Methanol

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As an automotive fuel & as a denaturant in Ethanol Blending Program (EBP)

name I am writing this article to highlight one of the important use of methanol, we are living in a world, where liquid energy is monopolized by the middle east region and the world is dependent on petroleum standards. The region of the middle east has always remained a region of tension such as the Saudi -Iran clash, the Iran nuclear program & ISIS terrorists. Unless we shift to other cheaper and indigenous suitable options, in future we will have to be a beggar for our liquid energy needs.

If we can change our liquid energy platform from petroleum standard to alcoholic standard, it will reduce our dependability on the middle east, we can produce electricity from wind, solar, hydroelectric, and nuclear power but liquid fuel is a key for energy independence & for our economy. Alcohol and Methanol are two important liquid energy sources on which we have hope.

In our country, the present government is aggressively trying to push forward a policy of the Ethanol Blending Program (EBP). 10% blending of ethanol is allowed in petrol. This program is not only reducing the burden on our forex but also helping farmers, sugar mills and distilleries to the great extent. In addition, EBP is also helping to reduce carbon emissions & air pollution. Blending with 10% ethanol does not require any alteration in the engine or fuel system of the vehicle. More than 10% EBP is also an option shortly which can be done by introducing a Flexible Fuel Vehicle (FFV). This article focused is made on methanol as an automotive fuel and as a denaturant in ethanol, used for EBP. Before going into the pros and cons of the use of methanol as automotive fuel or as a denaturant in EBP, first, we should understand and study about fundamental chemical properties and characteristics of methanol.

Methanol

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Methanol (CH3OH), is also called wood alcohol. Methanol is a simplest of a long series of organic compounds called alcohols, consisting of a methyl group (CH3) linked with a hydroxy group (OH). Methanol was formerly produced by the destructive distillation of wood. The modern method of preparing methanol is based on the direct combination of carbon monoxide gas and hydrogen in the presence of a catalyst. Increasingly, syngas, a mixture of hydrogen and carbon monoxide derived from biomass, is used for methanol production. Methanol can be made from agricultural products, biomass, natural gas or coal. Today most methanol is produced from methane through syngas. One solution is to produce it from syngas obtained by biomass gasification. For this purpose, any biomass can be used including wood, wood wastes, grass, crops and their by-products, animal waste, aquatic plants and municipal waste. There is no need to use food crops as in the case of ethanol from corn, sugar cane and wheat. India has thus a big advantage on the front of feedstock for methanol.

Biomass → Syngas (CO, CO2, H2) → CH3OH

Pure methanol is an important material in chemical synthesis. Its derivatives are used in great quantities for building up a vast number of compounds, among them many important synthetic dyestuffs, resins, pharmaceuticals, and perfumes. Large quantities are converted to dimethylaniline for dyestuffs and formaldehyde for synthetic resins. It is also used in automotive antifreeze, in rocket fuels, and as a general solvent. Methanol is also a high-octane, clean-burning fuel that is a potentially important substitute for petrol in automotive vehicles. Methanol is a colourless liquid that boils at 64.96 °C (148.93 °F) and solidifies at −93.9 °C (−137 °F). It forms explosive mixtures with air and burns with a nonluminous flame. It is completely miscible in water.

Methanol is highly toxic & fatal when ingested even in a small quantity of 30 ml, methanol smell and a test is very similar to that of ethanol or ethyl alcohol. Ethanol and methanol both have the same density and boiling point, as it poisons, it is most situated and traditionally used as a denaturant in ethyl alcohol, as without altering the chemical and physical properties, it renders ethyl alcohol unfit for human consumption. Methanol is water-soluble and biodegradable in the environment. The consequences of a spill would be much less than that of petroleum products.

Ethanol is edible, whereas methanol is toxic when drunk. This difference, though, should not be overdrawn, since in a petrol blending or in an FFV economy, both would be mixed with petrol. The breakdown products of both ethanol and methanol are much less noxious and both emit far fewer particulates than those from petroleum.

