Air Resources Board, as the Clean Energy Advisor to the Secretary of the California .... Both alcohols ethanol and methanol offer major advantages to auto.
A New Look at Methanol: Accelerating Petroleum Reduction and the Transition to Low Carbon Mobility January, 2016
Washington: 225 Reinekers Lane; Suite 205, Alexandria, VA 22314 USA +01 703 248 3636 Singapore: 10 Anson Road, #32-10 International Plaza, Singapore 079903 +65 6325 6300 Brussels: Avenue Jules Bordet, 1421140 Brussels, Belgium +32 276 116 59 Beijing: #511, Pacific Sci-tech Center, No. 52 Hai Dian Rd, Beijing 100871, China +86 10 6275 5984 www.methanol.org www.methanol.org.cn www.methanolfuels.org
ABOUT THE METHANOL INSTITUTE The Methanol Institute (MI) serves as the global trade association for the methanol industry. Our mission is to expand the use of methanol as a basic chemical building block and an emerging energy resource. The Methanol Institute has offices in Washington, Singapore, Brussels and Beijing. For more information, visit our web sites at www.methanol.org and www.methanolfuels.org.
ABOUT THE AUTHOR:
This report was authored by Paul Wuebben, a consultant to the Methanol Institute. He began his career as an EPA Fellow at the Harvard School of Public Health. He served as the Clean Fuels Officer for the South Coast Air Quality Management District, where he also managed the agency’s multi-million dollar Clean Fuels Program. He served as the Clean Fuels Advisor to the Chairman of the California Air Resources Board, as the Clean Energy Advisor to the Secretary of the California Environmental Protection Agency, and as the Chairman of the California Electric Vehicle Task Force. Following his public agency career, Mr. Wuebben has transitioned to the private sector as the Senior Director of Renewable Fuels for Carbon Recycling International. He received his BA in History/Urban Studies
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Summa Cum Laude from UCLA and his Master of City Planning degree from the Harvard University Graduate School of Design.
TABLE OF CONTENTS: Page Preface
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Highlights
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I. The California and U.S. National Context
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Vehicle Fuel
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i.
Ultra-high Efficiency Characteristics
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ii.
Methanol Air Quality and GHG Benefits
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iii. Fuel Production Pathways: Towards Fully Sustainable Liquids
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III. Methanol Marine Applications
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IV. The Way Forward: A Transition Path to Re-introducing Methanol
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References
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PREFACE California has led the nation in addressing climate change, energy efficiency, fuel diversification and clean air. Recent initiatives by California Governor Jerry Brown seek to build on this legacy by establishing a goal of replacing 50 percent of petroleum fuel use with most ambitious greenhouse gas (GHG) emission standards, advanced clean car regulations, zero emission mandates and low carbon fuel standard. Similarly, at the federal level, the U.S. Environmental Protection Agency and Department of Transportation are pursuing ambitious criteria emission and GHG reduction goals, all within the context of the federal fuel economy fleet-wide standard of 54.5 mpg. Taken in aggregate, these efforts present a complex and challenging set of requirements for auto manufacturers and energy companies. It is becoming increasingly clear, however, that additional tools will be needed, beyond those currently underway, to attain these ambitious goals. In this new context, methanol stands out as a scalable, high volume opportunity to optimize the synergies between vehicles and fuels and to expedite progress well before 2030. Recent advances point to methanol as the liquid fuel capable of enabling the highest efficiency possible with combustion engine technology, and one which readily integrates with its alcohol cousin, ethanol, to achieve numerous synergistic benefits. The basic building blocks for realizing such benefits a systems perspective is needed, that may also incorporate ethanol in a ethanol and methanol. The two alcohol fuels are very complementary; in fact ethanol is an excellent co-solvent for producing methanol/gasoline fuel blends. The technology evolution pathway centered on leveraging the significant potential of methanol is well within reach with concerted and reinforcing actions by regulatory agencies, auto companies, oil companies and the methanol industry.
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Recent advances in methanol production in the form of renewable methanol from CO2 feedstock coupled to renewable power generation have demonstrated that renewable methanol can play a major role in addressing the need for sustainable ultra-low carbon fuels. In the initial stages of a transition to high-octane/ultra-high efficiency methanol compatible vehicle technology, the use of abundant North American diversity and economic growth. The continuing evolution and deployment of ethanol flexible fuel vehicle (FFV) technology has demonstrated a very cost effective automotive technology option, while offering the consumer with the additional choice of pumping low-cost methanol and co-alcohol GEM blends will provide even greater fuel-on-fuel price competition with gasoline and diesel. Methanol use in optimized engines, both light and heavy duty, offers significant potential for NOx and PM emission reduction, as well as toxic emission benefits by replacing highly carcinogenic benzene and diesel particulate emissions with far less toxic methanol exhaust constituents. Ultimately, a transition may be feasible from oil refining to an industrial base dedicated to ultra-low carbon liquid fuels from the capture and conversion of CO2 and renewable hydrogen or the remote gasification of biomass, including municipal solid waste and other non-food feedstocks. This could provide a supportive path for California to entirely divorce from petroleum based fuels. Once such an industrial base is in place, it would enable the direct de-carbonization of the atmosphere. All of these benefits are of central relevance to attaining and maintaining strict air quality standards as well as GHG emission reduction goals. California took a leadership position in the 1980s/1990s to foster the development and use of methanol as a transportation fuel. While these efforts were technically successful, they did not achieve the full promise of methanol at that time, due primarily to the extremely low price of oil as well as the continued improvement in gasoline criteria emissions, albeit not constrained at that time by a 54.5 mpg efficiency target. 1 It is now appropriate to reexamine dated premises about the role of methanol in light of significant advances in production technology, engine efficiency trends, growing concerns uncertainty regarding the pace and scope of the ultimate market potential for battery electric and hydrogen fuel cell vehicles. Upon a careful updated examination, it is evident that methanol can play a significant role in helping California and the nation expedite the
For example, cold start catalysts have now matured such that formaldehyde emissions from methanol fuel combustion in FFVs easily comply with Califo standard.
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attainment of air quality, GHG, and energy efficiency goals, as well enhancing consumer value through savings at the pump. To be most effective, air quality and GHG environmental strategies must fit within a broader context that includes the need for secure and diverse energy supplies, cost competitiveness, production and end-use energy efficiency, renewable power utilization, and clean energy innovations such as the use of CO2 as a fuel feedstock. Methanol has great potential as a Towards that end, CARB and the Legislature should adopt an Open Fuel Standard which would provide incentives for auto manufacturers to deploy fully flexible fuel technology, capable of using both methanol and ethanol, to enhance consumer choice and to reduce the commercialization risks faced by renewable methanol producers to pursue this pathway as a means of expediting the success of the Low Carbon Fuel Standard. The including mixed alcohols containing methanol in GEM blends, as an explicit component of the CARB tool box. This paper lays out the major reasons that it is now time to add vehicles and marine applications.
