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Project Title: Developing advanced Biorefinery schemes for integration into existing
oil production/transesterification plants.
Project Start Date: 1st June 2008, Project End Date: 31st May 2010
Project Number: 213637

Document Author: WP3 Participants


Deliverables included in the report: 3.1 and 3.2
Tasks 1-5 completed and 6 to be completed by March 2009

WP 3: Optimisation of secondary processing

Content
Introduction __________________________________________________________ 4
Task 1. Novel routes to biodiesel that incorporate glycerol _____________________ 6
1.1. Introduction ___________________________________________________________ 7
1.2. New types of biodiesel to make up the glycerol as a by-product, which increases the
lubricant power of biofuel __________________________________________________ 10
1.3. Processing of oils and fats in the actual oil refining plants ____________________ 16
1.4. Second-generation technology for the production of biodiesel _________________ 17
1.5 References ____________________________________________________________ 23

Task 2. Glycerol from biodiesel production Existing and new glycerol purification
technologies _________________________________________________________ 30
2.1 Soap splitting as a glycerol pre-treatment step ______________________________ 32
2.2 Conventional processes for glycerol purification ____________________________ 33
2.3 Recent development in glycerol purification processes _______________________ 35
2.4 Chromatography and regenerative column adsorption _______________________ 37
2.5 Partly purified G-phase _________________________________________________ 39
2.6 References ____________________________________________________________ 41

Task 3. Transformation of glycerol into high-quality products through green


chemistry and biotechnology ____________________________________________ 42
3.1 Introduction __________________________________________________________ 42
3.1.1 The Glycerol Market ________________________________________________________ 42
3.1.2 Applications of Glycerol _____________________________________________________ 42
3.1.3 Green Chemistry ___________________________________________________________ 43
3.1.4
Recent Reviews _________________________________________________________ 44

3.2 Glycerol transforming processes _________________________________________ 46


3.2.1 Aqueous Phase Reforming ___________________________________________________ 46
3.2.1.1 Fischer-Tropsch __________________________________________________________ 47
3.2.2 Selective Reduction_________________________________________________________ 47
3.2.3
Halogenation ___________________________________________________________ 47
3.2.4
Dehydration ____________________________________________________________ 47
3.2.5
Etherification ___________________________________________________________ 48
3.2.6
Esterification ___________________________________________________________ 48
3.2.7
Selective Oxidation ______________________________________________________ 48
3.2.8
Pyrolysis ______________________________________________________________ 49
3.2.9 Biotransformation __________________________________________________________ 49

3.3 Valuable Chemicals from Glycerol _______________________________________ 49


3.3.1 Hydrogen_________________________________________________________________ 49
3.3.2
Succinic Acid___________________________________________________________ 50
3.3.3
Ethanol ________________________________________________________________ 50
3.3.4
Propylene glycol ________________________________________________________ 50
3.3.5
Dihydroxyacetone _______________________________________________________ 51

3.3.6
3.3.7
3.3.8
3.3.9

Acrolein _______________________________________________________________ 51
Glycerol Tertiary Butyl Ether (GTBE) _______________________________________ 51
Mono- and Di-acylglycerol (DAG) __________________________________________ 52
Citric Acid _____________________________________________________________ 52

3.4 Summary ____________________________________________________________ 54


3.5 Future Vision _________________________________________________________ 56
3.6 References ____________________________________________________________ 57

Task 4. Application of glycerol in adhesives for wood panels __________________ 60


4.1 Introduction __________________________________________________________ 60
4.2 Production of Bioglycerol _______________________________________________ 61
4.3 Glycerol uses __________________________________________________________ 61
4.4 Overview _____________________________________________________________ 64
4.5 Glycerol in aminoplastic resins ___________________________________________ 64
4.6 Glycerol in impregnation resins __________________________________________ 65
4.7 Glycerol in natural resins _______________________________________________ 67
4.8 Glycerol modifications for resin properties enhancement _____________________ 68
4.9 Glycerol derivatives uses in wood industry _________________________________ 70
4.10 References ___________________________________________________________ 74

Task 5 . Glycerol alkyl esters Production of Triacetin from crude glycerol______ 76


5.1. Current glycerol market and typical glycerol applications ____________________ 76
5.2. Glycerol alkyl esters Production of Triacetin from crude glycerol ____________ 80
5.2.1. Patents __________________________________________________________________ 80
5.2.2. Ionic liquid as a green catalytic reaction medium for triacetin synthesis ________________ 83
5.2.3. Production of triacetin from partly purified glycerol _______________________________ 84

5.3 References ____________________________________________________________ 88

Task 6 : Methods of Pre-treatment, hydrolysis, and fermentation of glycerol for


ethanol production. ___________________________________________________ 89

Introduction
The objective of the WP-3 in the SUSTOIL project is to investigate glycerol
purification and its different and marketable use. The WP-3 can be divided two parts:
Novel route to biodiesel
UCO and Seneca have reviewed novel routes to biodiesel and identified the major
technological challenges to their development. Among other potential routes, UCO and
Seneca have explored the possibility of using immobilised lipases that can yield high
purity glycerol and novel enzymatic glycerol-free routes to biodiesel production. One
example involves partial transesterification using lipases to obtain two fatty acid methyl
esters (FAMEs) and one molecule of 2-monoglyceride instead of three molecules of
FAME. Another potentially attractive route is the crosstransesterification of
triglycerides (TG) and methyl acetate, which yields three moles of FAMEs and one
molecule of glycerol triacetate, which can be used as a fuel. Both routes are potentially
attractive due to a current surplus of glycerol in the market which seriously hinders the
biofuel sector.
Applications for glycerol
Purity issue
Although a number of potential applications for glycerol have already been identified,
the generally low purity of crude glycerol (crude glycerol from a biodiesel process
currently contains only 35% to 50% glycerol) limits its potential applications. The high
cost of glycerol purification and increasing overcapacity forces small and medium
biodiesel producers to pay for the disposal rather than utilise the crude glycerol. Hence,
biodiesels future stability and viability is likely to be dependent on innovative and
economical technologies for the utilisation of the low-grade crude glycerol in order to
offset the cost of biodiesel production. Through SUSTOIL, UP and NEC worked
closely to review and assess the different technologies available to refine (e.g. filtration,
centrifugation, etc) and purify the glycerol (e.g. vacuum distillation, ion exchange and a
cost effective, simple chemical method).

Conversion of glycerol into valuable chemicals


Glycerol, as a three-carbon source, forms a potential carbon source for many microorganisms and as a triol, represents a tremendous platform molecule. Through
SUSTOIL, UoY has identified and evaluated the most promising chemicals, which can
be derived from glycerol through green chemistry and biotechnology.
Wood panel production
Based on the experience gained from various lignocellulosic materials CHIMAR has
assessed the opportunities and challenges of employing glycerol in adhesives
applications for the production of wood panels.
Production of triacetin
UP has carried out a techno-economic assessment of the production of triacetin (a
potential green solvent) from crude glycerol. NEC worked closely with UP on the
optimisation of the glycerol purification stage and elaborated a pilot plant suitable for
triacetin production. The data gathered in the course of this exercise will provide an
input for WP6, aiming at modelling and analysing the socio-economic and
environmental costs-benefits of SUSTOILs biorefinery schemes.
Alcohols and biogas production
Possibilities of biological conversion of the glycerol to alcohols and methane are
included in Task 3.

Task 1. Novel routes to biodiesel that incorporate glycerol


Felipa M. Bautistaa, ulio Berbelb, Veronica Caballeroa, Juan M. Campeloa, Jose M.
Hidalgob, Rafael Luquea, Diego Lunaa,b , Jose M Marinasa, Antonio A, Romeroa
a

Departamento de Qumica Orgnica, Universidad de Crdoba, Campus de

Rabanales, Edificio. Marie Curie, E-14014 Crdoba, Spain.


b

Seneca Green Catalyst, S.L. Urb. Santa Ana de la Albaida, 7, 14011-Crdoba,

Spain.

1.1. Introduction
Triglycerides (TG) of vegetable oils and fats are becoming increasingly
important as alternative fuels for diesel engines due to the diminishing petroleum
reserves. However, their high viscosity and low volatility do not permit their direct use
or in oil/petrol blends (McDonnel et al., 1995; Dorado et al., 2002), in any diesel engine
type (Monyem et al., 2001). Nowadays, the main process developed to overcome this
drawback is the methanolysis reaction to produce biodiesel, a biodegradable, non-toxic
diesel fuel substitute that can be used in unmodified diesel engines (Pinto et al., 2005;
Fukuda et al., 2001). It has a significant added value compared to petro-diesel because
of its higher lubricity, which extends engine life and reduces maintenance costs as well
as contributing to fuel economy (Kulkarni and Dalai, 2006). The conventional
methodology in the production of biodiesel primarily involves the use of NaOH and
KOH as homogeneous catalysts. Three molecules of fatty acid methyl esters (FAME)
and one molecule of glycerol are generated for every molecule of TG (Ma and Hanna,
1999).
However, the process is far from being environmentally friendly as the final
mixture needs to be separated, neutralised and thoroughly washed, generating a great
amount of waste in terms of salt residues. The catalyst cannot also be recycled. These
several additional steps inevitably put the total overall biodiesel production costs up,
reducing at the same time the quality of the glycerol obtained as by-product (Verziu, et
al., 2008). Ethanol could potentially be used instead of methanol, but the rates of
reaction are comparatively slower.
Several reports can be recently found on the production of biodiesel involving
other chemical (Kulkarni et al., 2006; Zong et al., 2007) or enzymatic catalytic
protocols as greener alternatives (Kaieda et al 2001; Ranganathan et al., 2008). The
increasing environmental concerns have led to a growing interest in the use of enzyme
catalysis as it usually produces a cleaner biodiesel under milder conditions (Salis et al.,
2007). It also generates less waste than the conventional chemical process. Many reports
on the preparation of biodiesel using free (Royon et al., 2007) or immobilised lipases
can also be found (Watanabe et al., 2000; Hsu et al., 2002; Macario et al., 2007).
Despite various attempts in which the enzyme was tested for the efficient production of
biodiesel, the FAME conversions were lower than 60% (Shah et al., 2004; Yesiloglu, et

al., 2004; Yadav, et al., 2005; Desai, et. al., 2006). Paula et al, (2007) have recently
shown that Biodiesel synthesis from babassu oil and ethanol, propanol or butanol was
feasible and regardless of the kind of alcohols, results revealed that the immobilized
PPL could efficiently convert triglycerides to fatty acid alkyl esters attaining yields
varying from 75 to 95%.
The major drawback of the process is the high cost due to the various steps
involved that can limit somehow the widespread use of enzymes. Moreover, the true
limitation of the enzymatic method compared to the conventional base catalysed process
deals with the alcoholysis of the 2-fatty acid esters of glycerol. Lipases have indeed a
peculiar 1, 3-regioselectivity which means that they selectively hydrolyse the more
reactive 1 and 3 positions in the triglyceride (Bornscheuer, 1995). In this regard, the
production of biodiesel using lipases needs to take into account such regiospecific
character (Li et al, 2008; Tter et al., 1999). In general, the challenging full alcoholysis
of triglycerides involves long reaction times and gives conversions lower than 70 wt%
in fatty acid methyl or ethyl esters (Rathore and Madras, 2007; Hernandez-Martin and
Otero, 2008).
A series of improvements in conversion levels and/or the use of methanol as
alcohol to mimic the results of the base catalysed transesterification reaction are
currently ongoing as a consequence of the present legal regulations for biodiesel
(EN 14214). Reasonably good results are sometimes reported due to the 1,2-acyl
migration in the monoglycerides (Oda et al., 2005; Du et al., 2005; Camacho et al.,
2006).
The current standard biodiesel production (under alkaline chemical conditions)
is considered to be the most technically simple way to reduce the viscosity of vegetable
oils from a range of 11-17 times (Vicente et al., 2007; Lang et al., 2001; Peterson and
Reece, 1996) to just about twice to that of petroleum diesel. Various fuel properties of
pure soybean oil, three B100 biodiesel types (soybean methyl esters, rapeseed methyl
esters and rapeseed ethyl esters) and high-grade petrodiesel are summarized in Table
1.1.1.

Table 1.1.1. Physico-chemical properties of soybean oil, biodiesel (B100) obtained from
soybean oil and rapeseed oil and No. 2 diesel (D2) (Peterson and Reece, 1996).

Properties

soybean oil FAMEa FAMEb

FAEEc

D2

Specific gravity (g cm-3)

0.920

0.86

0.8802

0.876

0.8495

Viscosity (40oC)

46.68

6.2

5.65

6.11

2.98

Cloud point (oC)

-2.2

-2

-12

Pour point (oC)

-9.4

-15

-10

-18

Flash point (oC)

274

110

179

170

74

Boiling point (oC)

357

366

347

273

191

Cetane number

48.0

54.8

61.8

59.7

49.2

Sulphur (%wt)

0.022

0.031

0.012

0.012

0.036

Heat of combustion (KJ/Kg)

40.4

40.6

40.54

40.51

45.42

FAME stands for fatty acid methyl esters from soybean oil

FAME stands for fatty acid methyl esters from rapeseed oil

FAEE stands for fatty acid ethyl esters from rapeseed oil
The viscosity is the only significant parameter that may affect the performance

of the diesel engine as the other parameters are very similar. Interestingly, the
diglycerides (DG) and triglycerides (TG) are mainly responsible of the increase in
viscosity of pure vegetable oils. Therefore, a novel biofuel containing a FAME/MG or
FAEE/MG blend (in which we exclude the presence of significant quantities of DG and
TG) can be expected to have a similar physical properties to those of conventional
biodiesel, eliminating the production of glycerol as a by product. Besides, the
transformation of glycerol to an alternative product miscible with FAME can also avoid
the formation of the by-product glycerol. The achievement of a glycerol-free biofuel is
most convenient and advantageous in a market flooded by the production of glycerol as
by-product (Behr et al., 2008 ; Corma et al., 2007; Yazdani et al., 2007; Dodds et al.,
2007; Pagliaro et al., 2007) in the preparation of biodiesel.
9

Furthermore, the biofuel obtained is cleaner and the efficiency of the production
can be increased more than 10% when the glycerol is somehow integrated into the
biofuel. The last step of washing and cleaning of the biodiesel in the conventional
synthetic process [to clean the biodiesel and remove the traces of glycerol up to 0.02%
glycerol (EN 14214)] can therefore be removed, reducing costs and generation of waste
water (Van Gerpen, 2005).
High levels of glycerol in the fuel causes various problems including coking, an
increase in the viscosity of the fuel and potential dehydration to acrolein which can be
further polymerised. Coking can also generate deposits of carbonaceous compounds on
the injector nozzles, pistons and valves in standard engines, reducing the efficiency of
the engines (Mittelbach, 1996; Mittelbach and Remschmidt, 2005).
Recent investigations have also shown that minor components of biodiesel,
usually considered contaminants under the biodiesel standard EN 14214, including free
fatty acids and monoacyl glycerols, are essentially responsible for the lubricity of
low-level blends of biodiesel and petrodiesel. Pure FAME exhibit a reduced lubricity
compared to the biodiesel containing these compounds (Hu, et al., 2005; Knothe et al.,
2005a, 2005b, 2005c, 2006, 2007). The presence of greater quantities of
monoglycerides and/or free fatty acids enhances the lubricity of biodiesel, which is
another key feature of this novel biofuel that incorporates high amounts of MG.
1.2. New types of biodiesel to make up the glycerol as a by-product, which
increases the lubricant power of biofuel
The pursuit of a biofuel that integrates the glycerol is currently a target of high
interest, given that the market is already virtually swamped by the production of
glycerol, obtained as a by-product from the manufacture of biodiesel. (Behr et al, 2008
and Corma et al 2007). Table 1.2.1 shows the changes in unit price in recent years.
Table 1.2.1. Changes in the price of glycerol in recent years (/kg). [Corma 2007]
GlycerolGlycerol

Ao 2000

Ao 2005

Ao 2010

Refined

1.50

0.90

0.60

Unrefined

1.10

0.60

0.30

10

In biofuels thus obtained not only is the generation of waste reduced but also
you get an increase in the yield of the process of the order of 10%, because the glycerol
is integrated into the reaction product. Moreover, the biofuel thus obtained can be used
without further processing. That is, avoiding the final step required for washing and
cleaning of biodiesel in the conventional process of synthesis [necessary to clean
biodiesel by removing traces of glycerol to 0.02% (EN 14214)]. This leads to
significantly reduce the costs of the process and avoid the generation of waste water.
(Van Gerpen, 2005).
The cleaning of the glycerol from bio-fuels is inevitable, when this is generated
in the process, as its presence is limited by the standard EN 14214 (< 0.02%) because
of its reaction with oxygen inside the engine at high temperature experiencing a process
of oxidation and polymerization to acrolein resulting in the emergence of carbonaceous
deposits on the injectors, pistons and valves that reduce the efficiency of engines
(Mittelbach, 1996 and Mittelbach and Remschmidt, 2005), Fig. 1.2.1.

