Eur. J. Lipid Sci. Technol.

2014, 116, 0000–0000 1

Special Feature
Understanding the glycerol market

Rosaria Ciriminna1, Cristina Della Pina2, Michele Rossi2* and Mario Pagliaro1

1
Istituto per lo Studio dei Materiali Nanostrutturati, Palermo, Italy
2
Dipartimento di Chimica, Università degli Studi di Milano, Milano, Italy

As a result of the booming biodiesel and oleochemicals manufacturing taking place worldwide since more
than a decade, 2 million tonnes of glycerol consistently reach the market every year, even though after a
decade of growth the total glycerol supply is expected to slightly decrease in 2014. Today the supply of
glycerol is entirely independent of its demand, as there is as much glycerol as the amount of vegetable oils
and animal fats are hydrolyzed to make oleochemicals, or transesterified to produce biodiesel. This
unique situation has led to consistently low glycerol prices, which initiated both the market penetration of
glycerol in countries where it was not used due to traditional high price, as well as new uses of glycerol as
raw material for the production of value added chemicals. This article sheds light on the market of this
uniquely versatile chemical whose number of applications is unique amid all existing chemicals.

Keywords: Biodiesel market / Glycerol / Glycerol‐derived products / Glycerol market / Glycerin / Oleochemicals market
Received: May 14, 2014 / Revised: June 10, 2014 / Accepted: June 17, 2014
DOI: 10.1002/ejlt.201400229

1 Glycerol, the eminent oleochemical i.e., the base for dynamite and cordite, the smokeless
gunpowder for all types of munitions. Invented by Sobrero
Glycerol (1,2,3‐propanetriol) is the oldest organic molecule in 1846, nitroglycerin in its natural liquid state is very volatile
isolated by man having being obtained by heating fats in the and extremely hazardous to handle. In 1866 Nobel discov-
presence of ash to produce soap since as early as 2800 BC [1]. ered that mixing nitroglycerin with siliceous sedimentary rock
Providing the molecular skeleton of all animal and vegetable “kieselguhr” (a form of silica mined in Germany) could turn
fatty oils, the triol is liberated at slightly more than 10% by the liquid into a malleable paste, known as “dynamite,” which
weight of tryglicerides level either in the hydrolytic synthesis could be kneaded and shaped into rods for blasting rock
of fatty acids (soap), and in the transesterification of oils and through a detonator activated by means of a strong shock.
fats with methanol to make biodiesel (Fig. 1). Glycerol shortly became a strategic military resource.
Along with FAME, fatty alcohols and fatty acids, glycerol Hence, when glycerol demand due to the 1st World War
is thus an eminent oleochemical. exceeded the supply from the soap industry, reasons of
With the price of one barrel of oil consistently above 100$, military security led to the first synthetic plants for glycerol
the oleochemicals industry in the last decade has been manufacture both in Europe and in the United States, where
growing steadily meeting the increasing demand of cheaper glycerol for weaponry was produced through microbial sugar
(and greener) alternatives to petrochemicals of ever increas- fermentation [4]. For example, when World War I began in
ing cost [2]. For example, in mid 2012 the Malaysian palm 1914, DuPont was the only company in the US which
and rubber plantation firm Felda Global Ventures Holdings manufactured smokeless powder and was the nation’s leading
raised up $3.1 billion at the Malaysia’s stock exchange, in the producer of dynamite (in 2 years DuPont’ sales increased
second largest 2012 initial public offering in the world [3]. from $25 million to $318 million) [5].
To understand today’s glycerol market it is relevant to In 1943 the German chemical cartel I. G. Farben started
look back at its historic development. Glycerol is the raw glycerol production from petroleum feedstock, using the new
material for manufacturing leading explosive nitroglycerin, high‐temperature chlorination of propene to allyl chloride
process. Similar plants were built after the 2nd World War in
Correspondence: Dr. Mario Pagliaro, Istituto per lo Studio dei Materiali Europe, in Japan, in Russia and in the United States. In
Nanostrutturati, CNR, via U. La Malfa 153, 90146 Palermo, Italy general, for more than 60 years about 25% of the global
E‐mail: [email protected]
Fax: þ39 091 680 92 47 
Additional Corresponding author: Prof. Michele Rossi
Abbreviations: EU, European Union; FFA, free fatty acid E‐mail: [email protected]