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HIGHLIGHTS
There is a pressing need for a robust range of options, including
Recen carefully scrutinized. Auto manufacturers are faced with an unprecedented integrative
reduction and air quality goals, including the deployment of much higher efficiency engines, downsized engines, ultra-low well-to-wheels GHG emissions, ultra low and near zero criteria and toxic emissions, and maximum application of electric drivetrain technology; To be fully successful, OEMs and oil companies will need to significantly broaden their engine and fuel design templates; Engines optimized for high octane methanol fuels offer high efficiency, inherently low PM and NOx, opportunities for engine downsizing, and help enable the commercialization of renewable methanol with ultralow carbon intensity. Pioneering innovations in the US, Europe, China, Israel and Australia have documented important opportunities for optimized methanol engines to achieve and exceed the energy efficiency of diesel engines; The atmospheric reactivity of methanol is recognized to have lower ozone forming potential compared to the olefins and aromatics present in gasoline; A recent major study by a team of experts from GM, Ford and FiatChrysler has shown that high octane oxygenated fuels can play a significant role in improving engine efficiency; The chemical simplicity of methanol is one of its important strengths, compared to the long hydrocarbon molecules present in finished gasoline. Unlike gasoline, there are no carbon-carbon bonds in methanol, which translates directly into low particulate matter or GEM blends offer an elegance direct path to market as they can be readily formulated to achieve the equivalent octane, latent heat, Btu content and air-fuel stoichiometry of E85 used in current flexible fuel vehicles (FFVs); Moving past low volume ethanol blends would provide a more favorable and broader mix of benefits and synergies with petroleum reduction, air quality and GHG reduction. Oxygenated fuels such as methanol have been shown to reduce polycyclic aromatic hydrocarbons which are the backbone of diesel toxicity.
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Ultra-low carbon intensity renewable methanol industrial scale commercialization is already underway in Iceland, the Netherlands, and Canada. If renewable methanol is coupled to ultra-efficient combustion, and thus a higher Energy Economy Ratio (i.e., EER values defined by CARB), and then applied to a Plug-in Hybrid Electric Vehicle (PHEV) platform, a strong synergy could be enabled such that up to an 80% GHG emission reduction could be achieved without necessitating 100% complete electrification through the total replacement of liquid fuels with electricity. Methanol should be considered as a leading option within the context of the the Department of Energy’s Co-Optimization of Fuels and Engines (OPTIMA) Initiative to achieve significant fuel efficiency, emission reductions and GHG benefits. Methanol can be used in fuel cell applications as a high density carrier of hydrogen for PEM fuel cells, and in direct methanol fuel cells. Methanol-based fuel cell vehicles are in current demonstration in Denmark by Serenegy. The deployment of over 17 million flexible fuel vehicles in the U.S. represents the largest alternative fuel compatible fleet ever achieved, and while ethanol demand for FFVs has remained flat at just 40 million gallons per year over the past five years, it is essential that this deployment be continued and leveraged fully. Methanol-based GEM blends offer an un-leveraged opportunity to extend the reach of the existing 14+ billion gallons of conventional ethanol, while also creating a clear market signal to OEMs and fuel providers to make long term investment in alcohol compatible infrastructure. Both alcohols ethanol and methanol offer major advantages to auto manufacturers when facing difficult emissions in-use compliance challenges associated with gasoline or diesel direct injection technology At a wholesale price of $1.05 per gallon FOB Gulf Coast (as of December 31, 2015), methanol remains generally cost competitive with gasoline at prices above $2.10 per gallon.
long term role for methanol, including renewable methanol, as a viable path to address increasingly stringent international rules on NOx and SOx emissions; The methanol industry urges the California Air Resources Board to take full advantage of the new opportunities available with advanced methanol technology, in the light duty, heavy duty, and marine segments. It is strongly recommended that CARB endorse the Open Fuel Act of 2015 (H.R. 4047), and pursue complimentary legislation for 8
California. Such legislation would be a profound step in creating a clear market signal to OEMs and fuel providers to make long term investment in alcohol compatible infrastructure. Once such signals are communicated to the market, a renaissance in methanol engine, methanol-compatible hybrids, fuel cell technology optimization and renewable methanol production from CO 2 feedstocks and renewable power generation will be unleashed.
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I. THE CALIFORNIA AND U.S. NATIONAL CONTEXT emission reduction targets to address the dire challenge of global climate change.2 To expedite the 80% reduction GHG emissions relative to 1990 by 2050 as called for under a state Executive Order, Governor Brown has proposed that California achieve a 50% reduction in petroleum use by 2030. Most recently, the California Air Resources Board (ARB) has sought comments and recommendations on a farexpedited basis. Such efforts are essential for focusing auto manufacturers, energy companies, investors, consumers and public interest groups on sustainable research, development and commercialization paths.3
Renewable Fuel Standard remains a major driving force in stimulating the use of oxygenated fuels such as ethanol and biodiesel. However, and population growth have been raised by a diverse range of stakeholders, notably by the Palo Alto Research Center: exists which globally is between 20% and 30% by energy at current usage 4 The Congressional Research Service has also noted that the projections for the supply of cellulosic biofuels are highly questionable: Questions exist about the ability of the U.S. biofuels industry to meet the expanding mandate for biofuels from non-corn sources such as cellulosic biomass materials, whose production capacity has been slow to develop, or biomass-based biodiesel, which remains expensive to produce owing to 5
approach to addressing several inter-related public health and energy imperatives. The severe and persistent air quality challenges in the South Coast Air Basin further amplifies the importance of expediting all feasible and cost effective measures to reduce NOx and PM2.5. According to the ARB, the emission trends reflecting the implementation of currently adopted standards will still result in a major non-attainment status for the South Coast Basin well beyond 2030. Furthermore, on a statewide basis, ARB projects a significant deficit in GHG emission control measures by 2030 and beyond. Figures 1 and 2 highlight the gap in NOx and GHG controls which need to be filled with additional emission control measures.6 All of these trends point to one unavoidable conclusion. Fundamentally, there is a pressing need to add additional tools to the
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significantly reduce community exposure to toxic emissions.
In light of the sobering need to address these issues, it is critically important that a sober and renewed assessment be made of the realistic steps needed to bring about a massive 50% transition away from petroleum based fuels within a 15 year time frame. The future deployment rates of full battery electric and hydrogen fuel cell vehicles, for example, remain highly uncertain. It is instructive, for example, that a recent E3 found that by 2030, even under a fast transition scenario for battery electric and fuel cell vehicle technologies, a 50% reduction in petroleum fuel use by 2030 would not be feasible, although a 36% reduction in GHG emissions in CA would be expected by that time.7 As the primary author of that study, Amber Mahone, testified to the California Assembly recently: are robust to uncertainties, 8
Adding to this perspective is a major study of diverse fuel substitution scenarios by the Great Lakes Bioenergy Research Center and the Wisconsin Energy Institute. This study found that low carbon liquid fuels are essential to ensure the Governor's petroleum and GHG goals for 2030 and beyond are met: -seven scenarios were benchmarked against a 50% petroleum-reduction target and an 80% GHG-reduction target. We found that even at a relatively high rate of electrification (40% of miles and 26% by fuel), an 80% GHG reduction could only be achieved with significant quantities of low-carbon liquid fuel in cases with low or moderate travel demand growth." 9 -90s, led by the California Energy Commission in cooperation with the California Air Resources Board, was fundamentally a technical success. The scope of the state’s methanol program was impressive:
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Sixty retail stations operated by seven major oil companies, all with integrated single payer credit cards; The first large scale production of Flexible Fuel Vehicles which reached 17,500 M85-compatible vehicles, the technology platform which became the foundation for the ethanol-based FFV Brazilian “miracle” which achieved the complete phase out of gasoline-only vehicles; Over 200 million miles of successful vehicle operating experience along with a zero-incident health and safety record; Successful demonstration of a commercial scale Methanol Fuel Reserve wholesale fuel distribution system, coupled to wide-scale consumer retail refueling in which fuel sales of up to 2 million gallons per month were realized; Wide scale OEM methanol FFV production, including the Ford Escort, Crown Victoria, and Taurus; GM Corsica and Lumina; Chrysler Intrepid and Concorde, Dodge Spirit, and Plymouth Acclaim and Voyager; Toyota Corolla, Mazda Protégé, Nissan Stanza and NX200, Mitsubishi Galant, Mercedes 300, Volvo 940 and the VW Jetta; At least one major oil company - Chevron – converted its entire downstream infrastructure of storage tanks, pipelines and tanker distribution to be compatible with methanol by the late 1990’s, although that was not acknowledged publicly until over a decade later.
