United States Patent Application: 0120225956
It is time we started openly talking about, and reporting on, the Natural Gas boom.
But, the Natural Gas boom we should be talking about isn't the one involving "America's" so-called "Clean Energy Alternative", that, as seen in:
After Disclosure of Sierra Club’s Gifts From Gas Driller, a Roiling Debate - NYTimes.com;
"The recent disclosure of the Sierra Club’s secret acceptance of $26 million in donations from people associated with a natural gas company has revived an uncomfortable debate among environmental groups about corporate donations and transparency. Carl Pope was the Sierra Club executive director when the group accepted $26 million in gifts from Chesapeake Energy. The Sierra Club used the Chesapeake Energy money, donated mainly by the company’s chief executive from 2007 to 2010, for its Beyond Coal campaign to block new coal-fired power plants and shutter old ones. Carl Pope, then the club’s executive director, promoted natural gas as a cleaner “bridge fuel” to a low-carbon future";
really is, in fact, pretty-darned dirty, in more ways than one; and which, as seen in:
Shale gas boom may quickly go bust, speaker warns City Club of Cleveland | cleveland.com;
"Shale gas wells often result in gushers that tail off quickly. The early results look good, ... but the staying power is weak";
might, rather sooner than later, go bust.
The Natural Gas we mean herein is going to be with us for the truly long haul; and, it's one that is so benign that it is an essential "nutrient" for the plants that make the fruit and vegetables we're supposed to eat with every meal. It is, in fact, the cornerstone of the natural food chain that, through botanical photosynthesis and all of the biological functions and processes that follow, ends up supporting the most dominant animals in the world: people.
And, it is so natural that, unceasingly, while we are alive, we make more and more of it on a continuous basis; and, respire it harmlessly in and out of our lungs.
And, just in recent years, at an accelerating pace, we, or at least some privileged few among us not content to live under the insulating pile of Baloney Sandwiches heaped upon us by our public press, have begun to realize what a valuable raw material resource it is, and, to make that realization manifest.
As we have lately documented in, for just a few examples, our reports of:
West Virginia Coal Association | The US Navy Recycles CO2 into Liquid Hydrocarbo?n Fuels | Research & Development; concerning: "United States Patent 8,017,658 - Synthesis of Hydrocarbons via Catalytic Reduction of CO2; September, 2011; Assignee: The United States of America as represented by the Secretary of the Navy; Abstract: A method of: introducing hydrogen and a feed gas containing at least 50 % carbon dioxide into a reactor containing a Fischer-Tropsch catalyst; and heating the hydrogen and carbon dioxide to a temperature of at least about 190 C. to produce hydrocarbons in the reactor"; and:
West Virginia Coal Association | May, 2012, CO2 to Gasoline and Jet Fuel | Research & Development; concerning: "United States Patent 8,168,143 - Systems, Methods and Compositions for Production of Synthetic Hydrocarbon Compounds; May 1, 2012; Assignee: Fuelcor, LLC; Abstract: A process and system for producing hydrocarbon compounds or fuels that recycle products of hydrocarbon compound combustion--carbon dioxide or carbon monoxide, or both, and water. The energy for recycling is electricity derived from preferably not fossil based fuels, like from ... renewable energy. The process comprises electrolysing water, and then using hydrogen to reduce externally supplied carbon dioxide to carbon monoxide, then using so produced carbon monoxide together with any externally supplied carbon monoxide and hydrogen in Fischer-Tropsch reactors, with upstream upgrading to desired specification fuels--for example, gasoline, jet fuel, kerosene, diesel fuel, and others"; and:
West Virginia Coal Association | Carbon Dioxide to Gasoline and Diesel | Research & Development; concerning: "United States Patent 8,198,338 - Process for Producing Liquid Fuel from Carbon Dioxide and Water; June 12, 2012; Assignee: CRI EHF, Iceland; Abstract: A process for producing high octane fuel from carbon dioxide and water is disclosed";
Carbon Dioxide, as it arises in only a very small way, relative to natural sources of emission, such as volcanoes, from our essential use of Coal in the generation of genuinely economical electrical power, can be harvested, and then efficiently be converted into anything, quite literally anything, we now squander our national treasure to buy from the often inimical, sometimes downright hostile, alien nations of OPEC.
One other Carbon Dioxide utilization technology about which we've reported is that seen in:
West Virginia Coal Association | Conoco Converts CO2 to Methanol and Dimethyl Ether | Research & Development; concerning: "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates; 2003; Assignee: ConocoPhillips Company; Abstract: A catalyst and process for converting carbon dioxide into oxygenates. The catalyst comprises copper, zinc, aluminum, gallium, and a solid acid. Claims: A catalyst composition comprising: copper; zinc; aluminum; gallium; and a solid acid (wherein) said solid acid (comprises) a zeolite (specified as) ZSM-5. A catalyst composition for converting carbon dioxide to methanol and dimethyl ether".
