Coal to Chemicals via MTO: Methanol to Olefins

Several leading industrial nations are beginning to substitute cheaper coal and and natural gas -- in place of more expensive crude oil -- in the production of high value "petrochemical" products, including valuable polymer feedstocks.

UOP LLC, a Honeywell company, announced today that China s Jiutai Energy (Zhungeer) Co. Ltd. has licensed Honeywell s UOP methanol-to-olefins (MTO) technology to convert methanol from coal into key plastics building blocks. Honeywell s UOP/Hydro MTO process converts methanol from gasified coal or natural gas to produce high yields of ethylene and propylene, building block materials used in the production of films, packaging, plastics and other petrochemicals. The breakthrough technology allows producers in countries such as China to tap abundant coal resources, rather than more expensive petroleum, to produce petrochemicals. _Equities.com

I. Overview of MTO Process

The Methanol to Hydrocarbons process was discovered at Mobil Oil in 1977. This process is used to convert methanol to products such as olefins and gasoline. The methanol can first be obtained from coal or natural gas. In the Methanol to Olefins (MTO) process, the methanol is then converted to olefins such as ethylene and propylene. The olefins can be reacted to produce polyolefins, which are used to make many plastic materials. An MTO process flow diagram advertised by Honeywell is shown below.

__UC Berkeley

Substituting cheaper and more abundant coal and natural gas, in place of crude oil, will make crude oil supplies go much further. Such substitution will also place a de facto ceiling, of sorts, on intermediate to long-term oil prices.

The real energy prospect is the world now faces a problem of newly found, or newly developed, and ever increasing energy resources and supplies - not a crisis of energy scarcity.

The turnaround has been lightning rapid, in at most 5 to 7 years, and has wrongfooted many analysts, most politicians, and the world's "historic major" energy corporations, as well as the green movement and "ecology politicians" who still claim energy supplies are rapidly declining and we face an inexorable energy crisis - very like their residual attempts to peddle global warming apocalypse. In fact the prospect of us facing energy penury, shortage and scarcity has been turned upside down. _The Energy Crisis that Wasn't

Besides displacing crude oil from the petrochemicals business, coal and natural gas will be displacing more and more crude oil from the petrofuels business. Gas to liquids (GTL) and coal to liquids (CTL) are gradually becoming more economically profitable, at the same time that crude oil prices have been creeping upwards.

As biomass to liquids (BTL), kerogens to liquids (KTL), and gas hydrates to liquids, become ever more viable, conventional crude oil will find itself competing with massive hydrocarbon resources amounting to many trillions of barrels of oil equivalent.

Yet another story about Russia's Gazprom being forced to confront the global reality of tight gas resources.

Russia's national oil & gas companies had been growing fat and lazy, not to mention corrupt. It looks as if Russia will be forced to ask for outside help to develop its huge tight oil & gas resources -- before it gets priced out of European and some Asian markets.

Sundrop's Methanol to Gasoline Plant to Use Exxon Mobil MTG

The methanol-to-gasoline (MTG) process developed by Exxon Mobil doesn't care where the methanol comes from originally. MTG turns methanol into gasoline regardless of the original source -- natural gas, coal, biomass, etc.

Exxon Mobil Methanol to Gasoline Process

Economics will dictate whether the overall process can be profitable in the current marketplace -- and business startups had best pay attention to a thorough economic analysis before the first shovelfull of dirt is dug.

Sundrop Fuels Inc. intends to fight the current economic conditions of cheap natural gas and cheap coal, in order to prove a point. Sundrop wants to prove that it can fight the markets and survive, while producing "green gasoline."

Sundrop Fuels will use a multi-phase process to convert sustainable forest waste into a bio-based drop-in gasoline for use in today’s combustion engines. A gasification process converts the forest waste combined with hydrogen from natural gas into a synthesis gas, which will then be converted into methanol and then into gasoline in a fixed bed reactor system via the MTG process.

The MTG process first dehydrates methanol to dimethylether (DME); an equilibrium mixture of methanol, DME and water is then converted to light olefins (C2-C4). A final step synthesizes higher olefins, n/iso-paraffins, aromatics and naphthenes. The shape-selective catalyst limits the synthesis reactions to 10 carbons.

MTG reactor product is separated into gas, raw gasoline and water. Raw gasoline is separated into LPG, light gasoline and heavy gasoline; heavy gasoline is hydro-treated to reduce durene content, then heavy and light gasoline are re-combined into finished MTG gasoline. The result is sulfur-free gasoline with a typical 92 Research Octane.

The gasoline yield represents 38% of the feed, and 87% of the hydrocarbon product. Water (H2O) represents 56% of the feed.

The company’s first facility will also provide an operational platform for Sundrop Fuels to begin field integration of its proprietary RP Reactor radiant particle heat transfer gasification technology. The super-efficient, ultra high-temperature process will drive Sundrop Fuels’ future massive-scale biofuels plants, planned to produce more than 300 million gallons of renewable, drop-in biofuels annually.

Plans are for Sundrop Fuels to achieve a combined production capacity of more than one billion gallons by 2020—a significant percentage of the cellulosic advanced biofuels goal set by the nation’s Renewable Fuels Standard (RFS).

