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Raw Glycerol as
Chemical Raw Material
Mario Pagliaro
g
CNR, Palermo (Italy)
Workshop on Glycerol: Marketing, Uses
and Chemistry
INNOVHUB, Divisione SSOG
Milano, 18‐Oct‐2012
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Today’s focus
Consiglio Nazionale delle Ricerche
1 The economic aspects of the bioglycerol
1.
issue
2 SSelected
2.
l t d chemical
h i l processes for
f th
the
conversion of bioglycerol into valued
chemicals
bioglycerol
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Bioglycerol: An industrially
relevant
l
issue
i
Consiglio Nazionale delle Ricerche
•
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Annual worldwide gglycerol
y
production
p
resultingg from biodiesel production
p
(1991–2009). Values calculated based on the stoichiometric relation between
glycerol and biodiesel from various sources.
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Bioglycerol: A scientific
relevant issue
Consiglio Nazionale delle Ricerche
•
The increase in the number of scientific publications related to glycerol
from 1880 to 2006
CEE Common Agriculture Policy
‰ In 1996 the implementation of mandated minimum volumes of biodiesel in
diesel fuel was enforced in the EU
‰ Subsidies to biodiesel manufacturers were enforced as tax exemption in main
CEE countries (Germany, Austria and France first and then Italy)
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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•
«In three to five yyears gglycerol
y
will be seen as an
environmentally friendly way of replacing
competing petroleum products.
•
«The technology to make biodiesel is simple and
cheap.
h
The
h price off oill is h
high
h and
d on a growth
h trend.
d
•
«All this makes the production of biodiesel an
inevitable reality, especially in countries with large
l d availability
land
il bilit
Trends identified
in 2007/2008
/
2008
•
«The overall consequence is that glycerol will
become an important raw material for the chemical
industry along with interesting novelties that,
industry,
that we
argue, will originate in Latin America, South‐East
Asia and also in Africa»
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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•
Today, glycerol‐based
biorefineries are convenient
Until late 2009 the impact of processes
actually using bio‐glycerol as raw material
has been surprisingly modest compared to
the number and scope of the new
chemoselective catalytic conversions of
glycerol into valued chemicals of the last
decade
2011
•
Now, however, the economic reasons
that caused little practical innovation are
over
•
Different biorefineries ‐‐ plants in which
bio‐glycerol is used as a primary building
block replacing raw materials of
petrochemical origin – are eventually
emerging
Milan, 18‐Oct‐2012
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Marketing, Uses and Chemistry
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Istituto per lo Studio dei Materiali Nanostrutturati
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Bioglycerol: Marketable
Glycerin?
•
«The problem with glycerine from biodiesel
production is that it has heavy contamination from
methanol. This makes it unsuitable to process for
the glycerine consumer market.
•
«As it was starting to be used,
used it was discovered that
it was unsuitable for most glycerine markets.
•
«It is obviously a major focus of biodiesel
manufacturers to produce a pharmaceutical grade
glycerine. Unfortunately, high temperature low
pressure distillation is the only way this can
currently be done.
•
For that reason, I believe that a large portion of
biodiesel glycerine goes into animal feed stock».
2008
Source: http://envirofuel.com.au/2008/01/23/the‐impact‐of‐biodiesel‐on‐the‐glycerine‐and‐tallow‐markets
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Uses of Refined Glycerol
•
Together the top three uses for refined
glycerol ‐‐ food, personal and oral care
products ‐‐ account for 64% of refined
glycerol global consumption
•
The remainder is used for alkyd resins,
cellophanes, explosives and other
miscellaneous uses throughout industry
•
The glycerin market, therefore, was
intrinsically fragmented with a large number
of companies
p
usingg relativelyy small amounts
of glycerol
Milan, 18‐Oct‐2012
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•
•
Bioglycerol composition
This glycerol stream typically contains a
mixture of glycerol with methanol, water,
inorganic salts (catalyst residues)
Also: free fatty acids, unreacted mono‐,
di‐, and triglycerides, methyl esters, and a
variety of other “matter organic non‐
gglycerol”
y
((MONG)) in varying
y g amounts.
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Material
wt %
Glycerol
88-95%
Ash
4-6%
Ether extract
0.1-0.4 %
Water
1-3 %
Sodium
0.1- 4 %
Potassium
0.1-5%
Iron
7-11 mg/Kg
g g
Phosphorous
60-110 mg/Kg
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•
EPR spectrum of bioglycerol
fractions: signal typical for
phenolic/semiquinone radicals
•
Signals were measured several
times remaining stable. The oldest
samples of glycerol fractions were
3 years old and EPR parameters
remained unchanged
Plenty of polyphenols
Maria Jerzykiewicz et al., Looking for new applications of crude glycerol fraction from
biodiesel production. J. Chem. Technol. Biotechnol. 2009, 84, 1196.