However, despite the establishment of a California Fuel Methanol Reserve (CFMR) the low oil price during that period presented major competitive challenges, as reflected in Figure 3.10 Figure 3
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In addition to the prevailing global oil price trends during that period, there were other structural market barriers which severely constrained the effective competition of methanol with gasoline. Although the CFMR effective established a competitive wholesale price for M85, the retail margins could not be controlled by the methanol industry, as they were heavily influenced by oil company retail zone pricing criteria . Other factors contributing to the decline of methanol at that time was the introduction of MTBE-based reformulated gasoline, along with evolutionary changes in engines and drive-trains, including hybridization. There were many important lessons learned that remain relevant for the re-engagement of methanol as an air quality, GHG, energy efficiency and energy diversification strategy. Among the positive outcomes of the California program was an extensive technical literacy which was gained in the following areas:
Distillation Properties Water Solubility Material Compatibility in FFVs Vehicle Emission Impacts (e.g., HCHO standard adopted and easily complied with via close coupled catalysts)
Octane Effects Blending Vapor Pressure Toxicity of Vapors Risk Mitigation (e.g., flame arrestors, antisiphoning devices)
FUEL i. Ultra-high Efficiency Characteristics: Methanol’s fuel properties provide certain key advantages with respect to vehicle engine efficiency. Past pioneering innovations by Lotus Engineering and EPA have led to important insights on the potential for ultra-high efficiency methanol engines, including the potential to exceed the efficiency of even diesel engines. 11 Research in China, Australia, Israel and the EU continues to build on this foundation. Methanol production and engine optimization research is underway at various EU universities, including Bath University in the UK, the University of Ghent and the DTU, the Technical University of Denmark. Fuel blending research, development and commercialization focused on Gasoline Ethanol Methanol (GEM) blends is also underway in Australia, by Coogee Chemicals in association with ProDrive and Orbital, through the testing of GEM vehicles including a 2013 Toyota Camry Altise and a 2012 Ford Mondeo Zetec.
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In Israel, Dor Chemical has undertaken an extensive field trial of methanol blends. And in China significant efforts are underway at several auto manufacturers including Geely, Cherry, Shanghai Automotive and Maple; at various universities including the State Key Lab of Engines at Tianjin University and the Center for Global New Energy Strategy Studies at Peking University; and other organizations such as the China Association of Alcohol and Ether Clean Fuels and Automobiles (CAAEFA) and the Shanxi New Energy Automobile Leadership Office.12 A new era of high-octane GEM fuels, combined with higher compression ratios, engine downsizing, higher torque response, higher horsepower is a tt Brusstar has shown that methanol use in spark ignition engines allows higher efficiencies by increasing the engine knock limit (see Figure 4), and that methanol has much higher flame speed (see Figure 5), which allows for tighter combustion control and more precise torque management. Improving knock performance is important to help avoid undesired detonation while also allowing for highly effective recovery of energy these character 110 is higher than premium unleaded gasoline at 93, its effective octane is even higher up to 130 when methanol is directly injected. Figure 4 - Efficiency vs Load @ 2,000 Figure 5 - Flame Speed vs F/A ratio rmp
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These factors allow methanol to run at much higher compression ratios than gasoline engines, allow higher turbo charging pressure, and opportunities for engine downsizing and down speeding. Methanol engines are also expected to facilitate the wider deployment of direct injection technology by having inherently lower PM mass and particle number due to the lack of carbon-carbon bonds in methanol, unlike gasoline. Cummins ethanol engine technology has also advanced significantly in this regard. MIT researchers have also found that methanol use in a diesel engine could allow downsizing of a 9 liter engine to 5.5 liters, while having 30% more power. Waste heat recovery can also allow for the use of hydrogen-rich gas, which would allow heavier EGR at lower load, compared to current technology diesel engines. When all of these inherent properties are considered holistically, super-efficient spark ignition methanol engines in the light duty and medium duty segment approaching the efficiency of fuel cells is feasible, as shown in Figure 6.13
Figure 6 – Efficiency Trajectory for Spark Ignited Methanol Engines
Lotus Engineering has also documented the substantial efficiency potential of Gasoline-Ethanol-Methanol (GEM) blends which have the same air fuel ratio as E85. These so-called iso-stoichiometric blends (i.e., blends with the same stoichiometric properties), provide substantial opportunity to extend the reach of ethanol by the blending of methanol 15
for use in flexible fuel vehicles. For example, the octane levels of all isostoichiometric GEM blends (i.e., blends with identical air/fuel ratios) have consistently higher octane than gasoline, as shown in Figure 7.14 With respect to GEM blends, Lotus has also found a remarkable positive synergies as all GEM blends have the same air fuel ratio, gravimetric and volumetric heating values, octane, heat of vaporization, and O2 sensor output as E85, and are therefore compatible with E85 calibrated FFVs from a combustion standpoint (see Table 1). Table 1
Figure 7 – GEM Octane Values
Although the energy density of methanol is roughly half that of gasoline on a nominal basis, Lotus Engineering has also found that there are other important properties which enable higher incremental efficiency. 15 A recent major study by a team of experts from GM, Ford and FiatChrysler has shown that high octane oxygenated fuels can play a significant role in improving engine efficiency. This OEM study concluded that there are several quantifiable benefits associated with the use of alcohol fuels: (1) a compression ratio increase enabled by an increase in knock resistance, (2) an efficiency increase from the CR increase, (3) an efficiency increase multiplier from additional downsizing, and (4) an efficiency increase from increasing alcohol content. The specific engine efficiency and CO2 emission benefits of alcohol-driven octane effects is provided in Table 2.16 Table 2 Summary of Recommended Parameters for Engine Efficiency and CO2 Emissions with Higher CR Enabled by Higher Octane Fuel
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ii. Methanol Air Quality and GHG Benefits Methanol offers a significant near and long-term opportunity for OEMs to through the optimized use of high octane methanol compatible vehicles, and ultimately through the introduction of renewable methanol from waste CO2 and renewable power generation as well as biomass environmental and emission reduction benefits, such as the following:
Inherently lower NOx and PM due to its low temperature combustion properties; A lack of carbon-carbon bonds which results in inherently ultra-low particulate emissions; In-sa -use catalyst performance, in contrast to diesel engine complex selective catalytic reduction (SCR) and Lean NOx Trap (LNT) with very narrow or non-existent margins of compliance (e.g., VW worse case); Potential for ultra-low well-to-wheel GHG emissions from the use of renewable methanol; High thermal efficiency due to the use of higher compression ratio engine downsizing; Ultra-low knock limit due to its high octane and latent heat properties, further enhancing turbo-charged high compression DI technology;
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Higher power and greater engine down-sizing potential than gasoline technology; Higher torque and power response for a given engine size, due to its faster flame propagation coupled to its high octane value; Strong synergy and reinforcement of hybridization and electric drive train utilization in electric and fuel cell vehicles; Low incremental cost of flexible fuel technology capable of running on gasoline-ethanol-methanol (GEM) blends; In-use emissions confidence for consumers, regulators and OEMs behavior to maintain system compliance, methanol engine out emissions are far lower than diesel engine out emissions and more amenable to less complex emission system design.
