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GLYCEROL TRANSFORMATIONS
RACHA ARUNDHATHI
[email protected]
[email protected]
 Experts realistically predict the end of cheap oil in 2040 at the latest, a
development that we can already witness as chemical manufacturers confront the
rising cost of oil and natural gas.
 The transition to a more biobased production system is currently underway, and
much attention has been given to the catalytic conversion of renewable feedstocks
and chemicals.
 Glycerol is a potentially important biorefinery feedstock, available as a
byproduct in the production of biodiesel by transesterification of vegetable oils or
animal fats. For every 9 kg of biodiesel produced, about 1 kg of a crude glycerol
byproduct is formed.
 Due to its highly functionalized nature, glycerol can be readily oxidized,
reduced, halogenated, etherified, and esterified to obtain alternative commodity
chemicals (Figure 1), such as dihydroxyacetone, mesoxalic acid,1,3-propanediol,
1,3-dichloropropanol, glyceryl ethers, glycerol carbonate, and glyceryl esters.
PROCESSS PATHWAY FOR PRODUCTION OF LIQUID FUELS FROM
BIOMASS BY INTEGRATED GLYCEROL CONVERSION
Vegetable oils and animal fats
Carbohydrates
Transesterification
Fermentation/Hydrolysis
Aqueous Glycerol
(25-85 wt%)
Biodiesel
Light alcohols
and polyols
Chemicals
and Solvents
Distillation
H2/CO
Reforming
Integrated glycerol conversion
with
Fischer-Tropsch synthesis
Gaseous alkanes
Aqueous solution of
oxygenated hydrocarbons
(acetone, methanol, ethanol)
Aqueous
Phase
Reforming
Selective
dehydration/
hydrogenation
Fuels
H2
Combustion
Liquid Hydrocarbons
Upgrading
Naptha, Diesel Fuel, Kerosene
Electricity and heat
 This
highly anticipated depicts how practical limitations posed by glycerol
chemistry are solved based on the understanding of the fundamental chemistry of
glycerol and by application of catalysis science and technology.
An employable, practical avenues applicable to convert glycerol into value
added products of mass consumption in understanding whether biodiesel and
glycerol refineries are convenient and economically sound.
GENERAL GLYCEROL REACTIONS
•Properties of Glycerol
1.Properties of Glycerol
2.Traditional Commercial Applications
3.Production of Bioglycerol and Commercial Trends
4.Glycerol as Solvent in Organic Reactions
5.Bioglycerol Purification
•Reforming
1.Glycerol as a Platform for Green Fuels
2.Production of Hydrogen via Aqueous Phase
Reforming
3.Production of Hydrocarbon Fuels via Aqueous Phase
Reforming
4.Industrial Applications
•Selective Reduction
1.Reduction of Glycerol
2.Hydrogenolysis to Propylene Glycol
3.Dehydroxylation to 1,3 Propanediol(PD)
4.Biological Reduction to 1,3 Propanediol (PD)
5.Commercial Applications
•Halogenation
1.Chlorination of Glycerol
2.Production of Epichlorohydrin
3.Industrial Applications
•Dehydration
1.Dehydration of Glycerol
2.Dehydration to Acrolein
3.Propane from Acrolein
4.Oxydehydration to Acrylic Acid
5.Dehydration to 3-Hydroxypropionaldehyde
6.Industrial Applications
7.Esterification of Glycerol
•Etherification and Telomerization
1.Etherification of Glycerol
2.Butylation of glycerol to tert-butyl ethers (GTBE)
3.Direct Telomerization and Etherification over CaO
4.Polymerization to Polyglycerol
5.Glycosylation to Glucosyl Glycerol
6.Industrial Applications
•Esterification
1.Esterification with Carboxylic Acids and Glycerolysis
2.Carboxylation to Glycerol Carbonate
3.Nitration
4.Industrial Applications
•Selective Oxidation
1.Selective Oxidation of Glycerol
2.Thermodynamic and Kinetic Aspects of the Aerobic
C-OH Oxidation
3.Platinum Group Metals Catalysis
4.Gold and Organocatalysis
5.Oxidation Using an Iron Catalyst
6.Electrochemical Oxidation
7.Biological Oxidation
•Bioglycerol in the Construction Industry
1.Polyols as Additives for Cement
2.Glycerol as Anticracking and Waterproofing Agent
3.Raw Glycerol as Quality Enhancer and Grinding Aid
4.Bioglycerol as Anticorrosive Lubricant
•Sustainability of Bioglycerol
1.Biofuels: A Triple Bottom Line Analysis
2.Bioglycerol Economics
3.Glycerol: A Platform Chemical for the Biorefinery
applications
Glycerol organic transformations
PROCESS
CATALYSTS
MAIN PRODUCT
MAIN
APPLICATIONS
REFERENCE
Reforming
Pt-Re/C
Syn Gas
Pt or Ni based-catalysts H2
FT synthesis
energy
[1]
[2,3]
Dehydration
Acid catalysts
acrolein
[4-8]
Sb-V-O
acrylic acid
acrylonitrile
Oxidation
Au based-catalysts
dihydroxyacetone
Chemical
intermediate
Polymers, resins,
paints, acrylic fibers,
etc.