In India, we are using ethanol which is denatured by various approve denaturants. At present in India, we are not using methanol for blending with petrol and not even using methanol as a denaturant in ethanol for EBP. In some countries methanol is now very widely used as blending fuel with petrol, China is a front-runner in the use of methanol as an automotive fuel. In European Union, the amended Fuel Quality Directive adopted in 2009 allows up to 3% v/v blendin of methanol in petrol. Brazil has allowed and encouraged the use of ethanol-methanol- petrol blended fuel. E85 fuel used by the Scania (the world's top automaker) also contains methanol in the 0.5%-1% range (specification E85 fuel). As per the BIS standard for EBP methanol below 0.3% is allowed as impurities in ethanol.

Denatured ethanol:

- Ethanol which is in use in EBP is a denatured ethanol, denatured ethanol is different from plain ethanol. In India plain ethanol/alcohol is heavily taxed by various State governments, as it is more prone and more lucrative for recreational use. hence if it is to be allowed for used for non-recreational or industrial purposes then to avoid heavy tax and more stringent & statutory time-consuming provisions, (such as supervision charges, transport charges, licenses fees, various permission, escort, no objection certificates and clearances for storing, using and transporting etc.) plain ethanol/alcohol is required to be denatured. Denatured ethanol is ethanol with added chemicals that make it poisonous, bad tasting, foul smelling or nauseating, to discourage its consumption. The only purpose of denaturing ethanol/alcohol is to make it undrinkable or to discourage its recreational use to avoid taxes and other very tight provisions of state excise, imposed from the revenue point of view.

Denatured alcohol is not, in itself, a product that would be normally demanded if given the alternative of normal ethanol. Denatured alcohol and its manufacture are a public policy compromise. The supply and demand for denatured alcohol arise from the fact that normal alcohol (which in everyday language refers specifically to ethanol, suitable for human ingestion as a recreational drink or extractive medium for medicinal tinctures) is very heavily taxed and is tightly controlled by the state excise department of various state governments for revenue purpose. If pure ethanol is made cheaply available for fuel, solvents, or medicinal purposes, some people might ingest it or some industrial units may misuse it by diverting it for potable or recreational purposes.

Denatured alcohol provides a solution to permit industrial use and manufacture of ethanol, whereby cheap ethanol can be made available for non-consumption use without the risk of its being converted for consumption. The process creates an ethanol-containing solution that is not suitable for drinking, as a result, there is no state excise duty and no stringent control or provisions on denatured alcohol in India, making it considerably cheaper and easier to procure or use or transport than pure ethanol. As a consequence, its composition is tightly defined by government regulations that vary from state to state. Denatured ethanol also reduces the burden and liability of state excise authorities as it does not require stringent watch and alert on storing, transporting and use of ethanol from the revenue point of view.

The main and traditionally used denaturant in India is 10% methanol, giving rise to the term "methylated spirits". Other typical denaturant includes isopropyl alcohol, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Nowadays OMC (oil marketing companies) companies are procuring denatured ethanol for EBP with a denaturant crotonaldehyde 0.2% (200 ml per 99.8 litres of ethanol

i.e. 0.2%) & with bitterant denatonium saccharide 4 grams per 100 litres of ethanol (4% in grams). If we compare methanol and crotonaldehyde on various parameters we will find that methanol is far better as a denaturant in ethanol used in EBP. A comparison of presently used denaturant, crotonaldehyde and methanol on various points is as below.

Health hazards: - It is already mentioned that the purpose of crotonaldehyde as a denaturant in ethanol is because of its pungent, suffocating and strong smell to make ethanol non-drinkable & unpalatable, but the very big disadvantage is that its exposure is highly hazardous, it has acute and chronic adverse health effect. The smell of crotonaldehyde provides a warning of hazardous concentrations. Crotonaldehyde is highly toxic by all routes. Exposure causes inflammation and irritation of the skin, respiratory tract, and mucous membranes. Delayed pulmonary edema

may occur after inhalation. Methanol on other hand is less health-hazardous in counts of its smell or its exposure, it is serious and health-hazardous only if it is ingested. on health hazards, grounds and the chronic or acute adverse health effect counts, methanol is less harmful than crotonaldehyde.