CH2OH-CHOH-CH2OH
glicerina

CH2=CH-CHO + 2H2O
acroleina

2 CH2=CH-CHO + O2
acroleina
COOH
C
C

COOH

C
C

C
C

(2)

2 CH2=CH-COOH
cido acrlico

COOH

(1)

COOH
+

CO2H CO2H

CO2H

CO2H
(3)

Figure 1.2.1. Dehydration, oxidation and polymerization reactions experienced by the


residual glycerol in biodiesel into diesel engines.
Recent research has also shown that the minor components of biodiesel (which
generally are considered pollutants under the standard EN 14214), including free fatty
acids and monoacyl glycerol or monoglycerides (MG), are mainly responsible for the
high lubricity that is obtained in the blends of biodiesel and petrodiesel, even at the
lower levels. Therefore FAMEs with very high purity show a high reduction of
lubricity, compared with biodiesel containing these byproduct compounds (Hu, et al,
2005) and (Knothe, 2005a, 2005b, 2006, 2007). The presence of large quantities of
monoglycerides and/or free fatty acids, and/or various derivatives of these, will lead to a
11

new type of biofuel, which due to the incorporation of some derivatives of glycerol, will
produce an increase in the lubricant power of biodiesel. The lubricity is a very important
feature of biofuels, which improves performance and preserves the life of the engines.
In this respect, interesting results so far have been obtained using lipases and in
particular pig pancreatic lipase (PPL) (Luna et al., 2007), in both free and immobilized
form, to obtain the transesterification 1.3 selective of TG to produce the corresponding
2-monoacyl derivatives of glycerol (MG), and two moles of FAEE, the ethyl esters of
fatty acids, the alcohol used to conduct the alcoholysis reaction. In this respect it is
interesting to note that enzymatic transesterification processes can be carried out with
different short-chain alcohol (ethanol, 1- and 2-propanol, 1- and 2-butanol, etc) and
their mixtures, and it is not in principle limited to the use of methanol, as it is usual
under conventional chemical reactions (with acidic or basic catalysis). The process is
summarized in Figure 1.2.2.

H2C-OOCR
HC-OOCR + 2 CH3-CH20H

PPL

H2C-OH
HC-OOCR

H2C-OOCR

H2C-OH

TRIGLYCERIDE

MONOGLYCERIDE

2 RCOOCH2CH3
FATTY ACID ETHYL
ESTER (FAEE)

ECODIESEL
Figure 1.2.2. Ecodiesel, is a biofuel which incorporates the glycerol, produced by
enzymatic technology and patented by the University of Cordoba (UCO). It is
composed of two moles of ethyl esters of fatty acids (FAEE) and a mole of
monoglyceride ( MG).

Likewise, today we are addressing other alternatives for preparing esters of fatty
acids from lipids, which directly generate various co-products, derived from glycerol, in
parallel with the production of FAME or FAEE. The transesterification reaction of
triglycerides with dimethyl carbonate (DMC) (Renga and Coms, 1993; Notari and
Rivetti, 2004; Kenar, 2005; Fabbri et al., 2007; Su 2007) Figure 1.2.3, produces a
mixture of three molecules of the FAME or FAEE and a molecule of glycerol carbonate
(GC). That mixture (FAME + GC), has physical properties suitable for use as ac fuel, so

12

it has been presented as a new biofuel called the DMC-BIOD (Notari and Rivetti, 2004;
Fabbri et al., 2007)

H2C-O
O
H2C-OOCR
Lipasa HC-O
HC-OOCR + CH3O-C-OCH3

C=O
+

H2C-OH

H2C-OOCR

GLICEROL CARBONATO

TRIGLICERIDO

2 RCOOCH2CH3
ESTER ETILICO
DE ACIDO GRASO

DMC-BIOD
Figure 1.2.3. DMC-BIOD is a patented biofuel (Notari and Rivetti, 2004) that
integrates the glycerine as glycerol carbonate, in a process that can be developed by
enzymatic technology (Su et al, 2007).
In a similar way, the Gliperol is another new biofuel recently patented (Kijeski,
2004). This consists of a mixture of three molecules of FAME and a molecule of
glycerol triacetate (triacetin). It can be obtained after the transesterification of a mole of
TG with three moles of methyl acetate using lipase as a catalyst (Xu et al., 2003, 2005,
Du et al, 2004; Kijeski et al., 2004; Kijeski, 2007). When ethyl acetate is used (Modi
et al., 2007) the corresponding FAEE with triacetin are obtained, following the
enzymatic process shown in Figure 1.2.4.

H2C-OOCR
HC-OOCR + 3 CH3-COOCH2CH3
H2C-OOCR
TRIGLYCERIDE

ETHYL ACETATE

Lipase

CH3COO-CH2
CH3COO-CH + 3 RCOOCH2CH3
CH3COO-CH2 FATTY ACID ETHYL
ESTHER (FAEE)

GLYCEROLTRIACETATE
(TRIACETIN)

"GLIPEROL"
Figure 1.2.4. The Gliperol is a biofuel patented by the Industrial Chemistry Research
Institute of Varsow (Poland), (Kijeski., 2004), consisting of a mixture of three moles
of FAME or FAEE and a mole of triacetin, obtained by the cross transesterification of
ethyl or methyl acetate and the corresponding triglycerides in an enzymatic catalyzed
process.

13

DMC-Biod, Gliperol and the Ecodiesel have in common that they incorporate
the glycerol as a by-product (carbonate, triacetate or monoglyceride) capable of forming
single homogeneous mixtures, thus avoiding the generation of waste or by-products in
their preparation processes. Another main difference with respect to conventional
biodiesel (FAME) is that in the process it does not require any additional separation
processes. The MG, the DMC or the triacetin may be incorporated (and thus burned)
with the FAME mixture in diesel engines. In terms of green chemistry, the
incorporation of glycerol in biodiesel also increases the efficiency of the process
(nominally from the current 90% to 100%), without causing substantial changes in the
physical-chemical properties of biofuels. The atomic efficiency also experiences the
corresponding improvement, given that the total number of atoms involved in the
reaction, is part of the final mixture that forms the biofuel.
The application of lipases, by taking advantage of their ability to obtain 1.3regiospecific alcoholysis of TG, with short-chain alcohols, or by using different
reagents to other alcohols, such as dimethyl carbonate and methyl or ethyl acetates, may
constitute, in the medium term, competitive procedures, compared with the procedure
based on the basic homogeneous catalysis, because they are able to obtain new biofuels
applicable in diesel engines, which incorporate the glycerol, thus reducing the
complexity of the process (avoid washes processes to remove the residual glycerol),
increasing the process yield and minimizing the waste generation. In addition, the
enzyme production processes are conducted in conditions are comparatively more
gentle (or green) than those commonly used for the production of biodiesel (pH,
temperature, pressure, etc.).
The actual existing limitations for the use of industrial lipases have been mainly
associated with their high production costs, which can be overcome through the
application of molecular technologies to achieve the production of enzymes purified in
sufficiently high quantities. However, in addition to the high cost of lipases for its
application in the production of biodiesel, the real constraint of the enzyme method
compared with conventional basic catalysts refers to its ability to produce the 2-fatty
acid esters of glycerol. This is due to the 1, 3 regioselective character of many lipases,
which means that they selectively hydrolyze positions 1 and 3 of triglycerides
(Bornscheuer, 1995).

14

The production of biodiesel with lipases must take into account the 1,3-stereoselective
character (Li et al, 2008; Tter et al., 1999). Thus, most of the described enzymatic
processes of producing conventional biodiesel (exclusively a mixtures of FAMEs)
described, involve long reaction times and conversions less than 70% by weight of the
methyl esters of fatty acids (Rathore and Madras, 2007; And Martin Hernandez-Martin
and Otero, 2008).
When a fluid or gas is subjected to temperatures and pressures in excess of its critical
point, there are a number of unusual properties exhibited. There no longer is a distinct
liquid and vapor phase, but a single, fluid phase present. Solvents containing a hydroxyl
(OH) group, such as water or primary alcohols, take on the properties of super-acids.
A non-catalytic approach is the use of a high (42:1) alcohol to oil ratio. Under
supercritical conditions (350 to 400 C and > 80 atm or 1200 psi) the reaction is
complete in about 4 minutes. Capital and operating costs can be more expensive, and
energy consumption higher. An intriguing example of this process has been
demonstrated in Japan, where oils in a very large excess of methanol have been
subjected to very high temperatures and pressures for a short period of time. The result
is a very fast (3 to 5 minute) reaction to form esters and glycerol. The reaction must be
quenched very rapidly so that the products do not decompose. The reactor used in the
work to date is a 5 ml cylinder that is dropped into a bath of molten metal, and then
quenched in water.
Clearly, while the results are very interesting, the scale-up to a useful process may be
quite difficult. Figure 1.2.5 depicts one conception of a configuration for a supercritical
esterification process (J. Van Gerpen, Shanks B., Pruszko R., 2002-2004).

Figure 1.2.5. Supercritical esterification process

15

1.3. Processing of oils and fats in the actual oil refining plants
An alternative technology to transform the triglycerides obtained from renewable
sources is to carry out their processing in conventional oil refineries, together with the
relevant portions of heavy crude oil of equivalent molecular weights. Thus, the
production of high quality diesel fuel from vegetable oils has been described (Huber et
al, 2007) by hydrocracking of triglycerides treated with high molecular weight
hydrocarbons in conventional oil refineries
In this way, renewable liquid alkanes can be produced by treatment of mixtures
of vegetable oils and fractions of heavy oil vacuum (HVO), in flows of hydrogen and
conventional catalysts (sulphured NiMo/Al2O3) under standard conditions of
temperature (300-450 C). The reaction produced involves hydrogenolysis of C-C
bonds of vegetable oils, which leads to a mixture of lower molecular weight alkanes by
three different routes: decarbonylation, decarboxylation and hydrodesoxygenation.
Figure 1.3.1. summarizes the indicated processes.

Figure 1.3.1. Production of high-quality biodiesel from vegetable oils, through overall
hydrotreatment with petroleum hydrocarbons in conventional refineries.

16

1.4. Second-generation technology for the production of biodiesel


The main second-generation technologies that are currently being investigated
intend to convert cellulose waste into biodiesel. However, currently the biggest
bottleneck of these technologies is its high cost, but a broader use of biodiesel is
hampered by the extensive acreage required for sufficient production of oilseed crops.
Therefore, processes are urgently needed to enable biodiesel production from more
readily available bulk plant materials like sugars or cellulose. Thermochemical
conversion processes can be subdivided into gasification, pyrolysis, supercritical fluid
extraction and direct liquefaction. Pyrolysis is the thermochemical process that converts
biomass into liquid, charcoal and non-condensable gases, acetic acid, acetone and
methanol by heating the biomass to about 750 K in the absence of air. If the purpose is
to maximize the yield of liquid products resulting from biomass pyrolysis, a low
temperature, high heating rate, short gas residence time process would be required. For
high char production, a low temperature, low heating rate process would be chosen. If
the purpose is to maximize the yield of fuel gas resulting from pyrolysis, a high
temperature, low heating rate, long gas residence time process would be preferred
(Demirba, 2001). Toward this goal, several methodologies have been described.
a. Microdiesel: Escherichia coli engineered for fuel production
The production of biofuels via microbial biotechnology is a very active field of
research (Wackett, 2008). It was recently described (Kalscheuer et al., 2006) the
biosynthesis of biodiesel-adequate FAEEs, referred to as Microdiesel, in metabolically
engineered Escherichia coli. This was achieved by heterologous expression in E. coli of
the Zymomonas mobilis pyruvate decarboxylase and alcohol dehydrogenase and the
unspecific acyltransferase from Acinetobacter baylyi strain ADP1. By this approach,
ethanol formation was combined with subsequent esterification of the ethanol with the
acyl moieties of coenzyme A thioesters of fatty acids if the cells were cultivated under
aerobic conditions in the presence of glucose and oleic acid. Ethyl oleate was the major
constituent of these FAEEs, with minor amounts of ethyl palmitate and ethyl
palmitoleate. FAEE concentrations of 1.28 g l1 and a FAEE content of the cells of 26 %
of the cellular dry mass were achieved by fed-batch fermentation using renewable
carbon sources. This novel approach might pave the way for industrial production of

17

biodiesel equivalents from renewable resources by employing engineered microorganisms, enabling a broader use of biodiesel-like fuels in the future.
b. Fischer-Tropsch diesel
Fischer-Tropsch technology is one of the options available for utilising
cellulosic biomass for fuel production and one of the most advanced second generation
processes that include gasification of biomass raw materials, cleaning and packaging of
synthesis gas, and subsequent synthesis of liquid (or gas) biofuel. This German process
is known since 1920, but in the past was used mainly for production of liquid fuels or
natural gas from coal. However, the process from biomass as raw material is still in
development. Any type of biomass can be used as raw materials, including wood, grass,
agricultural residues and forest (Klerk, 2008).
Fischer-Tropsch (FT) hydrocarbons can be produced by gasification of biomass,
followed by downstream gasification. The Fischer-Tropsch process itself is well known.
In South Africa, FT-liquids have been produced from coal for many years and Malaysia
has a plant producing FT-liquids from natural gas. Using biomass as a feedstock for FTsynthesis is relatively new, however, and brings with it several problems that still need
resolving, most of them in the gas cleaning phase (Figure 1.4.1.).

Figure 1.4.1. Fisher-Tropsch process

18

The biomass FT plant comprises:


Biomass pre-treatment (chipping, drying).
Gasification (resulting in syngas).
Gas cleaning and conditioning. The syngas needs to be purified to remove, inter alia,
organic (BTX) and inorganic impurities and tars as well as impurities that can
deactivate the FT and other catalysts.
FT-reactor.
Hydro-cracker.
As with the ethanol production process, different configurations are possible.
Most configurations produce electricity and heat as by-products. Overall process
efficiencies vary with plant design from 40% to 60-65%. (Hamelinck and Faaj, 2006).
Biomass is vaporized to produce synthesis gas, which is a mixture of carbon monoxide
(CO) and hydrogen (H2). Before the synthesis, this gas can be conditioned using steam
to achieve the ratio of H2/CO for the synthesis. The liquid products obtained from the
synthesis gas, which include several fractions of hydrocarbons, are very pure (free of
sulphides) can be converted to fuel for cars. The Fischer-Tropsch biodiesel can be
directly produced, however greater conversion can be achieved if the Fisher-Tropsch
wax materials obtained as by-products is followed by a process of hydrocracking.
The Fischer-Tropsch biodiesel properties are similar to diesel oil properties, such
as the energy content, density and viscosity and can be blended with petroleum diesel in
any proportion without making any changes in car engines. However, the FischerTropsch biodiesel has certain properties that make it a better fuel for example: higher
cetane number (best car ignition) and low in aromatics which results in lower NOx
emissions of particulates.
For the application of this technology, the main challenge is the production of
synthesis gas. This synthesis gas is produced by gasification at a high temperature,
which is used for the gasification of coal. Biomass has different properties than coal and
therefore, several modifications in the conventional process are needed.
First, the pre-treatment of biomass requires different processes, because the
grinding of biomass to small particles comparatively requires a lot of energy. Pyrolysis
pre-treatment process can solve problems that arise when plugging small particles
congregate in power lines.

19

Second, due to the high reactivity of the biomass (compared with coal)
gasification temperature decreases, resulting in higher efficiencies, thus requiring
special designs for the gasification process and burners.
Thirdly, the composition of the ashes of the biomass is different than that of
coal, which is manifested in different behaviours of ash and waste, which are important
factors in the gasifier and requires further consideration. The behaviour of the ashes and
waste is also important for the cooling of synthesis gas.
Moreover, further research is necessary to update the technology, such as
cleaning and packaging of synthesis gas, development of different catalysts, using byproducts for the generation of electricity, heat and steam. The Fischer-Tropsch process
from biomass is currently being investigated in Germany, Sweden and Austria. In
Germany the company Choren with the support of the German government,
Volkswagen and DaimlerChrysler, is building a demonstration plant with an annual
production capacity of 15,000 tons of biofuels. (Kampman et al., 2005).
c. HTU biodiesel
Hydro Thermal Upgrading (HTU) is a technology in very early stage of development,
(Petrus et al., 2006) which aims to convert biomass, whatever their origin in different
types of biofuels, according to the general outline of the Figure 1.4.2.

20

Figure 1.4.2. Strategies for production of fuels from lignocellulosic biomass adapted
from (Huber and Dumesic, 2006).

Hydrothermal technologies are broadly defined as chemical and physical


transformations in high-temperature (200600 C), high-pressure (540 MPa) liquid or
supercritical water. This thermochemical means of reforming biomass may have
energetic advantages, since, when water is heated at high pressures a phase change to
steam is avoided which avoids large enthalpic energy penalties. Biological chemicals
undergo a range of reactions, including dehydration and decarboxylation reactions,
which are influenced by the temperature, pressure, concentration, and presence of
homogeneous or heterogeneous catalysts. Several biomass hydrothermal conversion
processes are in development or demonstration. Liquefaction processes are generally
lower temperature (200400 C) reactions which produce liquid products, often called
bio-oil

or

bio-crude . Gasification processes generally take place at higher

temperatures (400700 C) and can produce methane or hydrogen gases in high yields
(Peterson et al, 2008), Figure 1.4.3.

