Biomethanol as a second-generation biofuel for transportation Biomethanol produced from by-product glycerin is a second-generation biofuel in its own right and a feedstock for other environmentally friendly fuels EElco DEkkEr and karEl lanTing BioMCN he European Union’s Renewable could use the existing gasoline Energy Directive (RED) has set a infrastructure with only slight changes. Vegetable Esterification 90% T 5.75% biofuels target for When the State of California evaluated oil plant biodiesel transport fuels by 2010 (10% by 2020). alternative fuels after recent oil price These ambitious figures will bring shocks, officials found that methanol 10% prolonged market growth for the “clearly stood out” as having the best Methanol glycerine foreseeable future. For some years, widespread potential for replacing ethanol and biodiesel have been seen as petroleum. The strongest growth in the two most viable biofuels to reduce demand for methanol is currently in Figure 1 Biodiesel production has glycerin as a major by-product CO2 emissions and to reduce energy Asia, and most of that is in China dependency in the transport sector. (among other applications, as a Recent developments have led to other feedstock for dimethyl ether (DME) not economic. Dutch start-up BioMCN alternatives, though. One of these, and as a blend component in gasoline). has, however, developed an innovative, biomethanol, now offers petrochemical Making methanol from organic large-scale industrial process that companies an attractive extra material is, in itself, nothing new. Its converts crude glycerin into opportunity to meet the EU biofuels origins go as far back as the ancient biomethanol. It is almost ironic that a mandate. Egyptians, who obtained methanol product which in origin is as old as the Methanol (CH3OH, methyl or wood (wood alcohol) from the pyrolysis of Pharaohs now qualifies as a second- alcohol) is the simplest of the alcohols. wood. Until now, though, biomethanol generation biofuel. However, high- It is an extremely versatile and widely production has been small scale and quality biomethanol made by used chemical building block, and can produce a whole range of polymer materials, including polyolefins, EU and member states’ biodiesel production polyesters, polyurethanes, phenolic resins, and acrylic paints and adhesives. EU-27 'ERMANY It burns with a non-luminous, bluish &RANCE EU-27 flame. It can be used either as a fuel in )TALY /THERS%5 its own right or as a feedstock for other 4OTAL%5 environmentally friendly fuels. Methanol is conventionally made S EU-25 NNE from fossil natural gas or by coal O 4 gasification, while biomethanol is made from biogas generated exclusively from EU-15 renewable and non-food crop resources. EU-15 That makes biomethanol a second- EU-15 generation biofuel. EU-15 EU-15 Nobel Prize winner George A Olah in 2005 proposed a complete methanol economy using synthetic (or, even better, sustainable) methanol as an energy storage medium. Unlike a fuel Figure 2 Growing biodiesel production brings with it huge amounts of glycerin like hydrogen, a methanol economy by-product (source: European Biodiesel Board) www.biofuels-tech.com BIOFUELS TECHNOLOGY 00 fuels. That could bring 70% reductions in CO emissions from each litre of 6EGETABLEOIL %STERIFICATIONPLANT BIODIESEL 2 gasoline saved. The industrial process to do this has "YCONVERTINGGLYCERINE been perfected and patented by INTOMETHANOL THEENERGY VALUECANBEMAINTAINED BioMCN. Founded in November 2006, FORTRANSPORTATIONFUELS "IOMETHANOL GLYCERINE THUSIMPROVINGPOTENTIAL BioMCN is owned by an international FOR#/EMISSION consortium of companies (Econcern, REDUCTIONS Teijin, NOM and ChemieInvest) and private individuals. It is the world’s /THERBIOFUELS BioMCN first company to start commercial production of biomethanol on an industrial scale. The company has Figure 3 Converting glycerin into methanol increases the energy value and CO2 already acquired two existing methanol emission reduction potential of the process plants in The Netherlands, with a combined capacity of approximately converting glycerin (itself a production will increase with it. That is one million tonnes per year, which until by-product) through a thermochemical true not only in Europe (Figure 2), but then had been running on natural gas. reaction process meets all of the second- also in the Americas and Asia, where In October 2007, BioMCN received generation criteria. several countries have also mandated the Biofuels Technology Innovation Biomethanol has another advantage: biodiesel quotas. Award for the largest contribution to besides being an excellent fuel to run Glycerin, also known as glycerol, is new biofuels developments. A year combustion engines, it can also be used a colourless, odourless and viscous later, in October 2008, BioMCN received to make biodiesel to run diesel engines liquid. It is soluble in water and a sugar the European Chemical Industry as well as a range of other sustainable alcohol with the formula C3H8O3, Council’s (CEFIC) Responsible Care fuels. And its production does not need containing three -OH