
from Chalmers University of Technology. His current research relates to
markets and processes for renewable
fuels and chemicals.

Christian Hulteberg
Christian Hulteberg is a post-doctorate
research associate at the Department
of Chemical Engineering at Lund University. His early research on hydrogen
systems earned him a PhD in 2007.
Since then he has worked with developing new processes for the efficient
use of renewable resources in the field
of chemical engineering.

2012 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 7:4351 (2013); DOI: 10.1002/bbb

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