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Crude glycerol as
anticorrosive soap
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•
The mixture of antioxidants with
glycerol, could be utilized as
anticorrosive soap with glycerol
•
This kind of employment could be
possible only for technical demands:
washing cars, tanks, lorries, trains, as
well as external building surfaces,
namely a market huge enough to
absorb a consistent fraction of gglobal
glycerol surplus
•
Glycerol Initial soap Final soap Corrosivity
fraction content [%] content [%] [g/m2]
D2
E
15
34
0.75
0 73
0.73
0.28
0 72
0.72
Radicals
scavenging
[% of remained
radical]
2
60
Sample prepared from glycerol fraction with high soap content (E) has lower
anticorrosive properties and lower free radical scavenging abilities than samples with
low initial soap content (D2).
In general, radicals scavenging
((antioxidant)) properties
p p
obtained
from EPR spectroscopy parallel
anticorrosive power
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Refining Crude Glycerol
•
Refined glycerol can be classified into three main
classes:
•
Technical ggrade – used as a buildingg block in
chemicals, not used for food or drug formulation
•
USP – glycerol from animal fat or plant oil sources,
suitable for food products, pharmaceuticals
•
Kosher – glycerol from plant oil sources, suitable for
use in kosher foods
•
Canada’s BIOX Corporation is upgrading its Ontario
biodiesel facility to improve the quality of its
glycerin from crude to technical grade by a glycerin
refinement facility
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Refined glycerol
Purity %
technical grade
95.5%
USP
96%, vegetable-based
USP
99.5%, tallow-based
USP/FCC-Kosher
S / CC
99.5%
%
USP/FCC-Kosher
99.7%
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Price of refined and crude
glycerine (1995‐2010)
(
)
•
The price for refined glycerol in
the EU decreased from € 4000 /t
in 2000 to less than € 450/t in
early 2010
•
Almost identical trend in the US
•
The price of bioglycerol dropped
to $ 0 per tonne, i.e. it became a
waste product
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
•
M. Pagliaro, M. Rossi Valorization of bio‐glycerol In P. Fornasiero, M. Graziani (Ed.s) Renewable
Resources and Renewable Energy: A Global Challenge, 2nd Edition, CRC Press, Boca Raton: 2011
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Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Bioglycerol discharged into
the environment
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A market dominated by
scarce, poor information
•
In this context, despite repeated claims that the
downward trend of the glycerol market price is
“now over”, this wishful scenario thus far has not
happened
•
For example, according to chemical market
analyst company ICIS, the prices for refined
vegetable glycerol in the US were “ready
ready for take‐
take
off”:
•
«American glycerol sellers expect price increases
of 10 dollar cents/lb (157 euro/tonne) in the next
few months and this will attract imports from
Asia and Europe where glycerol is priced lower».
•
B. Lefebvre, J. Taylor, «Glycerol prices ready to rocket, fatty alcohols and acids
see upward pricing pressure», ICIS Chemical Business 18 January 2010.
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Be critical: Do not believe into
wishful thinking
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Oxidation, for instance, is not
the conversion required
•
We h
W
have devised
d i d new clean
l
methods
h d to
selectively synthesize valued ketomalonic
(mesoxalic) acid and DHA
•
The market overall demand of these highly
valued drug and cosmetic product (as well
as synthons) together is less than 500 t/yr
•
Slightly higher figures concern other
glycerol selective oxidation products
R. Ciriminna et al., "One‐pot electrocatalytic oxidation of glycerol to DHA",
Tetrahedron Letters 47 (2006) 6993‐6995.
R. Ciriminna et al.,
R
al "One
"One‐Pot
Pot Homogeneo
Homogeneouss and Heterogeneo
Heterogeneouss Oxidation
O idation of Glycerol
Gl cerol
to Ketomalonic Acid Mediated by TEMPO", Advanced Synthesis and Catalysis, 345
(2003) 383‐388.
