United States Patent: 7704369

By way of acknowledgement, this dispatch will be, in essence, a repeat of core information we earlier made report of. But, it bears repeating since the focus of our discourse concerns the fact that our United States Government has, officially, confirmed that a Nobel Prize-winning chemist led the development of technology which enables the efficient electrolytic conversion of a blend of Carbon Dioxide and Water into a hydrocarbon synthesis gas blend of Carbon Monoxide and Hydrogen.

Such synthesis gas, or "syngas", we remind you, can be catalytically, chemically condensed into both liquid and gaseous hydrocarbons, as via, for one example, the now nearly-ancient Fischer-Tropsch process.

 

And, such processing of Carbon Monoxide and Hydrogen syngas, to form various hydrocarbon fuels and chemicals, has undergone some truly impressive development in recent years. We can now process syngas so that specific types of hydrocarbons can be produced, in processes that are not only product-specific, but which even enable the co-production of electrical power.

Those recent developments in syngas processing are the main impetus for our further exposition and explanation of our subject: a recently-validated technology which enables the efficient production of syngas from, as the primary raw material, Carbon Dioxide.

We've many times documented that electrical energy can be employed to effect the co-conversion of blends of CO2 and Water, H2O, rather directly into fuel alcohol Methanol, and, even, into Gasoline. Examples of our reports concerning such technology include some developed by our own United States Department of Energy, as seen in our reports of:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development | News; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Inventor: Meyer Steinberg, NY; Assignee: The USA as represented by the USDOE; Abstract: A method and system for synthesizing methanol from the CO2 in air using electric power. The CO2 is absorbed by a solution of KOH to form K2CO3 which is electrolyzed to produce methanol, a liquid hydrocarbon fuel. Summary: In accordance with a preferred embodiment of this invention, a solution of KOH is employed to absorb CO2 from air forming an aqueous solution of K2CO3, the solution is then electrolyzed to produce CH3OH (i.e., Methanol) and reform KOH in solution, the CH3OH is then removed, and make-up water is then added prior to repeating the aforementioned steps. Other products ... are also formed which can be separated and recovered as valuable products. By the process described above, it is seen that any source of electrical power may be employed, such as coal-fired power plants. However, from an environmental point of view ... solar energy generated power, would be preferred"; and:

USDOE Converts CO2 to Gasoline | Research & Development | News; concerning: "United States Patent 4,197,421 - Synthetic Carbonaceous Fuels and Feedstocks; 1980; Inventor: Meyer Steinberg, NY; Assignee: The United States of America (USDOE Brookhaven, NY, National Laboratory); Abstract: This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous sodium carbonate/bicarbonate solution, obtained from scrubbing atmospheric carbon dioxide with an aqueous sodium hydroxide solution, whereby the hydrogen generated at the cathode and the carbon dioxide liberated in the center compartment are combined thermocatalytically into methanol and gasoline blends. The oxygen generated at the anode is preferably vented into the atmosphere, and the regenerated sodium hydroxide produced at the cathode is reused for scrubbing the CO2 from the atmosphere".

Other expositions of such electrolytic technologies posit that Carbon Dioxide and/or Water, H2O, can be electrolyzed separately or together, as in, for only one example, our report of:

Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development | News; concerning: "United States Patent 4,668,349 - Electrocatalytic Reduction of CO2 by Square Planar Transition Metal Complexes; 1987; Assignee: The Standard Oil Company; Abstract: A process for the electrocatalytic reduction of carbon dioxide comprises immersing a transition metal complex with square planar geometry into an aqueous or nonaqueous solution which has been acidified to a (specified) hydrogen ion concentration ... , adding the carbon dioxide, applying an electrical potential of from about -0.8 volts to about -1.5 volts ... , and reducing the carbon dioxide to carbon monoxide";

to form the various components of hydrocarbon synthesis gas, Hydrogen and, as above "carbon monoxide", which can then be catalytically, chemically combined and condensed, again as via for example the Fischer-Tropsch synthesis, into alcohols, and both gaseous and liquid hydrocarbons.