Significant backing for Sundrop Fuels comes from Chesapeake Energy Corporation, the largest producer of natural gas in northern Louisiana’s Haynesville Shale Field and second-largest producer in the nation. Chesapeake invested $155 million in Sundrop Fuels in mid-2011. The company’s investors also include two of the world’s premier venture capital firms, Oak Investment Partners and Kleiner Perkins Caulfield & Byers. _GCC

As we mentioned in an earlier posting, Sundrop will prove much of its technology using natural gas as a feedstock Sundrop will use natural gas to power its gasifiers and as a hydrogen donour -- thus explaining their success at raising capital from Chesapeake Energy Corp. Chesapeake needs to prove that GTL can be profitable -- either using MTG or using Fischer Tropsch to make diesel -- and it needs to help boost as many other uses for natural gas as possible. Chesapeake doesn't care how the gas is used so long as it is profitable.

Sundrop's pragmatic move to the initial use of natural gas for its MTG plant instead of using solar powered gasifiers, demonstrates a certain flexibility that is extremely important, if a "green business" is to stay in business.

First establish a cash flow while proving and perfecting your processes. Then you can branch out.

CO2 to Methanol via Cascade Triple Catalysis

GCC
U. Michigan researchers have published a paper in the ACS Journal demonstrating the production of methanol from carbon dioxide using three catalysts operating in a single vessel -- "cascade catalysis."

Huff and Sanford targeted a cascade catalysis sequence involving:

hydrogenation of CO2 to formic acid
esterification to generate a formate ester
hydrogenation of the ester to release methanol
They used three different homogeneous catalysts—(PMe3 )4Ru- (Cl)(OAc); Sc(OTf)3; and (PNN)Ru(CO)(H)—operating in sequence in different combinations and under different conditions.

They found that a combination of the three operating at 135 °C demonstrated the viability of cascade catalysis, producing 2.5 turnovers of methanol—i.e., a proof of principle. However, they noted, the methanol yield was significantly lower than expected.

They found that the major problem for cascade catalysis was the deactivation of one catalyst by another. As a “low-tech” solution, they physically separated the cross-reactive catalysts within the high-pressure vessel. Two catalysts were placed in a vial in the center of the vessel, while the third was placed in the outer well of the reactor. This resulted in 21 turnovers of CH3OH from CO2 under an initial temperature of 75 °C, with a ramp to 135°C.

This communication has demonstrated the viability of cascade catalysis for the reduction of CO2 with H2. This approach offers the distinct advantage that it provides opportunities for detailed analysis of the molecular basis of catalyst incompatibilities, the modes of catalyst decomposition, and the slow step of the sequence. As such, we anticipate that it will enable rational tuning of each of the individual catalysts (A–C) in order to improve the turnover numbers and turnover frequencies for this process. Efforts in all these areas are currently underway in our group and will be reported in due course.

—Huff and Sanford

_GCC

We have been talking about "The Methanol Economy" for several years. Research groups from Europe to North America to Japan have been successful in devising ways of converting CO2 to methanol by various methods. But none of them are particularly economical -- nor are they likely to be any time soon.

Converting methane to methanol is another story, and we are likely to see a lot more of that particular conversion quite soon. Particularly since there are economical ways of converting methanol to gasoline (via the Exxon Mobil MTG process) as well as to a number of high value chemicals such as ethylene. Methanol is also used in the production of biodiesel, can be blended with gasoline or petro-diesel as a fuel extender, and can be used as a fuel in its own right. Methanol fuel cells are likely to become widely used at scales from power supplies for small consumer electronics, up to household and industrial sizes.

The idea of converting CO2 into fuels is something of a romantic idea -- a chemical version of "poetic justice," but it isn't practical in the modern economic climate. If you want to do something constructive with CO2, feed it to algae farms and green house plants.

Otherwise, feed it to the atmosphere. The Earth's atmosphere has dealt with far higher levels of CO2 than humans can conceivably produce, for billions of years.

Primus' Biomass-to-Gasoline Process to Cost $1.95/Gallon

More information on Primus
GCC article about Primus' plans

Primus’s process is based on a proprietary variant of the ExxonMobil Methanol-to-Gasoline process, simplified to produce standard gasoline without need for separation or further treatment, the company says. The Primus process consists of three main steps:

Gasification of biomass (feedstock flexible) to produce a syngas;

CO2 separation and scrubbing of the syngas; and

catalytic liquid fuel synthesis using a four-stage catalytic system (the MTG variant).

Primus says that its gasoline is cost-competitive with fossil fuels without subsidies, utilizing carbon-efficient and high fuel-yielding non-agricultural biomass that does not compete with foodstocks.

A February 2011 report from the US Department of Energy’s National Renewable Energy Laboratory (NREL) conclude that gasoline produced via the methanol-to-gasoline (MTG) route (earlier post) using syngas from a 2,000 dry metric tonne/day (2,205 US ton/day) biomass-fed facility could have a plant gate price (PGP) of $1.95/gallon US ($0.52/liter). _GCC

The biomass is pelletised, then gasified. The syngas is converted to methanol, and the methanol is converted directly to gasoline, via Exxon Mobil's highly efficient MTG process -- as modified by Primus. More on MTG:

In the MTG process, dimethylether (DME), the dehydrated derivative of methanol, is reacted over a ZSM-5 zeolite catalyst, on which the chain growth of molecules is sterically hindered, thus allowing only production of gasoline and lighter material. The gasoline product from the MTG process has more than 51 compounds, similar to straight-run gasoline in a petroleum refinery.