Milan, 18‐Oct‐2012
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Marketing, Uses and Chemistry
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•
Conversion to epichlorohydrin (100,000
tonne per year) at France’s Solvay
•
Hydrogenation to propylene glycol by
Archer Daniels Midland in a 100,000
100 000
tonne/year plant in Illinois
•
Direct
ect e
employment
p oy e t in new
e co
concrete
c ete
additives
•
Methanol production in the Netherlands
(Consortium Biomethanol, production
capacity of 250 million litres)
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Large‐scale, practical
achievements
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•
Epichlorohydrin is an essential feedstock
for the production of epoxy resins
manufactured by Solvay in France at its
Tavaux site since 2009 and by Spolchemie
in Czech since 2011
•
For 1 tonne of epi produced using the
Epicerol technology, 1.1 tonnes of refined
glycerin is used as feedstock and added
with hydrogen chloride
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Solvay glycerin‐to‐epi
Epicerol process
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Glycerin‐to‐epi benefits
•
The glycerin‐to‐epi technology divides water
consumption by 10, and volume of
chlorinated by‐products by 8 compared to
the traditional propylene based production
process of epichlorohydrin
•
The epi production does not rely anymore on
endless rising cost of propylene
•
Solvay's commissioned its 100,000
tonnes/year epichlorohydrin plant in
Thailand also planning to build another plant
i China
in
Chi
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Hydrogenolysis to propylene
glycol
l l
•
Hydrogenolysis (i.e., in the dehydration +
hydrogenation) of crude glycerol to PG
•
The method is a reactive distillation carried
out over a copper‐chromite catalyst
((CuO•Cr2O3) at 200 °C and less than 10 bar,,
eventually affording propylene glycol >73%
yield at significantly lower cost than PG
made from petroleum
•
Suppes optimized the system to operate at
about 220 °C and <10 bar versus about 260
°C and more than 150 bar for other systems
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
•
M. Dasari, P. Kiatsimkul , W. Sutterlin, G. J. Suppes, Low‐
pressure hydrogenolysis of glycerol to propylene glycol.
Appl. Catal. A: Gen. 2005, 281, 225.
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ADM glycerin‐to‐PG process
•
Archer Daniels Midland bio‐based
propylene glycol (PG) plant in Decatur,
Decatur
Illinois, using refined glycerin as
feedstock
•
The plant has a 100,000
100 000 tonne/year
and ADM claims its new facility is
capable of producing 25% of the
nation's propylene glycol (2 million
t/yr) at a competitive cost
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Biomethanol in Holland
•
BioMCN vaporisation process carried out
since 2009 in a retrofitted plant in Delfzij
with a capacity of 200,000 tonnes (world’s
largest biofuel plant).
•
y
shipped
pp from biodiesel
Crude gglycerine
plants in Europe and Argentina is purified in
a vacuum distiller and converted into gas by
heating and evaporation
•
Since glycerine decomposes very similar to
natural gas almost no changes had to be
made to the steam reformer tower in which
purified glycerine in gas form is fed and
where it is split into syngas
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Bioethanol from enzymatic
process
•
Glycos Biotechnologies and Malaysian
developer Bio‐XCell is building an
industrial plant in Malaysia, to be
completed in 2013 for producing
ethanol from crude glycerin (over a
known strain of E. coli following a
Ramon Gonzalez discovery)
•
The biorefinery will have initial
capacity of up to 30,000 tonnes by
2014
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
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Crude glycerol as additive for
cement: Best multifunctional
performance to date
•
Crude glycerol enhances cement
resistance to compression, lowers
resistance to grinding and diminishes
also its setting time.
•
Comparative mechanical tests
carried out on pure and crude
glycerol using three “clinkers”
•
In all cases, that crude glycerol yields
better mechanical and chemical
properties to those afforded by the
use of pure glycerol as well as
compared to several other
commercial additives (concrete
additives are added to the 60% of
the world’s cement)
Milan, 18‐Oct‐2012
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Marketing, Uses and Chemistry
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•
Studied for over 40 years (>20
industrial and academic patents)
•
Catalysts, (usually solid acids), work
but are unstable.
unstable Hence no glycerin‐
glycerin
to‐acrolein process has yet been
commercialized
•
We need a stable catalyst (as Franck
Dumeignil knows well…)
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Dehydration to Acrolein
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•
We have lately discovered a new
method to directly transform
glycerol into dendrimeric
polyaglycerol using a low cost solid
catalyst in one‐pot
•
Dendrimeric polyaglycerol is a
valued commercial polymer with
several applications.
pp
•
The process is unique as it affords
the polymer in one‐pot with no
applied external pressure carrying
out the reaction in a closed vessel at
220°C. No solvent is required and at
the end of the reaction, the polymer
(Figure) is easily separated from the
solid catalyst by simple filtration
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
New one‐pot glycerol
polymerization
l
i i
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•
Glycerol for the biorefinery is here to stay:
Readily available and low cost raw material
•
Poor market information has delayed
o at o
innovation
•
Most catalytic processes developed thus far
potentially target chemicals with relatively
p
to absorb the
small market,, uncapable
bioglycerine deluge
•
Processes that will be developed and
commercialized will use solid catalysts of
high stability to target chemicals with mass
consumption
Milan, 18‐Oct‐2012
Workshop on Glycerol
Marketing, Uses and Chemistry
Summary
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Acknowledgements
ƒ Dr. R. Ciriminna, Palermo
ƒ Prof. M. Rossi, Milan
ƒ Dr. C. Della Pina, Milan
ƒ Dr. G. Palmisano, Palermo
ƒ Dr. M. Sciortino, Palermo
ƒ Dr A.
A De Schrijver
Schrijver, Deinze (Belgium)
Milan, 18‐Oct‐2012
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Marketing, Uses and Chemistry
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Thanks
(And greetings from Sicily)
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