October 2006

Methanol as a Potential Contributor to Energy Independence

Methanol is often discussed as a potential contributor to energy independence because it is a liquid fuel that relatively easily can be manufactured from any source of carbon: fossil fuels, biomass, or waste (Clayton, 2006). By tapping its vast coal reserves to produce methanol, advocates claim the United States could significantly shift its dependence on imported petroleum for transportation fuel. Such claims, however, gloss over several important issues which would have to be overcome before such a transition could successfully occur. Methanols primary use as a fuel would be in gasoline or diesel-type vehicles, though methanol fuel cell vehicles are a possible alternative. Use of methanol as a motor fuel requires dedicated vehicles and a dedicated distribution system, and raises a new and potentially difficult to address set of health and safety issues. While advocates of U.S. energy independence promote methanol, California, which was the site of most of the experimental and demonstration work on methanol-fuelled vehicles, dropped this effort and moved on to other alternatives. There is no evidence of new programs to develop methanol-fuelled vehicles.

Manufacture of Methanol
Methanol (CH3OH) is manufactured in large volumes as an industrial chemical by reaction of carbon monoxide (CO) or carbon dioxide (CO2) with hydrogen (H2) over a metallic catalyst (Wikipedia, n.d.): CO + 2 H2 CO2 + 3 H2 CH3OH, CH3OH + H2O

The CO, CO2, and H2 are produced by gasification of fossil fuels. Natural gas is currently the fuel of choice for manufacture, because it is easiest to handle and produces the largest amount of hydrogen, but the process can be based on any sources of carbon (Hamelinck and Faaij, 2001). It is this flexibility that creates interest in methanol as a contributor to energy independence. Advocates envision methanol produced from coal, biomass, and waste. Beginning in 1997, a Department of Energy (DOE) project successfully operated a methanol-from-coal pilot plant at a Tennessee-Eastman facility in Kingsport, TN. The pilot plant used an innovative technology developed by Air Products and Chemicals Co. (DOE, 2003). This plant demonstrated that methanol could be produced from coal at reasonable costs. However, since costs are site-specific, DOE could not judge whether this technology was competitive with conventional methanol-from-naturalgas technology. DOEs project ended in 2003, but the pilot plant is still being operated by Tennessee-Eastman. Most of the methanol produced by this plant was used for chemical manufacture, but a small amount was processed further and used by DOE in vehicle test programs, which showed that methanol-from-coal was suitable for vehicle use. Design calculations indicated that the methanol could be used for clean coal electricity generation at
The Marshall Institute Policy Outlook series will periodically examine important issues affecting science and public policy. Particularly focused on the use of scientific information in formulating policy decisions, Policy Outlooks will aim to provide clarity and objectivity to policy-relevant discussions. The views expressed by the author are solely those of the author and may not represent those of any institution with which he is affiliated.
George C. Marshall Institute 1625 K Street, NW Suite 1050 Washington, DC 20006 202-296-9655 Fax 202-296-9714 info@marshall.org http://www.marshall.org ,

reasonable costs. However, there is no indication that any company is planning to use this technology to produce methanol on a larger scale.

Methanol as a Motor Fuel

The energy system requires several types of energy sources: 1. Primary energy for electricity generation 2. Liquid fuels for road transportation 3. Specialty fuels (e.g., jet fuel) Since methanol is a liquid, interest in its use has focused on its potential as a motor fuel, particularly as a gasoline replacement. Methanol has a high octane rating, well above that of premium grade gasoline, and has been used as a racing car fuel for decades. There also has been interest in its use as a diesel fuel replacement.

