We've made a number of previous reports on the University of Southern California's Carbon Dioxide-recycling, Nobel-certified, genius, George Olah, and his, and his colleague's, development of an array of technologies that enable the productive recycling of Carbon Dioxide, as collected from whatever source, in the synthesis of liquid hydrocarbon fuels.
Those reports have included, for instance:
West Virginia Coal Association | Southern California Recycles More CO2 | Research & Development; about:
"United States Patent 7,608,743 - Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products; 2009; George Olah and Surya Prakash; The University of Southern California; Abstract: An efficient and environmentally beneficial method of recycling and producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by chemical or electrochemical reduction secondary treatment to produce essentially methanol, dimethyl ether and derived products"; and,
"United States Patent 5,928,806 - Recycling of Carbon Dioxide into Methyl Alcohol; 1999; George Olah and Surya Prakash; Abstract: A regenerative electrochemical cell system based on a fuel cell to oxidize methyl alcohol or other oxygenated hydrocarbons coupled with a regenerative cell to reduce carbon dioxide to form oxygenated hydrocarbons is disclosed. Methods to reversibly interconvert oxygenated hydrocarbons and carbon dioxide, to recycle carbon dioxide produced as a by-product of industrial processes, and to store and release electrical and chemical energy are also disclosed"; and:
West Virginia Coal Association | California Converts Power Plant CO2 to Methanol | Research & Development; concerning:
"US Patent Application 20060235091 - Efficient and Selective Conversion of CO2 to Methanol; 2006; George Olah and Surya Prakash; Abstract: An environmentally beneficial method of producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by electrochemical reduction produces formic acid acid and some formaldehyde and methanol mixtures. The formic acid can be used as source of carbon as well as hydrogen to produce methanol, dimethyl ether and other products."
Very nearly two years ago, we also made report of:
West Virginia Coal Association | California Files CO2 Recycling Patents | Research & Development; which concerned, in part:
"United States Patent Application Title: Conversion of Carbon Dioxide to Methanol and/or Dimethyl Ether Using ... Methane; Inventors: George A. Olah and Surya Prakash; Abstract: The invention discloses a method of converting carbon dioxide to methanol and/or dimethyl ether using any methane source or natural gas consisting of a combination of steam and dry reforming, in a specific ratio to produce a 2:1 molar ratio of hydrogen and carbon monoxide with subsequent conversion of the CO and H2 mixture exclusively to methanol and/or dimethyl ether. This method is termed the BI-REFORMING(R) process. Dehydrating formed methanol allows producing dimethyl ether (DME) using any suitable catalytic method, including use of solid acid catalysts. When recycling formed water into the bi-reforming step the conversion of carbon dioxide with methane produces exclusively dimethyl ether without any by-product formation and complete utilization of hydrogen."
The above US Patent Application, which, at the time we made that report, we had to access via a secondary patent disclosure site, since the official United States Patent and Trademark Office electronic files of it weren't then, for whatever reason, available or accessible, discloses a technology which is closely-similar to other CO2-recycling technologies, developed by others; as seen, for example, in:
Standard Oil 1954 CO2 + CH4 + H2O = Syngas | Research & Development; concerning: "United States Patent 2,676,156 - Preparation of Synthesis Gas; 1954; Standard Oil Development Company; The present invention relates to the preparation of a gas comprising carbon monoxide and hydrogen. In accordance with the present invention, carbon dioxide, steam and a light hydrocarbon gas such as methane (are reacted) to produce carbon monoxide and hydrogen in proportions suitable for employment in the hydrocarbon synthesis process. By manipulation of the quantities of CH4, H2O and CO2 to be reacted, desired ratios of H2 to CO in the product may be obtained."
Examples of such technology are rather numerous, and have been known, or referred to, as, variously, both "bi-reforming" and "tri-reforming", although by their designation of "BI-REFORMING(R)", the University of Southern California seems not only to be patenting that specific sort of CO2-recycling technology, but claiming an exclusive trade name for it, as well.
In any case, we see herein that George Olah's and USC's application for United States patent protection on his "BI-REFORMING(R)" Carbon Dioxide-recycling process was successful, and resulted in, as excerpted from the initial link in this dispatch, with comment inserted and appended:
"United States Patent 7,906,559 - Conversion of CO2 to Methanol and/or Dimethyl Ether using Bi-Reforming of Methane or Natural Gas
Date: March 15, 2011
Inventors: George Olah and G.K. Surya Prakash, CA
Assignee: University of Southern California, Los Angeles
Abstract: The invention discloses a method of converting carbon dioxide to methanol and/or dimethyl ether using any methane source or natural gas consisting of a combination of steam and dry reforming, in a specific ratio to produce a 2:1 molar ratio of hydrogen and carbon monoxide with subsequent conversion of the CO and H2 mixture exclusively to methanol and/or dimethyl ether.
