United States Patent: 8212088
We've presented you by now with overwhelming evidence that Carbon Dioxide, as 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 electric power, is a valuable raw material resource.
We can reclaim Carbon Dioxide, from whatever convenient source, and, via any one of multiple processes, convert it, recycle it, into both liquid and gaseous hydrocarbons.
One of the most prolific sources of such CO2 recycling technology is the Loker Hydrocarbon Institute at the University of Southern California, USC, home to Nobel Laureate George Olah:
Loker Hydrocarbon Research Institute;
George A. Olah; Founding Director and ... Nobel Laureate
(The Nobel Prize in Chemistry 1994)
G.K. Surya Prakash; Director
Aware of the need for a long-range program of basic research and graduate education in the field of hydrocarbon chemistry, the University of Southern California established its "Hydrocarbon Research Institute" in 1977. A generous donation from Donald and Katherine Loker helped build an outstanding facility which opened its doors in 1979. The University renamed the Institute the Donald P. and Katherine B. Loker Hydrocarbon Research Institute in honor of the Lokers in 1984. In 1991, USC formally adopted "Guidelines" ascertaining the Institute's organization and its permanence.
Hydrocarbons derived from petroleum, natural gas or coal are essential in many ways to modern life and its quality. The bulk of the world's hydrocarbons is used for fuels, electrical power generation, and heating. The chemical, petrochemical, plastics and rubber industries are also dependent upon hydrocarbons as raw materials for their products. Indeed, most industriallysignificant synthetic chemicals are derived from petroleum sources. The overall oil use of the world now exceeds ten million metric tons a day. Ever increasing world population and energy consumption and finite non-renewable fossil fuel resources are clearly on a collision course.
Even if technologies to generate energy from other sources are further developed (i.e. atomic, solar, wind, etc.), a concentrated research effort will be required to find long-range solutions for future hydrocarbon needs. The effort must include the development of alternative hydrocarbon sources, a search for new chemistry directed towards exploitation of renewable fuels, as well as the development of more efficient ways of utilizing and recycling our present resources.
The final solution to the hydrocarbon shortage will come only when mankind can produce unlimited cheap energy as with the promise of safer atomic energy and other alternate sources. With abundant cheap energy, hydrogen can be produced from sea water and then combined with carbon dioxide to produce hydrocarbons."
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Among our reports have been infrequent installments of a series documenting the ongoing, sequential development, by Olah, Prakash, and others at USC, of various chemical pathways through which Carbon Dioxide can be transformed into, primarily, Methanol, and, through Methanol, into other hydrocarbons.
That statement is too much of a summary; and, as such, carries some inaccuracy within it, since initial conversion into Methanol isn't the only chemical pathway the USC team pursue.
We'll anchor and attempt to illustrate the other potentials as we go along. And, go along we will.
We've already seen in:
West Virginia Coal Association | Southern California Recycles More CO2 | Research & Development; concerning, in part: "United States Patent 7,608,743 - Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products; 2009; Inventors: George Olah and Surya Prakash; Assignee: 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:
West Virginia Coal Association | California Recycles More and More Carbon Dioxide | Research & Development; concerning: "United States Patent 7,704,369 - Electrolysis of Carbon Dioxide ... for Production of Methanol; 2010; Inventors: George Olah and Surya Prakash; Assignee: University of Southern California; Abstract: An environmentally beneficial method of producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning power plants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by an electrochemical reduction of carbon dioxide"; and:
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; 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";
(We'll interrupt the litany here to note, that. the above "United States Patent 7,906,559 - Conversion of CO2 to Methanol and/or Dimethyl Ether using Bi-Reforming of Methane" actually represents a multiple pathway for the recycling of Carbon Dioxide, as Olah and Prakash no doubt were and are aware, since it has also been established in the California university system, as seen in:
West Virginia Coal Association | California Bugs Convert CO2 into Methane | Research & Development; concerning: "United States Patent Application 20110171711 - Methods and Compositions for Production of Methane Gas"; 2011; Inventor: Daniel E. Koshland, Jr.; (University of California at Berkeley); Abstract: The present invention provides methods and compositions for sustained methane production from atmospheric CO2 and solar energy from the sun";
that, the Methane needed for the Olah and Prakash process of "US Patent 7,906,559 - Conversion of CO2 to Methanol and/or Dimethyl Ether using Bi-Reforming of Methane" can itself be synthesized from CO2.)