The chemical simplicity of methanol is one of its important strengths, compared to the long HC molecules present in finished gasoline. Unlike gasoline, there are no carbon-carbon bonds in methanol, which translates directly in low PM formation potential. Figure 8 shows the dominance of C1 compounds in M85 compared to the much higher carbon content of reformulated gasoline.17 Figure 8 – Carbon Number Distribution: M85, M50 and RFG
Figure 9 Ozone Yield for Various Exhaust Compounds
The atmospheric reactivity of methanol is recognized to have lower ozone forming potential compared to the olefins and aromatics present in gasoline, as shown in Figure 9.18 The lower flame temperature of methanol has been shown to have consistently lower NOx emissions compared to gasoline. A recent Ghent University study performed by the Department of Flow, Heat and Combustion Mechanics indicates that diesel-equivalent efficiencies are possible with M100 engines, with NOx emissions readily controlled (up to 95% reduction) using simple EGR systems. And research performed in China at the Tianjin University State Key Laboratory for Engines has shown that methanol use in diesel cycle engines can have a measurable and beneficial effect on particle size
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distribution, a key parameter in determining public health exposure levels to fine particle pollutants. These research finding are shown in Figure 10 below. Figure 10
Methanol Efficiency, NOx and PM Size Distribution Benefits 19
Other recent testing by Ghent University on a Volkswagen passenger car converted from a turbo diesel configuration to run as a port fuel injected methanol engine demonstrates dramatic efficiency and emission reduction benefits resulting from the inherent fuel quality advantages of methanol in terms of octane, latent heat of vaporization, and flame speed, as shown below in Figure 11: 20 Figure 11 – Methanol Properties and Efficiency Test Data
Significant NOx reduction of methanol has also been demonstrated in tests performed by Lotus Engineering and Saab, as reported at MIT and shown in Figure 12 21 Similar results have been confirmed recently in testing at Bath University, where NOx reductions of more than 70%
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relative to the 0.06 g/km NOx standard have been demonstrated in optimized engines, as shown in Figure 13. 22 Figure 12
-
Methanol NOx Reduction Figure
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GEM
Blend
NOx
Impacts
Potential
Methanol substitution for gasoline and diesel would also provide significant toxicity benefits even when formaldehyde emissions from methanol use are taken into account, as suggested in Table 3.23 Formaldehyde (HCHO) control technology in ethanol-compatible FFVs is now quite robust and such catalysts are expected to readily control methanol HCHO emissions as well. CARB certification data of comparable FFV and non-FFV Mercedes engine families, for example, 15 mg per mile standard, as shown in Table 4. Table 3
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Table 4 Mercedes C240 FFV Formaldehyde Emissions
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With respect to methanol substitution for gasoline, researchers at U.C. Riverside have recently found that increased alcohol fraction in gasoline can help reduce PM mass and black carbon (BC) associated with gasoline direct injection engines (GDI).25 With respect to diesel substitution with methanol, oxygenated fuels such as methanol have been shown to reduce polycyclic aromatic hydrocarbons (PAH) emissions which are the cornerstone of diesel toxicity. A recent study by the Technical Research Centre of Finland has documented such benefits: The HACA-mechanism for PAH (and soot) growth do not involve reactions with oxygenated 26 [i.e., such as methanol]. Methanol is also being used in fuel cell applications as a high density source of hydrogen for PEM fuel cells, and in direct methanol fuel cells such as Oorja Protonics material handling equipment. Methanol-based fuel cell vehicles are in current demonstration in Denmark by Serenegy. the largest independent fuel retailer in Denmark. As a frame of reference, a commercial methanol refueling station would offer significant capital cost savings compared to its hydrogen refueling station counterpart. A methanol station capable of refueling a large scale fleet of thousands of methanol fuel cell vehicles would have a throughput capacity of over 1,000 kg-equivalent per hour of hydrogen, comparable to gasoline, and cost less than 0.5% of the capital cost of a gaseous or cryogenic H 2 station with the same fuel throughput capacity. To put this into further perspective, 50 MW of power would be needed to produce 1,000 kg/hour of H2 through on-site water electrolysis. Methanol fuel cell vehicles, such as those being commercialized by Serenergy, therefore offer a significant path to realizing the ultimate sustainable mobility challenge laid out by California; such a path would avoid sacrificing the long recharge times associated with battery electric vehicles while avoiding the vast capital requirements inherent in any serious, large scale transition to a hydrogen refueling infrastructure capable of gasoline-equivalent station throughput.
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Argonne National Lab, in collaboration with General Motors, has evaluated a wide range of alternative fuel scenarios, including methanol, in terms of well-to-wheel GHG emissions. They have found that methanol fuel cells coupled to hybridized electric drivetrains utilizing on-board methanol reforming into hydrogen, similar to the Serenergy PEM fuel cell technology, would have significantly lower GHG emissions compared to fuel cell vehicles using either gaseous or cryogenic (liquid) hydrogen derived via electrolysis using natural gas from North America utilizing state-of-the-are combined cycle turbines, as shown in Figure 14. 27 Figure 14 – GHG Impacts of Methanol/Hybrid FC Vehicles vs H2 FC Vehicles
iii. Fuel Production Pathways: Sustainable Liquids
Towards Fully
The methanol supply resource base is especially robust, in the face of growing supplies of low-cost natural gas, as shown in Figure 15.28 A large scale re-introduction of methanol optimized vehicles could easily be served by growing methanol production capacity, particularly in North America, as shown in Figure 16.29 natural gas supply base for methanol production and use in the U.S. diversity. Methanol can be produced from captured methane emissions which would otherwise be flared at remote oil production sites. The methanol industry has a history 22
of providing excess production capacity to serve its core markets, and the transportation market would not be an exception to that practice. Figure 15
Figure 16
Methanol remains generally very cost competitive with gasoline as shown in Figure 17. 30 Figure 17
Methanol-based GEM blends offer a major opportunity to extend the reach of the existing 14+ billion gallons of conventional ethanol, while also creating a clear market signal to OEMs and fuel providers to make long term investment in alcohol compatible infrastructure. For example, at a wholesale price of $1.05 per gallon FOB Gulf Coast (as of December 31, 2015), methanol remains generally cost competitive with gasoline at prices above $2.10 per gallon.