This mixture is then separated using a process similar to that used in a gasoline refinery. The design utilized in the NREL model utilizes five distillation columns to separate the remaining gas, LPG, light gasoline, and heavy gasoline. The remaining gas is sent to the fuel combustor. The light gasoline continues without further treatment. The heavy gasoline could proceed through a durene isomerizer in order to eliminate the presence of the 1,2,4,5-tetramethylbenzenes by converting them to 1,2,3,5-tetramethylbenzenes. This stream would then be merged with the light gasoline. The two product streams are LPG and gasoline. _GCC

This is an entirely renewable biomass to gasoline process which is likely to impact the fossil fuels markets in good time. Perhaps the main obstacle to a large scale adoption of biomass to liquid fuels, is the current very cheap price of natural gas.

Taken from a previous article at Al Fin Potpourri

Coal to Syngas; Syngas to Methanol; Methanol to Gasoline

Synthetic fuels from coal, natural gas, biomass etc. will compose a larger share of the transportation fuels market over the next few decades. This will come about due to more economical processes for coal to liquids (CTL), gas to liquids (GTL), biomass to liquids (BTL), etc. combined with a long term trend of rising oil prices.

Ambre Coal to Liquids
The methanol-to-gasoline (MTG) process is the prime competitor to the Fischer Tropsch (FT) process, in the conversion of carbonaceous mass to liquid fuels. Ambre Energy of Australia is involved in the clean conversion of low quality coal to high quality liquid fuels, using the Exxon-Mobil methanol-to-gasoline process (PDF).

Methanol is usually synthesised from syngas, a mixture of H2, CO, CO2, methane, etc. Syngas can be produced via gasification of coal, natural gas, biomass, or any other carbonaceous material.

Methanol is used as a feedstock to produce fuels or other chemicals. Methanol can also be used as a fuel itself, or as a fuel additive. Methanol is also finding greater use in methanol fuel cells -- a market that is expected to grow very rapidly over the next several years.

Ambre CTL process
PDF description of Ambre CTL
Ambre is involved in a technical study agreement with Synthesis Energy Systems to develop an improved coal to liquids project which will produce both synthetic gasoline and LPG from methanol.

Converting Waste Petcoke from Oilsands Production to Methanol

The bitumen upgraders in the Fort McMurray area of Alberta and the refineries in the Edmonton area are large producers of petroleum coke (petcoke), which, historically, has had essentially zero market value in Alberta.

Petcoke, however, can be converted to methanol, which can be used as a gasoline blending component or marketed as chemical-grade material. _OGJ

OGJOnce you have converted waste petcoke and low grade sub-bituminous coal to methanol, what should you do with it? That depends upon the economic factors at that moment in time. Methanol can be used on its own as fuel or in fuel cells. Methanol can be converted to gasoline via F-T. Methanol can be blended with gasoline or used in the production of biodiesel. Etc.

The potential conversion of methanol to gasoline (MTG) deserves a few words. The first commercial MTG unit was licensed by Mobil Oil in New Zealand in 1985.1

The anticipated yield from 50,000 b/d of methanol could be 20,500 b/d gasoline (rvp 9 psia, before ethanol blending; 0.73 sp gr; RON 92, benzene 0.3 vol %). And it produces about 5,500 b/d of C3-C4 LPG.

On this basis, it is difficult to see any rationale in converting methanol to gasoline if the option of methanol-gasoline blending is available. According to information from the US Environmental Protection Agency, methanol blending into gasoline is not banned in the US.

Given the investment in MTG facilities and the shrinkage in energy content (8-9%), and energy consumed by the MTG plant, the cost of the MTG gasoline would be significantly above the cost of energy in the methanol.

In this context, it is worth adding that conversion of syngas to hydrocarbon liquids by Fischer-Tropsch synthesis is technically proven and produces high-quality diesel.2 At the same time the coproduced naphtha is very paraffinic, with an octane value of perhaps 35 to 40 and is essentially nonreformable for octane elevation. Further, no steam cracker for ethylene production in Alberta is adaptable for liquid naphtha feed. _OGJ

The infrastructure for proper treatment of wastes from Canadian oilsands production is not entirely in place. But the longer that oil prices remain relatively high, the greater the motivation for development of infrastructure such as ethylene crackers, F-T catalytic synthesis plants, and fermentation (of syngas) bioreactors for advanced chemicals and fuels. Algal and microbial bioreactors for conversion of the massive CO2 effluent to biomass, fuels, and high value chemicals should eventually come into the mix.

The CO2 produced may be used for many other purposes including EOR.

Here is a comparison of cost per gallon for various fuel liquids:

OGJNotice the high octane value and low cost of methanol -- helpful for blending with gasoline.

Methane to Methanol to Gasoline at Competitive Prices

GCC
Methane to methanol to gasoline for $2.85 a gallon, including a healthy $1.45 margin? That is what is being claimed for a combined "Gigamethanol" and MTG (methanol to gasoline) plant proposed for Alaska. Converting all the North Slope gas to gasoline could produce almost 500,000 barrels per day.

