44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

Bioglycerol a new platform chemical

Alexander Kaszonyi and Magdalna tolcov
Faculty of Chemical and Food Technology, Slovak University of Technology in
Bratislava
Institute of Organic Chemistry, Catalysis and Petrochemistry
Department of Organic Technology, Radlinskho 9, 81237 Bratislava 1

Bioglycerol is obtained as a by-product in four different processes: soap

manufacture, fatty acid production, fatty ester production, and microbial fermentation.
It can be prepared also by hydrogenolysis of glucose or other saccharides in the
mixture of other polyols. Synthetic glycerol is prepared from propylene, but this route
is at present economically unpleasant as a result of high crude oil prices.
The reaction for the direct transformation of vegetable oils and animal fats into
methyl esters (FAME) and glycerol have been known for over a century. However, it
is only recently, following many years of research and development, that the
transesterification of rapeseed, soybean or sunflower oils has gained significance for
its role in the manufacture of biodiesel with sufficient quality for modern fuels and fuel
components. Glycerol is normally generated at the rate of 1 mol of glycerol for every
3 mol of FAME, which represents approximately 10 wt% of FAME. The European
Union Directive EP 2003/30/ES stated that by the end of 2010 traffic fuels should
contain at least 5.75% of renewable bio-components. In 2020 fuels should contain 10
% of renewable components and 20 % of energy should by originated from
renewable sources. If the target of this directive is to be achieved, European
biodiesel demand could increase over 10 million tons per year by 2010, producing
more than 1 million tons of bioglycerol as by-product. In the USA almost 0.4 million
t/year of new glycerol would be added to the market.
However, there are relatively new solutions with incorporation of glycerol to
biofuel in the form of triacetin, glycerol carbonate or monoacylglyceride. The last from
them is the main lubricating agent in biofuel[1-3]. Some new processes
(CanmetENERGY

SUPERCETANETM

Technology

Canada,

Neste

NExBTL

technology, Porvoo 170000t/y, Singapore 800000 t/y) which transform vegetable oils
to biofuel by hydrogenolysis/pyrolysis, destroy also glycerol to low molecular product.
These processes can decrease the surplus of bioglycerine in the market. However,

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

processes which incorporate glycerol to biofuel till now are not realized in their
production.
Moreover glycerol can also be produced from carbohydrates, either directly or
as a by-product of the conversion of lignocelluloses into sugars and subsequently to
ethanol. Technical and economic analyses show that the co-production of glycerol
with ethanol lowers its production costs and increases the profit of lignocelluloses
conversion to fuel additives.
The result of mentioned processes is a volatile price of glycerol, which
decreased from 1200 (2000) to 400 (end of 2006) as a result of huge glycerol
surplus. Then it increased during 2007 to 950 (new processes for utilisation of
bioglycerol, Epicerol, propandiole). In March 2009 the price of glycerol is again 360380 /t[4] because the production of biofuels still increases. Global production of
bioglycerol from biodiesel climbed in EU from 200,000 t in 1995 to an estimated
1,200,000 t in 2008, growing at an annual growth rate of 50%. On the other hand
side Solvay started the production of epichlorohydrin (Epicerol) in a small unit (10
kt/y) in Tavaux, France by May 2007 and is planning to start a 100 kt/y
epichlorohydrin unit based on bioglycerol in Map Ta Phut, Thailand by 2009. New
production lines in EU are: Rheinberg (10kt/year), Tavaux (50 kt/year). In this
process glycerol is converted to dichloropropanol by HCl in the first step. The next
step, dehydrochlorination of dichloropropanol to epichlorohydrin, is nearly the same
as in the production of epichlorohydrin from propene. Epichlorohydrin is an essential
feedstock for the production of epoxy resins, increasingly used in applications in the
electronics, automotive, aerospace and windmill sectors. Because of the toxicity of
formed chlorinated compounds and HCl, corrosion and ecologic problems, this
process is designed mainly for companies experienced in the epichlorohydrin
production.
Several thousand tons of bioglycerol was used instead of ethylene glycol as
concrete additive in 2008 at W. R. Grace. The first thousand tons of propylene glycol
from crude glycerol was delivered to customers in the USA by Senergy Chemical
(and soon is planned by Dow, Huntsman and other companies): These are the first
three large-scale chemical processes using glycerol. Because there is not equilibrium
between increasing production and industrial utilization of bioglycerol in new
production lines, the price of glycerol is volatile.