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The industrial scale production of ultra-low carbon intensity renewable methanol is already underway in Iceland, Netherlands, and Canada. For example, in Iceland, Carbon Recycling International is capturing and reacting CO2 from geothermal power generation with renewable hydrogen produced via electrolysis into renewable methanol. In the Netherlands, BioMCN converts crude glycerin a residue from processing vegetables and animal fats into advanced second generation biomethanol. In Canada, bio-methanol is being produced from municipal solid waste feedstocks by Enerkem. Enerkem’s Alberta Biofuels facility in Edmonton has the capacity to convert 100,000 dry tons of MSW into 43 million liters per year of methanol, as well as other biofuel products such ethanol. Their remote plant, shown below, will bring Edmonton’s recycling rate from 60% to 90%.
Renewable methanol is fully miscible with conventional fossil methanol and offers a highly scalable renewable liquid fuel pathway without the risk of indirect land use change, fertilizer overuse, and top soil erosion risks associated with conventional corn ethanol. Renewable Methanol from the CRI facility has been independently reviewed by the International Sustainability and Carbon Certification protocol and been assigned a wellto-wheels carbon intensity less than 10 grams of CO2-e per MJ, as shown in Figure 19. 31
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Figure 19 Intensity
Renewable Methanol Carbon
Furthermore, if renewable methanol is coupled to ultra-efficient combustion, and thus a higher Energy Economy Ratio (i.e., EER values defined by CARB), and then applied to a Plug-in Hybrid Electric Vehicle (PHEV) platform, a strong synergy could be enabled such that up to an 80% GHG emission reduction could be achieved without necessitating the 100% complete electrification through the total replacement of liquid fuels with electricity. It is also instructive to compare the underlying energy efficiency of Power-to-Liquid (PtL) technology with Power-to-Gas technology, as both have a key role to play in utilizing stranded or underutilized renewable power capacity. Analysis performed by the Center for Solar Energy and Hydrogen Research (ZSW) in Stuttgart, Germany suggests that the PtL technology, similar to that utilized by CRI, is 10% more efficient than PtG technology used in such projects as the Audi EtoGas program, as shown in Table 5.32 A during the mid-1990s, Volkswagen undertook a detailed assessment of converting atmospheric CO2 and renewable hydrogen into renewable methanol, as summarized in Figure 20. However, it is noteworthy that VW chose not to pursue this technology trajectory, and instead embarked on its soReport, VW went so far as to specifically highlight the sustainability advantage of renewable methanol derived from a closed CO2 cycle, as shown in Figure 21.33
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Table 5
Figure 20
VW acknowledged the significant potential of methanol in this report as follows: the alcohols, methanol in particular and, with certain reservations, ethanol too represent interesting supplements or alternatives to conventional fuels. These are outstanding fuels for both diesel and spark-ignition engines, in part producing higher levels of efficiency while at the same time emitting less pollutants. Volkswagen and its partners will be developing a hybrid fuel cell vehicle incorporating methanol reformation in a project subsidized by the European Union. In addition to the extremely low emission levels of the proposed vehicle, amounting to between one-tenth and one hundredth of those of an ultralow emission vehicle (ULEV). Needless to say, VW would have been far better off to have seriously pursued this pathway rather than its dead end diesel LNT technology. Lotus Engineering has updated the renewable methanol vision as shown in Figure 22. California should vigorously endorse and support this powerful strategy as a means of enabling the ultimate de-carbonization of the atmosphere. 34
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Figure 21
VW CO2 Recycling Vision
Figure 22
Lotus Vision
III. METHANOL MARINE APPLICATIONS:
There is increasing international pressure, as well as CARB focus, on marine vessel emissions. Under the International Maritime Organization, Emission Control Areas (ECA’s) have been established to regulate both sulfur and NOx emissions. The California Air Resources Board has also adopted regulations which govern the fuel sulfur and other operational aspects of marine vessel operation within the state’s waters and its 24 nautical mile U.S. boundary. These regulations, which go beyond the IMO regulations, are designed to reduce particulate matter (PM) and NOx emissions to very stringent levels, as well as sulfur oxide emissions from oceangoing vessels. Both the CARB and local air quality management districts such as the South Coast Air Quality Management District have placed a high priority on reducing port-related emissions, which continue to present one of the most serious air quality and public health challenges. Stringent rules are already in place, and additional measures are under development in a variety of source categories, including harbor craft, ocean going vessel fuel use, ocean going vessel on-shore power, and ocean going speed restrictions. Methanol use in marine engines offers a significant means of supporting the implementation of both IMO and CARB
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requirements. Methanol use in marine engine applications would also provide significant NOx and PM benefits. Recent testing by Stena has demonstrated that NOx emissions can be decreased by up to 70% while achieving parity with diesel cycle marine engines, as shown in Figures 23 and 24. 35 Figure 23 Marine Engine NOx Emissions
Figure 24 - Marine Engine Methanol Efficiency
Unlike diesel cycle engines in either marine or on-road applications, methanol use does not present a tradeoff between low particulate emissions and low NOx emissions as an inherent aspect of fuel combustion. Testing by Wartsila in marine cycle medium speed engines has demonstrated these benefits, as shown in Figure 25.36 Figure 25 Methanol Marine Engine NOx and Efficiency Impacts
methanol, including renewable methanol, as a viable path to address increasingly stringent international rules on NOx and SOx emissions, incorporating an increasing penetration of renewable methanol, as shown in Figure 26.37 Figure 26
Stena Marine Fuels Assessment
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Major marine engine manufacturer Wartsila is especially optimistic on the potential for methanol to address a wide range of environmental and sustainability goals: "Methanol can be a competitive alternative. From the perspective of fuels, GHG targets can be fulfilled by gradually increasing the amount of GHG neutral methanol produced from captured CO2 and hydrogen produced with wind, water, sun and geothermal energy." 38
V. THE WAY FORWARD A TRANSITION PATH TO REINTRODUCING METHANOL 29
The deployment of over 17 million flexible fuel vehicles in the U.S. represents the largest alternative fuel compatible fleet ever achieved, and it is essential that this deployment be continued and leveraged fully. s vehicle fleet may stall considerably as the result of the expiration of CAFÉ credits after the 2016 model year. The development of Gasoline-Ethanol-Methanol or GEM blends offer an elegant direct path to market, as such fuel formulations can be readily formulated to achieve equivalent octane, latent heat, Btu content and air-fuel stoichiometry to E85 used in current flexible fuel vehicles. Figure 27 shows the robust flexibility in blending to achieve equivalence to E85 fuel properties. 39 The use of GEM blends would directly enhance the gasoline displacement potential of ethanol. The Energy Information Agency recently concluded in its December 2015 Short Term Energy Outlook that E85 consumption is not expected to increase in 2016. The incorporation of ethanol within the context of GEM blends would enhance its commercialization as GEM blends are expected to be cheaper than E85, especially given the persistent low price levels of natural gas feedstocks. Figure 27
GEM Blends Equivalent to E-85 Stoichiometry
Based on this elegant set of synergies, GEM blends offer an important enabling set toward realizing ultra-high efficiency combustion engines which incentivizes the production of FFVs and other clean fuel vehicles would be a powerful signal to the auto and the oil industry. The current trajectory of tougher and tougher tradeoffs for gasoline and diesel engines between PM and NOx emissions on the one hand, and fuel economy on the other, is neither necessary nor sustainable. Methanol30
based GEM blends offer an un-leveraged opportunity to increase octane levels while extending the reach of the existing 14+ billion gallons of conventional ethanol to a larger aggregate number of vehicles. The Open Fuel Act, of 2015 ( HR 4047 (Engel, NY) would codify an Open Fuel Standard. The basic idea behind the Open Fuel Act is that consumers are currently being denied broad and practical choices of alternative fuel vehicles. Under H.R. 4047, each fleet, in the aggregate, of a light duty vehicle manufacturer would be required to comprise of at least the following:
30% qualified vehicles in model year 2018, and 50% qualified vehicles in model year 2019 and each subsequent year.