and, in our most recent entry in the catalogue of Olah and Prakash CO2-recycling technologies:
West Virginia Coal Association | California March 2012 Efficient CO2 to Methanol | Research & Development; concerning: "United States Patent 8,138,380 - Electrolysis of Carbon Dioxide ... for Production of Methanol; March 20, 2012; Inventors: George Olah and G.K. Surya Prakash; Assignee: University of Southern California; Abstract: An environmentally beneficial method of producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning power plants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by an electrochemical reduction of carbon dioxide in a divided electrochemical cell that includes an anode in one compartment and a metal cathode electrode in a compartment that also contains an aqueous solution comprising methanol and an electrolyte. An anion-conducting membrane can be provided between the anode and cathode to produce at the cathode therein a reaction mixture containing carbon monoxide and hydrogen, which can be subsequently used to produce methanol while also producing oxygen in the cell at the anode. The oxygen produced at the anode can be recycled for efficient combustion of fossil fuels in power plants to exclusively produce CO2 exhausts for capture and recycling as the source of CO2 for the cell";
that:
Carbon Dioxide is a valuable, maybe even now a precious, raw material resource.
We can, through multiple direct and indirect chemical and electro-chemical pathways, efficiently convert Carbon Dioxide, along with other common or synergistically-obtained co-reactants, such as Water or Methane, into the chemical building blocks from which we can synthesize hydrocarbons and alcohols.
We note that the above "United States Patent 8,138,380 - Electrolysis of Carbon Dioxide ... for Production of Methanol", with it's electrically-stimulated "reduction of carbon dioxide in a divided electrochemical cell" with an "aqueous solution ... to produce ... a reaction mixture containing carbon monoxide and hydrogen", i.e., hydrocarbon synthesis gas, seems closely related in it's concept and process to other Carbon Dioxide recycling technology, known as "Syntrolysis", developed by our United States Department of Energy, as seen, for one example, in:
More USDOE CO2 "Syntrolysis" | Research & Development; concerning: "Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas; Fifth International Fuel Cell Science, Engineering and Technology Conference; July, 2007; J.E. O'Brien, C.M. Stoots, et. al.; Idaho National Laboratory, USDOE; and Ceramatec, Inc., Utah; Abstract: An experimental study has been completed to assess the performance of single-oxide electrolysis cells ... simultaneously electrolyzing steam and carbon dioxide for the direct production of syngas. Introduction: A research project is underway at the Idaho National Laboratory (INL) to investigate the feasibility of producing syngas by simultaneous electrolytic reduction of steam and carbon dioxide ... . Syngas, a mixture of hydrogen and carbon monoxide, can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes".
Finally, herein, we present, as excerpted from the initial link in this dispatch, the very latest United States Government-certified Olah and Prakash, USC Carbon Dioxide recycling process, as it just became available in the United States Patent and Trademark Office's electronic library, after having been awarded just a little more than one and a half months ago, the day before Independence Day:
"United States Patent 8,212,088 - Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products
Patent US8212088 - Efficient and selective chemical recycling of carbon dioxide to methanol ... - Google Patents
Efficient and selective chemical recycling of carbon dioxide to methanol, dimethyl ether and derived products - University of
Date: July 3, 2012
Inventors: George Olah and G.K. Surya Prakash, CA
Assignee: University of Southern California, Los Angeles
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 seconardy treatment to produce essentially methanol, dimethyl ether and derived products.
Claims: An environmentally beneficial method of preparing a renewable fuel, which method comprises: obtaining carbon dioxide from a natural or chemical source that would otherwise be present in or discharged into the atmosphere; and producing an energy storage and transportation material or a fuel sufficient to generate energy by hydrogenatively converting the carbon dioxide thus obtained under conditions sufficient to produce methanol as the material or fuel.