Denatured ethanol, when blended with the petrol with the strong smell of petrol itself, will make EBP a non-drinkable & unpalatable solution. hence one does not need a very hazardous strong smell of crotonaldehyde to discourage consumption. Methanol on other hand doesn’t have a hazardous smell and is better suitable as a denaturant in EBP.

Chemical & physical properties: - On a count of miscibility with ethanol, methanol is having an advantage. Methanol has around the same density as that of ethanol, methanol has a density of 791 (kg/m3) at 20 °C, while ethanol has 789 (kg/m3) at the same temperature.

methanol has strong miscibility with ethanol. Considering the boiling points crotonaldehyde has a boiling point of 104°C while methanol has the same boiling point of 65°C as ethanol at 79°C, methanol is more difficult to remove from ethanol

i.e. renature of ethanol denatured with methanol is highly difficult. Considering more health hazards issues of presently used crotonaldehyde for EBP, methanol is more suitable as a denaturant in EBP. Methanol has almost similar chemical and physical properties as that of ethanol, it is the most suitable denaturant as without any compromise in quality it can be used in place of plain ethanol.

Octane number: - it is a standard of measure of the performance of engine fuel. The higher the octane number, the more compression the fuel can withstand before detonating (igniting). In broad terms, fuels with a higher octane rating are used in high-performance spark-ignition petrol engines that require higher compression ratios. octane value of methanol is much higher than any other denaturant used in denatured ethanol. The octane value of presently used denaturant crotonaldehyde is much lower as compared to methanol which makes it a less favourable fuel/denaturant than methanol. Methanol has an octane value of 109. (RON) Methanol if used as a denaturant in EBP, will make fuel to be better Anti Knocking Index (AKI) fuel. This shows that the addition of methanol in ethanol as a denaturant or as a blending fuel will help in increasing the quality of petrol.

Price: - one of the biggest disadvantages of crotonaldehyde is that its price is very high as compared to methanol. The current market price of crotonaldehyde is Rs.110

litre as compared to Rs. 25 litre of methanol. Though the quantity of denaturant used is 0.2% in ethanol, which is when 10% blended in petrol, a total quantity of denatured becomes 0.018 % in total fuel. Though this % of the quantity is very low, if we consider a billion litres of total EBP, a considerable saving in the cost of denaturant in EBP is possible.

Energy density: - energy density of the methanol is much higher than crotonaldehyde, which makes methanol a more favourable fuel and denaturant in EBP. If we consider the energy density of methanol from a cost-per-kilometre point of view, methanol is cheaper than crotonaldehyde. If 1% or more methanol as a denaturant or as blending fuel is used in ethanol-methanol blended petrol, it will be a better option than ethanol-petrol blending. However, methanol has some disadvantages.

The main disadvantages of methanol are that it is more corrosive than crotonaldehyde, and it affects the copper and aluminium parts used in the fuel system. However, with just 0.01% in total volume in EBP, it may not be a measure issue, also this issue can be solved by the addition of anti-corrosive additives in small quantities.

The second big disadvantage of the methanol is that it is highly toxic/poisonous, if ingested it is fatal, there are chances of accidental ingestion as it has very similar properties as that of ethanol, its tests and smells are almost identical that those of ethanol. It does not provide any warning sign hence in some states, its use is not allowed as a denaturant. Methanol denatured ethanol though very difficult to renatured, when it is diluted with water the poisonous adverse effect of methanol can be reduced and it is difficult to prevent or discourage people, particularly of low strata to use it for recreational purposes at a very cheap cost. However, with the addition of bitterant denatonium saccharide, this issue can be easily solved. When it is blended with petrol, the unpleasant smell of petrol itself will also act as a discouragement for recreational use.