21

Figure 1.4.3. Strategies for biomass hydrothermal conversion processes (Peterson et al,
2008).

The oil productivity of many microalgae exceeds the best producing oil crops.
The emphasis is on hydrothermal liquefaction technology for direct conversion of algal
biomass to liquid fuel, Figure 1.4.4.

Figure 1.4.4. A conceptual model for integrated biomass production and conversion
integration system.

22

A problem associated with algal biomass is the relatively high water content. It
normally requires pre-treatments to reduce the water content and increase the energy
density. This requirement consequently increases the energy cost. However, direct
hydrothermal liquefaction in sub-critical water conditions can be employed to convert
the wet biomass to liquid fuel without reducing the water content. Overall, by adopting
integration approaches, such as wastewater treatment, nutrients and heavy metals
recovery by algae culture, whereby additional economic benefits are created the
obstacle of high cost of biodiesel production from algae may be overcome (Patil et al.,
2008).

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24

Kaieda, M., Samukawa, T., Kondo, A., Fukuda, H., 2001. Effect of Methanol and water
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25

Kulkarni, M.G., Gopinath, R., Meher, L.C., Dalai, A.K., 2006. Solid acid catalyzed
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26

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27

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29

Task 2. Glycerol from biodiesel production Existing and new glycerol


purification technologies
Zsanett Herseczki, Gyula Marton
University of Pannonia, Cooperative Research Centre for
Environmental and Information Technology, H-8200 Veszprem, POB 158, Hungary
Phone/Fax: +36-(88) 624-986, e-mail: hzsanett@almos.uni-pannon.hu
Sndor Ember
2657 TOLMCS, Arany J.u.2.
Tel: (35)-550-153, 550-038, 350-089
Fax:(35)-550-154, 350-190
e-mail: nek@wnet.hu
Glycerol is an inherent side product of the transesterification of triglycerides with a
monovalent alcohol (methanol, ethanol, etc.) to fatty acid alkyl esters, as is shown in the
figure below.

Figure 2.1. Reaction schematic of transesterification of triglycerides to biodiesel


Using stoichiometry it can be calculated that 10 wt% of glycerol is formed. However, that
value holds for pure glycerol. The so-called crude glycerol that falls free from biodiesel
synthesis usually has a purity between 55% and 90% where the larger biodiesel plants tend to
have the highest purities of often around 75% - 80%. The remainder of the crude glycerol
consists primarily of unconverted triglycerides, unconverted methanol, biodiesel, soaps and
contamination. This dilution means that the actual amount of glycerol formed is much larger,
between 100/90 (1,1) and 100/55 (1,8) times as much.

30

In the Table 2.1 some typical composition data for biodiesel-derived glycerol are given. Most
of the contaminants can be traced back to the biodiesel synthesis process, for example the
unreacted methanol that was not completely evaporated. Furthermore the concentrations of
Na and K can tell whether caustic soda (sodium hydroxide, NaOH) or potash lye (potassium
hydroxide, KOH) was used as a catalyst for the transesterification. Alkali metals like Na, K,
Ca and Mg are naturally present in vegetable oils. Sulphate and phosphate may remain from
neutralization of the mixture with sulfuric or phosphoric acid.
Table 2.1. Composition of G-phase
Property

Value

Unit

Genetically modified origin

Possible

Glycerol content

77-90 %

wt% A.R.

Ash content

3,5-7 %

wt% A.R.

Moisture content

0,1-13,5 %

wt% A.R.

Lower calorific value

14,9-17,5

MJ/kg A.R.

Kinematic viscosity

120

mm2/s

3-monopropylenediol

200-13 500

ppm

Methanol

0,01-3,0 %

wt%

MONG*

1,6-7,5 %

wt%

pH

4,5-7,4

Sulphate

0,01-1,04

wt%

Phosphate

0,02-1,45

wt%

Acetate

0,01-6,0

wt%

Na

0,4-20

g/kg

0,03-40

g/kg

Ca

0,1-65

mg/kg

31

Mg

0,02-55

mg/kg

Fe

0,1-30

mg/kg

Mn

<0,5

mg/kg

MONG* = matter organic non glycerol


The existing biodiesel-derived crude glycerol is of poor quality and requires expensive
refining before it is suitable for new product technologies. Current glycerol refining
technology requires significant economies of scale to be economical.
There are different processes for refining glycerol. However, all of them involve soap splitting
followed by two main separation steps: salt removal and methanol removal. Some of the
separation techniques should involve vacuum because glycerol is a heat sensitive compound
that splits into water and decomposes at 180C. Generally speaking, the following
technologies may be used to further purify glycerol (after the soap splitting step): fractional
distillation, ion-exchange, adsorption, precipitation, extraction, crystallisation, dialysis. The
glycerol soap splitting followed by a combination of methanol recovery/drying, fractional
distillation, ion-exchange (zeolite or resins) and adsorption (active carbon powder) seems to
be the most common purification pathway. Well-known companies who deliver crude
glycerol purification plants are Desmetballestra and Buss- SMS Canzler (ion exchange
equipment). Chemical companies like Rohm & Haas and Lanxess supply ion-exchange
granulates while a company like Norit supplies powder and granulated activated carbon.
[Brockmann et al., 1987; US Patent No. 4,655,879]
2.1 Soap splitting as a glycerol pre-treatment step
Three steps can be distinguished in the purification process. The first step involves
neutralization using an acid to remove catalyst and soaps. The reaction of an acid with soap
will give FFA and salt while its reaction with the base catalyst gives salt and water. Since the
FFAs are insoluble in the glycerol they will rise to the top so that they can be skimmed off.
Some salts which are insoluble in the glycerol will also precipitate out. The second step
involves removal of methanol. The methanol stream in the glycerol can be removed with flash
evaporation or using falling film evaporators. Falling film evaporators have an advantage of
keeping the contact time short and are best suited for our process because of the temperature
susceptibility of glycerol which can result in its decomposition. After removal of methanol the
purity of glycerol will be approximately 85%. In the third step, glycerol can be further be
32

purified to 99.5% using a combination of adsorption, vacuum distillation and ion exchange
processes [Knothe et al., 2005].
2.2 Conventional processes for glycerol purification
The conventional process for glycerol purification comprises of the following steps:
pretreatment, concentration, purification and refining. The pretreatment step is used to remove
colour and odour matters as well as any remaining fat components from crude glycerol. In the
pretreatment step sodium hydroxide is used for the removal of fat components by
saponification reaction where as activated carbon is used for bleaching purpose. The
concentration step involves the removal of ionic substances using ion exclusion
chromatography. In this process a bed filled with strongly acidic exchange resins is charged
with a glycerol stream. The principle used for the separation is Donnan exclusion. Ionic
substances are repelled from the resin surface remain in the liquid volume due to their charge
while the non-ionic ones can be accommodated in the pores of the resins. Afterwards the
column is rinsed with water which removes the ionic substances in the liquid first and the
non-ionic ones later. In some cases when the concentration of ionic substances in the glycerol
stream is very high, ion exchangers both cationic and anionic are used and they are exchanged
for wash water. The next step is purification which uses ion-exchangers. As mentioned before
the exchangers are used in pairs (cationic and anionic). In cationic exchangers positive ions
are exchanged for hydrogen ion while in anionic exchangers negative ions are exchanged for
hydroxide ions. This purification step will remove inorganic salts, fat and soap components,
colour and odour causing matters. The subsequent step is treatment of glycerol in multiple
vacuum flash evaporators (10-15kPa vacuum) which results in 90-95% concentration (Figure
2.2.1). An alternative way to do the same job is to use thin film distillation (Figure 2.2.2). In
thin film distillation the glycerol stream is distributed as a thin film on the wall of the
evaporator and heated externally. The glycerol will fall down to the bottom as a residue while
high volatile components like methanol and water are evaporated and collected at the top. The
final concentration of glycerol to 99.5% is carried out in vacuum (0.5-1kPa) in forced
circulation evaporators [R. Christoph et al., 2006; Ullmanns Encyclopedia of Industrial
Chemistry].

33

Figure 2.2.1. Continuous glycerol Concentration: a) Feed heater: b) Evaporator: c) Separator


with demister: d) Water Condenser: e) Glycerol heater: f) Glycerol heater/final product
cooler: g) Falling film evaporator: h) Glycerol condenser

Figure 2.2.2. Continuous glycerol distillation (Cognis):a)Economizer: b)End heater: c) Thinfilm distillation: d) Fractionating Column: e) Reboiler: f) Reflux Condenser: g) Glycerol
condenser h) water condenser

34

2.3 Recent development in glycerol purification processes


John E. Aiken has made some improvements in glycerol purification process. He proposed
five separation steps, which can be conducted in either batch or continuous mode (Figure
2.3.1). This process is claimed to be able to produce glycerol of higher than 99.5% purity
from typical crude glycerol, which contains a mixture of mono-, di- and triglycerides, excess
methanol, water, fatty acid alkyl esters, residual catalyst and salt [Aiken et al., 2006; US
Patent No.7,126,032 B1].
i) First reactor
Crude glycerol, whose purity is typically 86-92%, is preheated then fed to the first reactor.
The first reactor is used to recover triglycerides by reacting entrained methyl esters and
glycerol to produce glycerides and methanol (reversed biodiesel production reaction).
Nitrogen is sparged to provide agitation and to remove methanol and water; thus, the reaction
is shifted to glycerides formation. The temperature inside the reactor is maintained at 120160C. Gas effluent stream is then passed through a condenser. After separated from
condensed methanol and water in a condenser, nitrogen is recycled to the reactor.
ii) Second reactor
Liquid effluent stream from the first reactor is heated to maintain the second reactor at 120160C. In this reactor, unreacted methyl esters are reacted to produce methanol and
triglycerides. Wash water, which contains glycerol, is also added to the second reactor.
Similarly, sparging nitrogen is used to agitate the mixture inside the reactor and to remove
methanol and water. Entrained methanol and water are condensed. After being separated from
nitrogen, wash water is recycled. The operating conditions are adjusted in such a way that
glycerol effluent stream contains maximum 0.5 wt% of methanol and approximately 5 wt% of
water.
iii) Decanter
A decanter is placed after the second reactor. It serves as a feed tank for the flash distillation
column and a separator to remove oil layer of the glycerol stream by lowering the pH below 7
and skimming it from the glycerol layer. The recycle stream from the bottom of the flash
distillation column is mixed with the glycerol stream in this tank.

35

iv) Flash distillation column/stripper


The flash distillation column consists of a packed bed column with a steam-heated reboiler.
This column operates at a temperature of 185C and a pressure of 5-20 mmHg. There is no
reflux returned to the top of the column. About 80-90% of glycerol in the feed stream is
drawn as overhead product, which is then condensed in two condensers in series. The first
condenser is used to condense glycerol, while the second one is used to condense water which
will be sent to waste water stream.
The bottom product of the column, which contains glycerol and heavy compounds, is pumped
back to the decanter. Some of it is purged continuously or intermittently to prevent salts and
glycerol buildup in the decanter.

Figure 2.3.1. Simplified flow sheet of the recent development process, based on US 7,126,032
B1
v) Adsorption columns
The last step of glycerol refining is the removal of colour and trace impurities. There are lots
of material that may be used as adsorbent, such as activated carbon, ion exchange resins and
molecular sieves. The purified glycerol is then pumped to a storage tank.

36

2.4 Chromatography and regenerative column adsorption


Separation of glycerol by applying adsorption techniques is a proven technology. Some
biodiesel equipment vendors purify glycerol using activated carbon powder from suppliers
like f.i. Norit. The main components to separate are:
Glycerol (key component)
Water
Ions (like K+)
Saponification residues
Methanol traces
Activated carbon powder is, with surface areas between 500-1500 m2/g and sizes <150
micron, a very suitable adsorption medium to adsorb organic molecules, but is rather
expensive to regenerate the carbon. Operational costs will be high when using a column
adsorption, because of the high viscosity of the crude glycerol and the high pressure drop.
Activated carbon is applied because of its good properties in waste water cleaning. New
developments in adsorption techniques are mostly based on chromatography separation.
Originally this technique is applied to separate small amounts of samples in a laboratory.
Nowadays capacities and applications are increased. Table 5.4.1 shows some possible
chromatography techniques and its properties.
Table 2.4.1. Summary of chromatography separation processes
Method

Separation parameters

Important parameters

Gel permeation

Particle size

Column length

Ion exchange chromatography

Charge

pH, ionic strength

Hydrophobic interaction

Hydrophobicity

Polarity, ionic strength

Reversed phase

Hydrophobicity

Polarity, ionic strength

Affinity chromatography

Biospecific interaction

Ligand, eluent

37

The companies Rohm & Haas and Lanxess sell granular ion exchange resins which are also
used for glycerol purification (a.o. salts, colour and odour removal). But most important is the
separation of water and glycerol molecules based on affinity and particle size. Water
molecules that are bound to glycerol molecules are difficult to separate. It is therefore
important to find a suitable type of adsorbent with respect to high separation efficiency
(resolution) at a high volume flow capacity and low pressure drops. Table 2.4.2 summarises
some chromatographic techniques with their resolutions and volume flow capacities.
Table 2.4.2. Summary of chromatography separation processes
Chromatographic technique

Resolution

Capacity

Gel permeation

Moderate

Moderate

Ion exchange

Low/moderate

Very high

Hydrophobic interaction

High

High

Reversed phase

Very high

High

Affinity

Very high

High

It should be possible to design new types of adsorbent media specific for glycerol that meet
these process criteria. The first process set-up can be an ion exchange column with a second
column added. This column could be based on affinity properties adsorbent and (gel)
permeation principle. This principle is shown in Figure 2.4.1:

Figure 2.4.1. Gel permeation principle

38

Typical properties of gel permeation are:


Particle size: 0.1 0.2 mm
Column length: up to 1 metre
Liquid flux: up to 5*10-5 m/s 5x10-5 m.sec-1
These characteristics are difficult to apply on large scale, but new developments show
potential for higher fluxes at stable pressure drops, however these are far from economical
feasible applications.
2.5 Partly purified G-phase
University of Pannonia developed a simple refining process.
Due to the fact that composition of crude glycerol obtained from Hungarian Biodiesel factory
(Table 2.5.1) differs from composition offered by Mc Ketta (soaps, more water and salt), a
new purification process had to be developed.
Table 2.5.1. Composition of G-phases obtained from Hungarian biodiesel factories
Material
Glycerol
Water, methanol
Salt
Soaps

Composition (wt %)
45-50
10-15
10-15
30

In the industry the first step in physical refining is to remove fatty, insoluble or precipitated
solids by filtration and/or centrifugation. Then water is removed by evaporation. The final
purification of glycerol is completed using vacuum distillation with steam injection, followed
by activated carbon bleaching. The advantage of this approach is that this is a well-established
technology. The primary disadvantage is that the process is capital and energy intensive. Ion
exchange purification of glycerol is an attractive alternative to vacuum distillation for smaller
capacity plants. The ion exchange system uses cation, anion and mixed bed exchangers to
remove catalyst and other impurities. The advantage of this process is that all purification
takes place in resin vessels so the system is suited to smaller capacity operations. The
disadvantage is that the system is subject to fouling by fatty acids and soaps [J. Van Gerpen et

39

al, 2002-2004]. According to references [J.J. Mc Ketta, 1986; J. Van Gerpen et al 2002-2004]
the following views were accepted during our purification process:
Due to the high viscosity of the crude glycerol all purification steps were carried out at
elevated temperature. In this way we were able to decrease the load of agitators. It is not
practical to eliminate the methanol from crude glycerol at the beginning of technology,
because it has a favorable advantage of diluting the mixture. It is advisable to dilute the crude
glycerol with water to reduce the viscosity.
First step of our refining process was acid treatment. Phosphoric acid was used to reach pH=3
and mixture was stirred at 80 C, for 1 hour. After the treatment free fatty acid derived from
soaps were separated from crude glycerol by simple phase separation.
Next step was neutralization to separate applied acid in excess. Calcium-hydroxide was used
for precipitation, optimal pH of neutralization was found to be around 4.8. Formed Ca3(PO4)2
was eliminated by simple filtration. Filtrate coming from neutralization step is yellow or light
brown, if it is necessary, pigments and odor can be eliminated by adsorption on activatedcarbon (2 wt%/ crude glycerol).
Bleached solution contains only water, methanol and salt. Removal of whole amount
of water can be achieved only by distillation at 80C under vacuum (~ 3kPa). Unfortunately,
normal boiling point of glycerol is rather high (290C) and glycerol oligomerization starts
over 200C, so extremely deep vacuum should be used to distill glycerol from heavies
(inorganic salt). After this treatment partly purified G-phase is colorless and contains > 90 %
glycerol and salts.
Specific use of chemicals depends on the composition of crude glycerol. If esters of glycerol
are produced from crude glycerol, some purification steps can be eliminated like previous
distillation of water because water is removed azeotropically during ester formation.
Neutralization of phosphoric acid and preceding activated-carbon treatment are not necessary
because reaction is carried out in acidic media and product needs to be decolorized at the end
of the process (see Chapter 5).