A "qualified vehicle" is considered any of the following:
A vehicle that operates on natural gas, hydrogen, or biodiesel; A flexible fuel vehicle capable of operating on gasoline, E85, and M85; A plug-in electric drive vehicle; or A vehicle propelled solely by fuel cell or by something other than an internal combustion engine.
The legislation would authorize a manufacturer to request an exemption from such requirement from the Department of Transportation. An Open Fuel Standard in California would be a strong step in creating a clear market signal to OEMs and fuel providers to make long term investment in alcohol compatible infrastructure.40 Once such signals are communicated to the market, a renaissance in methanol engine, methanol-compatible hybrids, and fuel cell technology optimization will be unleashed. Ultimately such GEM blends could transition to dedicated and optimized alcohol vehicles designed to achieve even higher thermal efficiency than is possible solely with gasoline or ethanol alone, through low temperature on-board reforming of methanol to hydrogen, to further increase engine efficiency, based on technology developed at MIT.41 The role of methanol was highlighted in a major interdisciplinary study on the role of natural gas conducted by the MIT Energy Initiative. This study was chaired by MIT Professor of Physics and Engineering Systems Dr. Ernest Moniz, the current Secretary of the U.S. Department of Energy. Specifically, one of the major conclusions of the study was that methanol provides a very cost-effective path for both the auto and natural gas industry, and that an open fuel standard would provide significant advantages going forward: “The advantages of liquid fuel in transportation suggest that the chemical conversion of gas into some form of liquid fuel may be the best pathway to 31
significant market penetration. Conversion of natural gas to methanol, as widely practiced in the chemicals industry, could provide a cost-effective route to manufacturing an alternative. Gasoline engines can be modified to run on methanol at modest cost. The U.S. government should implement an open fuel standard that requires automobile manufacturers to provide tri-flex fuel (gasoline, ethanol, and methanol) operation in light-duty vehicles. Support for methanol fueling infrastructure should also be considered.42 A reinvigorated methanol focus in California would build on growing international efforts in that regard. For example, a recent report issued by the European Parliament’s Research Service highlighted the importance and relevance of CO2-tomethanol pathways for achieving sustainable transportation fuels. The Science and Technology Options Assessment (STOA) study proposes a series of policy options to promote the use of CO2 captured from flue gases for the production of methanol and use in transport. The report also recognizes the significant synergy between renewable methanol and an Open Fuel Act (H.R. 4047): “The conclusions in the form of policy options suggest possible answers on how to overcome the technological and economic difficulties presently associated to CO2 capture and conversion processes, as well as the opportunities which may arise from greater fuel variety in transport, among them methanol, and from putting recycled CO2 to use by turning it into a potentially valuable prime material. The revised, but not yet approved, flexible fuel standard in the US holds promise for the diversification of the transport fuel mix and new power-train technologies, which, applied to Europe, could theoretically raise methanol use in private gasoline cars to 41.8 - 71.1 million tons of methanol and lead to the recycling of 68.7 to 104.3 million tons of CO2.” 43 There are also important synergies between California and China which can be realized with respect to methanol vehicle research, development, regulatory refinement and vehicle commercialization. China has emerged as a 21 st century leader in methanol technology development and deployment. There are now 20 separate methanol models – ranging from M15, M30, M85 and M100 applications – in light duty and heavy duty applications. Chinese automakers like Cherry, Geely, Shanghai Automotive, and Maple have deployed cars that can run on methanol. In 2014, Geely commissioned China’s first high volume methanol vehicle production plant, capable of producing 200,000 methanol engines and vehicles per year, in the city of Jinzhong in Shanxi Province. Geely Group, the owner of Volvo, also recently announced a major strategic investment in the renewable methanol producer Carbon Recycling International. And in 2014, methanol fuel blending - primarily in the form of M15 - surpassed 3 billion gallons.
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The geographic scope of China’s methanol deployment has evolved to include 11 major cities in 5 provinces, as shown in Figure 28. 44 Figure 28 – Methanol Fuel Blends Used in China
The pathway for a viable re-launch of methanol as a transportation fuel option will require the concerted cooperation and investment by a wide range of stakeholders. Towards that end, the methanol industry, through the Methanol Institute, is participating in the Department of Energy’s Co-Optimization of Fuels and Engines (OPTIMA) Initiative aimed at identifying new combustion engine strategies optimized for “new fuels” which offer significantly higher efficiency and lower pollutant emissions combined with reduced GHG. This
goals, it is incumbent on California and national policy makers and decision leaders to not categorically reject methanol based on preinternet and pre-iPhone era assumptions and analysis. The methanol industry urges the California Air Resources Board to take full advantage of the new opportunities available with advanced methanol technology, in the light duty, heavy duty, and marine segments. The following Technology Evolution Pathway is illustrative of the sequential market and technology logic which should be considered as policies and control measures are fashioned.
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The methanol industry looks forward to working cooperatively will all stakeholders toward this vision.