Another set of problems is caused by water and methanols ability to dissolve in each other. Contact with small amounts of water will result in the water being incorporated into the fuel mixture. (Methanol is the active ingredient in fuel additives sold to remove water from vehicle fuel tanks.) Contact with large amounts of water, such as the water bottoms present in much of the gasoline distribution system, could result in the methanol being stripped from the fuel blend. Methanol has several other disadvantages as a vehicle fuel. 1. Since the methanol molecule contains oxygen, methanol contains only 53% as much energy per gallon as gasoline (Eberhardt, 2002). Methanol vehicles will require much larger fuel tanks, and suffer a weight penalty for having to carry the larger amount of fuel. 2. Methanol, with a flash point of +11C, is harder to ignite than gasoline, which has a flash point of -45C. Vehicles that use M100 require special ignition systems to overcome this problem. However, the usual approach is to use an M85 blend. The gasoline provides sufficient volatility for easy starting. 3. Methanol will corrode the metal components and attack the rubber components of conventional vehicle fuel systems (Howard, 1994). The solution to these problems is to use stainless steel for the metal parts and methanol resistant elastomers for the rubber parts of the fuel system. Methanol-tolerant components are more expensive than conventional gasoline vehicle fuel system components. 4. Methanol vehicles require special engine oil, which is more expensive than conventional engine oil (CEC, 1999). 5. Methanol-fuelled vehicles typically have lower hydrocarbon, carbon monoxide and oxides of nitrogen emissions, but higher

Methanol as a Gasoline Replacement

An ideal way to introduce methanol as a vehicle fuel would be in blends with gasoline at levels that allow the blends to be used in existing vehicles. Methanol-gasoline blend are designated by an M followed by a number indicating the percent methanol in gasoline. Thus, M85 is 85% methanol in gasoline and M100 is pure methanol. Several properties of methanol limit its use in existing vehicles. The most critical is the fact that methanol does not dissolve in gasoline at all proportions. The solubility of methanol in gasoline is a function of both the composition of the gasoline and temperature, but in general, mixtures between M15 and M80 separate into two phases, the way that gasoline and water separate. (Data on the solubility of methanol in isooctane and xylenes, pure components that represent a large fraction of gasoline can be found in Garcia Flores and Trejo, 2000.) As discussed below, fuel flexible vehicles (FFVs) can tolerate phase separation in the vehicle fuel tank, but phase separation would create unmanageable problems in the distribution system. There would be no way to control the quality of fuel being dispensed.
2

Marshall Institute Policy Outlook

formaldehyde emissions, than typical gasoline vehicles (EESTEC, 1999). Formaldehyde emissions from motor vehicles were specifically identified for control in the Clean Air Act Amendments of 1990. These emissions can be controlled by using more effective emission control catalysts, but these also will raise vehicle price. While solutions exist to all of the technical challenges to using methanol as a gasoline replacement, they make use of small amounts of methanol in gasoline blends unattractive. Vehicles using small amounts of methanol in gasoline would have to use more expensive, methanol-resistant fuel systems, more expensive emission control systems, and would suffer a fuel economy penalty because of the lower energy content of the methanol in the fuel. As a result, almost all of the discussion of methanol as a gasoline replacement has focused on the use of M85 or M100 in dedicated vehicles. These could be fuel flexible vehicles (FFVs), which can use M85, unleaded gasoline, or mixtures of the two. This would allow the vehicles to switch from unleaded gasoline to M85 at will. These vehicles could tolerate phase separation in the fuel tank because a sensor in the fuel line would adjust engine operating conditions to the fuel composition actual entering the engine. Approximately 13,500 demonstration methanol FFVs were sold in California between 1992 and 1998 as part of Californias program to promote alternative fuels. Essentially all were sold to fleet operators with dedicated fuelling facilities. (CEC, 1999). The introduction of these vehicles requires a dedicated fuel system, which would have to be in place before the vehicles were introduced. Both the vehicles and the infrastructure are expensive. In 1999, the California Energy Commission (CEC) estimated the cost of installing an M85 fuelling system (underground tank plus 1 dispenser) at $80,000. No estimate was made of the cost of the distribution system necessary

to bring the fuel to the service station. Adjusted for inflation and expanded to the entire U.S., a dedicated distribution system raises the costs to an extraordinary level. Auto manufacturers would have to be assured that fuel would be available before they committed to large scale manufacture of vehicles, and fuel marketers would have to be assured that the vehicles would be produced before investing in a methanol distribution system. This is the classic chicken-and-egg problem facing any new fuel/vehicle combination. While FFVs offer a partial solution to this problem, these vehicles will be more expensive than conventional gasoline vehicles and their sales highly limited unless M85 is widely available and significantly cheaper than unleaded gasoline.

