United States Patent Application: 0120115965
The document we enclose in this dispatch doesn't differ much in substance from many others we have already brought to your attention; it is just the most recent incarnation of Carbon Dioxide recycling and utilization technology we are at this time aware of having emanated from the brilliant mind of Nobel Laureate chemist George Olah, and his colleagues at the University of Southern California.
We remind you, by way of just one example out of now many, as in:
West Virginia Coal Association | California Awarded March, 2011, CO2-to-Methanol US Patent | Research & Development; concerning: "United States Patent 7,906,559 - Conversion of CO2 to Methanol and/or Dimethyl Ether using Bi-Reforming of Methane or Natural Gas; March 15, 2011; Inventors: George Olah and G.K. Surya Prakash; Assignee: University of Southern California; 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";
that, the Carbon Dioxide recycling technology developed by the University of Southern California is now so advanced and so well-developed that it has been awarded not just a suite of United States Patents defining and establishing it's technical parameters, but, a registered, commercial trade name, as well.
In sum: Carbon Dioxide can be efficiently reacted with Methane, and, depending on the mix of product gases desired, Water, with the result being a blend of Carbon Monoxide and Hydrogen synthesis gas, "syngas", suitable in composition for catalytic chemical condensation, via long-established and currently-utilized reaction pathways, into a full range of liquid and gaseous hydrocarbons suitable for use as fuels or the further synthesis of other valuable products, like plastics.
We note that the "Bi-Reforming"(TM) technology developed by Olah and colleagues at the University of Southern California is closely similar in concept in the "Tri-Reforming" Carbon Dioxide utilization technology being further refined, as seen for one example in our report of:
More Penn State CO2 Recycling with Methane | Research & Development; which explains the: "Catalytic Tri-reforming of Methane Using Flue Gas from Fossil Fuel-based Power Plants; Wei Pan, Jian Zheng, Chunshan Song; The Pennsylvania State University; The present work is an exploratory study on a new process for the production of synthesis gas (CO + H2) using CO2 in flue gas from fossil fuel-based electric power plants";
at the more local and familiar Penn State University.
Methane, CH4, is required by "Bi-Reforming"(TM) and "Tri-reforming" processes for the productive chemical consumption of Carbon Dioxide, and, we remind you, that, as seen for only one example in:
Chicago Recycles CO2 to Methane | Research & Development | News; concerning: "United States Patent 4,609,440 - Electrochemical Synthesis of Methane; 1986; Assignee: Gas Research Institute, Chicago; Abstract: A method is described for electrochemically reducing carbon dioxide to form methane by electrolyzing an aqueous solution containing carbon dioxide utilizing a cathode which comprises ruthenium. If desired, solar energy can be utilized to provide the potential for the electrolyzing";
not only can the Methane needed by such Carbon Dioxide-consuming processes be itself made from Carbon Dioxide, but, that, environmental and renewable, i.e., "solar", sources of energy can be harnessed to drive such Carbon Dioxide-to-Methane transformation reactions.
In any case, herein we see that Nobel Laureate George Olah and his fellow genius Surya Prakash, whom we have also cited many times, have recently even further refined the technology for reacting Carbon Dioxide with Methane, toward the end of producing Methanol, a simple alcohol of immense value, both in and of itself and because of the things which can subsequently be made out of it.
Comment follows excerpts from the initial link in this dispatch to the recent:
"US Patent Application 20120115965 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane
CONVERSION OF CARBON DIOXIDE TO METHANOL USING BI-REFORMING OF METHANE OR NATURAL GAS - University of Southern California
Patent US20120115965 - CONVERSION OF CARBON DIOXIDE TO METHANOL USING BI-REFORMING OF METHANE OR ... - Google Patents
Date: May 10, 2012
Inventors: George Olah and G. K. Surya Prakash, California
Assignee: University of Southern California, Los Angeles
Abstract: The invention provides for a method of forming methanol by combining a mixture of methane, water and carbon dioxide under specific reaction conditions sufficient to form a mixture of hydrogen and carbon monoxide which are then reacted under conditions sufficient to form methanol. The molar ratio of hydrogen to carbon monoxide is at least two moles of hydrogen to one mole of carbon monoxide and the overall molar ratio between methane, water and carbon dioxide is about 3:2:1. Methane, carbon dioxide and water are bi-reformed over a catalyst. The catalyst includes a single metal, a metal oxide, a mixed catalyst of a metal and a metal oxide or a mixed catalyst of at least two metal oxides.
(The catalyst composition is actually key to this variant of Bi-Reforming (TM) technology. Note that the amount of Carbon Dioxide consumed in this variant is low, relative to the other ingredients. But, again, the Methane, which is the major reactant, can, as confirmed by Penn State University in our report of:
Penn State Solar CO2 + H2O = Methane | Research & Development; concerning the: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; The Pennsylvania State University; 2009; Efficient solar conversion of carbon dioxide and water vapor to methane";
in a process driven by freely-available environmental energy, be itself made from Carbon Dioxide.)