The method ... wherein the methanol is produced by reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol.
The method ... wherein the methanol is produced by generating carbon monoxide from the carbon dioxide through a high temperature reaction with carbon, reacting the carbon monoxide with the previously produced methanol under conditions sufficient to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form additional methanol.
(For a little more information on the reactions alluded to above, see our report of:
West Virginia Coal Association | United Technologies Converts CO2 to Formic Acid | Research & Development; concerning both: "United States Patent 4,921,585 - Electrolysis Cell and Method of Use; 1990; Assignee: United Technologies Corporation; Abstract: The present invention discloses an improved solid polymer electrolysis cell for the reduction of carbon dioxide. ... The most prevalent reaction is the reduction of carbon dioxide to formic acid"; and: "The Electrochemical Conversion of Carbon Dioxide into Methanol: The Formic Acid Reduction Step; 1984; Naval Weapons Research Center, China Lake, CA; Abstract: Various studies have shown that the electrode reduction of CO2 in water using metal electrodes yields formic acid as the main product".)
The method ... wherein the methanol is produced by reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, augmenting the reaction mixture by reacting, without separation of the reaction mixture, the formaldehyde into methanol with some of the formic acid used as a hydrogen source, and reacting some of the formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form methanol.
The method ... wherein the methanol is produced by hydrogenatively converting the carbon dioxide to form a reaction mixture that contains methanol, formic acid and formaldehyde, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde and formic acid to methanol ... including reacting of the formic acid with methanol to form methyl formate, followed by hydrogenating the methyl formate under conditions sufficient to form double the starting amount of methanol.
(See, for a description of similar and related Carbon Dioxide recycling reactants, reaction sequences and products, our report of:
West Virginia Coal Association | Sweden Converts Carbon Dioxide and Water into Methanol | Research & Development; concerning; "United States Patent Application 20090246572 - Method And A Reactor For Making Methanol; 2009; Assignee: Morphic Technologies, Sweden; Abstract: Methanol is produced from carbon dioxide and water in a reactor comprising a cathode side with a cathode and catalyst for the cathode reaction (wherein) the carbon dioxide is exposed to a cathode reaction, and is reduced to formic acid, in a second step the formic acid is reduced to formaldehyde and water, and in a third step the formaldehyde is reduced to methanol.")
The method ... wherein the hydrogen needed for the hydrogenation of methyl formate is obtained at least in part from cleavage of the formic acid from the reaction mixture.
The method ... wherein the hydrogen needed for the hydrogenative conversion of carbon dioxide is obtained by the ... electrolysis of water using an available energy source.
(See, for just one example of so using "an available energy source" to generate "the hydrogen":
West Virginia Coal Association | General Motors Uses Sunshine to Make Hydrogen | Research & Development; concerning in part: "United States Patent 7,459,065 - Hydrogen Generator Photovoltaic Electrolysis Reactor System; 2008; Assignee: General Motors Corporation, Detroit; Abstract: An apparatus for creating hydrogen from the disassociation of water using sunlight.")
The method ... which further comprises dehydrating the methanol under conditions sufficient to produce dimethyl ether; using the dimethyl ether as the fuel or as a component of the fuel.
The method ... which further comprises utilizing. as the convenient energy storage and transportation materials, the methanol or dimethyl ether in order to minimize or eliminate the disadvantages or dangers inherent in the use and transportation of hydrogen, LNG or LPG.
(We can, in other words, by starting with Carbon Dioxide, Water and Sunshine, replace "LNG", "Liquefied Natural Gas".)
An environmentally beneficial method of preparing a renewable fuel, which method comprises: obtaining carbon dioxide from a natural or chemical source; and producing an energy storage and transportation material or a fuel sufficient to generate energy by hydrogenatively converting the carbon dioxide thus obtained under conditions sufficient to produce methanol as the material or fuel.
The method ... wherein the chemical source is an exhaust stream collected from the burning or combustion of a fossil fuel.
The method ... wherein the natural or chemical source of carbon dioxide is the atmosphere, an exhaust stream from a power or industrial plant, or a source accompanying natural gas.
