New Process for Direct Conversion of Glycerol to

Methanol
6 November 2008

Researchers at Oxford University (UK) have developed a new method to

produce methanol (CH3OH) directly from glycerol (C3H5(OH)3), a byproduct
of the transesterification process that produces biodiesel.

The new process catalytically

converts glycerol to methanol using
hydrogen under mild conditions.
Click to enlarge.

The process, developed by Professor Edman Tsang and his group at the
Department of Inorganic Chemistry, uses direct catalytic hydrogenolysis of
glycerol under mild conditions: 100°C and hydrogen at 20 bar pressure.
Earlier this year, Tsang’s research in new catalytic materials identified a
supported precious metal which efficiently converts glycerol to methanol.

Currently, around 90% of methanol is produced from fossil fuel via a

synthesis gas reaction. Glycerol is the major byproduct in biodiesel and
oleochemical production. For every 9 kg of vegetable oil processed, 1 kg of
glycerol is produced. Although glycerol is used in foods and personal care
products, there is no large-scale industrial demand.

Conversion processes for glycerol have focused on reforming to synthesis

gas, oxidation, dehydration, hydrogenolysis and polymerization. Until now
there has been no viable commercial process for glycerol’s direct conversion
to methanol.

Although catalytic hydrogenolysis of glycerol has been studied by others, the

main reported products from the glycerol and hydrogen reaction are
propanediols and ethylene glycols, which require a degree of carbon-oxygen
bonds cleavage accompanied by the addition of hydrogen under relatively
harsh conditions.
The Tsang process breaks the carbon-carbon bonds of glycerol without
cleaving carbon-oxygen bonds, thereby avoiding the production of gases
such as methane and CO2. The carbon-neutral process works very
selectively, producing methanol almost exclusively.

Essentially, this is a way of getting methanol ‘for free’ from biomass. Around
350,000 tonnes of glycerol are incinerated in the US each year, and
converting this to methanol gives you a portable store of energy, and
potentially an economically viable new biofuel business. When we say the
process in clean, we mean that the catalyst is very selective. The exclusive
product is methanol, so little additional processing is required.

—Edman Tsang

Isis Innovation, the technology transfer company for Oxford University, has
patented the technology and is seeking companies interested in
commercializing it.

The Oxford University’s Department of Chemistry has discovered a new method of

producing methanol from glycerol Waste. According to the research team, ninety percent
of methanol is currently produced from natural gas and the new process wont need to rely
on any fossil fuels.

“We’re turning a waste material – glycerol – directly into a very useful product – methanol,” said
Professor Edman Tsang, an expert in the development of new catalyst materials, and the main inventor
behind the new method. “Around 350,000 tons of glycerol is incinerated in the US each year, and
converting this to methanol gives you a portable store of energy, and potentially an economically viable
new biofuel business.”

“Essentially, this is a way of getting methanol ‘for free’ from biomass,” said Tsang. “Methanol itself is
useful either as a fuel on its own or in biodiesel manufacture. It is also used widely in industrial
chemistry.”

The advantage of the new process is that it is direct – not requiring multiple costly processing steps – and
it works at a low temperature and low pressure.

“In industry, temperature costs money, but high pressure is even more expensive. This process operates
under readily achievable, mild conditions of 100 degrees C and 20 bar of pressure.”

There is no large-scale industrial demand for glycerol right now, so utilizing this process would not only
use something that would otherwise be wasted, it will help save energy in the production phase.
Isis Innovation has patented the technology, and will be working with Prof Tsang to commercialize the
technology.

Source: Biofuel Review

Gas 2.0 (http://s.tt/12A3p)

ED&F Man (Netherlands) Signs Agreement to Source Crude

Glycerin From Argentina Firm BioMCN
Date Posted: April 9, 2012

Amsterdam—ED&F Man signed an agreement with BioMCN for the sourcing, risk management and
delivery of crude glycerine from Argentina.

Argentina is quickly becoming the world’s largest producer of biodiesel and its residue crude glycerine.

With this agreement BioMCN and ED & F Man will combine their mutual expertise in the area of
sourcing crude glycerine and will operate as one sourcing organization.

BioMCN is the largest second generation biofuels producer in the world, producing and selling industrial
quantities of high quality bio-methanol from sustainable renewable resources, including crude glycerine.

Bio-methanol can either be blended directly with gasoline, and/or it can be used as a feedstock for other
environmentally-friendly fuels such as bio-MTBE, biodiesel and bio-DME.

It is also used for a variety of bio-based chemical applications, including plastics and paints.

"We are very pleased with this agreement with BioMCN, as we see BioMCN as an important player in
the glycerine industry.

"We are proud to be chosen by BioMCN to source their crude glycerine and we look forward to our
ongoing relationship with them.

"We are one of the leading providers of sugar, coffee, financial services and liquid products for feed, food
or technical use, such as molasses and glycerine.

"In our chosen commodities we provide a comprehensive range of supply chain services from production,
sourcing, storage, delivery to risk management.
"This agreement is therefore a perfect fit for both companies", says Arie van der Spek, Trading Director
at ED & F Man.

Rob Voncken, CEO of BioMCN: "This agreement with ED & F Man is another important step in
securing the supply of renewable feedstock. We are particularly pleased with ED & F as partner, because
of its strong position and broad experience in Latin America.

"Their expertise in shipping bulk products is a valuable addition to our business.

"Furthermore ED & F Man is ISCC certified, meaning that we can demonstrate sustainability of our
feedstock throughout the entire supply chain."

For more information, call +31 20 754 01 11.

BIOMASS TO METHANOL PROCESS - Isis Project No 3680

A catalytic process to convert glycerol, the main by-product of biodiesel production, into methanol.
The new method is clean and operates at low temperature and pressure. Methanol has application as a
fuel and an industrial chemical.

The Oxford Invention

The Oxford invention produces methanol as an exclusive product from glycerol in a catalytic process
that is:

 Efficient
 Low temperature
 Low pressure
 Direct
 Clean

The new process takes glycerol, a largely unwanted by-product, and converts it directly & cleanly to
methanol, a highly useful industrial chemical and green fuel.

Today around 90% of methanol is produced from fossil fuel via the synthesis gas reaction. Methanol is
in demand as an industrial chemical and as a fuel for internal combustion engines and fuel cells. For
methanol to become a truly green fuel, an alternative production method that does not rely on fossil
fuels is needed. In nature, microorganisms produce methanol from biomass through fermentation, but
the process is too slow for industrial scale production.
Marketing Opportunity

Glycerol is the major byproduct in biodiesel and oleochemical production. For every 9 kg of vegetable
oil processed, 1 kg of glycerol is produced. Although glycerol is used in foods and personal care
products, there is no large-scale industrial demand; indeed around 350,000 tonnes are incinerated in
the US each year. Conversion processes for glycerol have focused on reforming to synthesis gas,
oxidation, dehydration, hydrogenolysis & polymerization. Until now there has been no viable
commercial process for glycerol’s direct conversion to methanol. The Oxford invention offers an
opportunity for companies in the biodiesel and oleochemicals sector to develop this catalytic process
to extract a valuable product from a waste material.

Patent Status

This work is the subject of patent application, and Isis would like to talk to companies interested in its
commercial development. Please contact the Isis Project Manager to discuss this further.