... a plant would produce methanol from natural gas on the North Slope using the proposed GigaMethanol technology. The resulting methanol would be blended with crude and transported via the trans-Alaska oil pipeline to Valdez, where it would be extracted from the oil and processed via Methanol-to-Gasoline technology into gasoline.

In January, ICIS reported that Eastman Chemical reached an agreement to sell a mothballed Texas methanol and ammonia plant to Pandora Methanol, a subsidiary of Janus Methanol.

The plant will have a capacity of 850,000 tonnes/year of methanol and 250,000 tonnes/year of ammonia, according to van Wijk. ...Van Wijk at the time said the new plant might consider the methanol-to-gasoline MTG process pioneered by ExxonMobil.
Eastman originally bought the plant in 2007 for a $1.6-billion coal-gasification project, but called off the project in late 2009 due to high capital requirements, the narrow difference between petroleum and natural gas prices and uncertain US energy policy....

Costs for a 63,000 barrel (of gasoline) per day system would be approximately $5.2 billion, he said. Gasoline could be delivered from Valdez at $2.65 to $2.85 per gallon, including a $1.45 margin.

In addition to providing a market for North Slope gas, the mix of methanol in the pipeline flow would help prevent problems with ice forming in the line, van Wijk, a former Methanex executive, suggested. If the entire daily output of North Slope gas (4.5 billion cubic feet, bcf) were converted to gasoline, it would produce 450,000 barrels per day, he suggested. _GCC

This is a different approach from the Oxford Catalysts and Sasol approaches. But the claims for efficiency and economic viability are difficult to beat, if true.

While the proposal is meant to take advantage of Alaskan natural gas, the same approach could conceivably be taken with shale gas or any other large gas deposits located anywhere.

A Methane Bonanza: What To Do With All the Gas?

A wealth of unconventional methane is exploding onto the energy scene, much to the dismay of dieoff doomers, Russian energy tsars, and carbon hysterics. But what is the world to do with all this methane -- which is difficult to transport, and cannot be easily used within the liquid fuels infrastructure?

The answer would seem to be to convert the gas into liquids, but what is the most economical way to do that? Liquified natural gas (LNG) is difficult and expensive to handle, Fischer-Tropsch gas to liquids (GTL) is likewise expensive and requires costly chemical plants (although microchannel FT architectures may alter the equation). What to do, what to do?

German researchers at Max Planck Institute for Carbon Research in Mulheim are trying to develop better ways of converting gaseous methane to liquid methanol -- which would open a world of economic possiblities.

Methanol is a useful starting material for many chemical syntheses, including fuels; it can also be added to conventional fuels to power fuel cell or used in combustion engines. Conventional processes for producing methanol from methane involve detours (synthesis gas), are complex and energy-intensive, and require high temperatures and pressures. By contrast, the enzyme methane monooxygenase does the job gently and efficiently. However, this is a very complex enzyme that cannot easily be produced and used in an artificial environment....

In contrast to time-consuming protein engineering, the present approach simply requires the addition of an appropriate chemically inert perfluoro fatty acid to the enzyme, thereby triggering a catalytically activating effect which originates from specific guest/host interactions in the binding pocket. A shift from an inactive low-spin state to a catalytically active high-spin state and a decrease in the effective volume of the binding pocket appear to be the crucial factors as shown by UV/Vis difference spectra as well as a theoretical analysis based on MD simulations and docking experiments.

The present approach not only allows methane to be oxidized with notable enzyme activity, but also opens the door for using perfluoro carboxylic acids, which can be expected to bind to most CPYs, to influence the catalytic profile of monooxygenases as catalysts in the functionalization of more complex organic compounds, including the control of regio- and stereoselectivity.
—Zilly et al.

_GCC

The dynamics of enzymes and how they work their semi-selective magic, is an area of frantic study. But as noted here recently, nanotechnological catalysts are likely to eventually take over for most biological enzymes, for high volume synthesis of potentially toxic chemicals such as hydrocarbons.

More Scientific Interest in Catching and Using CO2

Brian Westenhaus takes a look at a University of Cincinnati group that aims to turn CO2 into methanol (CH4) using a low temperature catalytic process.

The new paper published June 14th in the American Chemical Society journal Energy & Fuels reports a highly efficient nickel system for the catalytic hydroboration of CO2 to methoxyboryl species using a simple borane. The reactions operate at room temperature with turnover frequencies [495 h-1 based on B-H] at least 1 order of magnitude higher than those of the related reactions.

The improvement comes from the recent development of frustrated Lewis acid-base pair chemistry, which has led to alternative strategies for the reduction of CO2 to the methoxide level given either H2 or H3NBH3 9 as a hydrogen source.

The mechanism involves a nickel formate, formaldehyde, and a nickel methoxide as different reduced stages for the CO2. The reaction may also be catalyzed by an air-stable nickel formate.

_NewEnergyandFuel

An enzymatic approach to capturing CO2 for re-use comes from Codexis, and involves genetically modified enzymes made especially to withstand the higher temperatures involved. The new enzymes are said to be 100 times as efficient at CO2 capture as the standard solvent approach.

This recent scientific groundswell of interest in capturing CO2 and turning it back into fuels was spurred by this Sandia project of turning CO2 plus sunlight into fuels. It sounds almost poetic, even though we know that nuclear energy is far more reliable and potentially plentiful in concentrated form than solar energy.