40

2.6 References
Brockmann, R., Jeromin, L., Johannisbauer, W., Meyer, H., Michel, O. and Plachenka,
J.(1987).
Glycerol distillation process. US Patent No. 4,655,879
Knothe, G., van Gerpen, J. & Krahl, J. (2005). The biodiesel handbook. Illinois: AOCS Press.
R. Christoph, B.Schmidt, U.Steinberner, W. Dilla, R.Karinen. (2006). Glycerol, Ullmanns
Encyclopedia of Industrial Chemistry: electronic release, 6th ed.
Aiken, J.E. (2006). Purification of glycerol. US Patent No.7,126,032 B1
J. Van Gerpen, B. Shanks, R. Pruszko, 2002-2004. Biodiesel Production Technology
Subcontractor Report, National Renewable Energy Laboratory]
J.J. Mc Ketta, 1986. Encycl. of Chem. Proc. and Des. Vol. 24, 387.

41

Task 3. Transformation of glycerol into high-quality products through


green chemistry and biotechnology
Dr. Abbas Kazmi
Green Chemistry Centre of Excellence, University of York, York, YO10 5DD, UK
T: +44(0)1904434549 E-mail: ak584@york.ac.uk

3.1 Introduction
3.1.1 The Glycerol Market
The rapid rise of biodiesel production in the world has resulted in large amounts of Glycerol
by-product. Glycerol is commonly regarded as a waste product of the trans-esterification
process and can have many applications which add value to the entire process. The
importance of valorising this by-product is an urgent commercial and scientific challenge as
the European biodiesel industry is being crippled by subsidised US biodiesel imports ( K.
Simons, 2008).
Glycerol can be used as a building block for many chemicals such as 1, 3-Propanediol,
Lactate and Succinate. In fact many companies have initiated commercial plans to
manufacture high-value chemicals such as epichlorohydrin (Solvay SA) and proplylene diol
(Ashland/Cargill) from glycerol feedstocks. The market volatility in the price of Glycerol has
caused concern for these projects however the long term fundamentals remain strong.
3.1.2 Applications of Glycerol
Glycerol has been known since 2800 BC mainly as a by-product of soap production ( J. A.
Hunt, 1999). Currently glycerol has numerous applications in personal care, food, polyols,
alkyd resins, tobacco, detergents, cellophane, explosives and pharmaceuticals (M. Pagliaro et.
Al., 2007 ). Leffingwell and Lesser identified 1582 applications for glycerol in 1945
(Leffingwell and Lesser, 1945) however in recent times many glycerol production plants are
closing and new plants utilising glycerol as a raw material are opening (McCoy, 2006 ).
Global glycerol production has increased from 60,000 tons in 2001 to 800,000 tons in 2005
partly due to biodiesel production. The amount of glycerol being used in technical
applications is around 160,000 tons and this is expected to grow at a rate of 2.8% per year
(Bonnardeaux, 2006).
42

Glycerol is a raw material for the production of flexible foams and rigid polyurethane foams.
It is known to provide properties such as flexibility, pliability and toughness in surface
coatings and paint (Weiss, 1991) regenerated cellulose films, meat casings and special quality
papers. Glycerol has the ability to absorb moisture from the atmosphere and is therefore used
in many adhesives and glues to prevent early drying. In food applications glycerol which is
non-toxic is used as a solvent, sweetener and preservative. Many polyols such as sorbitol,
manitol and maltitol are used as sugar-free sweeteners however they are facing fierce
competition from glycerol. Glycerol has similar sweetness to sucrose and has the same energy
as sugar. Furthermore it does not raise blood sugar levels and does not feed plaque bacteria.
Glycerol is used as an emollient, humectants, solvent and lubricant in many products in the
personal care industry such as toothpaste, mouth-washes, shaving cream and soaps (Pagliaro
and Rossie, 2008).
3.1.3 Green Chemistry
The field of green chemistry is defined by a set of broad principles which focus on reducing
environmental impact. A major problem the world currently faces is the disposal of waste
and the green chemistry vision primarily is that waste generation should be prevented and if
not possible then valorisation methods should be implemented. One method of reducing waste
is to incorporate all materials used into a final useable product. The biodiesel industry
currently regards glycerol as a waste by-product however with novel methods being
indentified in this report and others, glycerol has the potential to be converted into high value
products. A more difficult challenge is making unnecessary the use of solvents and other
auxiliary substances in a chemical reaction such as methanol in biodiesel production. In any
chemical reaction or processing technology the energy requirements should be rationalised
and minimised. Energy costs have always been accounted for in a financial balance sheet
however it will not be long before CO2 is accounted for in life cycle analysis (LCA) data.
Optimising reactions and processes to work at ambient temperature and pressure would
decrease the environmental impact. In many cases the environmental impact over the life
cycle can be further improved if the feedstock is a renewable resource and the final product
biodegradable.
Other green chemistry principles include:

Synthetic methodologies should be designed to use and generate substances that


possess little or no toxicity to human health and the environment

43

Chemical products should be designed to preserve efficacy of function while reducing


toxicity

Unnecessary derivatisation should be avoided whenever possible.

Catalytic reagents are superior to stoichiometric reagents.

3.1.4 Recent Reviews


A detailed review of the glycerol transforming processes and applications is found in The
Future of Glycerol- New usages for a raw material authored by Mario Pagliaro and Michele
Rossi (Pagliaro and Rossi, 2008). The book was published in 2008 and focuses on key
chemical and biochemical transformations with detailed processing conditions. In this book
relevant information on sustainability and economics of glycerol and biofuel production is
discussed. The detailed synthetic chemistry involved in the transforming processes has been
reviewed by Behr et. Al. (Behr et. Al., 2008) in his paper titled Improved utilisation of
renewable resources: New important derivatives of glycerol.

A more detailed review on the chemicals that can be derived from glycerol was conducted in
2008 by Yuguo Zheng, Xiaolong Chen, and Yinchu Shen (Zheng et. Al., 2008) in
Commodity Chemicals Derived from Glycerol, an Important Biorefinery Feedstock. Many
important chemicals are identified which can be produced from glycerol-derived platform
chemicals and their respective industrial applications are discussed. Furthermore this review
maps the reaction pathways of a glycerol-derived platform chemical which can form many
other commodity chemicals that are not easily identifiable. Some of the important commodity
chemicals identified include acrolein, dichloropropanol, epichlorohydrin, dihydroxyacetone,
1,3-propanediol, 1,2-propanediol, glycerol carbonate, diacylglycerol (DAG), monoglyceride
(MG), oxygenate fuels, glyceric acid, tartronic acid, and mesoxalic acid.

Biochemical methods can be employed to transform glycerol into commodity chemicals and a
review in 2007 by Syed Yazdani and Ramon Gonzalez (Yazdani et. Al., 2007) titled
Anaerobic fermentation of glycerol: a path to economic viability for the biofuels industry
discusses this research. For some transformations a detailed description of the processes
involved are shown including the overall production costs as shown below;

44

Figure 3.1.4.1. Comparison of ethanol production from corn-derived sugars (dry grind
ethanol) with ethanol production from glycerol (Yazdani et. Al., 2007).
Some of the important commodity chemicals produced using anaerobic fermentation include
succinic acid, 1,3 propanediol, propionic acid, formic acid, butanol and ethanol. A recent
paper by Gervsio Silva, Matthias Mack and Jonas Contiero (Silva et. Al., 2009) published in
2009 reviews glycerol as a source for industrial microbiology. The review identifies microbial
reaction pathways for producing many chemicals from glycerol-derived platform chemicals
and an example is shown below.

45

Figure 3.1.4.2. Overview of some possible end products for different microorganisms during
glycerol degradation (Silva et. Al., 2009).
3.2 Glycerol transforming processes
3.2.1 Aqueous Phase Reforming
One of the major achievements in glycerol chemistry is the development of aqueous phase
reforming process (APR) which involves the conversion of glycerol to hydrogen and carbon
monoxide (Synthesis Gas). The process conditions are 250oC using a Pt-Re catalyst in a single
reactor (Soares et. Al., 2006). This process can also produce high yields of hydrogen from
glycerol at low CO concentrations due to favourable water-gas shift (WGS) thermodynamics.
This requires significantly lower energy consumption than traditional methane reforming.

46

3.2.1.1 Fischer-Tropsch
The synthesis gas can be used as a building block for chemicals and fuels using the FischerTropsch reaction. The syngas is converted to useful straight chained alkanes using Iron and
Cobalt catalysts however under certain conditions alkenes and alcohols can be produced. The
temperatures used in the process range from 150o to 300oC and pressures of one to a few
atmospheres are common. High temperatures lead to small alkanes whereas lower
temperatures and high pressures favour longer chain alkanes.
3.2.2 Selective Reduction
The main processes used to reduce glycerol to glycols are hydrogenolysis, dehydroxylation
and bacteria.
Propylene glycol is commercially produced via hydrogenolysis using a copper chromite
catalyst at 200oC with a pressure below 10 bar. Wang and others (Wang et. Al, 2003) showed
that it was possible to produce 1,3 propane-diol via selective dehydroxylation. The central
hydroxyl group of glycerol is selectively converted to a tosyloxyl group which is removed
using hydrogenolysis. The biological reduction to 1,3 propane diol involves the use of
bacterial strains from groups such as Citrobacter, Enterobacter, Ilyobacter, Klebsiella,
Lactobacillus, Pelobacter and Clostridium. In 1881 it was shown by Freund (Biebl et. Al.,
1999) that PDO could be produced using Clostridium, a widely available microorganism
found in nature. The process involves a two-step enzyme-catalysed reaction sequence in
which dehydratase catalyses the conversion of glycerol to 3-hydroxypropionaldehyde and this
is then reduced to PDO by NAD+-linked oxidoreductase.
3.2.3 Halogenation
The chlorination of glycerol yields an important and valuable chemical called epichlorohydrin
via 1,3-dichloro-2-propanol. 1,3-dichloro-2-propanol can be produced directly from glycerol
using HCl as a catalyst and subsequent dehydrochlorination using NaOH to generate
epichlorohydrin and NaCl.
3.2.4 Dehydration
The dehydration of glycerol can produce important chemicals such as acrolein, 3hydroxypropionaldehyde and acrylic acid. When glycerol is protonated it is more susceptible
to dehydration because the energy barrier is reduced therefore acrolein can only be produced
in acidic conditions. The reaction can be conducted in the liquid or gas phase under high

47

temperatures and/or vacuum to drive the dehydration. In the presence of molecular oxygen
acrylic acid can be produced via a one-step oxydehydration step.
3.2.5 Etherification
Glycerol alkyl ethers can be synthesised by etherification of alkenes such as isobutylene in the
presence of an acid catalyst at temperatures from 50oC-150oC. The typical molar ratios used
in the reaction are 1:2 (glycerol:isobutylene) and the yield can be improved by optimising the
reaction conditions. Glycerol can be etherified to form polyglycerol via anionic
polymerisation of glycidol through a cation exchange equilibrium initiated by partially
deprotonated 1,1,1-tris(hydroxymethyl) propane. The resulting polymer usually has a
polydispersity of below 1.5 and a molecular weight ranging from 1000 to 3000 gmol-1.
3.2.6 Esterification
Glycerol can be esterified (Budarin et. Al., 2007) with carboxylic acids or via carboxylation
and nitration. Reaction with carboxylic acids results in monoacylglycerols and diacylglycerol.
Monoacylglycerols are produced at commercial scale by either continuous chemical
glycerolysis of fats and oils [250oC, alkaline, N2 atmosphere] or by direct esterification with
fatty acids (Sonntag, 1992). The reaction of glycerol with dimethyl carbonate produces a high
yield of glycerol carbonate in the presence of a catalyst such as lipase. Glycerol can be
converted to glycidyl nitrate by treatment with nitrating and cyclising agents which
subsequently can be polymerised to form a valuable polymer.
3.2.7 Selective Oxidation
The oxidation of glycerol can be catalysed using highly active aerobic catalysts such as
platinum and palladium. Supported Gold catalysts are well known for catalytic stability,
resistance to oxygen and tolerance against inhibition by aliphatic and aromatic amines.
Organocatalysts such as 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) can be used for
selective oxidation of glycerol to mesoxalic acid. TEMPO has also been used in
electrochemical oxidation where glycerol is converted to 1,3 dihydroxyacetone (DHA). The
reaction proceeds by applying a small electric potential to a solution containing glycerol,
water and 15mol% TEMPO using a glassy carbon anode. DHA can also be produced using
biological oxidation via microorganisms or enzymes. Other oxidation products include
glyceraldehydes, glyceric acid, glycolic acid, hydroxypyruvic acid, oxalic acid and tartronic
acid.

48

3.2.8 Pyrolysis
Glycerol was identified as a feedstock for pyrolysis in 1985 (Antal et. Al., 1985), well before
the growth in the biodiesel market. Recent research by Valliyapan (Valliyapan et. Al, 2008)
and others has focused on optimising conditions for hydrogen or syn-gas production.
Pyrolysis carried out in a continuous down-flow fixed bed microreactor can occur with flow
rates of nitrogen from 30-70 mL/min, temperatures of 650-800oC and at atmospheric pressure.
It was shown that the type and size of packing material in the tubular reactor can affect the
conversion of glycerol and subsequent product distribution. Typical products include carbon
monoxide, hydrogen, carbon dioxide, methane and ethane. At lower temperatures (steam
(Antal et. Al., 1985) or supercritical water (Buhler et. Al., 2002)) longer molecules such as
acrolein, formaldehyde and acetaldehyde are observed.
3.2.9 Biotransformation
Glycerol can be converted to a very large number of chemicals using micro-organisms and
enzymes. The aerobic conversion of glycerol to 3-hydroxypropionaldehyde (3-HPA) was
reported in 1985 by Slininger and Bothast (Slinger and Bothast, 1985). The cells of klebsiella
pneumonia can be grown on a rich glycerol medium and when added to a buffer containing
semi carbazide and glycerol the production of 3-HPA starts. It was shown that a yield of up to
84% could be obtained however the production is sensitive to cell age and cultivation
medium. The optimal processing conditions for this experiment are 32oC, pH 7-8 and glycerol
concentrations of 20-50 g/litre.
3.3 Valuable Chemicals from Glycerol
3.3.1 Hydrogen
Hydrogen is the simplest element known to mankind and the most abundant element (75%)
but very rare in the molecular form (1%). Most hydrogen is found in water and hydrocarbons
and one of the cleanest methods of producing hydrogen from water is by using light,
photovoltaic cells and water electrolysis (Schlapbach and Zuttel, 2001). The current demand
for hydrogen (5x1010Kg/year) worldwide is met by the reaction of crude oil-derived methane
with water. The main application for hydrogen is as a reactant in the hydrogenation process. It
is also used for internal-combustion engines, gas-fired turbines and fuel cells (Pagliaro and
Rossi, 2008).

49

3.3.2 Succinic Acid


Succinic acid is a valuable chemical which has uses in food additives, soldering fluxes,
pharmaceutical products, surfactants, green solvents and biodegradable plastics. It is used as
an intermediate for the synthesis of 1,4 butanediol, tetrahydrofuran, -butyrolactone and linear
aliphatic esters (Silva et. Al., 2009). Novel biodegradable plastics can be synthesised such as
polybutyrate succinate and poly (1,3-propylene succinate). The U.S. market for succinic acid
is 4.5x108 Kg/year with a market price of $2.8/Kg (Kamm et. Al., 2006) and succinate is
currently produced from hydrocarbons for all non-food applications. For food applications
succinate is produced from fermentation of sugars (Zeikus et. Al., 1999) and it is know that
glycerol can be converted to succinate by fermentation with A. Succiniciproducens (Lee et.
Al., 2001). However due to high costs associated with separation and purification of succinate
from the broth and the formation of by-products, further optimisation of the process is
required (Song and Lee, 2006).
3.3.3 Ethanol
Ethanol is the most widely used biofuel in the world and is mainly produced in the U.S. (corn)
and Brazil (sugar cane). Conventional petrol motor engines can process low ethanol-petrol
blends without modification however some cars have been modified to process 85% ethanol
blends. Although most bioethanol is currently produced form sugar and starch, research is
being conducted on exploiting glycerol as a natural resource. Yazdani and Gonzalez have
shown that it is possible to efficiently convert crude glycerol to ethanol using engineered
Escherichia Coli (E. Coli) (Yazdani and Gonzalez, 2008).
3.3.4 Propylene glycol
1,3 propanediol is produced from crude oil-derived ethylene oxide using chemical catalysts
developed by Shell (Lam et. Al., 1997). It is also produced biologically by genetically
engineered E. Coli using glucose as a feedstock. When polymerised with terephthalic acid
novel polyester fibers are formed which are used in carpet and textile applications.
Furthermore 1,2 propoane diol is a high volume chemical (500,000 tonnes/year) which is used
to produce anti-freeze. Anti-freeze can be produced containing 70% propylene glycol and
30% glycerol directly from biodiesel facilities (Boswell, 2005). Mono propylene glycol
[E1520], diacetin [E1517] and triacetin [E1518] are approved solvents in the flavourings
industry ( EU directive 2006/52/EC). A joint venture by Ashland Inc. and Cargill will be
initially producing 65,000 tonnes/year of high grade propylene glycol from biodiesel glycerol.