It is already stated that use of the ethanol for recreational purposes can be discouraged by making it poisonous, bad tasting, foul-smelling or nauseating, many in the chemical fraternity have the opinion that either by merely giving a nauseating test or by merely giving strong & pungent smell it is 100% possible to discourage recreational drinking. If this opinion is accepted there is only a need to add either crotonaldehyde for a pungent smell or bitterant denatonium saccharide. If it is accepted there is no need to use crotonaldehyde, at the cost of health hazards, the mere addition of strong bitterant denatonium saccharide will suffice the purpose of denaturation, no need to use both. If we consider the notification dated 20.01.2011 by which methanol is notified as poison in Maharashtra State by the FDA department, it is mentioned that methanol must be sold with the addition of bitterant, denatonium saccharide if it is to be sold for the non-pharmaceutical purpose. This makes it very clear that the mere addition of bitterant denatonium saccharide is more than sufficient to render ethanol/methanol unfit for human consumption, even consumption under a misconception or accidental consumption is impossible for the ordinary human being. Methanol can be used as a denaturant with or without bitterant as after blending with petrol foul smell of petrol itself can act as an additional denaturant to discourage recreational use by an ordinary person.

Denatured ethanol is procured by PSU such as IOC, HPCL, IOCL

etc. there are no chances that these PSU will misuse or will divert denatured alcohol for a potable purpose. These PSU also have better stock management, there are remote chances of misuse of ethanol/alcohol hence if the central government approve, plain ethanol can also be supplied for EBP, recent judgment of the Bombay high court also supports the use of plain ethanol for industrial purpose without any state excise duty or taxes, license and tight provisions.

Methanol, however, can serve both the purposes as a denaturant and also as a blending fuel, thus methanol has advantageous for use as a denaturant than the existing denaturant used in EBP and also as fuel in blending with petrol. The mix of 1% - 3% methanol in petrol is allowed in some western countries, China is using methanol blended petrol. If methanol in 1%-3% is used as a denatured with or without bitterant, it will be high value-added as it will be cheaper, have more energy density, more AKI fuel & less health hazardous, and less carbon or air-polluting fuel.

In India, we can produce methanol from biomass, municipal waste and also from coal. Methanol, ethanol, and petrol are about equal in the levels of nitrous oxide and carbon monoxide produced when they are burned. Since it is made exclusively from agricultural products, ethanol acts as a counter to global warming. Methanol can as well, but only if its source is agricultural. Methanol produced from coal or natural gas has about the same impact on global warming as petroleum. India has a large reserve/stock of coal, hence in India methanol can also be produced from coal, this will reduce the transportation cost of energy, and will increase energy flexibility and our resource base.

In short considering cost, energy density, health hazards, quality of fuel, octane value and AKI, carbon emission, air pollution, and other economic, social, ecological and environmental benefits, methanol is a far better option as a denaturant to be used in ethanol for EBP with or without bitterant denatonium saccharide

Methanol as a blending fuel in a petrol-ethanol blend

Ethanol & Methanol both could be used very effectively, with roughly equal countervailing advantages. Methanol is cheaper than ethanol. It can also be made from a broader variety of biomass material, as well as from coal and natural gas and methanol is the safest motor fuel because it is much less flammable than petrol. (a fact that has led to its adoption by car racing leagues). On the other hand, ethanol is less chemically toxic than methanol, and it carries more energy per litre. Ethanol contains about 75 per cent of the energy of petrol per litre, compared to 67 per cent of methanol. Both thus achieve fewer miles per litre than petrol, but about as many kilometres per Rupee at current prices, and probably many more kilometres per litre at future prices.