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2 R. Ciriminna et al. Eur. J. Lipid Sci. Technol. 2014, 116, 0000–0000

Figure 1. Both saponification and transester-

ification reactions yield 10 wt% glycerol as
main by‐product.

glycerol demand was met by the petrochemical synthesis from Manufacturing Practices, affording glycerol aimed to phar-
propylene; and the other fraction was obtained from soap maceutical companies to a purity level of more than 99.7%.
manufacturing, where glycerol by‐product has been a source Synthetic glycerol, though, is now a negligible fraction of the
of revenues and profits for 60 years. Since 2003, however, yearly glycerol output (<5000 tonnes out of 2 million tonnes).
the synthetic glycerol market has been disrupted due to the In 2003 the Directive 2003/30/EC on the Promotion of
biodiesel and oleochemicals glycerol surplus. the use of biofuels and other renewable fuels for transport was
enforced in the European Union (EU). This new regulation
requiring minimum volumes of biofuels (5.75% by 2010) in
2 Biodiesel glycerol all transport fossil fuels (petrol and diesel), originated the
fiscal incentives that led to the biodiesel boom. In detail,
The global production of bioglycerol from biodiesel has subsidies to biodiesel manufacturers were enforced as tax
climbed from 200 000 tonnes in 2003 to 600 000 tonnes in exemption in main EU countries (Germany, France, Italy,
2006, progressing to >2 million tonnes in 2011. In 2012, it and Spain). The US soon enforced similar regulation with a
exceeded again 2 million tonnes including also the fraction due $1‐per‐gallon biodiesel tax incentive first implemented in
to oleochemicals manufacturing. Traditional market usages for 2005 [6].
refined glycerol in the United States, Asia, Latin America and The technology to make biodiesel is simple. In the
Europe suddenly were not capable anymore to absorb this traditional manufacturing process, biodiesel is produced
surplus, and most key players pulled out of the market. by the homogeneous transesterification reaction between
In Japan, the main glycerol production factories ceased vegetable oil and methanol, catalyzed by strong base. It is
operations in October 2005. In the US, Dow Chemical closed an equilibrium reaction with the stoichiometry shown in
its 60 000 tonnes/year glycerol plant (the world’s largest) in Scheme 1.
Texas in early 2006 when also Procter & Gamble shut down Like many homogeneous chemical processes carried out
its 12 500 tonnes/year plant near London. Few months later in batch, the traditional route to this important biofuel is
Solvay closed (and later retrofitted) its glycerol plant in obsolete affording plenty of waste made of spent catalyst, raw
Tavaux, France. glycerol (80 wt%), unreacted methanol, soaps and salts.
Today, Dow operates in Germany the only chemical plant Several alternative heterogeneously catalyzed processes have
where glycerol is synthesized according to current Good been introduced in the last decade [7], among which the

100 kg of oil + 10.5 kg MeOH = 100 kg methyl esters (biodiesel) + 10.5 kg glycerol

R2

O O OH H 3C H 3C H 3C
O O OH O O O
Catalyst
+ 3 CH3OH + + +
R1 R2 R3
R3 Metanol
O
HO O O O

R1 O Glycerol
Methyl Esters

Triglyceride Scheme 1. Transesterification of a triglyceride

with methanol.

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Eur. J. Lipid Sci. Technol. 2014, 116, 0000–0000 Understanding the glycerol market 3