Active ingredient of
sunless tanning skin
care preparations
Hydrogeneolysis
Ru/C or Cu-based
1,2-propanediol
Fermentation
Enzymes
Carboxylation
Zeolites, Zn-based, or
under supercritical
conditions
Mesoporous materials
Esterification
[11,12]
[13]
[14-20]
Mesoporus materials
Chemical
intermediate,
antifreeze
1,3-propanediol
Manufacture of
polyesters
Glycerol carbonate
Production of
polycarbonates and
polyurethanes
Glycerides, polyglycerol Emulsifiers
esters
DAG, TAG
Fuel additives
monoalurin, dilaurin
Pharmaceutical
industry
tBu ethers
Fuel additives
Sulphates
MAGEs
[40]
CaO-based
di- and tri-glycerol
Chlorides, sulfates
Etherification
[9,10]
Pharmaceutical
industry
[21-24]
[25-29]
[30-33]
[34,35]
[36]
[37-39]
[41]
Telomerization
Homogeneous catalysts C8 chain ethers
Surfactant chemistry
[42,43]
Epicerol
Carboxylic acids
Production of epoxy
resins
[44,45]
Epichlorohydrin
OXIDATION OF GLYCEROL
HO
OH
OH
Glycerol
(GLY)
OH
OH
HO
O
OH
Glyceric acid
(GLYA)
HO
OH
O
dihydroxyacetone
(DHA)
HO
O
O
Hydroxypyruvic acid
(HPYA)
 Designing chemoselective catalysts to orientate the glycerol oxidation
reaction towards either primary or secondary alcohol function.
 DHA used as a tanning agent in cosmetic industry, synthon in organic
synthesis.
 DHA and HPYA are the possible starting materials for DL-serine synthesis.
Traditionally the reaction has been carried out with supported Pt and Pd
catalysts, but they suffer oxygen poisoning.
Gold catalyst appeared to be more resistant to oxygen poisoning,
allowing the use of higher oxygen partial pressures.
HYDROGENOLYSIS OF GLYCEROL
Two types of catalysts have been reported in the literature for the hydrogenolysis of
glycerol: one is supported noble metal catalysts, the other is catalysts consisting of
transition metal oxides, such as Raney Ni, copper chromite or Cu-ZnO catalysts.
Noble metal based catalysts are usually more active than Cu based catalysts for the
hydrogenolysis reaction, but the selectivity to propanediols is lower. Furicado et al.
compared the catalytic performances of several supported metal catalysts (metal: Rh, Ru,
Pt, Pd; support: active carbon, SiO2, Al2O3).
1,2-PDO is an important commodity chemical, which finds use as antifreeze, aircraft
deicer and lubricant. 1,3-PDO is copolymerised with terephthalic acid to produce polyesters,
which are used for manufacturing carpet and textile fibres exhibiting strong chemical and light
resistance.
Reaction mechanism for conversion of glycerol to propylene glycol proposed by
Montassier et. al.,
Proposed reaction mechanism for conversion of glycerol to propylene glycol
CURRENT AND FUTURE DEVELOPMENTS
 The technology to make biodiesel is simple and it is evolving to reach a high degree
of efficiency with new heterogeneous processes that only afford pure glycerol as byproduct and use oil from high-yield seeds from non-edible crops such as the Jatropha
trees that are being planted in Africa and Latin America by BP. The raw materials are
not localized in a few countries, but instead their production is increasingly determined
by land availability.
The overall consequence is that glycerol will become a central raw material for the
chemical industry, along with interesting novelties.
Indeed, the scope and pace of the innovation in the last two years is impressive.
Progress is not limited to the reactions mentioned in this account. For example, new
catalytic aerobic oxidations over gold catalysts afford either 32% dihydroxyacetone or
valued ketomalonic acid derivatives.
It follows that a progressive move by the chemical industry towards renewable
feedstocks will become a necessity; and the transition to a more bio-based production
system in which biomass is catalytically converted to chemicals and transportation
fuels is now underway. In 3–5 years, glycerol will be seen as an environmentally
friendly way of replacing other competing petroleum products.
In conclusion, to paraphrase a biodiesel industry practitioner, glycerol stands up to
become “the next biodiesel”.
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THANK YOU!