Methanol as a Diesel Fuel Replacement

The CEC program promoting methanol had a heavy-duty vehicle component that promoted the use of methanol as a diesel fuel replacement. Detroit Diesel Corporation designed an engine that operated on M85. Some 550 of these engines were installed in school and transit buses. The cost of these engines was about double the cost of a conventional diesel bus engine, and when the costs of the other vehicle conversions required to use M85 were taken into consideration, CEC estimated: Conservatively, the incremental cost of a methanol fuelled transit bus is approximately $12,000. (CEC, 1999).

Methanol Fuel Cell Vehicles

Another approach for using methanol as a vehicle fuel is to use it in fuel cell vehicles. Fuel cells generate energy with higher efficiency than combustion engines and do not produce most air pollutants. However, fuel cells cannot use methanol directly. It first must be reacted with steam (H2O) to form hydrogen and carbon dioxide: CH3OH + H2O 3 H2 + CO2

October 2006

Unfortunately, some of the methanol decomposes directly to form hydrogen and carbon monoxide: CH3OH 2 H2 + CO Carbon monoxide is highly undesirable because it is an air pollutant and because it deactivates fuel cell systems. Most methanol fuel cell systems carry out the reaction to form hydrogen in an device known as a reformer, which is separate from the fuel cell (See, for example, the descriptions of the fuel cell buses under test at Georgetown University (2006), and the fuel cell passenger car being developed by DaimlerChrysler (BASF, 2006)). These systems typically add a reactor (the low temperature shift catalyst in the Georgetown buses) to convert the CO to CO2. Research is underway on a more advanced approach in which methanol is converted to hydrogen and carbon dioxide in the fuel cell itself. These fuel cells are known as direct methanol fuel cells (DFMCs) and are claimed to produce as little as 20 ppm CO (Green Car Congress, 2006). A major drawback to all methanol fuel cell systems is that the reformer, whether in an external device or in the fuel cell itself, will not work at room temperature. Typically the reformer or fuel cell must be heated to at least 50C (122F) (FCTec, 2006). This requires a source of power, typically the vehicle battery, and time the lower the outside temperature, the more power and time that are needed. Development of methanol fuel cell vehicles is at a very early stage and is not receiving much attention. At present, much more emphasis is being put on the development of hydrogen fuel cell vehicles, because they do not have the warm-up problem of the methanol-fuelled vehicles, and because hydrogen manufacture can be coupled with carbon capture and storage technology to significantly reduce emissions of carbon dioxide, which is the main human contributor to potential climate change. Use of methanol, either as a replacement for gasoline or diesel fuel or in a fuel cell vehicle, is not a low carbon dioxide alternative.
4

Health and Safety Considerations

The toxicity of methanol is well-known. Ingestion of relatively small amounts will lead to blindness, slightly larger amounts, to death. While individual responses to methanol vary widely, one report claims that ingestion of as little as 300-1000 mg/kg (0.85-2.85 ounces for a 150 lb. person) can cause death (Kavet and Nauss, 1990). There are no reliable studies of the effects of exposure to low levels of methanol in air, water, or food on human health. Because methanol dissolves in water, there are concerns that methanol spills could contaminate water supplies. Because methanol is odorless, and at low concentrations tasteless, such contamination would be undetectable. Methanol poses an interesting set of pros and cons from a safety standpoint. The pros are that it is harder to ignite than gasoline and, unlike gasoline fires, methanol fires can be extinguished with water. These considerations led the Indy racing car circuit to switch to methanol as a fuel in 1965. The con is that methanol flames are invisible, making detecting the source of a methanol fire much more difficult.