Esterfip continuous process is used since 2006 by the biodiesel and oleochemical companies mostly based in
Sofiprotéol group to produce 200 000 tonnes/year of biodiesel the Asia Pacific region (Malaysia, India, Indonesia, and
at a plant in the south of France over a solid basic catalyst [8]. Philippines, Table 1) [11].
The heterogeneous process affords much purer glycerol (90– To absorb this surplus, developing new chemical uses of
95%) and avoids the expensive distillation step to isolate pure glycerol as platform chemical suddenly became urgent [12].
glycerol. The number of research papers dealing with new usages for
Very soon countries with large availability of land such as glycerol published annually between 2000 and 2007 doubled
Argentina and Brazil or where palm or coconut oil plantations to more than 7000, and a number of new catalytic routes to
were in place, such as Malaysia, the Philippines, Indonesia, high added value products were discovered or re‐discovered,
Colombia, and Thailand started to manufacture and sell improved, and applied such as in the case of the acetic acid
vegetable oils to biodiesel manufacturers in Europe and in the catalyzed route to epichlorohydrin now successfully produced
US, and to and oleochemicals producers in Asia. by Solvay and by several other chemical companies in Asia
The outcome was a flood of glycerol that disrupted a and in Europe [13].
chemical market that in the above mentioned petrochemical/ Recent estimates on the new usages of the 2 million tonnes
oleochemical split existed since the early 1940s; even though of the 2015 refined glycerol market were projected to equal
production of soap‐derived glycerol (glycerine, or glycerin) the traditional usages of this versatile molecule finding broad
started as early as the late 1850s with the commercialization of application in the pharmaceutical, personal care and tobacco
the first personal care “consumer” products in Europe and in industries (Fig. 3) [14].
the US. In 2008 some of us wrote the first edition of a book [12] on
In brief, until 1999 the main glycerol supplier was the the emerging usages of glycerol as a platform chemical, as
oleochemicals industry. Ten years later the biodiesel industry chemical ingenuity was rapidly opening the route to glycerol
had become the main overall supplier (Fig. 2). derivatives for use in fields as diverse as fuels, chemicals,
In 2005 the top three global glycerol suppliers were pharmaceuticals, detergents, and the automotive and build-
Procter & Gamble, Cognis and Uniqema (now Croda) that, ing industries. In the book’s preface, we were writing that: “In
combined, had more than one third of the market share [10]. three to five years glycerol will be seen as an environmentally
Five years later, the main glycerol suppliers had become friendly way of replacing competing petroleum products.”
This forecast turned out to be true. Many of the glycerol
derivatives mentioned therein are now commercially manu-
factured. Examples include epichlorohydrin, propylene
glycol (1,2‐propanediol), and methanol; and many others

Table 1. Top glycerol producers in 2010

Cognis Corporation (USA)

Emery Oleochemicals (Malaysia)
Croda InternationalPlc (UK)
Dial Corporation (USA)
Dow Chemical Company (USA)
Godrej Industries Ltd. (India)
Sofiproteol Group (France)
IOI Oleochemical Industries Berhad (Malaysia)
Acidchem International Sdn Bhd (Malaysia)
Kao Corporation (Japan)
Pacific Oleochemicals Sdn Bhd (Malaysia)
Palm‐Oleo Sdn Bhd (Malaysia)
Procter & Gamble Chemicals (USA)
PT Cisadane Raya Chemicals (Indonesia)
PT Sinar Oleochemical International (Indonesia)
PT Sumi Asih Oleochemical Industry (Indonesia)
Setuza A. S. (Czech Republic)
Unilever (Malaysia) Holdings Sdn Bhd (Malaysia)
United Coconut Chemicals, Inc. (Philippines)
Figure 2. Main drivers affording glycerol before (top) and after
(bottom) the biodiesel boom (reproduced from Ref. [9], with kind Source: Glycerol: Global Industry Analysts, A Global Strategic Business
permission). Report, 2011.

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4 R. Ciriminna et al. Eur. J. Lipid Sci. Technol. 2014, 116, 0000–0000

Figure 3. Current and future glycerol applica-

tions (image reproduced from Ref. [14], with
kind permission).