The method ... wherein the carbon dioxide is captured and obtained from the source and is converted under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol.
An environmentally beneficial method of reducing the carbon dioxide content of the atmosphere by recycling carbon dioxide and producing methanol using a reductive conversion of an available source of carbon dioxide from a natural or chemical source, which method comprises:
(A) reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol; or:
(B) augmenting the reaction mixture of (A) by reacting the formaldehyde with some of the formic acid as a hydrogen source, without separation of the reaction mixture, into methanol, and by reacting some of the formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form methanol; or:
(C) generating carbon monoxide from the carbon dioxide through a high temperature reaction with carbon, reacting the carbon monoxide with methanol produced in (A) under conditions sufficient to form methyl formate, followed by catalytic hydrogenation of the methyl formate under conditions sufficient to form methanol.
(Concerning the above "generating carbon monoxide from the carbon dioxide through a high temperature reaction with carbon", see, for just one example:
Carbon Dioxide Recycled in the Manufacture of Plastics | Research & Development; concerning, in part: "United States Patent 4,564,513 - Process for the Production of Carbon Monoxide; 1986; Assignee: Bayer Aktiengesellschaft (AG), Germany; Abstract: Carbon monoxide is produced in an improved process in a carbon-filled, water-cooled generator in the configuration of a truncated cone in the longitudinal section, by the gasification of said carbon with a mixed gas of oxygen and carbon dioxide".)
Description and Background: 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 gas, are composed of hydrocarbons with varying ratios of carbon and hydrogen, and is non-renewably used when combusted, forming carbon dioxide and water.
Despite their wide application and high demand, fossil fuels present a number of disadvantages, including the finite reserve (and) alternative sources of energy are needed.
One such alternative frequently mentioned is hydrogen, and the so-called "hydrogen economy." Hydrogen is beneficial as a clean fuel, producing only water when combusted. Free hydrogen, however, is not a natural energy source, and ... is also not a convenient energy storage medium because it is difficult and costly to handle, store, transport and distribute. As it is extremely volatile and potentially explosive, hydrogen gas requires high-pressure equipment, costly and non-existent infrastructure, special materials to minimize diffusion and leakage, and extensive safety precautions to prevent explosions.
It was suggested that a more practical alternative is methanol. Methanol, CH3OH, is the simplest liquid oxygenated hydrocarbon, differing from methane (CH4) by a single additional oxygen atom.
Methanol is not only a convenient and safe way to store energy, but, together with its derived dimethyl ether (DME), is an excellent fuel. Dimethyl ether is easily obtained from methanol by dehydration and is an effective fuel particularly in diesel engines because of its high cetane number and favorable properties.
Methanol and dimethyl ether can be blended with gasoline or diesel and used as fuels, for example in internal combustion engines or electricity generators.
Contrary to gasoline, which is a complex mixture of many different hydrocarbons and additives, methanol is a single chemical compound. It contains about half the energy density of gasoline, meaning that two liters of methanol provides the same energy as a liter of gasoline.
(As explained, however, for just one example, in our report of:
West Virginia Coal Association | ExxonMobil "Clean Gasoline from Coal" | Research & Development; concerning: "'Methanol to Gasoline (MTG): Production of Clean Gasoline from Coal; So Advanced, Yet So Simple'; ExxonMobil Research and Engineering Company’s (EMRE) Methanol-to-Gasoline (MTG) process converts coal to high quality clean gasoline when coupled with commercially proven coal gasification and methanol synthesis technology";
if we prefer, Methanol, no matter which of our vast natural resources, Coal or Carbon Dioxide, we make it from, can be catalytically converted through known and commercial processes into Gasoline.)
Methanol can also be used in the manufacture of biodiesel fuels by esterification of fatty acids.