50

The initial capital investment is about 100 million dollars and the plant is to be constructed in
Europe (Chem. Eng. Tech., 2007). Selective reduction can be employed to produce 1,2 and
1,3 propanediol from glycerol via hydrogenation using metallic catalysts. Propylene glycol
can also be produced via dehydroxylation and biological reduction as discussed earlier.
3.3.5 Dihydroxyacetone
Dihydroxyacetone (DHA) has a global market of only 2000 tonnes (Pagliaro and Rossi, 2008)
however it is very valuable and is used in the cosmetics industry as an artificial tanning agent
and as a synthon in organic synthesis (Wei et. Al., 2007). DHA affects the sensory quality of
wine with a sweet/etherish property. It is also known to react with proline to produce a crustlike aroma and has anti-microbial properties. DHA can be produced via electrochemical
oxidation, microorganisms and enzymes.
3.3.6 Acrolein
Acrolein is an important intermediate in the chemical industry and is used to produce
polyester resin, polyurethane, propylene glycol, acrylic acid, acrylonitrile and glycerol. A
direct application of acrolein is its use as a herbicide for managing aquatic plants. Methionine
is produced from acrolein and is used for animal feed to ensure sufficient growth, health and
reproduction. Several million tonnes of Acrolein are produced each year however it has
serious health risks. Due to its toxic and explosive nature, high safety standards are required.
Acrolein is currently produced industrially by oxidation of crude oil-derived propene. Recent
developments have led to hybrid processes where glycerol and propylene are converted to
acrolein simultaneuously. The first facility of such kind is being developed by Arkema, Texas
(Pagliaro

and

Rossi,

2008).

Glycerol can be dehydrated to

acrolein and

3-

hydroxypropionaldehyde as discussed earlier.


3.3.7 Glycerol Tertiary Butyl Ether (GTBE)
Glycerol Tertiary butyl ethers can be added to diesel fuels which will help meet European
biofuel targets and reduce particulate matter, carbon monoxide and unregulated aldehydes
(Liotta et. Al., 1994; Spooner-Wyman et. Al., 2003; US Patenet , 1993) in the emissions.
Furthermore the addition of these ethers into biodiesel decreases the cloud point which is
normally around 0oC to a value closer to conventional diesel (-16oC) (Noureddini, 2001). In
2007 Appleby and Spooner-Wyman (Appleby and Spooner-Wyman, 2007) have shown that
glycerol ethers can significantly reduce the NOX emissions generated from the burning of

51

pulverised coal. These ethers are produced by etherification of alkenes such as Isobutylene in
the presence of an acid catalyst. Industrially these ethers are produced from by-products of the
biodiesel and ethanol industries using olefins derived from crude oil (www.cpsbiofuels.com).
A number of companies and projects in the USA and Europe (Eureka Network) are involved
in commercialising GTBE.
3.3.8 Mono- and Di-acylglycerol (DAG)
Mono- (MAG) and Di-acylglycerol (DAG) are amphiphilic molecules and used as ingredient
blending (Jackson and King, 1997) agents in dairy/bakery products, maragarines and sauces.
They are used as texturing agents for improving the consistency of creams and lotions
(Stevenson et. Al., 1993). These molecules have excellent lubricating and plasticising
properties and are used in oils for textile machines (Coteron et. Al., 1998). Currently there are
two industrial methods for manufacturing acylglycerols which are either continuous chemical
glyceorlysis (250oC, alkaline, N2) or direct esterification of glycerol with fatty acids (Sonntag,
1992). It is also possible to produce these molecules using biological processes as Vicente and
others (Vicente et. Al., 2005) have shown by enzymatic conversion which offers high
selectivity, lower temparatures and pressures than conventional chemical conversion.
Furthermore the costs of enzymatic conversion can be reduced significantly by economies of
scale making it an attractive commercial method.
3.3.9 Citric Acid
Citric acid is industrially produced from sugars using cultures of Aspergillus Niger and is
used as a food preservative, flavourant, metabolite, environmentally benign cleaning agent
and an antioxidant. Furthermore it is used as an additive in the pharmaceutical, cosmetic and
toiletry industries (Soccol et. Al., 2006). Glycerol is being considered as a cheaper alternative
to sugar feedstock as Papanikolaou and others have shown by producing citric acid from raw
glycerol using Yarrowia lipolytica (Papanikolaou et. Al., 2002). When citric acid is reacted
with glycerol novel biodegradable polyesters are formed which have potential applications in
packaging and similar products (Rita, 2005; Pramanick and Ray, 1988). Rectangular slabs of
highly cross-linked citric acid - glycerol copolymer matrix have been shown to release in vitro
drugs such as sulfadiazine, paracetamol, diazepam, quinine hydrochloride, and doxycycline
hydrochloride (Pramanick and Ray, 2003). Jiugao and others investigated the effects citric
acid would have on the properties of glycerol-plasticised thermoplastic starch (GPTPS)
(Jiugao et. Al., 2005). Results showed that the addition of citric acid increased adhesion

52

between citric acid, glycerol, water and starch in thermoplastic starch. Rheological
investigations showed that citric acid can decrease the shear viscosity and increase fluidity of
thermoplastic starch.

53

3.4 Summary
There are several chemicals that can be produced from glycerol using well established
techniques. One of the major challenges the biodiesel industry faces is purifying raw glycerol
to a standard which can be used as a reagent. In this report chemicals and methods have been
identified which use raw glycerol as the starting material. Some chemicals can be produced
from glycerol using chemical or biochemical methods and these have been identified. Further
experimental research could be based on comparing these methods for a certain chemical and
evaluating the economic and environmental benefits.
Table 3.4.1. An alphabetical list of chemicals that can be derived from glycerol via chemical
(C) or biochemical (B) methods. The respective applications for each chemical are listed.
Chemical

Acetaldehyde

B
B

Method

Applications

Pyrolysis

Intermediate in the production of acetic acid, certain


esters, and a number of other chemicals
Synthetic Chemistry

Acetol

Microorganism
(Enterobacteriaceae)
Dehydration

Acrolein

Dehydration, Pyrolysis

Acrylic Acid

Oxydehydration

Alcohols

Fischer-Tropsch

Alkanes

Fischer-Tropsch, Pyrolysis

Alkenes

Fischer-Tropsch, Pyrolysis

Acetate

Butanediol (2,3)

Butanol

Butyraldehyde

Carbon Monoxide

C
B

Citric Acid
Diacyl Glycerol

DichloroPropanol (1,3)

Dihydroxyacetone

Epichlorohydrin

Used in the preparation of polyester resin,


polyurethane, propylene glycol, acrylic acid and
acrylonitrile
Plastics, coatings, adhesives, elastomers, floor
polishes and paints.
Beverage (ethanol only), as fuel and for many
scientific, medical, and industrial utilities
Fuels, Chemicals, Waxes, Bitumen and numerous
other applications
Synthesis and numerous other applications

Microorganism (KlebsiellaUsed in the resolution of carbonyl compounds in gas


pneumoniae)
chromatography
Microorganism
(C.used as a solvent, as an intermediate in chemical
Pasteurianum)
synthesis, and as a fuel
Microorganism
(C.Chemical intermediate and has many other
Pasteurianum)
applications
Aqueous Phase Reforming,Chemical building block
Pyrolysis
Micro-organism (YarrowiaFlavouring and preservative in food, water softener,
lipolytica)
detergents and other uses
Esterification, Enzymes
Additive, Emulsifier
Halogenation

Ethanol
Ethylene Glycol

Intermediate in Propane diol (1,2) synthesis

Intermediate in Epichlorohydrin synthesis

Electrochemical Oxidation,Tanning, winemaking


Microorganisms,
Enzyme
(Glycerol Dehydrogenase)
Halogenation,
Building block in the manufacture of plastics, epoxy
Dehydrochlorination
resins, phenoxy resins and other polymers. Used as a
Solvent and a precursor to Glycidyl Nitrate.
Bacteria (Escherichia Coli) Solvent, fuel, antiseptic, antidote and many others
Reduction

Coolant, Hydrate Inhibition, Manufacturing,


chemistry, geothermal, laboratory and other uses.

54

Formaldehyde

Formic Acid

Pyrolysis
B

Oxidation By-product

Chemical building block, textiles, disinfectant,


photography and other uses.
Preservative, antibacterial agent, Organic chemistry,
fuel cells and others
Intermediate in Succinate synthesis

Glyceraldehyde

Anaerobic
(Anaerobiospirillum
succiniciproducens)
Oxidation

Glycerol Carbonate

Esterification

Solvent, additive and chemical intermediate

GlycerolDimethacrylate

Esterification

Building block for polymers, medical applications

Glycerol tert butyl ethers

Etherification

Fuel additive

Glycidyl Nitrate

Esterification

Energetic binder, smoke propellant, explosives

Fumarate

Hydrogen

HydroxyPropionaldehyde

Hydroxybutanone

Intermediate in Carbohydrate metabolism

Aqueous Phase Reforming,Internal-combustion engines, gas-fired turbines, fuel


Pyrolysis,
Bacteriacells, chemical building block
(Escherichia Coli)
Dehydration,
AerobicChemical intermediate and precursor to acrolein
conversion
(klebsiella
pneumonia
),
Enzyme
(Glycerol Dehydratase)
Microorganism
Food and Cigarette additive

Hydroxyethanoic Acid

Oxidation By-product

Skin care products, organic synthesis and other uses

Hydroxypyruvic Acid

Oxidation

Intermediate in biological synthesis

Microorganism
(Enterobacteriaceae)
Microorganism

Polymer precursor, plastics and other uses.

Oxidation
Esterification, Enzymes

Chemical intermediate,
poisoning
Additive, Emulsifiers

Lactate

Malate

Intermediate in Fumarate synthesis

Mesoxalic Acid

Monoacyl Glycerol

Monobenzoyl Glycerol

Esterification

Chemical intermediate

Oxalic Acid

Oxidation

Chemical intermediate and many other uses


Intermediate in Malate synthesis

antidote

to

cyanide

Oxaloacetate

Microorganism

Phosphoenolpyruvate

Enzyme (Dihydroxyacetone Intermediate in Pyruvate synthesis


Kinase)
Hydrogenolysis,
Moisturiser, Lubricant, Food additive, anti-freeze,
Dehydroxylation, Bacteriacoolant and many other uses.
(Clostridium)
HydrogenolysisPolyester fibers, carpets and textiles
Dehydroxylation,
Acetalisation-Detosylation,
Bacteria
(Clostridium),
Enzyme (1,3 Propane diol
dehydrogenase)
Hydrogenolysis
Solvent in the pharmaceutical industry, resins and
cellulose esters
Dehydration, Hydrogenation Pesticide and chemical building block

Propanediol (1,2)

Propanediol (1,3)

Propanol

Propenol (2,1)

Propionate

Pyruvate

Succinic acid

Tartronic Acid

Bacteria (PropionibacteriumFood preservative, chemical intermediate, pesticide,


acidipropionici)
pharmaceutical, flavouring solvent
Enzyme (Dihydroxyacetone Intermediate in Biosynthesis
Kinase)
Anaerobic
Food additives, soldering fluxes, pharmaceutical
(Anaerobiospirillum
products, surfactants, green solvents, biodegradable
succiniciproducens)
plastics and chemical intermediate.
Oxidation
Chemical intermediate in Mesoxalic acid formation

55

3.5 Future Vision


The biodiesel market worldwide is at an early stage of its evolution. This is evident by the
collapse of several large biodiesel manufacturers such as D1 oils and Biofuels Corporation in
the UK. On the other hand many producers from the USA are exporting diesel to Europe and
the rest of the world. In the future it is likely that the world largest oil producing countries
such as Brazil, Indonesia and Malaysia will be producing biodiesel and exporting it rather
than just exporting the oil. Recent developments on utilising Indias hundreds of millions of
hectares for Jatropha oil production on brownfield land could further affect the biodiesel
markets. Therefore the market for glycerol is likely to remain volatile in the near future.
Chemical industries need to be approached at a local, national and international level to
determine their requirements and then research needs to be conducted on glycerol in
association with biodiesel producers, chemists, biologists and engineers to provide a solution.

56

3.6 References

K. Simons, Challenges and opportunities for glycerol as a renewable feedstock, Focus on


catalysts, 2008, June
J. A. Hunt, Pharm. J. 1999, 263, 985.
M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi, C. D. Pina, Angew. Chem. Int. Ed., 2007, 46,
4434 4440
G. Leffingwell, M. Lesser, Merk index, 11th edition, 1945, 705
M. McCoy, Chem. Eng. News, 2006, 84, 6, 7
M. McCoy, Chem. Eng. News, 2006, 84, 2, 32
J. Bonnardeaux, Glycerin Overview, Report for theWestern Australia Department of
Agriculture
and
Food.
November,
2006
www.agric.wa.gov.au/content/sust/biofuel/glycerinoverview.pdf
K. D. Weiss, Prog. Polym. Sci., 1991, 22, 203-245
M. Pagliaro and Michele Rossi, The future of Glycerol, RSC, 2008
A. Behr, J. Eilting, K. Irawadi, J. Leschinski, F. Lindner, Green Chem., 2008, 10, 1330
Yuguo Zheng, Xiaolong Chen and Yinchu Shen, Chemical Reviews, 2008, 108, 52535277
S. Yazdani and R. Gonzalez, Current Opinion in Biotechnology, 2007, 18, 213219
Gervsio Silva, Matthias Mack and Jonas Contiero, Biotechnology Advances, 27, 2009, 30-39
R. R. Soares, D. A. Simonetti and J. A. Dumesic, Angew. Chem. Int. Ed., 2006, 45, 3982
K. Wang, M. C. Hawley, S. J. DeAthos, Ind. Eng. Chem. Res., 2003, 42, 2913
Biebl H, Menzel K, Zeng AP, Deckwer WD, Appl. Microbiol. Biotechnol., 1999, 52, 289
V. L. Budarin, J. H. Clark, R. Luque, D. Macquarrie, A. Koutinas, C. Webb, Green Chem.,
2007, 9, 992-995
N.O.V. Sonntag, J. Am. Oil Chem. Soc., 1992, 59, 795
M.J. Antal Jr., W.S.L. Mok, J.C. Roy, T.A. Raissi, J. of Analytical and Applied Pyrolysis,
1985, 8, 291
T. Valliyappan, N.N. Bakhshi and A.K. Dalai, Bioresource Technology, 99, 2008, 4476-4483
W. Bhler, E. Dinjus, H.J. Ederer, A. Kruse and C. Mas, J. Supercritical fluids, 2002, 22, 37

57

P. J. Slininger and R. J. Bothast, Applied and Environmental Microbiology, 1985, 50, 14441450
Schlapbach and Zuttel, Nature, 414, 2001, 353-358
B. Kamm, Gruber, Kamm, Biorefineries- Industrial Processes and Products, 2006, Vol 1
JG Zeikus, MK Jain, P Elankovan, Applied Microbiology Biotechnology, 1999, 51, 545-52
PC Lee, WG Lee, SY Lee, HN Chang, Biotechnol. Bioeng., 2001, 72, 41-48
Song and Lee, Enzyme Microbiol. Technol., 2006, 39, 352-61
Yazdani and Gonzalez, Metabolic Engineering, 10, 2008, 340-351
KT Lam, JP Powell and PR Wieder, Preparing 1,3-Propanediol, WO9716250, 1997
C. Boswell, Chemical marketing reporter, 24 January, 2005
EU directive 2006/52/EC
Chem. Eng. Technol., 2007, 30, 6, 681
S. Wei, Q. Song, D. Wei, Prep. Biochem. Biotechnol., 2007, 37, 67
F.J. Liotta, Jr., L.J. Karas, H. Kesling, Diesel Fuel, US5308365, 1994
J. K. Spooner-Wyman, D. B. Appleby and D. M. Yost, SAE Spec. Publ., 2003, SP-1791, 1
14.
US Pat., 5 308 365, 1993.
H. Noureddini, Process for producing biodiesel fuel with reduced viscosity and a cloud point
below 32oF, US6174501, 2001
D.B. Appleby, J.K. Spooner-Wyman, Method for combustion of pulverised coal with reduced
emissions, US7195656, 2007
www.cpsbiofuels.com
GTBE: A renewable remedy for diesel soot emissions project funded by the European
Eureka Network
M.A. Jackson and J.W. King, J. Am. Oil Chem. Soc., 1997, 74, 103
DE Stevenson, RA Stanley, RH Fumeaux, Biotechnol. Lett., 1993, 15, 1043
A Coteron, M Martinez, J Aracil, J. Am. Oil. Chem. Soc., 1998, 75, 657
N.O.V. Sonntag, J. Am. Oil. Chem. Soc., 1992, 59, 795
M. Vicente, J. Aracil and M. Martinez, BREW symposium: Bioperspectives, 2005, 11 May

58

CR Soccol, LPS Vandenberghe, C Rodrigues, A Pandey, Food Technol Biotechnol, 2006, 44,
1419
S. Papanikolaou , L. Muniglia, I. Chevalot, G. Aggelis, I. Marc, J. Appl Microbiol., 2002, 92,
73744
D'Aquino, Rita, Citric Acid Rejuvenates Glycerol, Chemical Engineering Progress, Oct 2005
Pramanick and Ray, Polymer Bulletin, 19, 1988, 365-370
Pramanick and Ray, J. Appl. Polymer Sc., 40, 2003, 1511-1517
Y. Jiugao, N. Wang and X. Ma, Starch, 57, 2005, 494504

59

Task 4. Application of glycerol in adhesives for wood panels


Dr. Katsampas Ilias Chimar Hellas S.A.
CHIMAR HELLAS S.A.
88 Them. Sofouli - 55131 Kalamaria, Thessaloniki, HELLAS
Tel. : +30-2310-316312
E-mail : ikatsamp@ari.gr & office@ari.gr

4.1 Introduction
Lately, there has been considerable industrial interest in the development of green, wood
adhesives to substitute the classical synthetic thermosetting resins as adhesives for wood
panels because of an undue increase in the cost of oil and mounting environmental pressure
worldwide. Incorporation of glycerol into polymers or compounding into new materials is a
quite potential area of use of this compound[1].
The primary scope of this summary is to investigate and to identify uses of glycerol being a
by-product in biodiesel production.and its derivatives in adhesives for the wood panel
industry, thus another profitable sector will be added in the glycerol market (Fig. 4.1.1).