This method is termed the BI-REFORMING.TM. process. Dehydrating formed methanol allows producing dimethyl ether (DME) using any suitable catalytic method, including use of solid acid catalysts. When recycling formed water into the bi-reforming step the conversion of carbon dioxide with methane produces exclusively dimethyl ether without any by-product formation and complete utilization of hydrogen.
Claims: A process of making exclusively dimethyl ether from carbon dioxide and a methane source which comprises: preparing methanol from carbon dioxide and a methane source by: combining wet reforming and dry reforming of sufficient amounts of methane, carbon dioxide and water under reaction conditions sufficient to produce an essentially 2:1 molar mixture of hydrogen and carbon monoxide; and converting the essentially 2:1 hydrogen and carbon monoxide mixture under conditions sufficient to form methanol; dehydrating the methanol thus produced; and recycling any water that is present under conditions sufficient to utilize only carbon dioxide and methane from the methane source to produce exclusively dimethyl ether.
(Our guess is that Olah specifies the alternative for Diesel fuel and substitute for natural gas, the versatile "dimethyl ether", as the end product to differentiate his technology from others somewhat related, such as those similar to that seen in:
Mobil Oil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline; 1984; Assignee: Mobil Oil Corporation;
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 ... 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";
wherein the Methanol, no matter what we make it from, can be converted, instead, into Gasoline We are, though, uncertain, likely due to our own personal insufficiencies, how it varies enough from others, such as:
Conoco Converts CO2 to Methanol and Dimethyl Ether | Research & Development; concerning: "United States Patent 6,664,207 - Catalyst for Converting Carbon Dioxide to Oxygenates; Assignee: ConocoPhillips Company, Houston; 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";
to achieve patent status.)
The method ... wherein the combining of the wet and dry reforming is conducted either in separate two steps or combined in a single step with the methane, carbon dioxide and water present in sufficient stoichiometric amounts to provide the hydrogen and carbon monoxide for production of methanol.
The method ... wherein the methane, carbon dioxide and water present in the single combined bi-reforming step are present in a mole ratio of about 3:1:2 to provide a mixture of hydrogen and carbon monoxide in a mole ratio of about 1:2.
The method ... wherein substantially all of the carbon monoxide and hydrogen are converted to methanol.
(And) wherein the combined bi-reforming is conducted at a temperature range of about 800 to 1100C.
The method ... wherein the bi-reforming is conducted in the presence of a combination of a metal and a metal oxide catalysts (consisting of) Ni and V2O5; Ni2O3 and V2O5; or Ni2V2O7 and Ni3V2O8.
(Nickel and Vanadium Oxides, as above, aren't all that exotic, hard to make, or expensive. And, they're not consumed or used up to any appreciable extent in the process, where they serve as catalysts. We'll presume everyone is comfortable with Nickel. As far as Vanadium goes, it is readily available and usually sold in alloy with Iron, or, as the above "V2O5" oxide. The metal itself can also be had, if we want to compound our own catalyst blends, and has fluctuated recently in price from under $20 per pound to right around $40. But, again, it isn't used up and only serves as a catalyst.)
The method ... wherein the combined wet and dry reforming is conducted in the presence of an added catalyst that includes single or mixed catalysts based on V, Ti, Ga, Mg, Cu, Mo, Bi, Fe, Mn, Co, Nb, Zr, La or Sn.
(Some of the above, such as Iron (Fe), Cobalt (Co) and Copper (Cu) aren't all that hard to get, either.)
The method ... wherein the methane source is natural gas, coal bed methane, methane hydrates, or aluminum carbide based methane.