Regardless, the human imagination has been unleashed in an attempt to solve a perceived problem -- rather than to merely whine about the perception. It will be fascinating to watch and see what problem-solving human minds can devise.

Update 27July2010: DOE to Award $106M to Six CO2 Conversion Projects; $156M in Matching Private Funding

Phycal, LLC (Highland Heights, OH) Phycal will complete development of an integrated system designed to produce liquid biocrude fuel from microalgae cultivated with captured CO2. The algal biocrude can be blended with other fuels for power generation or processed into a variety of renewable drop-in replacement fuels such as jet fuel and biodiesel. Phycal will design, build, and operate a CO2-to-algae-to-biofuels facility at a nominal thirty acre site in Central O’ahu (near Wahiawa and Kapolei), Hawaii. Hawaii Electric Company will qualify the biocrude for boiler use, and Tesoro will supply CO2 and evaluate fuel products. (DOE Share: $24,243,509)

Touchstone Research Laboratory Ltd. (Triadelphia, WV) This project will pilot-test an open-pond algae production technology that can capture at least 60% of flue gas CO2 from an industrial coal-fired source to produce biofuel and other high value co-products. A novel phase change material incorporated in Touchstone’s technology will cover the algae pond surface to regulate daily temperature, reduce evaporation, and control the infiltration of invasive species. Lipids extracted from harvested algae will be converted to a bio-fuel, and an anaerobic digestion process will be developed and tested for converting residual biomass into methane. The host site for the pilot project is Cedar Lane Farms in Wooster, Ohio. (DOE Share: $6,239,542)

Skyonic Corporation (Austin, TX) Skyonic Corporation will continue the development of SkyMine mineralization technology-a potential replacement for existing scrubber technology. The SkyMine process transforms CO2 into solid carbonate and/or bicarbonate materials while also removing sulfur oxides, nitrogen dioxide, mercury and other heavy metals from flue gas streams of industrial processes. Solid carbonates are ideal for long-term, safe aboveground storage without pipelines, subterranean injection, or concern about CO2 re-release to the atmosphere. The project team plans to process CO2-laden flue gas from a Capital Aggregates, Ltd. cement manufacturing plant in San Antonio, Texas. (DOE Share: $25,000,000)

Calera Corporation (Los Gatos, CA) Calera Corporation is developing a process that directly mineralizes CO2 in flue gas to carbonates that can be converted into useful construction materials. An existing CO2 absorption facility for the project is operational at Moss Landing, Calif., for capture and mineralization. The project team will complete the detailed design, construction, and operation of a building material production system that at smaller scales has produced carbonate-containing aggregates suitable as construction fill or partial feedstock for use at cement production facilities. The building material production system will ultimately be integrated with the absorption facility to demonstrate viable process operation at a significant scale. (DOE Share: $19,895,553)

Novomer Inc. (Ithaca, NY) Teaming with Albemarle Corporation and the Eastman Kodak Co., Novomer will develop a process for converting waste CO2 into a number of polycarbonate products (plastics) for use in the packaging industry. Novomer’s novel catalyst technology enables CO2 to react with petrochemical epoxides to create a family of thermoplastic polymers that are up to 50% by weight CO2. The project has the potential to convert CO2 from an industrial waste stream into a lasting material that can be used in the manufacture of bottles, films, laminates, coatings on food and beverage cans, and in other wood and metal surface applications. Novomer has secured site commitments in Rochester, NY, Baton Rouge, Louisiana, Orangeburg, SC and Ithaca, NY where Phase 2 work will be performed. (DOE Share: $18,417,989)

Alcoa, Inc. (Alcoa Center, PA) Alcoa’s pilot-scale process will demonstrate the high efficiency conversion of flue gas CO2 into soluble bicarbonate and carbonate using an in-duct scrubber system featuring an enzyme catalyst. The bicarbonate/carbonate scrubber blow down can be sequestered as solid mineral carbonates after reacting with alkaline clay, a by-product of aluminum refining. The carbonate product can be utilized as construction fill material, soil amendments, and green fertilizer. Alcoa will demonstrate and optimize the process at their Point Comfort, Texas aluminum refining plant. (DOE Share: $11,999,359)

More Efficient CO2 to Methanol Conversions

University of Cincinnati researchers claim to have developed a "highly efficient" reduction and hydrolysis of CO2 to methanol.

A paper on their work was published online 14 June in the ACS journal Energy & Fuels.

Transforming CO2 into methane, the most reduced form of carbon, under homogeneous conditions can be accomplished using silanes as the reducing reagents. Reducing CO2 to methanol would be even more desirable for the advantages of transporting a liquid fuel rather than a gas.

...In this paper, we report a highly efficient nickel system for the catalytic hydroboration of CO2 to methoxyboryl species using a simple borane. The reactions operate at room temperature with TOFs [495 h-1 based on B-H] at least 1 order of magnitude higher than those of the related reactions described above.

Further studies to elucidate the mechanistic details and improve the catalytic efficiencies are in progress. _GCC

The details are rather technical. Availability of CO2 in pure, concentrated form can be problematic as well. The concentration of CO2 in the atmosphere is only 0.04 per cent.

Methanol Fuel Cells Make Sense

Brian Westenhaus takes a look at a successful California manufacturer of methanol fuel cells for fork lift vehicles. A Nissan assembly plant in Tennessee recently ordered 60 units of the relatively new methanol fuel cell.