Figure 4.1.1. Market for glycerol (volumes and industrial uses). (Source: Novaol, May 2002.)

4.2 Production of Bioglycerol


Glycerol is the main secondary product of oleochemistry and its utilization can add value to
the competitiveness of oleochemical processes. It is produced by hydrolysis or
transesterification of fatty acids triacyl esters (oils and fats) and in minor amount by chemical
synthesis from propene[2-3].
Glycerol provides the molecular skeleton of all animal and vegetable fats (triglycerides, the
energy reservoir for materials in nature). It is also the oldest organic molecule isolated by
man, obtained by heating fats in the presence of ash to produce soap as early as 2800 BC.17 It
constitutes on average about 10% by weight of fatty matter. When the body uses fat stores as
a source of energy, glycerol and fatty acids are released into the bloodstream. The glycerol
component is converted to glucose in the liver and provides energy for cellular metabolism.
Natural glycerol is obtained hydrolytically from fats and oils during soap and fatty acid
manufacture and by transesterification (an interchange of fatty acid groups with another
alcohol) during the production of bio diesel fuel. It therefore comes as no surprise that in these
energy intensive days glycerol has become a hot topic in industry at large.
In the traditional manufacturing process bio diesel is produced by a transesterification
reaction between vegetable oil and methanol, catalyzed by KOH. It is an equilibrium reaction
with the following stoichiometry:
100 kg of oil + 10.5kgMeOH = 100 kg methyl esters (bio diesel) +10.5 kg glycerol
4.3 Glycerol uses
Glycerol production comes mainly from countries with significant oleochemical industries
such as United States, Europe, Japan, and South-East Asia. The United States, Japan and
more recently, China, are the major importers of glycerol while Europe and South-East Asia
region are the dominant exporters of glycerol.[4] Glycerol is most commonly used without
modification, or very basic structural modifications, as an additive to materials. Its uses
number in the thousands with large amounts being used in the manufacture of food and
beverages, tobacco, pharmaceuticals, personal care products, urethane foams, and synthetic
resins. Although the personal care industry has seen an increasing demand for glycerol due to
consumer desire for eco-friendly natural products, the majority of these markets are
relatively mature. Absorbing excess glycerol into these markets by replacing petrochemically
derived polyols such as ethylene glycol, propylene glycol, and pentaerythritol used in
automobile antifreeze, aircraft deicers and alkyd resins may partially alleviate glycerol
61

surpluses. The development of innovative applications for glycerol appears to be the most
constructive approach to utilize excess glycerol. Practically, developing glycerol as a primary
chemical building block that may be converted into other value added chemicals becomes
more attractive as crude glycerol prices drop. Currently, industry, government and academe
are increasing their efforts to develop new and improve existing glycerol chemistry, and Fig.
4.3.1 depicts some of the platform chemicals that can be derived from glycerol[5].

Figure 4.3.1. Platform chemicals derived from glycerol. (Source: J. A. Kenar, Lipid
Technology, November 2007, Vol. 19, No. 11.)
As shown, various reactions based on chemical and biochemical oxidation, reduction, bond
breaking, and polymerization reactions are available to the glycerol molecule to derive these
value added chemicals of commercial interest. Because of the high functionality of glycerol
(two primary and one secondary hydroxyl group), reactions can proceed along multiple
reaction pathways to give mixtures of products. Therefore, careful development of catalysts
and reaction conditions is of paramount importance to selectively obtain desired products.
Continued research should improve these aspects and provide new opportunities to better
utilize glycerol and its products as many of these materials have high costs associated with
their current preparation methods.
Improving glycerol value has two facets:
a. Developing the usage in current applications (for example by substitution of other polyols).
b. Identification of new usages.

62

Glycerol plays an important role in nearly every industry. Glycerol is used very extensively in
the pharmaceutical industry. Because of its valuable emollient and demulcent properties,
glycerol is an important ingredient in innumerable pharmaceutical and cosmetic preparations.
Glycerol is used as a solvent in the preparation of tinctures. As a humectant, glycerol
constitutes an important pharmaceutical ingredient to prevent the drying out of preparations,
particularly ointments and creams. Since it is a sweet-tasting liquid it is used as a sweetening
agent to impart sweetness to a preparation. It is used as a levigating agent to reduce the
particle size of a drug powder. Due to its preservative qualities, it is used as a stabilizer and an
auxiliary solvent in conjunction with water or alcohol. Glycerol is also used in the
pharmaceutical industry to extract and prevent inert materials from precipitating upon
standing. It is used as a plasticizer to enhance the spread of the coat over tablets, beads and
granules.
In the food industry, glycerol is an important moistening agent for baked goods. It is also
added to candies and icings to prevent crystallization. Glycerol is used as a solvent for food
colors and carrier for extracts and flavouring agents. The smoothness of lotions, creams and
toothpaste is due to the presence of glycerol.
Because of its humectant properties, glycerol is sprayed on pre-processed tobacco to prevent
crumbling. With dibasic acids, such as phthalic acid, it reacts to make the important class of
products known as alkyd resins, which are used as coatings and in paints. Glycerol draws
water from its surroundings and the heat produced by the absorption makes glycerol feel
warm. Due to this property, glycerol is added to adhesives and glues to keep them from
drying too fast. Many specialized lubrication problems have been solved by using glycerol or
glycerol mixtures. Many millions of pounds of glycerol are used each year to plasticize
various materials, like sheets and gaskets. The flexibility and toughness of cellophane, meat
casings and special quality papers can be attributed to the presence of glycerol[1-2].
The chemical industry uses glycerol in the manufacture of sealing compounds and antifreeze.
Glycerol is a major starting material for nitroglycerine also called nitroglycerol, which is used
in the manufacture of dynamites and propellants. Nitroglycerine is also an active ingredient in
pain-relieving drugs for heart patients. A large variety of mono- and diesters of higher fatty
acids are commercially manufactured from glycerol. These esters are used as emulsifiers in
foods, preparation of baked goods and modification of alkyd resins.

63

4.4 Overview
The three-carbon polyol structure of glycerol can offer several alternatives for chemical and
biochemical transformations. The more relevant are: a) O-H. bond functionalizations, b) C-H
and C-O bond

functionalizations (oxidation, reduction, substitution), c) C-C bond

fragmentation to C2 and C1 units (including complete oxidation to CO2), d) a combination of


the above, e) incorporation of the three carbon atom framework into polymers.
4.5 Glycerol in aminoplastic resins
Aminoplastic resins which comprise formaldehyde, urea, melamine resins are widely used
products. The minoplastic resins[6], though an excellent petrochemical have certain draw
backs. Polycondensation of urea or melamine with formaldehyde usually results in
hydrolytically sensitive bonds, strong interchain hydrogen bonding, and low cross-link
density which invariably increases sensitivity to losses in stress - bearing applications. As a
consequence, these wood products are normally confined to interior, non - structural
applications because of their tendency to hydrolyze when exposed to high humidity and/or
temperature. In acid environment, both the rates of hydrolysis and cure are catalyzed. From
some experimental results it has been proved that the addition of glycerol as flexibilizer into
the stiff chain of aminoplastic resin would increase the resins molecular flexibility,
hydrophobicity as well as achieves a prolonged cure period for the resin by significantly
decreasing the abrupt discontinuity in viscosity of the resins with time during cure.
The wood panels industry relies on polycondensation resins, among them urea formaldehyde
(UF) and melamine-urea formaldehyde (MUF) resins, as adhesives. Performance standards
for these resins as wood adhesives have been established throughout the world. Recently,
several different approaches have been proposed to improve the performance of UF and MUF
resins, the latter of which have much lower proportions of melamine. Most of these
approaches are based on the use of additives during resin application. The techniques include:
The use of polyols, glycerol, 1,2,6-hexanetriol, sorbitol and others. All of these additives
function by addition to the end of the resin after preparation, or by addition to the glue-mix
before resin application[7-8].
The action of these additives has been attributed to a variety of causes. The main ones are:
their use as more effective solvents for melamine and higher molecular weight melamine resin
fractions, their disruption of the colloidal state of UF and MUF resins, both of which function

64

as facilitators of homogeneous phase reactions, their use as a buffer of the resin in the correct
hardening pH range to ensure better uniform network formation.
The similarity of the structures of these additives indicates, however, that part of the
improvement observed might be due to an additional effect, one not yet defined. This effect
might result from the characteristic structure of the additives themselves.
Glycerol derivatives can also used as "latent", acid liberating hardeners for curing melamine
resins. 3-Chloro-1,2-propanediol is also known as glycerol--monochlorohydrin and is
described, for example, in Kirk-Othmer, Encyclopedia of Chemical Technology, Volume 5, p.
854 et seq. (3rd edition, 1979, Wiley Interscience).. Thus it is also recommended by Shell
Fine Chemicals, London (Technical Bulletin, FC:64:1:TB, 2nd Edition) as a versatile
intermediate for use in the pharmaceutical industry, in the polymer industry, in textile and
metal processing, as well as for miscellaneous applications. One of the different utilities
mentioned in the polymer industry is also as a catalyst for melamine moulding materials, but
without any further particulars being given in this regard. The use of reaction products of
melamine and formaldehyde as brightening agents in the electrodeposition of zinc from
alkaline electrodepositing baths is disclosed in U.S. Pat. No. 3,745,099. The melamine resins
soluble in the electrodepositing baths can also be prepared, for example, in the presence of
large amounts of glycerol--monochlorohydrin.
Glycerol--monochlorohydrin phenyl ether, together with other compounds, is described as a
catalyst for the curing of melamine moulding compositions by Z. Wirpsza et al., in Polimery
(Warsaw), 1974, 19(9), 441-443. Glycerol dichlorohydrin (1,3-dichloro-2-propanol) is also
disclosed as a hardener for curing melamine/formaldehyde resins in the production of
laminates.[9]
4.6 Glycerol in impregnation resins
Woodbase materials, especially chipboard, which are coated with aminoplastic-impregnated
paper webs are used in the manufacture of, for example, furniture components and work
surfaces[10-11]. The impregnation confers the required hardness, resistance to chemicals, and
heat and flame resistance on the surface of the furniture. For paper impregnation, glycerol
is applied in small amounts to the aminoplastic resins which facilitate either the processing or
functional stages of laminate production.

65

Thermoset melamine resins are widely used in the manufacture of laminates and as coatings.
Typically, these resins are formed from the aqueous copolymerization of melamine and
formaldehyde in a 1: 1 to 1: 3.5 ratio. Though these resins have achieved great acceptance in
the art, several disadvantages still persist. Among the most problematic is the high level of
volatile free formaldehyde that is emitted by this resin, both in its manufacture, and in final
products made there from.
Further, the formaldehyde and melamine resin components undergo rapid cross-linking once
combined, reducing their flowability and/or sprayability unless immediately used.
Accordingly, processes and apparatuses utilizing this class of resin are conventionally
encumbered with at site preparation of the resin, in addition to applying the resin.
Improvements in the form of additives to the basic melamine/formaldehyde system have been
a constant pursuit of the prior art. Polyvinyl acetate and/or glycerol have also been used in
prior art melamine/formaldehyde resin systems. The addition of glycerol reduce further the
formaldehyde emissions by binding up remaining free volatiles into the polymer matrix
and/or reacting with formaldehyde moieties to produce less volatile cyclic and polymeric
formals.
Compounds containing hydroxyl groups, primarily glycols, or amido- or amino groups serve
as plasticizers for impregnated papers. Glycerol is used most widely, however, due to the
comparatively high cost of glycerol; it is combined with other chip substances. One of the
most readily available additives for glycerol based plasticizers is synthetic urea.
In Fig. 4.6.1 we show a technological scheme for the preparation and use of a mixed
plasticizer[13]. Glycerol from storage reservoir 1 is pumped into reactor 2, where it is
preheated to 60-65C. Then the calculated amount of urea necessary for obtaining a solution
of the assigned concentration is delivered into the reactor. After complete solution of the urea
in the glycerol, the solution is delivered by centrifugal pump 3 into the delivery tank 4.

66

Figure 4.6.1. Technological scheme for prepar- ation and use of glycerol--urea mixed
plasticizer : i) reservoir for glycerol storage; 2) reactor; 3) centrifugal pump; 4) delivery tank;
5) metering device; 6) plasticizing vats; 7) receiving tank for spent solution.
4.7 Glycerol in natural resins
Environment-friendly, fully biodegradable, green composites based on plant based fibers and
resins are increasingly being developed for various applications as replacements for nondegradable materials derived from petroleum that are currently being used[14]. Unlike
petroleum, plant based proteins, starches and fibers are yearly renewable. In addition, these
green composites may be easily composted after their life, completing nature's carbon cycle.
An interesting natural binding system which has been examined is soy flour (SF) modified by
cross-linking with glutaraldehyde (GA). Without the plasticizer, SF was found to be brittle,
weak and difficult to process into useful binder. Glycerol has been reported to increase the
flexibility and extensibility of soy protein plastics by reducing the interaction between protein
molecules. Hence the addition of glycerol will give better tensile and flexural properties on
the composites binded with the natural resin.
Soy protein (SP) is commercially available in isolate (SPI), concentrate (SPC) or defatted
flour (SF) forms. Processed soy proteins, though brittle, have been modified into suitable
resins for use in green composites with the help of plasticizers such as glycerol and sorbitol. It
is used stearic acid and gluteraldehyde (GA) to modify SP resins. These modifications have
resulted in significant improvements in soy protein resin properties. Once reacted with soy

67

protein, stearic acid and glycerol acts as an internal plasticizer and its hydrocarbon chain
reduces the moisture absorption of the soy protein resin. GA reacts with the amine groups in
soy protein to form crosslinked soy protein resin and improve its mechanical properties.
Another interesting and enviromently friendly mixture is glyoxal/glycerol/ boric acid. These
mixtures are suitable for wood dimensional stabilization. The chemicals used are all waterborne and the treatment involved is a standard vacuum/ pressure cycle followed by heating to
polymerize chemicals. Leaching of boron from wood is retarded by the formation of
boronates complexes which hydrolyze progressively to release boric acid. Rapid biological
tests against Poria placenta indicate an inhibition of fungal growth on treated wood blocks.
Further studies concerning the use of more hydrophobic polyols in order to increase stability
of the treatment to moisture are currently under investigation.
A potential additive in natural wood adhesives could also be the glycerol ester of gum rosin
which is made from gum rosin or refined gum rosin through esterification with glycerol; and
with the properties of high viscosity, excellent hear and aging stability, excellent polymer
compatibility etc. It is a good tackifying resin. Soluble in tar, ester, turpentine oil and similar
solvents; insoluble in alcoholic solvents; partially soluble in petroleum products; mix well
with vegetable oils; light colored; resistant to yellowing; heat resistant; highly adhesive. It can
help to improve the initial and persistent viscosity of wood adhesives adhesive and has good
cold resistance ability. It can also be used for ester glue phenolic resin paints (through
polymerization with vegetable oils); it is widely used in glue industry as low cost enhancer for
hot-melt, pressure-sensitive and other types of adhesives.
4.8 Glycerol modifications for resin properties enhancement
Urea-formaldehyde resins (UFs) are produced in amounts exceeding 5 million metric tons
annually. They are thermosetting resins, not only used as adhesives in wood and furniture
industry, but also as lacquers or bulk molding compounds. In order to enhance their
mechanical, adhesive and physiochemical properties, intensive research on UFs modifications
has been carried out for decades[15-17].
Dendritic and hyperbranched polymers with terminal functional groups represent a new class
of polymeric compounds that attracts attention of many research groups. This class of
macromolecules is reported in the literature to be effective tougheners for thermosetting
resins, such as epoxies, bismaleimide, and vinylesters.