will emerge in the near term including the manufacture of and handling aid for cement) replacing petrochemical
acrylic acid via glycerol dehydration to acrolein. amines and glycols.
In this highly dynamic and somehow uncertain context, Bioglycerol streams normally contain 65–85% (w/w)
one might wonder whether bioglycerol as platform chemical glycerol and >20% methanol. The rest is a mixture of water,
will remain economically sustainable. Or if ceasing of methyl esters and lipids, inorganic salts (catalyst residues),
biodiesel fiscal incentives will lead to a rapid fall of the FFAs, unreacted mono‐, di‐, and triglycerides, and a variety
glycerol output and to unsustainable price increases. The of other “many organics non‐glycerol” (MONG) in varying
answer to these questions requires a better understanding of amounts (Table 2).
the glycerol market in today’s global economic and energy Biodiesel manufacturing started in Austria in 1985 [20].
contexts. Out of the 31 biodiesel plants an Austria’s leading company
(BDI‐BioEnergy) has built globally, 26 of them use a proven
homogenous potassium‐based catalyst. Potassium‐based
3 The problem with biodiesel glycerol catalysts are better than NaOH, particularly for feedstocks
with high FFA content (up to 20%), as they ease separation
The problem with crude glycerol from biodiesel production is and recovery of soaps and FFA from glycerol, with further
that it has heavy contamination from toxic methanol and has a yield increase.
high salt and free fatty acids (FFAs) content and a substantial Methyl alkoxides are the current industry standard as they
color (yellow to dark brown) [15]. allow almost quantitative biodiesel yields [21]. Hence, plants
This makes crude glycerol unsuitable for most traditional using hydroxide catalysts are switching to methylate catalysts
glycerol markets. The conventional biodiesel manufacturing (the industry has now moved to >30% sodium methylate).
process utilizes a 6:1 molar ratio of methanol to oil in order to Companies such as BASF and Evonik, for instance, recently
drive the reaction to completion. Most of the excess alcohol built sodium methylate manufacturing plants in Brazil and
ends up in the bioglycerol layer from which costly methanol is Argentina to reduce catalyst transportation and storage costs.
recovered via relatively inexpensive flashing or distillation. Rapeseed, soybean and palmitic oils have the most
Purifying high boiling point glycerol via distillation, however, suitable physico‐chemical charateristics for transformation
is much more expensive. Hence, perhaps not surprisingly, a into biodiesel. The raw oil is refined by degumming
number of bioglycerol leakages from biodiesel plant were
soon reported, such as in the case of the Alabama Black
Table 2. A typical range of bioglycerol composition (adapted from
Warrior river contaminated in 2007 [16].
Ref. [19], with kind permission)
Still today, a large portion (16%, Fig. 3) of the overall
production of glycerol goes into animal feed stock. Cattle, Material wt%
indeed, can tolerate poisonous methanol contaminating raw
glycerol, and still efficiently absorb the energy content of Glycerol 65–85%
the molecule. Adding 7.5 wt% crude glycerol to cattle Ash 4–6%
rations improves the animal’s feed to weight‐gain ratio, as Methanol 23.4–37.5%
Water 1–3%
ruminants can handle toxic methanol and its breakdown
Sodium 0.1–4%
product, formaldehyde [17]. Discovered by us in 2008 [18],
Potassium 0.1–5%
the only other major use of crude biodiesel glycerol is as Iron 7–11 mg/kg
superior additive for manufacturing cement of enhanced Phosphorous 60–110 mg/kg
performance (enhanced concrete strength, and grinding

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Eur. J. Lipid Sci. Technol. 2014, 116, 0000–0000 Understanding the glycerol market 5