(We suggest, instead, some other "methane source"s, such as those described in:
Penn State Solar CO2 + H2O = Methane | Research & Development; concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; Oomman K. Varghese, Maggie Paulose, Thomas J. LaTempa, and Craig A. Grimes; Materials Research Institute, The Pennsylvania State University; American Chemical Society, January 2009; Efficient solar conversion of carbon dioxide and water vapor to methane"; and:
Chicago Converts CO2 to Methane | Research & Development; concerning: "US Patent 3,766,027 - Method and Apparatus for CO2 Conversion to Methane; 1973; Assignee: Institute of Gas Technology, Chicago; Abstract: A process of fixation and conversion of carbon dioxide from the atmosphere or other sources to produce methane and oxygen. Carbon dioxide is scrubbed from a CO2 -containing source and separated by process of chemical concentration. A special cell is provided in which hydrogen is produced and reacted with the separated CO2 at methanation conditions to produce methane"; and:
GE Converts Coal to Methane and Recycles Carbon for USDOE | Research & Development; concerning: "United States Patent 4,558,027 - Catalysts for Carbon and Coal Gasification; 1985; Assignee: The USA; The invention relates to improved catalysts for carbon and coal gasification and improved processes for catalytic, coal gasification. The United States Government has rights in this invention pursuant to Contract No. DE-AC21-80MC14591 between the U.S. Department of Energy and General Electric Co. Abstract: Catalyst for the production of methane from carbon and/or coal by means of catalytic gasification".)
Description and Background: Methanol and DME ...provide a number of important advantages as transportation fuels. Contrary to hydrogen, methanol storage does not require any energy intensive procedures for pressurization or liquefaction. Because it is a liquid at room temperature, it can be easily handled, stored, distributed and carried in vehicles. DME although gaseous at room temperature can be easily stored under modest pressure and used effectively in admixture with diesel fuels and CNG, or used in residential gas mixtures.
In addition to use as fuels, methanol, DME and derived chemicals have also significant applications in the chemical industry. Today, methanol is one of the most important feedstock in the chemical industry. Most of the some 35 million tons of the annually produced methanol is used to manufacture a large variety of chemical products and materials, including basic chemicals such as formaldehyde, acetic acid, ... as well as various polymers, paints, adhesives, construction materials, and others. Worldwide, methanol is used to produce ... (various) chemical intermediates (which) are then processed to manufacture products such as paints, resins, adhesives, antifreeze, and plastics. Formaldehyde, produced in large quantities from methanol, is mainly used to prepare (various) resins ... used as adhesives in a wide variety of applications, e.g., manufacture of particle boards, plywood and other wood panels.
(In all of which, by the way, the CO2 consumed, via the process of our subject herein, "United States Patent 7,906,559 - Conversion of CO2 to Methanol", would be productively, and profitably, "sequestered".)
Various catalysts, e.g., synthetic aluminosilicate zeolite catalysts, such as ZSM-5 (a zeolite developed by Mobil) ... have been found to be active in converting methanol to ethylene and propylene at a temperature between 250 and 400C. When using an MTO process developed by Lurgi with ZSM-5 catalysts, mostly propylene is produced at yields above 70%. A process developed by ExxonMobil, with ZSM-5 catalyst, produces hydrocarbons in the gasoline and/or distillate range at selectivity greater than 95%."
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So, as confirmed herein by our own United States Government, through their issuance of our subject, "United States Patent 7,906,559 - Conversion of CO2 to Methanol", we can, starting with Carbon Dioxide and Methane, synthesize Methanol, which we can then convert into Gasoline at a rate "greater than 95%".
And, actually, we don't really need much of anything but Carbon Dioxide, and a little Water, H2O, to do all of that, since, as seen, for just one more example, in:
US Air Force 1965 CO2 to Fuel Conversion | Research & Development | News; concerning:
"Catalytic Reduction of Carbon Dioxide to Methane and Water; This report summarizes the work accomplished under contract AF 3"(615)-1210, for research on catalytic reduction of carbon dioxide to methane and water This work was performed under project 6146, "Atmosphere and Thermal Control",- and task 614622, "Oxygen Recovery From Carbon Dioxide." The work was monitored by Lt. Derry W. Marshall, Environmental Control Branch (FDFE), Air Force Flight Dynamics Laboratory, Research and Technology Division, Wright-Patterson Air Force Base, Ohio.The overall objective of this project was to develop a catalyst that would efficiently promote the Sabatier process, i.e., reduction of carbon dioxide with hydrogen at low temperature to form water and methane in high yields. The optimum catalyst was determined to be pure ruthenium metal powder (and, with) this catalyst ... complete (>99%) single-pass conversion of CO2 (to methane) was achieved";
we make the needed Methane, pretty-darned efficiently, out of Carbon Dioxide itself.
So, starting with, essentially, nothing but Carbon Dioxide and Water as the raw materials, we can wind up with Gasoline, through the intermediate Methanol produced herein, via the process of our subject, "United States Patent 7,906,559 - Conversion of Carbon Dioxide to Methanol".