Claims: A method of preparing methanol from carbon dioxide and a methane source which comprises: conducting wet reforming of methane from the methane source with water to form carbon monoxide and hydrogen as follows: 2CH4 + 2H2O = 2CO +6H2;
conducting dry reforming of methane from the methane source with carbon dioxide to form carbon monoxide and hydrogen as follows: CH4 + CO2 =.2CO + 2H2; combining the carbon monoxide and hydrogen from the wet and dry reforming without separation of components to produce a molar mixture of hydrogen and carbon monoxide wherein the hydrogen is present in an amount such that the molar ratio of hydrogen to carbon monoxide is at least 2:1; and converting molar mixture of hydrogen and carbon monoxide under conditions sufficient to exclusively form methanol, as, follows: 4CO + 8H2 =.4CH3OH.
The method ... wherein the ratio of hydrogen to carbon monoxide is between 2:1 and 2.1:1
The method ... wherein the combining of the wet and dry reforming is conducted in two separate steps.
The method ... wherein the combining of the wet and dry reforming is combined in a single step with the methane, carbon dioxide and water present in sufficient stoichiometric amounts to provide the recited molar mixture and ratio of hydrogen and carbon monoxide.
The method ... wherein the methane, carbon dioxide and water are reacted in the single combined bi-reforming step to provide a mole ratio of about 3:1:2 as follows: 3CH4 + 2H2O + CO2 in order to provide the recited molar mixture and ratio of hydrogen and carbon monoxide.
The method ... wherein the molar mixture of hydrogen and carbon monoxide is present at a ratio of 2.05 to 1 and substantially all of the carbon monoxide and hydrogen reactants are exclusively converted to methanol.
The method ... wherein the bi-reforming is conducted without any significant coke formation.
The method ... wherein the bi-reforming is conducted in the presence of a combination of a metal and a metal oxide catalysts (and) the catalyst combination is Ni and V2O5; Ni2O3 and V2O5; or Ni2V2O7 and Ni3V2O8.
(Concerning the Nickel, "Ni", our good friends in Canada, specifically nearby Ontario, have plenty. Ditto the Vanadium, "V"; although there are several currently-idle Vanadium mines in Arkansas that could be reopened. Neither is used up in this process, as they serve only as catalysts, so the need for them wouldn't, in any case, be that great.)
The method ... wherein the catalyst combination is supported on a high surface or nanostructured support.
(Concerning the above "nanostructured support", the "nano" just means really, really small; and, there is a specific small size range that qualifies as being so described. The CO2-recycling scientists at Penn State use the terms a lot, as well; and, as we will document in some coming reports, the making of such "nanostructured supports", and other "nano" stuff, is established, well-understood in certain circles and perfectly feasible/do-able. It ain't none-such pixie dust, or something somebody just dreamed up.)
The method ... wherein the support comprises silica, alumina, a metal oxide or a metal (and) wherein the combined wet and dry reforming is conducted in the presence of a combination of metal oxide catalysts.
Description and Background: This application is a continuation of ... U.S. Patent No. 7,906,559.
(As in our earlier report, cited in our introductory comments, concerning: "US Patent 7,906,559 - Conversion of CO2 to Methanol and/or Dimethyl Ether using Bi-Reforming of Methane"; wherein the "Bi-Reforming(TM)" trademark was established. The technology being disclosed herein can be seen as an advancement, or improvement, on, or just a variant of, that somewhat precedent CO2-recycling technology.)
Hydrocarbons are essential in modern life. Hydrocarbons are used as fuel and raw material in various fields, including the chemical, petrochemical, plastics, and rubber industries. Fossil fuels, such as coal, oil and natural gas, are composed of hydrocarbons with varying ratios of carbon to hydrogen. Despite their wide application and high demand, fossil fuels also have limitations and disadvantages, particularly due to their finite reserve, irreversible combustion and contribution to air pollution ... .
(New) sources and ways for recyclable and environmentally benign carbon fuels are needed. (And, one)alternative frequently mentioned non-carbon fuel is hydrogen, and its use in the so-called "hydrogen economy." Hydrogen is thought to be beneficial as a clean fuel, producing only water when combusted. Free hydrogen, however, is not a natural primary energy source on earth, due to its incompatibility with the atmospheric oxygen. It must be generated from hydrocarbons or water, which is a highly energy-consuming process. Further, ... hydrogen is difficult and costly to handle, transport and distribute. As it is extremely light, volatile and potentially explosive, it requires high-pressure equipment. The needed non-existent infrastructure also necessitates special materials to minimize diffusion and leakage, and extensive safety precautions to prevent explosions.
Methanol is a convenient safe liquid easily obtained from existing coal ... sources via methods developed and practiced since the 1920's.
However, these methods using conversion (reforming) of coal ... to syn-gas (a mixture of H2 and CO) are highly energy consuming and produce large amount of CO2 as a by-product.