Fuel cells can be much more quickly and easily re-fueled than a large battery bank can be recharged. Using fuel tanks, fuel cells can easily hold far more energy than batteries as well. Methanol is safe and easy to handle and store, and is inexpensive, when compared to hydrogen -- which is the fuel usually thought of for fuel cells -- or other gases besides hydrogen.

Oorja’s Protonics’ methanol fuel cells eliminate the dangerous and time-consuming task of switching out and recharging batteries and owning the extra sets Oorja’s OorjaPac fuel cell sits on the forklift and feeds electrons to the battery pack, charging it as the day progresses. Filling up the fuel cell at the beginning of a shift, ideally, provides enough power for the day. A 3.4 gallon-storage tank of methanol powers a vehicle for 10 hours.

...The Nissan factory in Smyrna Tennessee has tested Oorja’s product over 18 months and then ordered 60 units. Mark Sorgi, senior manager of material handling at Nissan said the factory would save near $225,000 per year and avoid spending $300,000 for battery replacements. Oorja’s fuel cells also save time and reduce its greenhouse gas emissions. “We can probably run anywhere from 14 to 16 hours on one tank of methanol,” Sorgi said. “It takes 60 seconds to refill versus battery change-out that takes 15 minutes.”
Methanol, a one-carbon atom chemical is one of the mostly commonly produced chemicals in the world, costs about $1 to $2 a gallon and doesn’t have to be transported under pressure so it’s easy to ship. It’s the main chemical in windshield washer fluid. Methanol can be delivered in large plastic drums and is fully biodegradable.
Oorja has improved the performance of its fuel cell. The new 1.6-kilowatt Model H is about 25 percent to 30 percent smaller than the previous version, at $16,000 costs about 50 percent less than the earlier version, and can be refilled with methanol in about a minute. _NewEnergyandFuel

Entrepreneurs are oriented toward problem solving -- because that is how they make a living. Academics and pundits, on the other hand, are oriented toward magnifying problems and extending a problem's lifespan. That makes sense, because academics and pundits make a living by studying problems, not by solving them.

It may well be that when fuel cells, batteries, and supercapacitors reach their next limitational plateus, that the best electric vehicle will include a combination of a fuel cell feeding the batteries and supercapacitor, a medium sized battery pack between the fuel cell and the motor, and a modest supercapacitor for quick bursts of power. The battery will be kept topped off by the fuel cells, and will provide normal cruising. Supercapacitors will provide rapid acceleration, and will likewise be kept charged by the fuel cells.

Such a combination would come close to matching the performance of an internal combustion engine -- and would beat the ICE at low speed torque.

It's All In the Texture: Methanol Fuel Cell Catalysis

MIT, JIST, and BNL researchers have combined to advance the cause of methanol fuel cells by devising a textured platinum fuel cell electrode.

A team of researchers from MIT, the Japan Institute of Science and Technology, and Brookhaven National Laboratory have found that changing the surface texture of platinum used in a methanol fuel cell electrode—specifically, creating nano surface steps instead of using a smooth surface—can significantly increase the catalytic activity.

In a paper published online 13 October in the Journal of the American Chemical Society, they show a linear relationship between the intrinsic activity and the amounts of surface steps. Increasing surface steps on Pt nanoparticles of ~2 nm led to enhanced intrinsic activity up to 200% (current normalized to Pt surface area) for electro-oxidation of methanol.

The researchers believe that further development of these surface structures could end up producing far greater increases, yielding more electric current for a given amount of platinum. _GCC

Such an approach may seem intuitively obvious to those who understand the relationship between surface area and catalytic activity, but I suppose highly specialised researchers take more time to realise the obvious.

Regardless, methanol fuel cells are potentially one of the most important advances in the race to develop alternatives to fossil fuel transportation and electricity. The sooner they are perfected the better.

Efficient On-Site Conversion of Methane to Methanol

CH4 + H2SO4 + SO3 → CH3OSO3H + H2O + SO2 (a)

CH3OSO3H + H2O → CH3OH + H2SO4 (b)

SO2 + ½O2 → SO3 (c)

ΣCH4 + ½O2 → CH3OH (d)

Biomass to methane, via anaerobic digestion, is fairly easy. Now researchers at Max Planck Institute have devised a solid catalyst for efficient conversion of methane to methanol. This development opens the door to small-scale, local and regional biomass to methanol plants.

Methanol is one of the most ideal biofuels for fuel cell use -- better than hydrogen in many ways. It can also be a useful supplement / substitute for gasoline in automobiles, AND is an excellent feedstock for chemical synthesis of longer chain hydrocarbons.

Converting biomass to a denser form of energy, is one of the challenges facing the project to replace fossil fuels with biofuels. Local and regional conversion / densification plants will make the entire enterprise more feasible, and will bring some level of economic prosperity back to the outlands.

Turning CO2 Into Methanol: Mitsui Plant Opens

Last summer, Brian Westenhaus reported on a Mitsui process for turning CO2 into methanol. Now a Mitsui Chemicals pilot plant for producing methanol from CO2 has begun operations.

Mitsui Chemicals (MCI) has begun operating its pilot plant for synthesizing methanol from CO2. (Earlier post.) The pilot plant will produce approximately 100 tonnes of methanol per year as a base material for plastics from the CO2 released during ethylene production at the Osaka Works petrochemical complex.....