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REFERENCES 1
2
For example, the annual average price of oil between 1986 and 2000, according to the EIA, was $15.22. http://www.eia.gov/dnav/pet/hist/LeafHandler.ashx?n=pet&s=f000000__3&f=a The Global Warming Solutions Act, California Assembly Bill 32 (AB32), 2006
3 The fundamental need for these targets is underlined by the persistent rise in atmospheric CO2 concentration now at 400 ppm and steadily rising, and its implications for dire disruption of ecological cycles, water resources, air quality, economic growth, public health and welfare, and even national security. 4
5
6
7
8
9
10
“Extending the Supply of Alcohol Fuels For Energy Security and Carbon Reduction”, R.J. Pearson and J.W.G. Turner, Lotus Engineering, and M.D. Eisaman and K.A. Littau, Palo Alto Research Center, SAE 2009-01-2764; "Renewable Fuel Standard (RFS): Overview and Issues", by Randy Schnepf, Specialist in Agricultural Policy Brent D. Yacobucci Section Research Manager, Congressional Research Service, March 14, 2013 “Mobile Source Strategy Discussion Draft”, California Air Resources Board, September 2015,http://www.arb.ca.gov/planning/sip/2016sip/2016mobsrc_dd.pdf “Summary of the California State Agency’s PATHWAYS Project: , Long-term Greenhouse Gas Reduction Scenarios”, https://www.ethree.com/documents/E3_Project_Overview_20150127.pdf Amber Mahone, Testimony to Hearing on the Future of Transportation Fuels in California, Assembly Select Committee on California’s Clean Energy Economy, Assembly Bill Quirk chairman, June 17, 2015. “Potential for Electrified Vehicles to Contribute to U.S. Petroleum and Climate Goals and Implications for Advanced Biofuels", by; Paul J. Meier et al, Great Lakes Bioenergy Research Center and Wisconsin Energy Institute, Biological Systems Engineering Department, University of Wisconsin, and Biomass Conversion Research Laboratory, Department of Chemical Engineering and Material Science, and Great Lakes Bioenergy Research Center, Michigan State University, Environmental Science & Technology, Vol. 49: Issue. 14: Pages. 8277-8286, Volume publication date: July 2015. “Methanol as an alternative transportation fuel in the US: Options for sustainable and/or energy-secure transportation”, Bromberg and Cohn, MIT, Sloan Automotive Lab, November 2010
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11
Numerous studies have been published by Lotus and EPA related to methanol engine development and optimization. Among these studies are the following: (a) “Extending the Supply of Alcohol Fuels for Energy Security and Carbon Reduction”, R.J. Pearson and J.W.G. Turner Lotus Engineering, Norwich, Norfolk, UK; and M.D. Eisaman and K.A. Littau, Palo Alto Research Center, Palo Alto, CA, USA, SAE 2009-01-2764, http://www.ourenergypolicy.org/wpcontent/uploads/2011/12/2009_LotusEngineeringP ARC_ExtendingAlcoholFuelSupply.pdf (b) “Alcohol-Based Fuels in High Performance Engines”, J. W. G. Turner, R. J. Pearson, B. Holland and R. Peck Lotus Engineering, SAE 2007-01-0056, http://www.pballandmore.com/Download/Alcohol_fuels_in_High_Performance_Engine s.pdf (c) "Economical, High Efficiency Engine Technologies for Alcohol Fuels”, M. Brusstar, EPA http://www.eri.ucr.edu/ISAFXVCD/ISAFXVAF/SuTCAF.pdf
12 In the EU, several university research efforts are underway: (a) Bath University: “GEM Fuels Development”, Jamie Turner, Bath University (formerly of Lotus Engineeing), 2015 European Methanol Forum, Brussels, Oct. 13 + 14, 2015 (b) Ghent University: Experimental and Numerical Work at Ghent University on Methanol Combustion in SI Engines,”, Prof. Sebastian Verhelst, Methanol Workshop, Lund, Sweden, March 17, 2015 (c) DTU: “Methanol Production from biomass and intermittent power”, Søren Højgaard Jensen, Senior researcher at DTU Energy, Lund University, Department of Energy Conversion and Storage http://www.lth.se/fileadmin/mot2030/filer/5._Hojgard__Methanol_Production_from_Biomass_and_Intermittent_Power.pdf see also: Jesper Schramm, "Development of HCCI Engines for DME", http://orbit.dtu.dk/files/52916634/Development_of_HCCI_Engines.pdf In Australia, Coogee and Orbital have undertaken significant testing: “Gasoline, Ethanol, Methanol (GEM): Australia’s Methanol Fuel Blending Program,” Coogee Chemicals, Nov. 14, 2013, http://www.fuelchoicesinitiative.info/files/gallery/Methanol_Fuel_Blending.pdf In Israel, Dor Chemical is undertaking a major assessment of M15, for which they received the 2014 Israeli Chemical Society for the Chemical Green Industry: http://techmail.technion.ac.il/22eab5511949a8fc06aaf81170fdebfe68e31e4f.pdf
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In China, numerous studies and deployment efforts are underway, including the following: (a) "Methanol Applied to Heavy Duty Vehicles in China", Professor Chunde Yao, State Key Laboratory of Engines, Tianjin University, Methanol on Heavy Duty Applications Workshop in Beijing, June 17, 2015 (b) "Methanol Fuel and Vehicles in China: An Overview of Industrial Applications", The China Association of Alcohol and Ether Fuel and Automobiles, 2014. 13
“Cleaner, More Efficient Vehicles Using Methanol Engines”, Daniel Cohn and Leslie Bromberg, MIT Energy Initiative, discussion ppt for Carbon Recycling International, September, 2015. see also: “Effective Octane And Efficiency Advantages Of Direct Injection Alcohol Engines”, Bromberg and Cohn, MIT Plasma Science and Fusion Center and MIT Laboratory for Energy and the Environment, https://mitei.mit.edu/system/files/200801-rp.pdf
14 “Extending the Supply of Alcohol Fuels for Energy Security and Carbon Reduction”, R.J. Pearson and J.W.G. Turner Lotus Engineering, Norwich, Norfolk, UK; and M.D. Eisaman and K.A. Littau, Palo Alto Research Center, Palo Alto, CA, USA, SAE 200901-2764, http://www.ourenergypolicy.org/wpcontent/uploads/2011/12/2009_LotusEngineeringP ARC_ExtendingAlcoholFuelSupply.pdf 15
“Alcohol-Based Fuels in High Performance Engines”, J. W. G. Turner, R. J. Pearson, B. Holland and R. Peck Lotus Engineering, SAE 2007-01-0056, http://www.pballandmore.com/Download/Alcohol_fuels_in_High_Performance_Engine s.pdf
16 “Team from GM, Ford, FCA reviews how to calculate engine efficiency benefits of high octane fuels”, August 25, 2015, http://www.greencarcongress.com/2015/08/20150825octane.html , Thomas G. Leone, James E. Anderson, Richard S. Davis, Asim Iqbal, Ronald A. Reese, II, Michael H. Shelby, and William M. Studzinski (2015) “The Effect of Compression Ratio, Fuel Octane Rating, and Ethanol Content on Spark-Ignition Engine Efficiency” Environmental Science & Technology doi: 10.1021/acs.est.5b01420 17 “FTP Emissions Test Results from Flexible-Fuel Methanol Dodge Spirits and Ford EconolineVans”, by Kenneth J. Kelly, Brent K. Bailey, and Timothy C. Coburn, National Renewable Energy Laboratory; Wendy Clark, Automotive Testing Laboratories, Inc., Leslie Eudy, ManTech Environmental Technology; Inc. and Peter Lissiuk, Environmental Research and Development Corp., Presented at Society for Automotive Engineers International Spring Fuels and Lubricants Meeting, Dearborn, MI, May 6-8, 1996 18 “Methanol Gasoline Blends”, http://methanol.org/Energy/Transportation-Fuel/FuelBlending-Guidelines/Blenders-Product-Bulletin-(Final).aspx
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19 “Experimental and Numerical Work at Ghent University on Methanol Combustion in SI Engines,” Prof. Sebastian Verhelst, Methanol Workshop, Lund, Sweden, March 17, 2015. http://www.lth.se/fileadmin/mot2030/filer/3._Verhelst__Ghent_Univ_on_methanol_com bustion_in_engines PM data from: “Methanol Applied to Heavy Duty Vehicles in China”, Professor
Chunde Yao, State Key Lab of Engines, Tianjin University, presented at Methanol in Heavy Duty Applications Workshop, Beijing, June 17, 2015 20 Verhelst, Ibid. 21
Turner, James, “Evolution of Alcohol Fuel Blends Towards a Sustainable Transport Energy Economy,” by J.W.G. Turner and R.J. Pearson of Lotus Engineering, E. Dekker of BioMCN, B. Iosefa of Methanex, G. Dolan of the Methanol Institute, and K. Johansson and K. Bergstrom of Saab Automobile Powertrain AB, presented at 2012 MIT Energy Initiative Symposium on Prospects for Flexible- and Bi-Fuel Light Duty Vehicles, April 19, 2012 https://mitei.mit.edu/system/files/2012-mitei-symposium-turner.pdf See also: “Demonstrating the Feasibility of Methanol Gasoline Blends to Reduce Petroleum Use in the United States”, by Michael Jackson and Peter Ward, for Fuel Freedom Foundation, Feb. 17, 2013. http://www.fuelfreedom.org/wp-content/uploads/MDJ-AFA-study.pdf
22 “GEM Fuels Development”, Jamie Turner, Bath University (formerly of Lotus Engineeing), 2015 European Methanol Forum, Brussels, Oct. 13 + 14, 2015, https://eu-ems.com/agenda.asp?event_id=269&page_id=2466 23
California Air Resources Board, Consolidated Table of OEHHA/ARB Approved Risk Assessment Health Values, March 2005; http://www.arb.ca.gov/toxics/healthval/healthval.htm
24 CARB certification. data compiled by the Paul Wuebben, Clean Fuels Officer, South Coast Air Quality Management District, 2006 25 “Components of Particle Emissions from Light-Duty Spark-Ignition Vehicles with Varying Aromatic Content and Octane Rating in Gasoline”, Environ Sci Technol. 2015 Sep 1;49(17):10682-91. doi: 10.1021/acs.est.5b03138. Epub 2015 Aug 17. 26 “Future Combustion Technology for Synthetic and Renewable Fuels in Compression Ignition Engines (REFUEL)” - Final report, Technical Research Centre of Finland (VTT), 2012, pg. 21, https://aaltodoc.aalto.fi/handle/123456789/7748. “The formation and growth of polycyclic aromatic hydrocarbons (PAH) is based on the HACA model by Frenklach et al. HACA is an abbreviation of H-abstraction C-addition. Additional reaction paths of PAH formation and growth for PAH between benzene and pyrene were adopted from Richter et al., together with several reaction paths for large polycyclic aromatics.”