And, in passing, we note that the above, Conoco-specified, "zeolite ... ZSM-5", which can help to convert Carbon Dioxide into Methanol, is the same one specified by ExxonMobil, as seen, for just two examples, in:
West Virginia Coal Association | Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984; Mobil Oil Corporation, NY; Abstract: A process for producing a wide slate of fuel products from coal is provided by integrating a methanol-to-gasoline conversion process with coal liquefaction and coal gasification. The coal liquefaction comprises contacting the coal with a solvent under supercritical conditions whereby a dense-gas phase solvent extracts from the coal a hydrogen-rich extract which can be upgraded to produce a distillate stream. The remaining coal is gasified under oxidation conditions to produce a synthesis gas which is converted to methanol. The methanol is converted to gasoline by contact with a zeolite catalyst. Solvent for coal extraction is process derived from the upgraded distillate fraction or gasoline fraction of the methanol-to-gasoline conversion"; and in:
West Virginia Coal Association | Mobil Uses Tax Money to Improve CoalTL | Research & Development
"United States Patent 4,207,208 - Method for (Improving) Syngas Conversion Catalyst; 1980; Mobil Oil Corporation; Abstract: A method is disclosed for the treatment of single particle iron-containing syngas (synthesis gas) conversion catalysts ... . Government Interests: The Government of the United States of America has rights in this invention pursuant to Contract No. E(49-18)2276 awarded by the U.S. Energy Research and Development Administration. Recently, it has been discovered that the conversion of synthesis gas into valuable products can be greatly enhanced by employing a special type of crystalline alumino-silicate zeolite exemplified by ZSM-5 in admixture with a conventional Fischer-Tropsch catalyst";
to help convert Coal, through Methanol, into Gasoline.
Herein, we see that our United States Department of Energy, as they did with Mobil Oil in the above "United States Patent 4,207,208 - Method for (Improving) Syngas Conversion Catalyst", helped to finance further development of the other part of Conoco's Carbon Dioxide conversion catalyst, as detailed in the above-cited "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates"; further development which just recently, it has become clear, makes the conversion of Carbon Dioxide into Methanol much more efficient.
As seen in excerpts, with comment inserted and appended, from the initial link in this dispatch to:
"United States Patent Application 20120225956 - Catalysts for the Reduction of Carbon Dioxide to Methanol
Catalysts For The Reduction Of Carbon Dioxide To Methanol - Patent application
Catalysts For The Reduction Of Carbon Dioxide To Methanol - The Board of Trustees of the Leland Stanford Junior University
Date: September 6, 2012
Inventor: Felix Studt, et. al., California, Denmark and Germany
Assignee: Trustees of the Leland Stanford Junior University, California
(Note: "the Leland Stanford Junior University" is the full, formal name of the college we all know far better and more famously as just plain old "Stanford".
For an explanation, see: Stanford University - Wikipedia, the free encyclopedia.)
Abstract: A catalytic composition is provided for methanol production. The composition includes an alloy of at least two different metals M and M', where M is selected from Nickel, Palladium, Iridium, and Ruthenium, and M' is selected from Gallium, Zinc, and Aluminum. A molar ratio of M to M' is in the range of 1:10 to 10:1, and the alloy is configured to catalyze a reduction of CO2 to methanol.
(Note the similarities to Conoco's "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates", as cited above.)
Government Interests: This invention was made with Government support under Grant No. DE-AC02-76SF00515, awarded by the Department of Energy. The Government has certain rights in this invention.
Claims: A catalytic composition for methanol production, comprising: an alloy of at least two different metals M and M', wherein M is selected from Ni, Pd, Ir, and Ru, and M' is selected from Ga, Zn, and Al, a molar ratio of M to M' is in the range of 1:10 to 10:1, and the alloy is configured to catalyze a reduction of CO2 to methanol.
The catalytic composition ... further comprising a support medium, and the alloy is disposed adjacent to the support medium.
The catalytic composition ... wherein M is Nickel, and M' is Gallium or Zinc.
A process for methanol production, comprising: providing a catalyst including at least two different metals M and M', wherein M is selected from transition metals of Group 8, transition metals of Group 9, and transition metals of Group 10, and M' is selected from transition metals of Group 4, transition metals of Group 12, and post-transition metals of Group 13; and contacting a feed stream including CO2 with the catalyst.
The process ... wherein contacting the feed stream with the catalyst is carried out at a reaction temperature in the range of 100 C to 400 C and a reaction pressure in the range of 0.5 bar to 10 bar.
(It doesn't, in sum, need really high temperature or really high pressure to operate.)
The process ... wherein the feed stream includes CO2 and H2 collectively amounting to greater than 50% of the feed stream, expressed in terms of moles.
The process ... wherein a molar ratio of CO2 to H2 is at least 1:1.
