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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: 100C and hydrogen at 20 bar pressure. Earlier this year, Tsangs 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 glycerols 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 Universitys 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.
Were 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 AmsterdamED&F Man signed an agreement with BioMCN for the sourcing, risk management and delivery of crude glycerine from Argentina. Argentina is quickly becoming the worlds 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 glycerols 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.

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