Later examples of CO2 and H2O electrolysis combine the two electrolytic processes so that both Carbon Monoxide and Hydrogen - - with, as in the above-cited  "United States Patent 4,197,421 - Synthetic Carbonaceous Fuels and Feedstocks", byproduct Oxygen - -, are evolved together and treated as hydrocarbon synthesis gas.

Such "co-electrolysis" of Carbon Dioxide and Water, for the co-production of Carbon Monoxide and  Hydrogen, is often specified to be conducted at higher temperatures where the co-reactants, CO2 and H2O, are both in the gaseous state, as in our report of:

Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development | News; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Inventors: Joseph Hartvigsen, et. al., Utah; Assignee: Ceramatec, Inc., Salt Lake City; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell. Synthesis gas is also produced by the coelectrolysis of carbon dioxide and steam in a solid oxide fuel cell or solid oxide electrolytic cell. The synthesis gas produced may then be further processed and eventually converted into a liquid fuel suitable for transportation or other applications".

And, we make note of the above "US Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water" since the United States Patent Application from which it evolved is cited as precedent art by the exposition of Carbon Dioxide utilization technology we submit to you herein.

We remind you that we have already reported to you many times on the almost-vast array of Carbon Dioxide utilization technologies developed by the Nobel Prize-winning genius, George Olah, and his colleagues, fellow-genius Surya Prakash perhaps primary among them, at the University of Southern California.

One example would be that seen in:

Southern California Recycles More CO2 | Research & Development | News; concerning: "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, 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 secondary treatment to produce essentially methanol, dimethyl ether and derived products. Claims:  An environmentally beneficial method of reducing the carbon dioxide content of the atmosphere and preparing a renewable fuel ... , which method comprises: separating the carbon dioxide from such source and producing methanol by hydrogenatively converting the carbon dioxide thus separated under conditions sufficient to produce methanol; utilizing the methanol thus produced as an energy storage and transportation material or as a fuel sufficient to generate energy ... . (And) wherein the carbon dioxide obtained from such source is hydrogenatively converted to methanol or derived products by catalytic, photochemical or electrochemical processes. (And) wherein the methanol is produced by hydrogentatively 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. (And) The method ... wherein the utilizing step further comprises dehydrating methanol under conditions sufficient to produce dimethyl ether ... . (And) The method ...  which further comprises utilizing the methanol or dimethyl ether as convenient energy storage and transportation materials in order to minimize or eliminate the disadvantages or dangers inherent in the use and transportation of hydrogen, LNG or LPG".

In the above "United States Patent 7,608,743 - "Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products", and others developed by Olah and his USC colleagues, the end products are produced by the rather direct hydrogenation of Carbon Dioxide with Hydrogen extracted from Water, H2O by "photochemical or electrochemical processes", to form the end products, "methanol or dimethyl ether". Further, we remind you, that, as explained in our reports of:

Mobil Oil 1977 Coal-Derived Alcohols to Gasoline | Research & Development | News; concerning: "United States Patent 4,025,575 - Process for Manufacturing Olefins; 1977; Assignee: Mobil Oil Corporation; Abstract: A lower alcohol and/or ether feed is selectively converted to a mixture of light olefins, including ethylene and propylene, by catalytic contact of the feed, for example methanol or dimethyl ether, ... with certain crystalline aluminosilicate zeolite catalysts exemplified by HZSM-5"; and:

Mobil Oil Coal to Methanol to Gasoline | Research & Development | News; 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";

Methanol, no matter which of our precious and abundant natural resources, whether Coal or Carbon Dioxide,  we make it from, can then be converted via known processes into both certain high-volume plastics and polymer raw materials, "ethylene and propylene", and, Gasoline. The "dimethyl ether", can as well be converted into Gasoline, although, as is, it can serve as a substitute for both Diesel fuel and "LPG", liquefied petroleum gas.