The process ... further comprising reactivating the catalyst by contacting a reactivation stream including H2 with the catalyst.
(Yes, free, elemental Hydrogen is required. And, as seen, for just one example, in:
West Virginia Coal Association | Pittsburgh Hydrogen for Coal Liquefaction | Research & Development; concerning: "United States Patent 3,888,750 - Electrolytic Decomposition of Water; 1975; Assignee: Westinghouse Electric Corporation, Pittsburgh; Abstract: Electrolysis and catalytic thermochemistry are combined to decompose water while minimizing the energy demanded to accomplish the decomposition. The electrolyte is H2SO3 produced by supplying SO2 and the water to be decomposed to the electrolyzer";
we do have available to us some efficient ways of getting it.)
Background and Field: The invention generally relates to the production of methanol and, more particularly, to catalysts for the production of methanol.
Nature reduces carbon dioxide (CO2) photo-chemically to store energy, and it remains one of the grand challenges in modern chemistry to design a process and catalysts to do the same. An initial stage in such a process could involve the generation of molecular hydrogen through a photo-electrochemical process or an electrochemical process using electrical power from photovoltaic cells or wind turbines. If this initial stage is followed by a heterogeneously catalyzed process to reduce CO2 to methanol, a sustainable source of a liquid fuel would have been established. Although certain copper-based (Cu-based) catalysts are currently used for industrial, hydrocarbon-based processes, these catalysts may not be appropriate for the reduction of CO2 to methanol, particularly if such reduction is carried out in smaller scale, decentralized plants. Specifically, Cu-based catalysts can suffer from complex synthesis as well as deactivation that is substantially irreversible.
It is against this background that a need arose to develop the catalysts and related systems and processes described herein.
Summary: One aspect of the invention relates to a catalytic composition for methanol production. In one embodiment, the composition includes an alloy of at least two different metals M and M', wherein M is selected from Ni, Pd, Ir, and Ru, and M' is selected from Ga, Zn, and Al. A molar ratio of M to M' is in the range of 1:10 to 10:1, and the alloy is configured to catalyze a reduction of CO2 to methanol.
Another aspect of the invention relates to a process for methanol production. In one embodiment, the process includes:
(a) providing a catalyst including at least two different metals M and M', wherein M is selected from transition metals of Group 8, transition metals of Group 9, and transition metals of Group 10, and M' is selected from transition metals of Group 4, transition metals of Group 12, and post-transition metals of Group 13; and:
(b) contacting a feed stream including CO2 with the catalyst."
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And, yes, again, the "feed stream" would need to include Hydrogen, as well as "CO2". And, as seen in:
West Virginia Coal Association | Japan Maximizes Hydrogen Production from Wind Power | Research & Development; concerning: "United States Patent 7,667,343 - Hydrogen Production System Using Wind Turbine Generator; 2010; Assignee: Hitachi, Ltd.; Abstract: A wind turbine-driven hydrogen production system controlling a power converter system such that the wind turbine stays in its operable range for a longer time and thus the hydrogen production system produces hydrogen for a longer time";
we shouldn't have any trouble making some in the breezier parts of US Coal Country.
And, if the breeze is blowing hard enough to make Hydrogen, then, as seen in:
West Virginia Coal Association | US Navy and Columbia University Recycle Atmospheric CO2 | Research & Development; concerning, in part: "United States Patent 7,833,328 - Scrubber for Capturing Carbon Dioxide from Air; 2010; Columbia University; The present invention is directed to methods for removing carbon dioxide from air";
we should be able to scrape some of the raw material needed by the process of our subject herein, "United States Patent Application 20120225956 - Catalysts for the Reduction of Carbon Dioxide to Methanol", that is, Carbon Dioxide, out of that breeze, and start making for ourselves our own, domestic liquid fuels, including, as seen alternatively in:
West Virginia Coal Association | ExxonMobil "Clean Gasoline from Coal" | Research & Development;
"Methanol to Gasoline (MTG): Production of Clean Gasoline from Coal; So Advanced, Yet So Simple; High energy prices and volatility in 2008 have helped to spur worldwide interest in finding and developing additional sources of energy to meet increasing demand. Coal is expected to play a key role as an energy source in the rapidly growing economy in countries such as China, India and even the United States, in
the coming decades, despite its higher CO2 intensity. To meet the need to increase supply while protecting the environment, continued technology advances will be needed. One such consideration is the conversion of coal into high quality, clean-burning transportation fuel. (And, one) commercially proven alternative for converting coal to gasoline through methanol (is) ExxonMobil Research and Engineering Company’s (EMRE) Methanol-to-Gasoline (MTG) process (which) converts coal to high quality clean gasoline when coupled with commercially proven coal gasification and methanol synthesis technology";
through Methanol, as synthesized from any source, whether Carbon Dioxide or Coal, Gasoline.