Methanol can also be used as the raw material to produce dimethyl ether, a completely clean-burning diesel fuel which could be used by trucks, locomotives, and ships. Many cars could also eventually use diesel. Diesel engines are substantially more efficient than traditional internal combustion engines and equal to anything realistically possible from far more expensive, and as yet impractical, fuel cells. By promoting agriculture, ethanol/methanol liquid energy also act as a global cooling agent. Plants draw CO2 out of the atmosphere. They increase water evaporation, and the water vapour thus produced transports heat from the Earth’s surface to the upper atmosphere, where most of it is released to space.

The use of alcohol also reduces air pollution. Environmental advantages were the motivation for the initial development of the alternative fuel for an internal combustion engine. The era of Rs. 25 per litre of petrol, pleased ecological activists, but it was economically disadvantageous. Recently, however, the comparative economics of alcohol fuels and petroleum fuels have changed radically.

THE ECONOMICS AND TECHNOLOGY for ALCOHOL SOLUTION

: - Two developments make a rapid transfer to high-alcohol fuels possible. One is the recent rise in oil prices, making methanol and ethanol economically attractive. The other is a technological innovation: the development of a sensor capable of continuously measuring the alcohol content in mixed alcohol/petrol fuel and using this information to regulate the engine.

To liberate ourselves from the threat of foreign economic domination we must devalue petroleum resources and increase the value of our agriculture base resources. We can do this by taking the world off the petroleum standard and putting it on an alcohol standard. This may sound like a huge and impossible task, but with oil prices well over 100$ per barrel, the means to accomplish it are now at hand. The government could make an enormous step in flexible-fuel vehicles (FFV) capable of burning any combination of petrol & ethanol/methanol. India has by far the better production potential for both. Ethanol is made from agricultural products. Methanol can also be made from biomass, as well as from natural gas or coal. India has sufficient coal reserves for methanol production as well it can be produced from municipal waste, methanol produced as a by-product in fertilizer production is also available for fuel blending. Ethanol can currently be produced for about Rs. 40 per litre and methanol is currently selling for Rs. 25 per litre. With petrol having roughly doubled in price recently, and with little likelihood of a substantial price retreat in the future, high alcohol-to-petrol fuel mixtures are suddenly practical. Cars capable of burning such fuel are now no futuristic dream. The engineering difference is in one sensor and a computer chip that controls the fuel-air mixture, and the employment of a corrosion-resistant fuel system. The difference in price from standard units ranges only from Rs. 40,000 to 50,000.

The use of alcohol blended fuel and flexible-fuel vehicles (FFVs) will offer the flexibility of our liquid energy needs, we will not be dependent alone on OPEC but can counter effectively any situation of energy crisis. We can procure liquid energy from many countries such as Brazil, Australia, Canada fueled

etc. If all cars had to be flexible-fueled

, foreign manufacturers would also mass-produce such units, creating a large market for methanol and ethanol, much of which would be produced in India. Instead of being the world’s fuel importer, our country can become self-sufficient or a net fuel exporter. This will change the economic perspective and landscape of our country. India has an advantage for alcohol/methanol as we have more skill in agriculture.

ETHANOL OR METHANOL

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To date, ethanol-blended or methanol blended fuel is used in the internal combustion engine, all FFVs have been either methanol/petrol designs or ethanol/petrol designs. Combined methanol/ethanol/petrol blended fuel or FFVs have not yet been produced. However, methanol in 1%-3% can be used in EBP or it can serve both purposes as fuel for blending and as a denaturant, it will not need any modification in the engine. Also, the development of FFV poses only modest challenges, however. The question is, which alcohol would be the best one upon which to base our future alcohol-fuel economy? Methanol is cheaper than ethanol. It can also be made from a broader variety of biomass materials, as well as from coal and natural gas. And methanol is the safest motor fuel because it is much less flammable than petrol (a fact that has led to its adoption by car racing leagues). On the other hand, ethanol is less chemically toxic than methanol, and it carries more energy per litre. Ethanol contains about 75 per cent of the energy of petrol per litre, compared to 67 per cent of methanol. Both thus achieve fewer kilometres per litre than petrol, but about as many kilometres per rupee at current prices, and probably many more kilometres per rupee at future prices.

