GLYCEROL TRANSFORMATIONS

RACHA ARUNDHATHIracha@cheng.es.osaka-u.ac.jparundhathirc@gmail.com

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.

Electricity and heat

Combustion

H2

Vegetable oils and animal fats Carbohydrates

Transesterification Fermentation/Hydrolysis

ReformingDistillation Integrated glycerol conversion

with Fischer-Tropsch synthesis

AqueousPhase Reforming

Selective dehydration/hydrogenation

Upgrading

Aqueous Glycerol (25-85 wt%)

Gaseous alkanes

Biodiesel

Chemicals and Solvents

Aqueous solution of oxygenated hydrocarbons(acetone, methanol, ethanol)

Fuels

Liquid Hydrocarbons

Naptha, Diesel Fuel, Kerosene

H2/CO

Light alcohols and polyols

PROCESSS PATHWAY FOR PRODUCTION OF LIQUID FUELS FROM BIOMASS BY INTEGRATED GLYCEROL CONVERSION

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

Glycerol organic transformations

PROCESS CATALYSTS MAIN PRODUCT MAIN APPLICATIONS

REFERENCE

Reforming Pt-Re/C Syn Gas FT synthesis [1]Pt or Ni based-catalysts H2 energy [2,3]

Dehydration Acid catalysts acrolein Chemical intermediate

[4-8]

acrylic acid Polymers, resins, paints, acrylic fibers, etc.

[9,10]

Sb-V-O acrylonitrile [11,12]

Oxidation Au based-catalysts dihydroxyacetone Active ingredient of sunless tanning skin care preparations

[13]

Hydrogeneolysis Ru/C or Cu-based 1,2-propanediol Chemical intermediate, antifreeze

[14-20]

Fermentation Enzymes 1,3-propanediol Manufacture of polyesters

[21-24]

Carboxylation Zeolites, Zn-based, or under supercritical conditions

Glycerol carbonate Production of polycarbonates and polyurethanes

[25-29]

Esterification Mesoporous materials Glycerides, polyglycerol esters

Emulsifiers [30-33]

DAG, TAG Fuel additives [34,35]

Chlorides, sulfates monoalurin, dilaurin Pharmaceutical industry

[36]

Etherification Mesoporus materials tBu ethers Fuel additives [37-39]

Sulphates MAGEs Pharmaceutical industry

[40]

CaO-based di- and tri-glycerol [41]

Telomerization Homogeneous catalysts C8 chain ethers Surfactant chemistry [42,43]

Epicerol Carboxylic acids Epichlorohydrin Production of epoxy resins

[44,45]

OXIDATION OF GLYCEROL

HO OH

OH

HO O

OH

HO OH

O

HO O

O

OHOH

Glyceric acid (GLYA)

dihydroxyacetone (DHA)

Hydroxypyruvic acid (HPYA)

Glycerol (GLY)

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, aircraftdeicer 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 by-product 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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REFERENCES

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THANK YOU!