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Home , Methanol economy, Methanol fuel

Biomethanol as a second-generation 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

Energy Directive (RED) has set a infrastructure with only slight changes. Vegetable Esterification 90% T 5.75% target for When the State of California evaluated oil plant transport fuels by 2010 (10% by 2020). alternative fuels after recent oil price

These ambitious figures will bring shocks, officials found that 10% prolonged market growth for the “clearly stood out” as having the best Methanol glycerine foreseeable future. For some years, widespread potential for replacing 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 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 (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 alcohol) from the 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 or by O 4 , while biomethanol is made from 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 medium. Unlike a fuel Figure 2 Growing biodiesel production brings with it huge amounts of glycerin like , a 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 , 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 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 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 ) into methanol. Here, three Biodiesel is now made in large-scale applications in the pharmaceuticals and stages — , synthesis production from a variety of feedstocks, other industries, with products ranging and distillation — produce 99.85% including , soy oil and 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 , a mixture of

alcohol group for another. Most as biodiesel production is running at monoxide (CO), (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. So (apart from expensive C14 analysis) it is not possible to identify whether a methanol molecule has a natural gas or glycerin origin. As for performance and applications, there is no difference whatsoever.

Production capacity March 2008 saw the successful start-up of a pilot plant producing 20 000 tonnes of biomethanol per year. In the meantime, construction of the first large production unit is well under way. The next step in the process is to fully convert both methanol production lines from natural gas to biogas. The transition will be performed in stages over the coming years, in steps of Placement of the purification column during the construction of a new biomethanol plant 200 000 tonnes capacity at a time. The

www.biofuels-tech.com BIOFUELS TECHNOLOGY 00 first large unit is scheduled to be building block for a range of fuels. The methanol with bioMTBE made from operational by March 2009. RED includes several fuels that can be biomethanol (Figure 4) made from biomethanol. These include • During the biodiesel transesterifi- Biomethanol: a building block for bioMTBE, biodiesel, biohydrogen, cation reaction, methanol is used to sustainable fuels bioDME, MTG and gasoline blends: produce methyl esters. Feeding back Biomethanol is chemically identical to • Methyl tertiary butyl ether (MTBE) the biomethanol instead of regular regular methanol and meets or even is used primarily as a fuel component methanol therefore further improves

exceeds internationally accepted in gasoline. Oxygenates like MTBE biodiesel’s potential for reducing CO2 specifications published by the Inter- increase the and help emissions. This is of particular interest national Methanol Producers and gasoline to burn more cleanly. The EU applied to those types of biodiesel

Consumers Association (IMPCA). Since biofuels mandate led to many MTBE where default CO2 reduction values are

it is chemically identical, it can be used facilities being converted to produce below the anticipated future CO2 in the same wide range of applications ethyl tertiary butyl ether (ETBE), using reduction target of the RED for which regular methanol is used ethanol as the renewable component. • Despite its good performance in today, including production of However, MTBE is today still being reducing tailpipe emissions, one of the formaldehyde and acetic acid. However, produced and used in gasoline. Without drawbacks of hydrogen is the fact that the drive to go green in most of these needing to change anything in their it is still today mostly made from a fossil markets does not compare to the need processes or formulations, petrochemical feedstock: natural gas. One way to for viable second-generation biofuels companies can now easily convert a overcome this is by converting for transportation. further portion of their total fuel output biomethanol into biohydrogen. Its four Biomethanol can be used either as a to meet renewable targets by simply hydrogen atoms make methanol a very fuel in its own right or as a chemical replacing regular MTBE made from convenient way of storing hydrogen. It therefore has a high hydrogen content for its weight. This brings another advantage to converting methanol into hydrogen at point of use: it avoids the difficulties of transporting a gas like hydrogen, which needs a heavy tank pressurised to around 700 bar, or a cryogenic container at near -270ºC. Biomethanol can either be converted to hydrogen at the filling station or in the car itself by using direct methanol- to-hydrogen fuel cells. Other applications of direct cells (DMFC) include laptop batteries and mobile phones • In Europe, DME is used primarily as a propellant in (cosmetic) spray cans. In Asia, however, DME is blended with LPG for heating and several projects have run diesel engines on DME. Tests have shown that DME is one of the cleanest fuels in terms of emission levels. When used in conventional diesel engines, soot emissions are reduced to virtually zero, even without a soot filter. DME is conventionally made from methanol. When made from biomethanol, the overall well-to-wheel performance improves even further • Methanol to gasoline (MTG) was first introduced in the 1970s. The resulting gasoline is very similar to regular gasoline specifications, which BioMCN is converting two existing methanol plants to the biomethanol process means it can fuel existing combustion