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

In the past, most bioglycerol based products utilized unmodified glycerol or

simple modifications of glycerol molecules as the production of more complex
chemical compounds were too expensive. The lower price of glycerol could open
many significant new markets for resins, polymers, ethers, polyurethanes and other
fine chemicals. From a chemical point of view, glycerols multifunctional structure and
properties can be tailored by several different reaction pathways. In the near future,
the potential conversion of renewable resources into valuable commodity chemicals
can facilitate the replacement of some petroleum-based products, e.g. propanediol,
acrolein, acrylonitrile, epichlorohydrin, etc. Furthermore, the conversion of glycerol to
syngas or hydrogen can further contribute to the use of clean renewable energy
sources. It is clear that a very large number of fine chemicals could be derived from
glycerol. In Beilstein database is more than 1500 reaction products from glycerol.
Accordingly, the number of research papers dealing with glycerols new usages
published between 2000 and 2007 has doubled to .>7000, and the first book on the
topic appeared in mid 2008 [5].Therefore the huge amount of bioglycerol in the
market can be a new platform chemical.
Catalysis represents a critical approach to green chemical technology in the
activation and utilization of glycerol. Recently, a series of novel catalytic conversion
processes that transform glycerol into useful chemicals was reported in the literature
(Scheme 1).
Acrolein is one of important by-products of glycerol dehydration at higher
temperatures. It is usually used as a synthetic intermediate of derivatives (e.g. acrylic
acid) that are synthesized on the site of production to minimize the transportation of
acrolein from the manufacturer to the client. The essential reason is linked to the
toxicity of acrolein, which leads manufacturers to avoid the storage and transportation
of this dangerous chemical product. The most commonly used process for producing
acrolein was based on the gas-phase catalytic oxidation reaction of propylene with
atmospheric oxygen. The acrolein thus obtained is incorporated directly into an
acrylic acid manufacturing process. When acrolein is used as starting material for the
synthesis of methionine (a synthetic protein used as an animal feed supplement )or
for fine chemistry reactions, a purification section is needed for removal of the
reaction by-products, mainly carbon oxides, acrylic acid, acetic acid and
acetaldehyde.

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

HCl

H
H2C C CH2

-HCl

H
H2C C
O

Cl OH Cl

hydrogenolyzis

H
H3C C CH2

OH OH

H2C OH

OH

fermentation

H2C OH
i-butene

OH

C C CH2
H2 H2

other products

glycerol ethers
as fuel additives

catalytic oxidation
[30]
condensation

O
O
HO C C
H2 H

dehydration

OH

epoxy resins

polyesters DuPont

OH

C C CH2
H2 H2

HC OH

C Cl
H2

O
CH2

dimers and oligomers

H
amoxidation H C C CN
H2C C C
2
H
H
O

Scheme 1
It has been known for a long time that glycerol can lead to the production of acrolein.
To obtain acrolein, it is necessary to use a sufficient temperature, and partial vacuum
to increase the formation of acrolein. The reaction commonly catalyzed by acids may
be performed in the liquid phase or in the gas phase[6-10]. The reaction is generally
accompanied by side reactions leading to the formation of hydroxypropanone,
propanaldehyde, acetaldehyde, acetone, adducts of acrolein with glycerol, glycerol
polycondensation products, cyclic glycerol ethers, etc., but also phenol and
polyaromatic compounds, which are the cause of the formation of coke on the
catalyst. This results in deactivation of the catalyst, reduction of yield and the
selectivity towards acrolein. The presence of by-products in the acrolein, such as
hydroxypropanone or propanaldehyde, which are moreover difficult to isolate,

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

necessitates separation and purification steps, which lead to high recovery costs for
the purified acrolein. Moreover, it is necessary to regenerate the catalyst regularly in
order to regain satisfactory catalytic activity. The best catalysts (yield of acrolein over
70 %) are the most acidic catalysts with Hammett acidity constants Ho between -10
and -16. At lower acidity the yield of acrolein are below 60 % and the catalyst is
relatively easily deactivated[11-13]. Most recently, however, Corma and co-workers
have developed a dehydration process resulting in full glycerol conversion to acrolein
which makes use of the solid acid catalyst ZSM-5 zeolite [31]. The catalyst and the
reaction products are separated, and the catalyst is continuously regenerated. The
method has a number of advantages because (i) it can process glycerol solution in
whatever concentration; (ii) it does not need any co-solvent to carry out the reaction;
and (iii) it continuously regenerates the catalyst so that catalyst activity can be
maintained over large periods of time, even with contaminated feeds. Furthermore,
the less valuable heavy by-products of the reaction can be burned inside the
process, thus generating the heat that is necessary to carry out the process, as water
vaporization requires large heat input.
Most recently, a highly selective process for reacting glycerol with ammonia to form
acrylonitrile in gas phase at 400 C has been reported [14]. The proposed reaction
scheme involves a combination of the glycerol dehydration mechanism followed by a
C-N bond formation. High yield of acrylonitrile needs special catalysts from Al,V, Sb
an Nb oxides[14].
The catalytic hydrogenolysis of glycerol is another alternative route to increase
the

profitability

of

biodiesel

production

plants.