68

It was hypothesized that the addition of hyperbranched polyether with hydroxyl end groups
(HBP) to UF resin would affect and enhance the mechanical properties of the cured UF+HBP
blends.
Thus, an attempt to employ hyperbranched polyether with hydroxyl end groups suitable for
condensation with the UF resin has already investigated from several scientists.
Hyperbranched polyether (HBP) obtained from glycerol blended with urea-formaldehyde
(Fig.4.8.1) improves the hardness (16%) and the compressive shear strength (17%) of the
cured urea - formaldehyde polymer, whereas water absorption remains unaffected. It was also
shown that blending UF resins with hyperbranched polyethers can be an effective tool for
controlling mechanical properties and dimensional stability of the polymeric systems. Low
hyperbranched polymer addition to a UF resin results in the improvement of hardness and
compressive shear strength of the cured blend. It was also found that, for the compositions in
which HBP content is higher than 4wt%, the plasticizing effect overwhelms the hardening
effect and subsequently lowers both hardness and compressive shear strength.

Figure 4.8.1. Anionic polymerization of glycerol carbonate to hyperbranched polyether


(HBP), using partially deprotonated trimethylolpropane (TMP) as an initiator
The main results for those investigations conclude that the low hyperbranched polymer
addition to a UF resin results in the improvement of hardness and compressive shear strength
of the cured blend. It was also found that, for the compositions in which HBP content is
higher than ca 4%w/w,

the plasticizing effect overwhelms the hardening effect and

subsequently lowers both hardness and compressive shear strength. Volumetric shrinkage for
the best-performing formulation remains at acceptable level of 23%when compared to the
control polymer. For the compositions with higher content of the hyperbranched polyether,
despite deteriorated mechanical properties, lower linear and volumetric shrinkage occurs, thus

69

better dimensional stability is observed. It may be concluded that blending UF resins with
hyperbranched polyethers allows controlling the mechanical properties of the systems and
provides dimensional stability control tool. Further investigation on application of HBP to
modifying urea-formaldehyde resins seems to be worth considering.
4.9 Glycerol derivatives uses in wood industry
A selection of the chemicals that can be obtained using glycerol as reaction substrate are
illustrated in Figure 4.9.1.

Figure 4.9.1. Families of Possible Glycerol Reactions


Incorporation of glycerol into polymers is a quite potential area of use, either as monomer or
as telomer and polymer, exploiting its polyol nature. The higher potentiality is related to: 1)
selective telomerization to polyglycerols or co-telomerization with other glycols, and 2) copolymerization with largely available difunctional co-reagents (i.e. urea, formaldehyde, etc.)
making available new cheap materials or formulations with specific application field.
Therefore, in this area the chemistry needs to explore fundamental aspects of reactivity and
selectivity in combination with engineering solution for related processes.

70

Some interesting glycerol derivatives that already used in the wood panel industry are the
following:
a. Glycerol triacetate (triacetin)[18-19] a very interesting substance which could be used as a
cure accelerator in various binder formulation such phenol formaldehyde and tannin or
lignin binder systems.
Phenolic-formaldehyde (PF) resins have so far been dominant binding agents in the
production of OSB and LVL boards, as well as HB boards. The application of these resins
makes it possible to obtain adhesive-bonded joints exhibiting high mechanical properties and
high moisture resistance. The produced adhesive bonds are also relatively elastic, resistant to
vibrations and thermally stable, which results in the better service life of boards bonded with
PF resin. However, to harden they require considerable amounts of thermal energy to be
supplied, i.e. either longer pressing times or higher pressing temperatures. Long pressing
times lower the efficiency of production lines, whereas the application of higher temperatures
results in decreased thermal economics due to the high thermal gradient and no heat recovery
from the pressed boards. For this reason studies are conducted to improve the technological
and economic indexes of the manufacturing process of reconstituted products bonded with PF
resins through improving their reactivity by resin modification.
The method found preferable by numerous researchers and manufacturers of wood-based
materials is the modification of ready to use resins with the addition of substances
accelerating the curing process and/or lowering the curing temperature.
The PF resins curing can be accelerated further by adding an ester accelerator, glycerol
triacetate (triacetin), to reach gel times as fast as those characteristic of catalyzed aminoplastic
resins, but at unimpaired strength values.
Tannin adhesives have been used extensively in several countries in the Southern Hemisphere
and are starting now to be used industrially in Japan and there is also interest for their use in
Europe. The quest to decrease or completely eliminate formaldehyde emission from wood
panels bonded with adhesives, although not really necessary in polyflavonoid tannin
adhesives due to their already low emission (as for most phenolic resins), has nonetheless
promoted some research to further improve their formaldehyde emission. As part of the quest
for zero formaldehyde emission adhesives, tannin adhesives based on tannin autocondensation
with glyoxal using glycerol triacetate as catalyst-accelerator has investigated thoroughly in the

71

literature. The aforementioned system could be characterized as a totally natural adhesive


system.
b. Poly-glycerol and poly-glycerol ethers and esters[20-21], are also very interesting compound
due to their high content of hydroxyl groups that can be either react with formaldehyde
(scavenger) or with urea or melamine to improve overall resin properties.
c. Diglycidyl ether (DGE) and polyglycidyl ether (PGE) type compounds could also react
with condensed tannins and/or lignin. Due to the demonstrated reactivity of diglycidyl and
polyglycidyl ether compounds with hydroxylated reactants for different applications in
general and with lignin, with potential application in the wood adhesives field it is important
to consider the relative chemical similarity of lignin with tannin structures, both being
polyphenolic in nature.
d. In many areas of the world, the unwanted growth of mold and mildew is an annoying
problem. The rapid growth of mold and mildew on wood surfaces, is particularly troublesome
in hot, humid climates[22-24].
Once mold and mildew appeared on a surface it is very difficult to remove.
A costly problem occurs when mold and mildew is present on a wood surface that needs to be
painted. In order to paint or repaint properly a surface that has become infested with mold or
mildew, it is necessary to remove the mold and mildew completely. The most widely used
method for removing mold and mildew is to scrub vigorously or the use of toxic fungicide
agents on the infected area until the mold and mildew removed.
If one can regulate the moisture content in wood to 1520%, the risk of fungi attacks is
reduced. Therefore, one could obtain a longer lasting material while incorporating less
fungicide agents. For this application, glycerol derivatives can substitute polyethylene
glycols, designated as toxic. Hygroscopicity of glycerol derivatives allows good performances
according to the first trials implemented by XYLOCHIMIE (Grenoble) and the University of
Nancy. Inside and outside carpentry and joinery are concerned. With an effective formulation,
the performances of wood could compete with those of PVC.
Development of water-borne treatments based on diester by-products such as glycerol and
polyglycerol derivatives made it possible to improve dimensional stability of wood. The best
results obtained with polyglycerol methacrylate. When the wood structure was impregnated
with the latter, it allowed us to obtain the formation of a polymeric network after
72

polymerisation, increasing wood dimensional stability and resistance to fungi. Further studies
are currently under investigation using glycerol carbonate. Research on wood modification
has been investigated since the 1930s. However, wood chemical composition alterations,
experimental conditions and costs of the treatment did not allow a large development of such
methods. Manufacturers prefer to use much cheaper wood species, often tropical species, with
good natural properties. In addition, they have also used cheap preservative treated timber.
Conventional wood preservation systems involve generally impregnation of broadly active
biocides into the wood.
A number of wood-polymer composites have been investigated to improve the dimensional
stability of wood.They involved either the bulking of wood cell walls with various chemicals
like polyethyleneglycols (PEGs), polyglycerol methacrylate (PGMA) to improve wood
properties. The advantages of PGMA compared to the existing methods lie in the fact that a
part of the starting materials are renewable matters and that the treatment can be carried out in
aqueous phase limiting the rejection of volatile organic compounds. Like polyethyleneglycols,
polyglycerols (PGs) are polyethers, able to bulk the cell walls, keeping wood in a partially
swollen state improving its dimensional stability.

73

4.10 References
1. Mario Pagliaro, Michele Rossi, The Future of Glycerol: New Uses of a Versatile Raw
Material. RSC Publishing, Cambridge: 2008, ISBN: 978-0-85404-124-4.
2. M. Pagliaro, M. Rossi, C. Della Pina, R. Ciriminna, H. Kimura, From glycerol to
value-added products, Angewandte Chemie, 2007, 46, 4434-4440.
3. James A. Kenar Lipid Technology November 2007, 19, 249-253.
4. L. Bournay, D. Casanave, B. Delfort, G. Hillion and J. A. Chodorge, New
heterogeneous process for biodiesel production: A way to improve the quality and the
value of the crude glycerine produced by biodiesel plants. Catal. Today, 2005, 106,
190.
5. G. Rothenberg, Catalysis: Concepts and Green Applications, Weinheim: WileyVCH,
2008, ISBN 978-3-527-31824-7.
6. James A. Kenar. Lipid Technology. 2007, 19, 249-253.
7. M. Pagliaro, R. Ciriminna, H. Kimura, M. Rossi, and C. Della Pina. Angew. Chem.
Int. Ed. 2007, 46, 4434 4440.
8. C. Zhao, A. Pizzi, A. Kuhn, S. Garnier. Journal of Applied Polymer Science. 2000, 77,
249259.
9. S. Claude. Fett/Lipid. 1999, 101, 101104.
10. P. Soulounganga, B. Loubinoux, E. Wozniak, A. Lemor, P. Gerardin. Holz Roh
Werkst. 2004, 62, 281285.
11. R. Soto et al. / Bioresource Technology 2005, 96, 95101.
12. N. Mosier et al. / Bioresource Technology 2005, 96, 673686.
13. M. Mariusz L., P. Jerzy , Z. Aleksander , P. Pawel, International journal of polymeric
materials, 2007, 56, 453-460.
14. A. Pizzi, Advanced Wood Adhesives Technology, Marcel Dekker Inc., New York,
1994
15. M. Maminski, J. Pawlicki, A. Zado, P. Parzuchowski. International Journal of
Polymeric Materials. 2007, 56,453460.
16. Ebewele, R. O., Myers, G. E., and Koutsky, J. A., J. Appl. Polym. Sci. 1991, 42, 1483.
17. P. Soulounganga , B. Loubinoux , E. Wozniak , A. Lemor , P. G_rardin Holz Roh
Werkst, 2004 62, 281285.
18. Trosa A, Pizzi A 2001, 59, 266271
19. Pizzi A, Meikleham N, Dombo B, Roll W Holz Roh- Werkst 1995, 53, 201204

74

20. Hoffmann P Holzforschung 1990, 44, 8793


21. Meyer JA Adv Chem Series 1984, 257289
22. Barnes HM, Murphy RJ Forest Prod J 1995, 45, 1623
23. Nakano T Wood Sci Technol 1994, 28, 2333
24. G. Rokicki, P. Rakoczy, P. Parzuchowski, M. Sobiecki, Green Chem. 2005, 7, 529535.

75

Task 5 . Glycerol alkyl esters Production of Triacetin from crude glycerol


Zsanett Herseczki, Gyula Marton
University of Pannonia, Cooperative Research Centre for
Environmental and Information Technology, H-8200 Veszprem, POB 158, Hungary
Phone/Fax: +36-(88) 624-986, e-mail: hzsanett@almos.uni-pannon.hu
Sndor Ember
2657 TOLMCS, Arany J.u.2.
Tel: (35)-550-153, 550-038, 350-089
Fax:(35)-550-154, 350-190
e-mail: nek@wnet.hu

5.1. Current glycerol market and typical glycerol applications


Important applications of glycerol are regionally determined. For Europe the largest identified
single application is personal and oral care (22%). In Japan the largest single application of
glycerol (25%) is for pharmaceuticals. Some 10% of the European glycerol market is intended
for application in food and beverages, with an 8% contribution for pharmaceuticals. Polyether
polyols have their largest share in the European market with about 12% compared to 8% in
the USA and 6% in Japan.
Most of the existing glycerol applications from the pie-chart are explained below:
Drugs
Used in medical and pharmaceutical preparations, mainly as a means of improving
smoothness, providing lubrication and as humectants. Also may be used to lower intracranial
and intraocular pressures.
Laxative suppositories and cough syrups.
Personal care:
Used in toothpaste, mouthwashes, skin care products, hair care products and soaps.
Serves as an emollient, humectants, solvent and lubricant in personal care products.
Competes with sorbitol although glycerol has better taste and higher solubility.

76

A component of glycerol soap.


Foods and beverages
Serves as humectants, solvent and sweetener, may help preserve foods.
Solvent for flavors (such as vanilla) and food coloring.
Humectants and softening agent in candy, cakes and casings for meats and cheeses.
Manufacture of mono- and di-glycerides for use as emulsifiers
Used in manufacture of polyglycerol esters going into shortenings and margarine.
Used as filler in low-fat food products (i.e., cookies).
Glycerol has approximately 27 food calories per teaspoon and is 60% as sweet as table
sugar.
Polyether polyols
One of the major raw materials for the manufacture of polyols for flexible foams and to a
lesser extent rigid polyurethane foams.
Glycerol is the initiator to which propylene oxide/ethylene oxide is added.
Alkyd resins (plastics) and cellophane
Used in surface coatings and paints.
Used as a softener and plasticizer to impart flexibility, pliability and toughness.
Uses include meat casings, collagen casings (medical applications) and non meat packaging.
Plasticizer in cellophane.
High-explosives
Nitroglycerine is extremely powerful. A mere 10 ml will expand 10,000 times into 100 litres
of gas at an explosive velocity of 7,700 metres per second (17,224 miles per hour) - more
powerful than TNT.

77

Heart disease drug


In one of the more curious coincidences of science, the first modern high explosive nitroglycerine - also became one of the very first man-made drugs. To this day, it remains the
most commonplace treatment for chronic angina, the chest pain of heart disease.
Love potion
Nitroglycerines action as an effective vasodilator led in 1998 to the release of RESTORE, the
first ever fully tested, effective topical cream for the safe treatment of male erectile
dysfunction (impotence).
Restore contains 1% nitroglycerine and is effective within minutes of application of achieving
an erection of up to 45 minutes duration.
Safe sweetener
Glycerol is an alcohol (glycerol) and is used as a preservative in the food industry, as well as a
sweetener: it is very sweet, yet it contains no sugar. This makes it an ideal sweetener for
patients who cannot take sugar, such as the increasing number of Candida sufferers.
Vegetable glycerol is said to be the "only acceptable sweetener" for Candida patients.
Health supplement
Health supplement for sportsmen -- Glycerol increases blood volume, enhances temperature
regulation and improves exercise performance in the heat, or so it is claimed. It helps
"hyperhydrate" the body by increasing blood volume levels and helping to delay dehydration.
Following glycerol consumption, heart rate and body core temperature are lower during
exercise in the heat, suggesting an ergogenic (performance enhancing) effect. In long duration
activities, a larger supply of stored water may lead to a delay in dehydration and exhaustion.
Preserving plants
It is used in preserving foliage, cut sprigs or leaves.
Burning glycerol
The glycerol by-product burns well, but unless it's properly combusted at high temperatures it
will release toxic acrolein fumes, which mainly form at between 200 and 300 C (392-572
F). At natural gas prices around 9 /GJ, crude glycerol will have a natural gas substitution

78

value around 100-140 /ton. The disadvantage of using crude glycerol as a fuel is that high
dust emissions need to be prevented and thus dust filters need to be used.
Glycerol and biogas
Approximately 600 m3 of biogas for each ton of crude glycerol can be produced. The addition
of crude glycerol in digestion plants can dramatically increase the gas production. The biogas
is used as fuel in diesel engines which power electricity generators.
Glycerol in poultry and pig diets
Crude glycerol is, in compliance with f.i. German animal feed regulations, more and more
used as a cheap 2-5% component in animal diets.
Other applications:
Manufacture of paper as a plasticizer, nitroglycerine, humectant and lubricant.
Humectants for pet foods to retain moisture and enhance palatability.
Used in lubricating, sizing and softening of yarn and fabric.
Used in de-/anti-icing fluids, as in vitrification of blood cells for storage in liquid nitrogen.
Patent applications have been filed for detergent softeners and surfactants based on glycerol
(i.e.,alkyl glyceryl ethers) instead of quaternary ammonium compounds.
Can be added to solutions of water and soap to increase that solution's ability to generate
soap bubbles that will last a long time.
Use as antifreeze in cryogenic processes.
Used in fog machine fluids.
Used in hookah tobacco mixtures (called "ma'assel" or "shisha" tobacco), often along with
molasses and/or honey.
Glycerol is also a source of lecithin (used in foods as a fat emulsifier, and a vital component
of all cell membranes in the body) and of tocopherols (vitamin E). It is used in skin
moisturizers, lotions, deodorants, makeup, toothpaste, sweets and cakes, pharmaceuticals and
patent medicines, in paper manufacturing, printing ink, in textiles, plastics, and electronic
components [Ir. A. Hoogendom et al.]