The process relies on hydrogen obtained from water photolysis and ultra-high activity electrocatalysts consisting of zinc oxide and copper. _GCC

In truth, we do not have enough CO2 to do all the things we could be doing with it. Plants need it to grow and fruit. Single cell algae and other microbes thrive on CO2. But there is very little of it in the atmosphere -- it is only a trace gas constituting less than 0.4 % of all atmospheric gases. Mitsui chemists are tapping into industrial processes that produce CO2 as a waste product.

Methane to Liquid Fuels for Efficient Transport

Methane is a relatively clean fuel, but is often less practical to transport longer distances than liquid fuels, such as methanol. The University of Virginia is to develop a new center to develop technologies for converting methane gas and other hydrocarbon and fossil resources into methanol and other readily transportable and higher-value liquid fuels. Methanol figures to become important due to its multifunctionality in various types of fuel cells, combustion engines, and in flex-fuel engines.

Natural gas, which is largely made up of methane, is an extremely abundant energy resource in the world, but many of the largest fields are located in remote areas, such as Alaska's North Slope, making access extremely difficult and expensive. The only feasible way to transport this energy resource would be to convert it from a gas to a liquid, thereby condensing the energy into transportable units. Transporting methane as a gas would require a substantial build-up of infrastructure and cost tens of billions of dollars for new pipelines.

"If we can find new technologies that will allow the large-scale utilization of methane, particularly in the transportation sector, the U.S. could very quickly supplant our use of petroleum and greatly reduce our dependence on foreign petroleum," Gunnoe said.

Methanol, if produced in massive quantities, could be mixed with gasoline like current ethanol/gasoline formulas, and therefore would not require changes to the way motor vehicle engines are designed. And current "flex fuel" engines that run on 85 percent ethanol with 15 percent gasoline still could run on an 85/15 mix of methanol/gasoline. _biofueldaily

Peak Oil is for Idiots (Global Warming Too)

Methanol is an interesting fuel -- more energy-dense than the densest form of hydrogen, usable in combustion engines, in direct methanol fuel cells, and in "indirect" methanol fuel cells that use steam reforming to produce protons. Methanol can also be used in the production of biodiesel from vegetable oils. Methanol may even become the basis for a methanol economy, as a primary mobile energy source for transportation (instead of petroleum, ethanol, or hydrogen).

So isn't it fascinating that scientists in Singapore have discovered a relatively easy and efficient way of making methanol from CO2?

In the international chemistry journal Angewandte Chemie, the IBN researchers report that by using organocatalysts, they activated carbon dioxide in a mild and non-toxic process to produce methanol, a widely used industrial feedstock and clean-burning biofuel...

....The scientists made carbon dioxide react by using N-heterocyclic carbenes (NHCs), a novel organocatalyst. In contrast to heavy metal catalysts that contain toxic and unstable components, NHCs are stable, even in the presence of oxygen. Hence, the reaction with NHCs and carbon dioxide can take place under mild conditions in dry air.

The IBN scientists showed that only a small amount of NHC is required to induce carbon dioxide activity in a reaction...Hydrosilane, a combination of silica and hydrogen, is added to the NHC-activated carbon dioxide, and the product of this reaction is transformed into methanol by adding water through hydrolysis. _SciLive

You might even call it a CO2 economy, since the methanol will come from CO2. And how idiotic is it to worry about CO2 when it is becoming the very basis of your energy infrastructure? Don't forget that oil-producing algae thrive on very high levels of CO2. And how pathetic is it to worry about "peak oil" when no one will be using oil anyway? When everyone is using bioenergy, enhanced geothermal, space solar, and advanced nuclear energy instead of petrol?

Well, sure, you can make methanol from biomass quite easily as well, via either fermentation or thermochemical methods. Methane, methanol, ethanol, butanol, etc etc etc There is no reason ever to run out. In fact, as the technology improves, supplies will keep growing as long as there is demand.

Peak oil and global warming: two obsessions fit for assholes. The K-Y jelly will cost extra.

Exxon-Mobil Looks at Gasoline from Coal

Synthesis Energy Systems (SES) has entered an agreement with Exxon-Mobil Research and Engineering to examine and develop gasoline from coal, via gasification produced methanol. The methanol approach is a competitor to the Fisher-Tropsch method of producing liquid hydrocarbon fuels from syngas.

This approach to converting coal to gasoline first gasifies the coal, then converts the resulting syngas to methanol for use by the MTG process. The conversion of methanol to hydrocarbons and water is virtually complete and essentially stoichiometric in the MTG process. The reaction is exothermic with the reaction heat managed by splitting the conversion in two parts. In the first part, methanol is converted to an equilibrium mixture of methanol, dimethyl ether (DME), and water.

In the second part, the equilibrium mixture is mixed with recycle gas and passed over a shape-selective catalyst to form hydrocarbons and water. Most of the hydrocarbon product boils in the gasoline boiling range.

ExxonMobil calculates that a feed of around 4.6 million t/year of coal can produce about 1.4 million t/a gasoline—about 36,000 barrels per day. Yield and capital costs are dependent on the coal quality: ash content, moisture content, sulfur and heating value. _GCC

If this process is a more economical producer of gasoline-from-coal than the F-T process, it may see a lot of use. The big obstacle to advanced energy from coal, oil shale, oil sands, heavy oils, and other sources (such as nuclear) is the Luddite US Congress--and the threat of a new Luddite administration in the White House if Obama/Biden are elected.