Closely related and derived from methanol, and also a desirable alternative fuel is dimethyl ether. Dimethyl ether (DME), the simplest of all ethers, is a colorless, nontoxic, non-corrosive, non-carcinogenic and environmentally friendly chemical that is mainly used today as an aerosol propellant in spray cans, in place of the banned CFC gases. DME ... is, however, easily handled as liquid and stored in pressurized tanks, much like liquefied petroleum gas (LPG). The interest in dimethyl ether as alternative fuel lies in its high cetane rating of 55 to 60, which is much higher than that of methanol and is also higher than the cetane rating of 40 to 55 of conventional diesel fuels. The cetane rating indicates that DME can be effectively used in diesel engines. Advantageously, DME, like methanol, is clean burning, and produces no soot particulates, black smoke or SO2, and only very low amounts of NOx and other emissions even without after-treatment of its exhaust gas.
Methanol is also an attractive source of fuel for static applications. For example, methanol can be used directly as fuel in gas turbines to generate electric power. Gas turbines typically use natural gas or light petroleum distillate fractions as fuel. Compared to such fuels, methanol can achieve higher power output and lower NOx emissions because of its lower flame temperature. Since methanol does not contain sulfur, SO2 emissions are also eliminated. Operation on methanol offers the same flexibility as natural gas and distillate fuels, and can be performed with existing turbines, originally designed for natural gas or other fossil fuels, after relatively easy modification.
(So, we can directly replace Natural Gas for power generation, where it is being inefficiently used for such, with Methanol - - made from Carbon Dioxide collected from the "flue gases of ... powerplants".
Methanol and dimethyl ether are also very convenient materials for storage and transportation of energy without the great disadvantage and potential danger of using hydrogen. Hydrogen can readily converted with CO2 to methanol and/or DME thus providing a convenient safe form for storing and transporting energy produced from any source.
In addition to these uses as fuels, methanol and methanol-derived chemicals have other significant applications in the chemical industry. Today, methanol is one of the most important feedstock in the chemical industry. Most of the 32 million tons of annually produced methanol is used to manufacture a large variety of chemical products and materials, including basic chemicals such as ... various polymers, paints, adhesives, construction materials, and ... plastics.
(And, in which immediately-above "construction materials, and ... plastics", we submit, the Carbon Dioxide consumed via the process of our subject, "United States Patent 8,212,088 - Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products", for the initial synthesis of the Methanol, would be forever, and productively, and profitably, "sequestered".)
Our invention relates to various embodiments of an environmentally carbon neutral use of utilizing and recycling carbon dioxide from industrial or natural sources, as well as from the air itself into methanol dimethyl ether and derived products. This method comprises separating the carbon dioxide from any available source containing same and producing methanol by reducing the carbon dioxide thus obtained under conditions sufficient to produce methanol ... .
The carbon dioxide obtained from such sources is typically converted to methanol by catalytic, photochemical or electrochemical hydrogenation. The conversion to methanol, however, forms a reaction mixture also containing formic acid and formaldehyde. These can be without separation of the reaction mixture, in a subsequent treatment step conducted under conditions sufficient to produce formaldehyde and formic acid themselves converted to methanol "
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Yes, some Carbon-free source of energy would be preferred to drive the Carbon Dioxide-recycling process of our subject, "United States Patent 8,212,088 - Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products".
And, yes, as seen, for just two examples of available potentials, in:
http://hydropower.inl.gov/resourceassessment/pdfs/states/wv.pdf; concerning: "U.S. Hydropower Resource Assessment for West Virginia; 1998; U.S. Department of Energy"; and:
http://hydropower.inl.gov/resourceassessment/pdfs/states/pa.pdf; concerning: "U.S. Hydropower Resource Assessment for Pennsylvania; 1997; U.S. Department of Energy";
we do have some to work with.
What we don't have, apparently, is printer's ink; at least enough of it to print the good news in Coal Country newspapers; the good news that:
Carbon Dioxide - - as confirmed herein by the United States Government, through the recent issuance of "United States Patent 8,212,088 - Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products" - - is a valuable raw material resource.
We can collect CO2 from the exhaust stacks of our Coal-fired power plants, or even from the atmosphere itself, and convert it, efficiently and selectively, into the valuable alcohol, Methanol, and the substitute Diesel fuel, Dimethyl Ether.
Sounds like "good news" to us.
Too bad no one in the Coal Country public news media seems to think so.