(The above isn't necessarily true. As seen, for only one example, in our report of:
Conoco 2011 Coal + CO2 + H2O + O2 = Syngas | Research & Development; concerning: "United States Patent 7,959,829 - Gasification System and Process; 2011; Assignee: ConocoPhillips Company; Abstract: A system and process for gasifying carbonaceous feedstock ... . Dry solid carbonaceous material is partially combusted, then pyrolyzed along with a first slurry stream comprising carbonaceous material in two separate reactor sections, thereby producing mixture products comprising synthesis gas. (Wherein) a second slurry stream (comprises) particulate carbonaceous material in a liquid carrier and ... wherein said carrier liquid is selected from group consisting of water, liquid Carbon Dioxide, (or) mixtures thereof";
in properly-designed and structured Coal gasification processes, Carbon Dioxide can actually be utilized and consumed, along with Coal, as one of the reactants in a syngas production facility. Or, as seen in:
Texaco 1951 Coal + CO2 + H2O + O2 = Syngas | Research & Development; concerning: "United States Patent 2,558,746 - Carbon Monoxide and Other Gases from Carbonaceous Materials; 1951; Assignee: The Texas Company; Abstract: This invention relates to a process and apparatus for the generation of gases comprising carbon monoxide from carbonaceous materials. In one of its more specific aspects it relates to a process and apparatus for the generation of a mixture of carbon monoxide and hydrogen, suitable as a feed for the synthesis of hydrocarbons, from powdered coal. An object of this invention is to provide a process for the generation of carbon monoxide and hydrogen (and) to provide a process particularly suited to the generation of a feed gas for the synthesis of hydrocarbons from coal. In the gasification of carbonaceous material with oxygen, particularly solid fuels, the reaction between oxygen and fuel results in the production of carbon dioxide ... . The oxidation reaction, being highly exothermic, releases large quantities of heat.The carbon dioxide, so produced, in contact with hot carbon, in turn, reacts with the carbon to produce carbon monoxide. Steam also reacts with heated carbon to produce carbon monoxide and hydrogen";
Coal gasification processes can be structured so that any Carbon Dioxide that is produced in them can be further reacted, within the gasification system itself, with more hot Coal to make more Carbon Monoxide, thus eliminating, or nearly so, any net co-production of Carbon Dioxide. - JtM)
Methanol not only represent a convenient and safe way to store and transport energy, but together with its derived product dimethyl ether (DME), is an excellent fuel. Dimethyl ether is easily obtained from methanol by dehydration or from methane with CO2 via a bi-reforming process. It is a particularly effective fuel for diesel engines because of its high cetane number and favorable combustion properties. Methanol and dimethyl ether exceedingly blend well with gasoline or diesel oil to be used as fuels in internal combustion engines or electricity generators.
(Concerning the above, as seen, for only one example, in our report of:
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 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";
the commercial technology also exists to convert Methanol, no matter which of our abundant resources, whether Carbon Dioxide or Coal, we make it from, directly into Gasoline.)
In addition to use as fuels, methanol, dimethyl ether and derived chemicals have significant applications in the chemical industry. Today, methanol is one of the most important feedstock in the chemical industry. The majority of the some 35 million tons of the annually produced methanol are used to manufacture a large variety of chemical products and materials, including basic chemicals such as formaldehyde ... as well as various polymers, paints, adhesives, construction materials, and others.
Methanol is also a feedstock for chloromethanes, methylamines, methyl methacrylate, and dimethyl terephthalate, among others. These chemical intermediates 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 phenol-, urea- and melamine-formaldehyde and polyacetal resins as well as butanediol and methylene bis(4-phenyl isocyanate) MDI foam, which is used as insulation in refrigerators, doors, and in car dashboards and bumpers. Formaldehyde resins are predominantly used as adhesives in a wide variety of applications, e.g., manufacture of particle boards, plywood and other wood panels."
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We'll close our excerpts there so that we can emphasize a key point implied by the immediately-above passage:
Any CO2 consumed by the process of our subject, "US Patent Application 20120115965 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane", which wound up, in the product Methanol, being ultimately utilized in the synthesis of final products like "paints, resins, adhesives, ... and plastics", would be forever, and productively and profitably, "sequestered".
Further, and again, since Methane is required by this CO2-recycling process, we remind you that, as in:
West Virginia Coal Association | Chicago Bugs Convert CO2 into Methane | Research & Development; concerning: "United States Patent Application 20090130734 - The Production of Methane from CO2; 2009; Inventor: Lauren Mets, Chicago; (Presumed Assignee: The University of Chicago); Abstract: A method of converting CO2 gas produced during industrial processes comprising contacting methanogenic archaea with the CO2 gas under suitable conditions to produce methane";
we can, via a selection of available processes, make that needed Methane from Carbon Dioxide, which again, and now indisputably, we must now start thinking of and treating for what it truly is:
A valuable raw material resource; a resource of, as herein affirmed, potentially immense value; a resource blessedly, even miraculously, co-produced by our essential, indispensable use of Coal in the generation of abundant and truly, genuinely, economical electric power.