Current Status of Methanol as a Vehicle Fuel

The CEC program to promote methanol as an automotive fuel effectively ended in 1999. A 2001 CEC (CEC, 2001) report stated that no major motor manufacturers were offering methanol-fuelled vehicles for sale at that time. By 2005, a CEC report on commercialization of alternative fuels did not even mention methanol (CEC, 2005). In 2002, DOE reported that the number of methanol-fuelled vehicles in the U.S. peaked at about 19,000 in 1997 and declined thereafter (Joyce, 2002). The report indicated no further development of methanol engine vehicles, but cited plans by DaimlerBenz/Chrysler to market 100,000 methanol fuel cell vehicles starting in 2004. These plans have not materialized, and essentially all current discussion of fuel cell vehicles is about
Marshall Institute Policy Outlook

hydrogen fuel cells. A Web search for programs to develop methanol as an automotive fuel found no indication of new programs.

References
BASF, 2006: Mobility beyond gasoline and diesel: BASF catalyst for NECAR 5 fuel cell car. http:// corporate.basf.com/en/stories/loesungen/ necar/?id=V00-R2YJA94BUbcp*9G CEC, 1999: ABCs of AFVs, 5th edition. www. energy.ca.gov/afvs/reports/1999-11-500-99013.pdf CEC, 2001: California Clean Fuels Market Assessment 2001. www.energy.ca.gov/ reports/2001-08-18_600-01-018.pdf CEC, 2005: Alternative Fuels Commercialization. www.energy.ca.gov/2005publications/ CEC-600-2005-020/CEC-200-2005-020.pdf Clayton, Mark, 2006: Gasolines fledgling rivals: the race to power your car. Christian Science Monitor, August 1. www.csmonitor. com/2006/0801/p01s02-usec.html DOE, 2003: Commercial-Scale Demonstration of the Liquid Phase Methanol (LPMEOHTM) Process: A DOE Assessment. www.netl.doe. gov/technologies/coalpower/cctc/resources/p dfs/estmn/LPMEOH_PPA.pdf Eberhardt, J.J., 2002: Fuels of the future for cars and trucks. Paper presented at the 2002 Diesel Engine Emissions Workshop, San Diego, CA, Aug. 25-29, 2002. www.osti.gov/ fcvt/deer2002/eberhardt.pdf EESTEC, 1999: A review of methanol as a fuel

for spark ignition engines. www.eestec.org/ resources/files/1999.12-newsletter.pdf FCTec, 2006: Direct Methanol Fuel Cells (DMFC). www.fctec.com/fctec_types_dmfc.asp Garcia Flores, B.E. and A. Trejo, 2000: Liquidliquid phase diagrams of multi-component systems as a function of temperature. Paper presented at the 14th Symposium on Thermophysical Properties, Boulder, CO, June 25-30, 2000. www.symp14.nist.gov/ PDF/CHE04GAR.pdf Georgetown University, 2006: The Georgetown/UTC Fuel Cell Bus In Depth. http:// fuelcellbus.georgetown.edu Green Car Congress, 2006: Chinese Demonstrate Methanol Reformer/Fuel Cell Integration. www.greencarcongress.com/2006/06/ chinese_demonst.html Hamelinck, C.N. and A.P Faaij, 2001: Future .C. prospects for the production of methanol and hydrogen from biomass. www.chem. uu.nl/nws/www/publica/e2001-49.pdf Howard, L., 1994: Biodiesel vs. other alternative fuels. www.biodiesel.org/resources/reports database/reports/gen/19940315_GEN002.pdf Kavet, R. and K.M. Nauss, 1990: The toxicity of inhaled methanol vapors. Critical Reviews in Toxicology, Vol. 21, Pg. 21-50. Cited in Chronic methanol/formaldehyde poisoning from aspartame. www.holisticmed.com/ apertame/methanol.faq Wikipedia, n.d.: Methanol. http://en.wikipedia. org/wiki/methanol

October 2006