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5.2. Glycerol alkyl esters Production of Triacetin from crude glycerol


Triacetin is a clear, combustible and oily liquid with a bitter taste and a fatty odor. It has
properties of both glycerol and acetate. Triacetin is found in some food like butter as it is used
as a food additive both as a flavouring solvent and a humectant for the solvency of
flavourings for the function of humectant. It is used as an antifungal agent in external
medicine for topical treatment of superficial infections of the skin. It is a potential green
solvent for extraction and a potential fuel additive.
Triacetin has become a relatively important chemical in manufacturing and is used in many
industries, including the food, drug, and plastics industries. Triacetin is commonly prepared
by esterification of glycerol with acetic anhydride or acetic acid, or by reacting ketene with
glycerol, or by the oxidation of allyl acetate in the presence of acetic acid. Crude triacetin
typically contains acetic acid, acetic anhydride and smaller quantities of other impurities.
Volatile impurities such as acetic anhydride and acetic acid are usually removed by
distillation. The remaining triacetin is then usually distilled to remove nonvolatile impurities
and to eliminate color and odor. However, distillation generally requires relatively high
temperatures that initiate additional reaction products, and thus even after distillation, triacetin
typically has an odor and a yellow color, both of which must be eliminated for the triacetin to
qualify as pure triacetin.
5.2.1. Patents
Several processes exist for eliminating the color and odor associated with crude triacetin. U.S.
Pat. No. 3,108,133 teaches a process for purifying triacetin which includes an initial flash
distillation to remove the majority of excess acetic acid. The initial distillation is conducted
first at atmospheric pressure, and in the later stages at subatmospheric pressures. A major
portion of acetic acid is removed in the initial distillation step. A second distillation is then
conducted at high temperature and low pressure and triacetin is recovered overhead. A third
distillation is then conducted in the presence of water to take off additional acetic acid, and
the bottoms of such distillation are recovered.
Other conventional processes for purifying triacetin include contacting the triacetin solution
with activated carbon. U.S.S.R. Patent 535286 teaches a process for purifying crude triacetin
by distilling off acetic acid, treating the resulting triacetin with an aqueous solution of sodium
bicarbonate and sodium sulfate, and passing the resulting organic layer of triacetin through a
column packed with activated carbon. German Patent 0152 333 teaches a process for

80

purifying triacetin which includes adding sodium carbonate or sodium bicarbonate to partially
purified triacetin, eliminating water with a vacuum distillation and contacting the resulting
triacetin with activated carbon. In both of the above processes sodium bicarbonate or sodium
carbonate is used to neutralize the triacetin, and activated carbon is used to substantially
reduce the color. However, activated carbon is relatively costly.
German Reference 29 00 023 discloses a method for purifying triacetin which includes
treating crude triacetin for 0.5 to 5 hours with water steam at 3-14 mbar and 100C-130C.
The resulting solution is then treated with an inert gas such as nitrogen and/or carbon dioxide.
German Reference 1568 04 teaches a process for purifying triacetin which includes reacting a
solution of crude triacetin with a lower alcohol such as methanol or ethanol, heating the
solution to approximately 145C and distilling off excessive alcohol and other reaction
products until the temperature of the solution reaches the boiling point of triacetin. Such
process must be conducted carefully because alcoholysis of triacetin occurs in which diacetin
isomers and lower alcohol acetate are readily formed.
U.S. Pat. No. 4,381,407 patent teaches a continuous process for preparing triacetin which
includes charging liquid glycerol into a top portion of a reaction column having a plurality of
plates, and charging acetic acid and acetic anhydride vapors into a bottom portion of the
column. The reaction occurs in a counter current mode, and is conducted at 100C to 250C
and from 0.2 bar to 30 bar. The resulting product is then purified by distillation in a
rectification column.
U.S. Pat. No. 5,387,713 teaches a process for purifying carboxylic acids having iodide and
oxidizable impurities by contacting the solution with hydrogen peroxide and recovering the
purified carboxylic acids by distillation or evaporation.
U.S. Pat. No. 2,913,492 teaches a process for removal of formic acid from mixtures of formic
acid and other organic components. The process includes contacting the solution with a
catalytic ingredient such as chromium oxide and copper oxide which decomposes the formic
acid into CO2 and H2.
U.S. Pat. No. 5,399,751 teaches a method for recovering carboxylic acids such as formic acid
and acetic acid from aqueous solutions. The method includes contacting the aqueous solution
with a solvent consisting essentially of mixed trialkylphosphine oxides in a counter-current
liquid-liquid extraction flow.

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U.S. Pat. No. 5,371,279 teaches a method for removing acetic acid from liquid ether acetates
by contacting the liquid ether acetates with alumina.
U.S. Pat. No. 4,729,818 teaches a process for separating acetic acid from water. The process
includes adding an acid such as benzoic acid or hexanoic acid to the acetic acid and water
mixture. The addition of such an acid to the mixture improves the relative volatility of the
water to the acetic acid and allows separation of the water from acetic acid by distillation.
Thus, the teachings above, and others known to us require either multiple distillations at
relatively high temperatures and relatively low pressures, or require the use of costly activated
carbon to achieve pure triacetin. It is apparent that there is a need for a relatively inexpensive
process which does not require activated carbon, nor excessive heat and high vacuum
distillation to purify triacetin.
U.S. Pat. No. 5,777,157 teaches a process for producing and purifying triacetin. The method
includes an initial separation of triacetin from a crude composition of triacetin and impurities.
The separated triacetin is then contacted with an aqueous solution containing an oxidant, and
results in an odorless and colorless purified triacetin.
One object of the invention is to provide a process for producing and purifying triacetin
without a need for relatively costly activated carbon.
It is another object of the invention to provide a process for purifying triacetin which achieves
colorless and odorless triacetin.
These and other objects are achieved in a process for purifying triacetin which includes
initially separating the triacetin from the major portion of the impurities inherent in crude
triacetin, such as acetic acid and acetic anhydride, and then contacting the resulting triacetin
with an oxidant to eliminate any residual odor and color. According to one preferred
embodiment of this invention, the crude triacetin is passed through a column packed with
members, such as glass rings. The column is preferably heated between about 100C to about
130C, and has a pressure between about 20 mm Hg to about 50 mm Hg. The majority of the
impurities is withdrawn from the overhead of the column, while partially purified triacetin is
continuously withdrawn from the bottom of the column.
The partially purified triacetin is then preferably contacted with an aqueous solution
containing a relatively strong oxidant. Suitable oxidants include sodium, potassium, calcium
or other metal hypochlorites, permanganates, peroxodisulfates, chromates, hydrogen peroxide,

82

chlorine, ozone and other strong oxidants. Preferably the oxidant is about 0.5% to about 5.0%
by weight of the aqueous solution.
According to another preferred embodiment of this invention, the aqueous solution also
includes an alkali or alkali earth metal hydroxide, or a salt of an alkali or an alkali earth metal
and a weak acid. Such embodiment not only removes color and odor, but also reduces any
residual acidity.
If necessary, the resulting relatively pure triacetin can then be passed through a column again
to eliminate any residual water content.
5.2.2. Ionic liquid as a green catalytic reaction medium for triacetin synthesis
Organic esters are valuable intermediates in chemical industry. Recently, effort has been
made in order to replace the traditional inorganic acid, e.g. sulfuric acid and to develop clean
catalytic method such as supported sulfuric acid or solid superacid for the syntheses of
organic esters. On the other hand, although many organic reactions, including
oligomerization, polymerization, alkylation and acylation, have been reported to be proceeded
in room temperature ionic liquids with excellent yields and selectivities, to date, the
esterification of carboxylic acids with alcohols in room temperature ionic liquids as a catalyst
and reaction media, however, have not been reported in literatures yet, probably due to strong
and detrimental interactions between the organic acids or water and the aluminium chloride
based ionic liquid, such as 1-butylpyridinium chloride aluminium(III) chloride ionic liquids.
In order to compare the catalytic performances between the ionic liquid and the sulfuric acid
further, the esterification of glycerol with acetic acid was also conducted since the reaction of
glycerol with acetic acid to produce triacetin is relatively difficult due to three hydroxyls in
glycerol. Reactions between glycerol and acetic acid resulted in five esters, i.e. monoacetins
(monoacetin-1 and monoacetin-2), diacetins (diacetins-1,3 and diacetins-1,2) and triacetin. At
lower reaction temperature, i.e. 30C, the glycerol was almost completely converted into
esters with the ionic liquid used as catalyst, and the corresponding yield of triacetin was
higher than that with sulfuric acid as catalyst. The yields of total monoacetins and triacetin
reached a minimum and maximum, respectively, at ca. 75C for ionic liquid as catalyst. While
the yields of total monoacetins and triacetin kept decreases and increases, respectively, with
the increases of temperature for sulfuric acid. Furthermore, it can be seen that the yields of
1,3-diacetins from ionic liquid was always higher than that from sulfuric acid, while the yields

83

of 1,2-diacetins from ionic liquid was always lower than that from sulfuric acid. It is well
known that the aluminium chloride based ionic liquids can be Lewis acidic or Lewis basic if
the mol ratio of aluminium chloride/butylpyridine chloride is greater or less than 1.0.
Obviously, the ionic liquid used in this study was Lewis basic, and therefore we conjecture
that the mechanism of esterification in ionic liquid may be different from that in sulfuric acid.
Although detailed reaction mechanism of esterification in ionic liquid is not clear at this stage,
the preliminary experimental results showed that esterification in the ionic liquid as a novel
environmental friendly catalyst is not only possible but also quite satisfactory. The
outstanding advantage is that the resultant esters may not dissolved in the ionic liquid and
therefore they could be isolated easily. The ionic liquid as a catalyst and reaction medium is
particularly suitable to those esterifications between aliphatic acids and alcohols at mild
reaction conditions [Youquan Deng et al., 2001].
5.2.3. Production of triacetin from partly purified glycerol
University of Pannonia developed a potential process for utilization of crude glycerol.
Synthesis of glycerol and acetic acid was investigated (Figure 5.2.3.1). Partly purified
glycerol was used as raw material (see Chapter 2).
O

HO

OH
OH

3 H3C
OH

3 H2 O

O
O

Figure 5.2.3.1. Reaction scheme for esterification of glycerol with acetic acid
The esterification reactions were carried out in a glass flask (500 ml) with magnetic stirring.
Acetic acid was used in excess to shift reaction equilibrium towards the product. The reaction
was carried out by help of entraining solvent (n-hexane, methylisobutyl-ketone or toluene) to
remove water azeotropically and solvent was recirculated. After the reaction sulfuric acid was
neutralized with NaOH. Salt was removed by filtration. The unreacted acetic acid and residual
water were distilled off at 80-100C under reduced pressure (3 kPa). The most difficult
problem in connection with crude glycerol refining is removal of salt which is formed during
neutralization of the catalyst (KOH, NaOH) in biodiesel production. Due to the fact that

84

presence of salt does not disturb the reaction and it is insoluble in triacetin, this problem could
be solved by simple filtration.
Homogeneous catalysts, although effective, lead to serious contamination problems that make
essential the implementation of good separation and product purification protocols, which
translate into higher production costs. The appropriate solid catalysts could be easily
incorporated into a packed bed continuous flow reactor, simplifying product separation and
purification and reducing waste generation.
Currently, the esterification of acids with alcohols is commercially achieved using liquid
catalysts, such as sulfuric acid, hydrofluoric acid, and p-toluene-sulfonic acid. The scientific
literature contains a good number of reports about the use of heterogeneous acid catalysts for
esterification. For instance, esterification has been carried out using ion-exchange resins such
as Amberlyst-15 and Nafion with good results [Chen et al., 1999; Heidekum et al.].
Table 5.2.3.1. Comparison of H2SO4, Amberlyst 15 and Amberlyst 36 catalysts for
esterification of glycerol (reaction temperature was 110-120 C in case of toluene as
entraining solvent and 68-75C in case of n-hexane as entraining solvent)
Molar
Ratio
(AA/G)

Raw
material

Catalyst

Pure
glycerol

H2SO4

Glycerol
cont. salt

H2SO4

Pure
glycerol

H2SO4

Glycerol
cont. salt

H2SO4

Pure
glycerol

A15

Glycerol
cont. salt

A15

Distribution of products wt%

XG

STA

Glycerol

MA

DA

TA

100

100

100

100

94

100

92,6

92,6

100

100

100

100

97

100

98,3

98,3

25

75

100

70

70

1,3

55

36

100

36,6

36,6

Procedure

Raschig
tower
distillation
+ n-hexane
Raschig
tower
distillation
+ n-hexane
Raschig
tower
distillation
+ toluene
Raschig
tower
distillation
+ toluene
Raschig
tower
distillation
+ n-hexane
Raschig
tower
distillation
+ n-hexane

YTA
%

85

Pure
glycerol

A36

Glycerol
cont. salt

A36

Raschig
tower
distillation
+ n-hexane
Raschig
tower
distillation
+ n-hexane

4,3

52

43

100

37,4

37,4

8,8

59

31

100

26,2

26,2

In general, when using organic resins, the catalytic activity strongly depends on their swelling
properties. Resin swelling capacity is fundamental since it controls substrate accessibility to
the acid sites and, therefore, affects its overall reactivity. Once swelled, the resin pores usually
become macropores. This means that big molecules with long hydrocarbon chains show no
diffusion limitations and can readily access the acid sites in the bulk.
Most ion-exchange resins are not stable at temperatures above 140 C, which limits their
[Zhang et al.] application For reactions require higher temperatures inorganic acid catalysts
are generally more suitable, Amberlyst 15 and 36 were investigated. In case of partly purified
glycerol yield of triacetin was lower (92,6 % in case of n-hexane as entraining solvent and
98,3 % in case of toluene as entraining solvent) than in case of pure glycerol but promising.
According to the analytical results (Table 5.2.3.1) it seems that Amberlyst type ion exchange
resins are not strong enough to catalyze the reaction of glycerol and acetic acid properly.
Unfortunately salt content of partly purified glycerol deactivates active sites of these catalysts.

86

Crude glycerol
Water,
Phosphoric acid

Dilution,
acid
treatment

Phase
separation

Fatty acids,
salt
Methanol

Glycerol, water,
Esterification
methanol, salt
H2SO4

Water,
Toluene

Phase
separation

Toluene
Water

Acetic acid

Acetic acid,
(water)

NaOH
Triacetin,
acetic acid,
(water),
catalyst, salt
Filtration

Neutralization
Triacetin,
acetic acid,
(water), salt

Salt

Distillation

Filtration
Triacetin

Salt

Figure 5.2.3.2. Scheme for production of triacetin from crude glycerol

Figure 5.2.3.2 shows a potential process for utilization of crude glycerol. This scheme can be
applied to produce other glycerol esters like glyceryl tripropionate, glyceryl tributyrate.
If esters of glycerol are produced from crude glycerol, some purification steps can be
eliminated like previous distillation of water because water is removed azeotropically during
ester formation. Neutralization of phosphoric acid and preceding activated-carbon treatment
are not necessary because reaction is carried out in acidic media and product needs to be
decolorized at the end of the process.

87

5.3 References
Ir. A. Hoogendom, Ir. T. Adriaans, Glycerine purification via bio-catalysis and column
adsorption for high quality applications, Pr. nr.: 0656.632
U.S. Pat. No. 3,108,133
U.S.S.R. Patent 535286
German Patent 0152 333
German Reference 29 00 023
German Reference 1568 04
U.S. Pat. No. 4,381,407
U.S. Pat. No. 5,387,713
U.S. Pat. No. 2,913,492
U.S. Pat. No. 5,399,751
U.S. Pat. No. 5,371,279
U.S. Pat. No. 4,729,818
U.S. Pat. No. 5,777,157
Youquan Deng, Journal of Molecular Catalysis A: Chemical 165 (2001) 3336
Chen, X.; Xu, Z.; Okuhara, T., 1999. Liquid-phase esterification of acrylic acid with 1butanol catalyzed by solid acid catalysts. Appl. Catal., A, 180, 261-269
Heidekum, A.; Harmer, M. A.; Hoelderich, W. F., 1999. Addition of carboxylic acids to
cyclic olefins catalyzed by strong acidic ion-exchange resins. J. Catal., 181, 217-222
Zhang, Z. Y.; Hidajat, K.; Ray, A. K., 2001. Determination of adsorption and kinetic
parameters for methyl tert-butyl ether synthesis from tert-butyl alcohol and methanol. J.
Catal., 200, 209-221

88

Task 6 : Methods of Pre-treatment, hydrolysis, and fermentation of


glycerol for ethanol production.
Rafiqul Ghani, DTU-Biocentrum, Denmark

89