Methanol is more corrosive than ethanol. This can be dealt with by using appropriate materials in the automobile fuel system. A fuel system made acceptable for methanol use will also be fine for ethanol or pure petrol. However, if methanol is blended only in a small quantity of 1%-3%, then there is no need for any changes in the engine and fuel system. Both ethanol and methanol are water-soluble and biodegradable in the environment. The consequences of a spill of either would be much less than that of petroleum products. In short, either methanol or ethanol could be used very effectively, with roughly equal countervailing advantages. This has not stopped proponents of either fuel from vociferously arguing their unique advantage and pushing for FFVs based exclusively on their favoured product.

The question might well be asked: why not just go with the stronger side and implement an exclusively ethanol/ petrol blending or FFV economy? The answer has to do with the total resource base. If we want India to be energy independent, we need a larger production base than ethanol alone can deliver So, if we are to use alcohol fuels to achieve energy independence, a broader resource base is needed. This can be provided by methanol, which can come from both a broader array of biomass materials and also from coal and natural gas.

Methanol production from coal is particularly important, as coal is much cheaper than agricultural products, so methanol can be made from coal at a low cost. By mixing it at various rates with ethanol over time, we can increase supplies, reduce prices, maximize environmental benefits, and vastly increase the flexibility of our alcohol economy. Insisting that future vehicles have the capability to burn both alcohols is thus critical.

With ethanol - methanol in the mix, the shifting of the world from petroleum to an alcohol standard would remain a great boon to farmers. Our farmers would enjoy the benefits—not only from a vastly increased market for their products but also from the collapse of petroleum prices (which currently threaten crushing fertilizer and tractor fuel prices). This adds a strong humanitarian case for the transition to flexible fuels, by providing populations with an extensive source of income, the alcohol economy would also give them the wherewithal to buy other products That would improve economic outcomes for our nations. Energy conservation offers only a strained strategy for enduring economic oppression with very slightly ameliorated pain. If we are to win the critical energy battle, there is only one way to do it. We must take ourselves, and the rest of the world, off the petroleum standard. Methanol-Ethanol- Petrol fuel blending is thus one of the best options for our liquid energy strategy, as it widens our resource base, reduces the cost of fuel and also the quality of fuel (better AKI) the economic perspective and landscape of our country, as it will help to shift petroleum standard to alcohol standard. There will be more flexibility in the procurement of liquid energy.

I think that at least we can start immediately with (1%-3%) methanol, (methanol has more than 3% solubility at ordinary room temperature in ethanol) at (9% -7%) ethanol & remaining 90% petrol blended fuel without any changes in engine and fuel system. OMC can immediately allow EBP with ethanol, denatured with methanol instead of crotonaldehyde with or without bitterant denatonium saccharide. This will reduce fuel costs with better quality of fuel without health hazards and with less air pollution and will pave the way for the future energy revolution in the world. Another technical study on the blended fuel done by various technical universities also concluded the test results which indicated that ethanol–methanol–petrol blends (E-M-P) burn cleaner than both ethanols

–petrol blends (E-P) and the neat petrol fuel (P). the study pointed out that to get low moderate emissions of CO and UHC (unburned hydrocarbon) as well as a high moderate volumetric efficiency, torque and power, we should use Ethanol-Methanol-petrol fuels. Thus, a strategy to shift to methanol-ethanol-petrol blended fuel will be the best possible option to counter future energy crises.

With this, I request the Automotive Research Association of India to think about the above proposal and to recommend the government with the appropriate suggestion in making the policy regarding EBP and BIS for blended fuels and the use of methanol as a denaturant and as a blending fuel.

By—

Mohan S. Varde, BE (Mech), M.S. (Tech.Oprn.)

Superintendent State Excise, Nandurbar (MS)