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27
“Well-to-Wheels Analysis of Advanced Fuel/Vehicle Systems — A North American Study of Energy Use, Greenhouse Gas Emissions, and Criteria Pollutant Emissions”, by Norman Brinkman, General Motors Corporation, Michael Wang, Argonne National Laboratory; Trudy Weber, General Motors Corporation; and Thomas Darlington, Air Improvement Resource, Inc., May 2005. http://www.transportation.anl.gov/pdfs/TA/339.pdf
28 “Natural Gas Based Liquid Fuels: Potential Investment Opportunities in the United States”, conducted by Miles Light, Leeds School of Business, University of Colorado at Boulder, June 2014. 29 “Overview of Global Methanol Industry”, Mike Nash, Global Business Director, Syngas Chemicals, IHS Chemical, presented at 2015 European Methanol Forum, Brussels, Oct. 13 + 14, 2015, https://eu-ems.com/agenda.asp?event_id=269&page_id=2466
See also: IHS Chemical Market Advisory Service: Global Methanol (formerly CMAI), Methanol Global Supply Forecast, 2015 https://www.ihs.com/products/chemical-market-methanol-global.html 30
“Methanex Investor Presentation”, February, 2015. https://www.methanex.com/sites/default/files/investor/MEOH%20Presentation%20%20February%202015.pdf
31
"Certification schemes for CO2 based fuels and chemicals", Meo Carbon Solutions GmbH, Dr. Norbert Schmitz (ISCC), ppt presented at NOVA 2nd Conference on CO2: Carbon Dioxide as a Feedstock for Chemicals and Polymers, Oct. 7, 2013, as reported in "Proposals for a Reform of the Renewable Energy Directive to a Renewable Energy and Materials Directive (REMD)", NOVA Institute, May, 2014 http://www.nova-institut.de/download/nova-paper-4-remd See also: “Practical Marine Applications of Renewable Methanol”, Paul Wuebben, Senior Director, Renewable Fuels, Carbon Recycling International, at Symposium on the Evolution of Marine Fuels, University of Southern California, Sea Grant Program and Loker Hydrocarbon Research Institute, July 21, 2014 http://dornsife.usc.edu/assets/sites/291/docs/Presentations/WUEBBEN__MARINE_F UELS.pdf
32 “Experimental Data on Renewable Methanol / Methane Generation from Atmospheric CO2 in Pilot Plants”, Michael Specht, Ulrich Zuberbühler, Andreas Bandi, Centre for Solar Energy and Hydrogen Research (ZSW), Stuttgart, IASS PotsdamWorkshop, 2011, http://www.iass-potsdam.de/sites/default/files/files/specht_zsw_p2g.pdf
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33 http://en.volkswagen.com/content/medialib/vwd4/de/Volkswagen/
Nachhaltigkeit/service/download/umweltberichte/umweltbericht_1997eng lisch27mb/_jcr_content/renditions/rendition.file/umweltberichte_par_0015 _file.pdf 34 inable Organic Fuels for Transport (SOFT) Compatible Affordable Mobility Using CarbonPearson1, J.W.G. Turner, et al., Op. cit.
A Concept for
35 “A Ship Owners Perspective”, http://www.marinemethanol.com/publications/category/4methanol-as-a-marine-fuel See also: “Methanol as a Marine Fuel”, Wartsila, Lennart Haraldson, Gothenburg Promsus Workshop, May 8, 2014.
see also: "Methanol as a Marine Fuel Report", Professor Karin Andersson, Chalmers University of Technology, and Carlos Salazar, FCBI Energy, prepared for the Methanol Institute, October 2015 36
, Methanol Adaptation, Wartsila Sweden AB, Goteborg, +46 31 744 47 72, at 2015 European Methanol Forum, Oct. 13 + 14, 2015 https://eu-ems.com/agenda.asp?event_id=269&page_id=2466
37 Report from the Workshop , Gothenburg, Sweden, May 6-7, 2014 http://www.marinemethanol.com/phocadownload/promsus/promsus_folder-web.pdf
38 Per Stefenson, Stena, ppt presented at 2015 European Methanol Forum, Oct. 13 + 14, 2015. https://eu-ems.com/event_images/presentations/Per%20Stefenson_1.pdf A Concept for
39 Compatible Affordable Mobility Using CarbonPearson1, J.W.G. Turner, et al.,
see also: Energy Information Agency, "Short Term Energy Outlook", December 2015, http://www.eia.gov/forecasts/steo/pdf/steo_full.pdf 40 The Open Fuel Standard Act (H.R.2493) introduced by Congressman Engel (D-NY) and Congresswoman Ros-Lehtinen (R-FL) would phase in a requirement that up to 50 percent of new vehicles would be required to operate on non-petroleum fuels in addition to or instead of petroleum based fuels. See the following for more information: http://www.openfuelstandard.org/2013/06/the-open-fuel-standard-has-been.html
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41 sustainable and/or energyW.K. Cheng , Prepared by the Sloan Automotive Laboratory Massachusetts Institute of Technology, Nov. 28, 2010. http://www.afdc.energy.gov/pdfs/mit_methanol_white_paper.pdf
42
43
44
"The Future of Natural Gas: An MIT Interdisciplinary Study”, MIT Energy Initiative, http://mitei.mit.edu/system/files/NaturalGas_ExecutiveSummary.pdf
“Methanol: a future transport fuel based on hydrogen and carbon dioxide?”, Science and Technology Options Assessment, European Parliamentary Research Service, European Parliament, April, 2014. http://www.europarl.europa.eu/RegData/etudes/etudes/join/2014/527377/IPOLJOIN_ET(2014)527377_EN.pdf “Avenues for Collaboration: Recommendations for U.S. - China Transportation Fuel Cooperation”, United States Energy Security Council, 2015. http://www.iags.org/USChinaFC.pdf
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