groups: Award in the Small and Medium to take valuable land otherwise used Enterprise (SME) category for its for the production of food crops. OH innovative approach. OH Using crude glycerin as a feedstock HO Biomethanol production process Biodiesels are mono alkyl (methyl or Biomethanol production is based on the ethyl) esters and can be used on their original methanol production process, own or blended with conventional Today, much of the crude glycerin which converts natural gas (CH4, diesel in unmodified diesel engines. produced is purified for many different methane) into methanol. Here, three Biodiesel is now made in large-scale applications in the pharmaceuticals and stages — steam reforming, synthesis production from a variety of feedstocks, other industries, with products ranging and distillation — produce 99.85% including palm oil, soy oil and rapeseed from toothpaste to paint. However, pure methanol. oil. A major by-product of biodiesel demand is nowhere near enough to After purification, natural gas is production is glycerin, and this gives it consume the ever larger amounts of cracked in a steam reformer. Steam a significant advantage as a renewable crude glycerin coming onto the market, reforming mixes the methane with large feedstock: there is already a growing and production is forecast to grow amounts of steam. The methane/steam oversupply. significantly over the coming years. mixture flows through pipes over a Biodiesel is commonly produced by Market prices for crude glycerin are catalyst and is heated to 500–850°C. the transesterification of vegetable oil therefore rather volatile, with a tendency After the steam reformer, the methane or animal fat, exchanging one to fall rapidly to very low levels as soon is split into syngas, a mixture of carbon alcohol group for another. Most as biodiesel production is running at monoxide (CO), carbon dioxide (CO2) transesterification reactions use higher rates of capacity utilisation. The and hydrogen (H2). methanol to produce methyl esters, and energy potential of this crude glycerin The syngas is cooled to an ambient these produce glycerin as a by-product. is at the moment not being fully utilised temperature and compressed to close to Every tonne of biodiesel manufactured (Figure 3), which is a waste, because 100 bar before it is fed to the synthesis produces 100 kg of glycerin (Figure 1). converting it to biofuels could make a reactor. In this reactor, the syngas Demand for diesel is increasing, and valuable contribution to emissions components react to form methanol. regulations worldwide will demand a reductions. This methanol contains about 17% corresponding increase in supplies of Converting crude glycerin into water, which is removed by distillation. biodiesel. So, as biodiesel production biomethanol can convert its energy In the distillation process, water, light continues to grow, crude glycerin content into a variety of transportation alkanes and the heavy ends — the 00 BIOFUELS TECHNOLOGY www.biofuels-tech.com denser fractions — are removed from feedstock to the evaporation unit has to the main stream. The outcome is 99.85% have a high purity level with a low pure methanol. chloride and sulphur content. The glycerin is purified in a vacuum Using glycerin instead of methane distillation process, where it can be as feedstock evaporated below its degradation The production process for biomethanol temperature to remove unwanted is no different to the production of components. The organic matter (heavy regular methanol. What is different is fractions) that has been removed from the origin of the gas stream going into crude glycerin can be used in the methanol reformer. Instead of fermentation units to produce biogas natural gas, the feedstock is glycerin. It for generating green electricity (so also is not possible to feed liquid glycerin to contributing to the reduction of the reformer directly. It first has to be CO2 emissions). converted to the gas phase. The glycerin The purified glycerin is heated and is purified and evaporated in a process fed to an evaporator, which is optimised patented by BioMCN. to prevent early glycerin degradation. The crude glycerin contains several Glycerin vapour is fed to the existing impurities, mainly water, sodium and steam reformer, just like natural gas in potassium salts and a certain amount of the original process. undefined organic components. These In the reformer, just as with natural First sample of biomethanol at BioMCN have to be removed, since the glycerin gas, the glycerin is split into syngas (The reformer can also be fed with a mixture of biogas and natural gas.) When converting a significant amount of glycerin, the carbon monoxide/ carbon dioxide ratio in the syngas is slightly different to that of syngas produced from natural gas only, but this is of no consequence for the feed to the methanol synthesis. Steam reforming of glycerin produces no components other than those to be expected in a conventional syngas mixture. Hence, methanol synthesised from natural gas and biomethanol produced from glycerin are chemically identical.