00 BIOFUELS TECHNOLOGY www.biofuels-tech.com engine designs. Using biomethanol also effectively makes the resulting gasoline )SOBUTYLENE renewable. And processes other than MTBE plant &OSSIL-4"% -ETHANOL MTG can also convert biomethanol into fuels very similar to their fossil )SOBUTYLENE MTBE/ETBE plant "IO%4"% counterparts "IOETHANOL

• As with bioethanol, biomethanol )SOBUTYLENE MTBE/ETBE plant "IO-4"% can also be blended into gasoline "IOMETHANOL blends. Materials used in flexi fuel vehicles (FFVs) as fuel linings and seals, for instance, are actually already typically tested with methanol to Figure 4 Biomethanol enables the use of MTBE fuel formulations as an additional way to determine their resistance to corrosion. meet the RED requirements In the US and Europe, FFV engines are optimised for a blend of 15% emissions figures. And, finally, it is is a fuel that will benefit motorists in maximum gasoline with 85% anhydrous liquid at standard temperature terms of driving experience. For ethanol ( fuel). The ethanol content and pressure. example, the Exige 270E Tri-fuel is limit reduces ethanol emissions to avoid Group Lotus remarked after tests quicker to 60 mph from standstill and problems of cold starting at temperatures with biomethanol: “As well as being has a higher top speed when using below 11ºC. Field trials with green, the great benefit of sustainable 100% sustainable methanol fuel than commercially available FFVs have also methanol is that it would use similar with conventional gasoline. Sustainable shown that driving on biomethanol is engines and fuel systems to those in methanol is also ideally suited to feasible. Driving on biomethanol in fact current cars; and sustainable methanol pressure charging, a trend already reduces tailpipe emissions even further can be stored, transported and retailed well under way as carmakers look than with ethanol (Figure 5). in much the same way as today’s liquid to downsize engines to reduce Like most fuels, methanol is fuels such as gasoline and diesel. fuel consumption. hazardous when exposed to heat or Sustainable methanol also possesses “The low carbon number alcohol flame. It is safer than gasoline, though, properties better suited to internal fuels, methanol and ethanol, give being harder to ignite and releasing less combustion than today’s liquid fuels, more power when burned in the engine heat when it burns. Although toxic, it is giving improved performance and than conventional gasoline (petrol) not as toxic to the body as conventional thermal efficiencies. And it is ideal for fuel. The performance benefits come gasoline. If it is spilled, methanol is pressure charging (turbocharging and largely from the high heats of oxidised within days in the presence of supercharging) already being vapourisation of methanol and ethanol, sunlight to carbon dioxide and water. introduced. which give strong charge-cooling Mixed with surface water, it “Sustainable methanol is better suited effects, and the increased octane quickly biodegrades aerobically or to spark-ignition combustion than ratings. There are other, secondary anaerobically, and so should not persist today’s liquid fuels, delivering better thermodynamic effects. Methanol’s in the environment. It is therefore performance and thermal efficiencies higher heat of vapourisation leads to a more environmentally benign than due to its higher octane rating, giving it slightly higher performance relative to conventional gasoline. better resistance to knock. As a result, it ethanol.” Biomethanol is also, in its own right, one of the best performing fuels, with properties matching or better than those CO2 emission (tailpipe) of gasoline. It has, for example, a much  higher octane index. It also has a  significantly higher latent heat, which, M K 