(elimination of lecithins and phosphorus) and deacidification upwards of $20 million, which excludes small‐to‐medium‐
(elimination and recovery of FFAs which comprise some 2% scale biodiesel plants.
of the original product).
The refined oil is thus charged into large batch reactors
and heated at 55–60°C with an excess mixture of methanol 4 A unique chemical market
and sodium or potassium methylate, using a methanol:
oil ¼ 6:1 molar ratio. After reaction for 2 h, the mixture is left For decades the glycerol market was mainly devoted to direct
to stand. The glycerol–methanol solution is heavier than usage with only two major chemical end‐uses as raw material,
methanol and the esters, and is run off from the bottom of the namely in the manufacture of nitroglycerine and in alkyd
reactor. resins production. Highly pure glycerol was sold at high
To find use in food grade and pharmaceutical applica- price (2500–4000$/tonne) to pharmaceutical and personal
tions, the bioglycerol stream must be purified. We remind care product manufacturers and, prior to the biodiesel boom,
here that fatty acid and fatty alcohol producers refine glycerol the related revenues were an important part of the profitability
making a clean glycerol co‐product (the “splitter crude”) that of the soap and oleochemicals industries. Since 2003,
is not sold into the commercial market, but moves directly however, the rapidly increasing glycerol oversupply caused
into the refining process to become USP certified or kosher/ a dramatic fall in the price of both refined and crude glycerol
halal certified if the process and feedstocks are free of animal (Fig. 4).
contaminants. Refined glycerol is classified into three main In detail, the price for refined glycerol (99.5% Kosher
classes: grade) decreased from about 4000s/tonne in year 2000 to less
than s450/tonne in early 2010, when the price of crude glycerol
 Technical grade – used as a building block in chemicals, went to s0 per tonne, i.e., bioglycerol had become a waste product
not used for food or drug formulation; of no economic value, whose only use was as low‐energy content
 USP glycerol from animal fat or plant oil sources, suitable fuel for incineration or for cattle feeding.
for food products, pharmaceuticals; On the other hand, such unprecedented low prices
 Kosher glycerol from plant oil sources, suitable for use in generated new demand in China, India, Russia and Latin
kosher foods. America, namely large regions of the world where glycerol in
various areas such as oral and personal care, pharmaceuticals,
Purified glycerol is generally sold as 99.5% or 99.7% pure. and food and beverage products was historically not used due
Crude biodiesel glycerol, even at 80% purity, cannot be used to its high price. The rapidly rising living standards of
by traditional oleochemical refiners because it would damage consumers in these large countries met the offer of low cost
expensive pipe and storage equipment. Prior to use it must be of glycerol. Hence, for example, in 2010 the main consumer
refined to an acceptable purity level in dedicated refineries of EU glycerol was Russia, absorbing 30% of the total
and then either sold at low price as “technical‐grade” refined Europe’s export deliveries [23].
glycerol or, more conveniently, further refined to USP or In affluent economies, too, glycerol consumption rose
kosher/halal grade (Table 3). susbstantially (in the EU in 2010 it increased in one year only
A 2011 analysis aimed to estimate the cost of glycerol by 21%, to 319 698 tonnes). Similar double‐digit growth
purification up to 98 wt% (by combination of neutralization, was recorded in the United States and in South East Asia
centrifugation, evaporation, and column distillation) con- (“Asia‐Pacific”).
cluded that the lowest cost for glycerol purification was 0.15$
per kg [22].
Traditional purification of crude glycerol employs high
temperature, vacuum‐distillation. Glycerol at atmospheric
pressure indeed boils at 290°C. The process is energy‐
intensive and thus a cost‐efficient refinery using distillation
requires large‐scale operation. Such a refinery can cost

Table 3. Purification quality of glycerol can be identified by its grade

Refined glycerol Purity

Technical grade 95.5%

USP 96%, vegetable‐based
USP 99.5%, tallow‐based
USP/FCC‐Kosher 99.5%
USP/FCC‐Kosher 99.7% Figure 4. The change of the market price of 99.5% Kosher grade
glycerol in the in US and Europe (realized by the Author, 2010).

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6 R. Ciriminna et al. Eur. J. Lipid Sci. Technol. 2014, 116, 0000–0000