The

products

of

glycerol

hydrogenolysis can easily replace the chemical compounds, which at present are
industrially produced mainly from sources based on crude oil. Propylene glycol is an
important medium-value commodity chemical with a 4% annual growth in the market
size. It is used for polyester resins, liquid detergents, pharmaceuticals, cosmetics,
tobacco humectants, flavors and fragrances, personal care, paints, animal feed,
antifreeze, etc. Traditionally, it is produced by the hydration of propylene oxide
derived from propylene. There has been a rapid expansion of the market for 1,2-PD
because of the growing concern over the toxicity of ethylene glycol-based products to
humans and animals. 1,3-PD is also a high-value specialty chemical that is mainly
used in specialty polyester fibers, films, and coatings. 1,3-PD is copolymerized with
terephthalic acid to produce the polyester SORONA (DuPont), or CORTERRA

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

(Shell), which has unique properties in terms of chemical resistance, light stability,
elastic recovery, and dyeability[15-18]. The catalysts for glycerol hydrogenolysis at
present are optimized only partially for industrial technologies of production of
commodity chemicals[19]. The transformation of glycerol to propandiole consist of
two steps. The first is dehydration of glycerol to acetol and the second is
hydrogenation of acetol to propandiole. The first step is catalyzed by acids, the
second by metals, so mainly bifunctional catalyst are used. Several combination of
strong acids, up to superacids, and typical hydrogenation catalyst were studied. Most
of them produce low yield of propandiole. For dehydration are pleasant low pressures
because of increasing amount of molecules. However for hydrogenation are better
higher pressures because of kinetical and thermodynamical reasons. The most
effective catalyst is based on copper chromite[20] with 85 % selectivity and 47 %
yield, where copper is catalyses both reactions, dehydration and hydrogenation.
Overall, the process results in an antifreeze product (70% PG 1 30% glycerol) that
can be produced, easily refined and marketed directly by the existing biodiesel
facilities
Glycerol can be converted into branched oxygen-containing components by
catalytic etherification with either alcohols (e.g. methanol or ethanol) or alkenes (e.g.
isobutene). Among these, tert-butyl ethers have potential to be used as diesel fuel
additives and offer an alternative to oxygenates. The etherification of glycerol can be
catalyzed by acidic homogeneous catalysts (e.g. p-toluene sulfonic acid and
methane sulfonic acid) and preferentially by heterogeneous acid catalysts such as
zeolites. It is worthwhile to evaluate strong acid ion exchange resins as suitable
catalysts for the production of commercial ethers from glycerol[20-21]. The
technology of catalytic etherification of bioglycerol by isobutene is prepared for
industrial realization. The main problem to be solved is the availability of isobutylene.
A relatively low content of renewable component in di- and tri tert-butyl ethers (45
wt.% and 35 wt.%, respectively) and higher prices of these ethers may be a problem,
too. This situation can be partially solved by ketalether, which in the first step is
prepared by reaction of glycerol and relatively cheap acetone and in the next step by
etherification of formed solketal by isobutylene. All raw materials for the production
of this type of compounds are produced in Slovnaft a.s. !
Glycerol carbonate is a new and interesting material for chemical industry. It
has been used as a component of polyurethane foams, gas separation

44th International Petroleum Conference, Bratislava, Slovak Republic, September 21-22, 2009

membranes[22], and some surfactants[23], a component in coatings, paints and

detergents, and a nonvolatile reactive solvent for several types of materials.
Inexpensive glycerol carbonate could serve as a source of new polymeric materials
for the production of polycarbonates and polyurethanes[24].

A reaction with

phosgene or with a dialkyl carbonate are known as a method of glycerol carbonate

preparation from glycerol. Mouloungui et al.[25] patented a process for the
manufacture of glycerol carbonate by reacting glycerol with cyclic organic carbonate
(ethylene or propylene carbonate) in the presence of organic carbonates or mixture
of carbonates as solvents. Aresta et al.[26,27] investigated the direct carboxylation of
glycerol with CO2 using transition metal alkoxides as catalysts (n-Bu2Sn(OMe)2, nBu2SnO or Sn(OMe)2), n-Bu2Sn(OMe)2 was the most active catalyst. One possible
method for the synthesis of glycerol carbonate is by the reaction of glycerol with urea
in the presence of a metal oxide catalyst such as zinc oxide, an alkaline earth metal
oxide, e.g. magnesium oxide, or performing the reaction in the presence of new no
patented catalyst[33].

Acknowledgements
This work was supported by the Slovak Research and Development Agency under
the contact number APVV-20-036805.

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