The fear of CO2 -- which has what plants need -- is one of many pseudo-environmental concerns that has wrapped frigid fingers of fear around the minds of western government leaders. So much so, that they flirt with disastrous and suicidal policies of energy starvation, which contribute to the inevitable economic hardships they cause by over-regulation, over-taxation, and rampant corruption. It is time for things to change, but unfortunately, these corrupt and fearful "leaders" are fixed in place--barnacle-like leeches.

Methane, Methanol: Simple Fuels Making Sense

Methane is CH4, methanol is CH3OH. The simplest hydrocarbon, the simplest alcohol. Small molecules that promise to explode the petroleum monopoly on liquid fuels, likely leaving Mssrs. Chavez, Putin, Ahmedinejad, Qadafi and company in tears. Why? Because they're cheap and easy to make, and besides working in IC engines and fuel cells as is, they can be chemically converted to more complex hydrocarbons, plastics, and other organic compounds.

MCI has been pursuing the development of a process for the synthesis of methanol (CH3OH)—later used in the production of olefins and aromatics—using the CO2 emitted from factories and hydrogen obtained from water photolysis. The effort is part of the company’s strategy to develop innovative processes to contribute to significant reductions of greenhouse gases.

The pilot plant, located at MCI’s Osaka plant, will have a production capacity of approximately 100 tonnes of methanol per year, using about 150-160 tonnes of CO2 emitted the Osaka plant. Construction of the ¥1.5 billion (US$13.7 million) plant will begin in October, and is due for completion in February 2009. The plant is projected to come online in March 2010. _GCC

While using CO2 from emissions may make sense from a "greenhouse gas" point of view, the biosphere could really use that CO2. Much more reasonable to grow the biosphere and then make methanol from biomass. Brian Westenhaus looks at the prospects for methane in automobiles etc.

I have a certain confidence that.....the compressed methane route for fuel is going to have a few good years. It may be much longer than that should the biomass people come up with a cheap process to convert biomass carbon back to hydrocarbon in methane form. This is a crack in the gasoline monopoly..... Just to throw out another bit for the future - methane is one of the leading contenders for fuel cells too....Methane is way past being a fuel to watch. It’s time to look into how it might work and the costs to change over. _NewEnergyand Fuel

In other energy news, giant conglomerate ADM is collaborating with John Deere and chemical giant Monsanto to develop productive uses for corn stover and other crop residues.

The companies will work together to identify environmentally and economically sustainable methods for the harvest, storage and transport of corn stover—the stalks, leaves and cobs of corn plants. Corn stover can be used in feed for animals, as biomass to generate steam and electricity or as a cellulosic feedstock for biofuel production.

Stover is usually left on the field, where, in proper amounts, it helps reduce soil erosion and build up soil organic matter. A 170-bushel-per-acre corn crop, which was the average last year in Iowa, also produces about four dry tons of stover. The United States Department of Agriculture forecasts that in 2008, farmers will harvest 12.3 billion bushels of corn, resulting in approximately 290 million tons of stover. _GCC

While you were sleeping, hundreds of thousands of people were dreaming up ways to create more energy cleanly and economically. The news media will be the last to know what is going to happen.

Methanol Instead of Hydrogen for Fuel Cells

Methanol as fuel has a long history, going back to the early days of automobiles. Methanol will fuel internal combustion engines, and will have use in flex-fuel vehicles.

Methanol will have a particularly important role in future fuel cells. It will be used instead of hydrogen gas because it is safer and easier to handle. How much methanol can we make?

....a ton of wood would make between 165 to 185 gallons of methanol. The U.S. alone generates 240 million tons of wood waste each year, which would yield at least 39.6 billion gallons of methanol. U.S. paper mills could add another 9.3 billion gallons. The uncounted tons of trash and garbage would add still more. Methanol can be made from oil, natural, gas, coal and there remains more than half of the U.S. farm acreage that isn’t in production now that could add hundreds of millions of tons annually. Methanol can even be made from CO or CO2 with a hydrogen source made available.

Industry is aware; from 2004 to 2007 the world saw seven new methanol production plants start up making an additional 10 million metric tons of methanol – a 25% increase in world capacity.

....The Direct Methanol Fuel Cell known as DMCF is a technology well worth keeping an eye on. It can’t be too long until a new battle ensues between batteries and fuel cells. _NewEnergyandFuel

Methanol is a liquid at normal temperatures, easy to store in a regular fuel tank. It does not require special high pressure containment vessels and protection. Methanol fuel cells do not run at the high temperatures that hydrogen fuel cells do. While methanol micro fuel cells already power small consumer electronic devices, scaling methanol fuel cells up to drive automobile electric motors should be doable.

The roller coaster of oil prices has driven the world economies through peaks and valleys for too long. It is time for alternate fuels to come on the scene. Oil dictatorships such as Russia, Venezuela, Saudi Arabia, Libya, etc. have been given too much clout to affect world affairs.

The world still needs fossil fuels, along with expanded nuclear capacity. But it also needs a much larger variety of fuels, produced in a much wider range of locations.