The latter region surpassed Europe as the largest market 5 Conclusions and perspectives
in 2009. Today, Asia‐Pacific represents the largest as well as
fastest growing regional market for glycerol worldwide with The glycerol’s price is historically volatile. Prior to the
increased demand for all applications, including new markets biodiesel boom, when one fourth of the global (and relatively
for refined glycerol, such as production of epichlorohydrin. low) demand was met by synthetic glycerol and the rest from
Almost concomitantly, indeed, new industrial processes for soap and oleochemicals manufacturing, the price was dictated
the production of epichlorohydrin propylene glycol, that primarily by weather and by the fluctuating demand of soap
require refined (and not crude) glycerol, were established in and fatty alcohols. This volatility, that once was linked to the
China, Thailand and, to a lesser extent, in Europe and in the volatile demand of a chemical mainly used by the pharmaceu-
US [13]. tical and personal care industries, today originates from the
Low cost glycerol is used as low‐glycemic sweetener and is volatile nature of the glycerol supply; which in its turn is
replacing previously cheaper polyols in many applications. influenced by two main factors: politics (i.e., fiscal incentives
For example, today glycerol is less expensive than other to biodiesel in the EU and in the US; and subventions to
humectants such as propylene glycol and sorbitol. Hence, biodiesel and oleochemicals manufacturing in many coun-
glycerol has become an essential component for cereal tries) and oil.
manufacturers and dried fruit processors due to its capability In other words, as glycerol today originates as a by‐
to enhance shelf life of products (glycerol not only prevents product of biodiesel and fatty acids and fatty alcohols
moisture loss but preserves the texture of food products, manufacturing, its supply is entirely independent of market
building humectancy of cereals, raisins, and dried fruits). demand. There is as much glycerol as much vegetable oils are
Thanks to the combination of new applications, market converted into biofuels, and oleochemicals. Said otherwise,
expansion in traditional markets and replacement of other this is one of the few examples in economics of a good whose
polyols, the price of glycerol partly recovered since the 2009 price is not affected by the demand for various end‐use
historic lows. As of mid 2014, in the US pharmaceutical grade segments.
glycerol could be bought for $900 per tonne, whereas crude This explains the so called glycerol‐derived products
glycerol (80% pure) was sold at 240$/tonne [24]. Yet prices “pyramid of value.” In order to generate profits, a company’s
never reached the high levels expected by many analysts. product obtained from glycerol needs to be positioned close
Showing the price trend for refined glycerol up to 2003, to the top of the pyramid of value, namely there where price
Figure 5 contains the prediction of a researcher that by 2010 fluctuations of glycerol will not make its product uneconomic.
the glycerol price could be “as low as $0.35 per lb” [26]. Otherwise, sitting at the bottom of the pyramid – for
Subsequent developments have shown that the above example all usages of raw glycerol as such, like in cattle
prediction was too conservative. The refined glycerol price feeding or as concrete additive – customers will simply shift to
plunged even more rapidly. In early 2007 it was 29–35 cents/ the less pricey alternatives. Epicholorohydrin, propylene
lb; while at the end of 2009 prices were in “the low‐to‐mid glycol, 1,3‐propanediol, methanol, acrolein, glyceric acid,
30s” [27]. dihydroxyacetone, and similar derivatives obtained by
In early 2012, the price started to recover with prices of chemoselective catalytic processes sit close to the top of the
vegetable glycerol in the US recorded at $838/tonne–1014/ pyramid, where also highly pure glycerol for pharmaceutical
tonne [28], and at $700–780/tonne in Asia [29]; with good and personal care usages resides.
global demand across several key end‐uses, particularly in Recent market analysis projects that demand for glycerine
food‐grade and pharmaceutical applications. Eventually, in by‐product of oleochemicals and biodiesel production will
late 2013 (tallow) glycerol contract prices in the US were expand at an annualized average rate of 7% during 2007–
around $900/tonne [30]; and Asia’s (vegetable) refined 2021; with a 6 million tonnes overall production in 2025 [6].
glycerol prices were reported at an average of $965/tonne Graphs such as the one shown in Figure 6, produced by a
due to higher feedstock (vegetable oil) prices [31]. reputed analyst company [6], are commonly presented in
research papers and market reports.
Yet, after a decade of growth, the total glycerol supply is
expected to slightly decrease in 2014 due to a 11% reduction in
the global biodiesel production following lower output of
biodiesel in the US, Argentina and Indonesia [33]. With
about 60–65% of total glycerol output being generated as a
by‐product of biodiesel, this clearly shows the reliance of low‐
cost glycerol availability on biodiesel global production.
However, the price of crude oil as well as of petrol fuels
remains at historic highs despite a global recession that
Figure 5. Price trend of industrial glycerol (reproduced from caused a dramatic reduction of the world’s industrial output
Ref. [25], with kind permission). since the global financial crisis started in 2008. Such high cost

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Eur. J. Lipid Sci. Technol. 2014, 116, 0000–0000 Understanding the glycerol market 7

many extraordinary chemical and physical properties to

continue to waste it in such 1st‐generation biorefinery
practices. Bioglycerol will be an eminent raw material for
the 2nd‐generation biorefinery [36].

This article is dedicated to University of St Andrew’s Professor

David Cole‐Hamilton, on the occasion of his wonderful lecture at
Palermo’s FineCat 2014. We thank Doris de Guzman, Green
Chemicals Blog, and Dr Thibaud Caulier, Solvay, for helpful
discussion. Their contribution towards a research article useful to
practitioners of the oleochemicals, biodiesel and glycerol industries
is gratefully acknowledged.

The authors have declared no conflict of interest.

Figure 6. World crude glycerol production NY sector. Actual and

projected values, 2000–2025 (reproduced from Ref. [32], with kind
permission). References
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