G  combined with a relatively low N O I

stochiometric air-fuel ratio (AFR), S

S  I

reduces the cycle temperature. Its M E  

specific energy ratio is high, as is its / flame speed, which improves exhaust #  gas recirculation tolerance. It also has a  high molar ratio of reactants to products 0ETROL % - - and a low combustion temperature, meaning less heat rejection. The carbon Figure 5 Tests performed with a 2.0 litre FFV engine (Euro 4) show the low CO2 emissions when running on M85 (a blend of 85% biomethanol and 15% gasoline) number is low, with good gCO2/MJ

www.biofuels-tech.com BIOFUELS TECHNOLOGY 00 Towards a certificate of origin

Each EU member state has a different way of ensuring the RED’s fuel batches, a biofuel Guarantee of Origin system registers the targets are being met. There are penalty systems, subsidies and quality and amount of biofuels entered into and taken out of the incentives. However, the RED not only sets targets for the share fuel system. of energy from renewable sources in transport fuels. Article 15 Bio-GOs use the same approach as the RECS to provide the also addresses the need to meet specific targets for reductions in necessary proof that biofuels are made from renewable resources. CO emissions — for sustainability and for land use. This is where 2 They also provide extra information about sustainability and CO2 things become more complicated, because in this respect ethanol reduction: the green value becomes more transparent. Bio-GOs is different from bioethanol, and diesel is different from biodiesel. generate a demand pull for sustainable biofuels. All market players And there is more. Besides gasoline and diesel (or combinations are involved in and benefit from the trade of green value. They of both), the EU directive includes other biofuels such as ensure standardisation between different EU member states and biomethanol, biohydrogen, bioDME and bioMTBE. Meanwhile, avoid double counting. GOs can be traded across the borders of EU improvements in the production processes of existing second- member states.

generation biofuels are bringing further CO2 emissions reductions This system is much less bureaucratic than other options, and better sustainability. That means the individual biofuels make thus reducing the overall system cost for market players and different contributions to the EU targets. governments. Rather than waiting for a system to be enforced, the There are many different channels to convert feedstocks to industry has the opportunity (see www.biofuelgo.org) to propose fuels. It is impossible to track individual molecules, so how can and implement a system that will work for all parties involved. The we verify that all EU targets are being met? The answer may lie biofuelGO Association is now working with the biofuels industry in a system that has already been working for over ten years to implement Bio-GO certificates. The first EU member to adopt for renewable electricity: the Certificate them has been The Netherlands, which has developed a system and System (RECS). Instead of trying to trace the flow of individual is now deploying it.

technologies and a choice of feedstocks. This could dramatically reduce emissions and improve security of supply. It also promises to avoid the problems biofuels have introduced to food production and land use. To ensure sustainability, BioMCN uses renewable feedstocks exclusively derived from organic waste materials and crops other than for food consumption. Besides crude glycerin, organic materials like wood, wood waste, grass, algae and agricultural and The Lotus Exige 270E Tri-fuel is capable of running on any mixture of gasoline, ethanol other organic by-products are also and (bio)methanol being investigated as alternative feedstocks for gasification to replace Inputs from renewable, non-food providing additional information about natural gas. crop sources sustainability and CO2 emission BioMCN is one of the founding reductions. Since biomethanol is made Eelco Dekker is Chief Marketing Officer of members of biofuelGO, an initiative from biomass, it will be supplied with BioMCN, Delfzijl, The Netherlands. He focuses established to implement a pan- such a green certificate that declares the on the marketing and positioning of biomethanol, and on sourcing crude glycerin. European system to certify information origin of the renewable resources (see He is also the Chairman of biofuelGO. on the sustainability of a range of Towards a certificate of origin, above). Email: [email protected] biofuels including biodiesel and Biomethanol has the potential to Karel Lanting is a Process Engineer with ethanol. GO stands for guarantee of produce least-cost, carbon-neutral BioMCN, Delfzijl, The Netherlands. He is origin. It guarantees that biofuels are biofuels, with a network of biofuel working on the development of the biomethanol made from renewable resources, while production chains, conversion production process.

00 BIOFUELS TECHNOLOGY www.biofuels-tech.com