And, although we haven't emphasized it perhaps as much as we should have in our past reports, Methanol, as can be made from Carbon Dioxide, can also be used to capture Carbon Dioxide, and, then, serve, along with Water, in the further conversion of that additional Carbon Dioxide, through the electrolytic generation, as in "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water", cited above, of a synthesis gas blend of Carbon Monoxide and Hydrogen which can then be catalytically, chemically condensed into a greater amount of Methanol.

All as explained by Nobel laureate George Olah, and Surya Prakash, in excerpts from the initial link in this dispatch to:

"United States Patent 7,704,369 - Electrolysis of Carbon Dioxide in Aqueous Media to Carbon Monoxide and Hydrogen for Production of Methanol

http://www.freepatentsonline.com/7704369.html

(The importance of this technology became enhanced for us when further research revealed that the University of Southern California saw fit to protect it not only with US, Canadian and World Intellectual Property Organization patents, but, with patents applied for in and issued by a number of other individual nations, as, for one important example, China:

https://www.google.com/patents/CN101743343A?dq=7,704,369&ei=Qp7rU-2pFuHksAT4qoLIDA.

Further, again, note: This is not a process or technology for the production, necessarily, of "Methanol" alone from Carbon Dioxide. It is, instead, a technology for converting Carbon Dioxide and Water, "Aqueous Media", into syngas, "Carbon Monoxide and Hydrogen", which then, if wanted, can be converted into "Methanol". Other end products, as well, can be synthesized from the true core product "Carbon Monoxide and Hydrogen. That fact will figure in reports to follow. - JtM)

April 27, 2010

Inventors: George Olah and Surya Prakash, California

Assignee: University of Southern California, Los Angeles

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 cell compartment and a metal cathode electrode in another cell compartment that also contains an aqueous solution comprising methanol and an electrolyte of one or more alkyl ammonium halides, alkali carbonates or combinations thereof to produce 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.

Claims: An environmentally beneficial method of producing methanol by recycling and reductive conversion of any available source of carbon dioxide, which comprises: providing a divided electrochemical cell comprising an anode in a first cell compartment and a metal cathode electrode in a second cell compartment that also contains an aqueous solution or aqueous methanolic solution of an electrolyte of one or more alkyl ammonium halides, alkali carbonates or combinations thereof; recycling carbon dioxide from an existing source into the second cell compartment; electrochemically reducing the recycled carbon dioxide and solution in the second cell compartment to produce therein a reaction mixture containing carbon monoxide and hydrogen gas; and obtaining the carbon monoxide and hydrogen gas of the reaction mixture from the second cell compartment and directly reacting the reaction mixture in the presence of a catalyst to produce methanol while also producing oxygen in the first cell compartment at the anode to benefit the environment by reducing atmospheric carbon dioxide.

The method ... wherein the carbon monoxide and hydrogen gas are obtained in the reaction mixture in a ratio of at least about 1:2 or with excess amounts of hydrogen gas, and without adding hydrogen from outside of the cell.

The method ... wherein the carbon monoxide and hydrogen gas are present in the reaction mixture in a ratio of 1:2 to 1:2.1 (and) wherein the electrolyte comprises (1) one or more multi-alkyl ammonium halides, one or more alkali carbonates or bicarbonates; and (2) methanol or water (and) wherein the multi-alkyl ammonium halides are tetrabutylammonium halides (as further specified, and) wherein the alkali carbonates are sodium or potassium bicarbonates.

The method ... wherein the metal cathode electrode is a Cu, Au, Ag, Zn, Pd, Ga, Ni, Hg, In, Sn, Cd, Tl, Pb or Pt electrode.

(An additional claim seems to indicate that, out of the above, Gold, "Au", is preferred. It is a precious and costly metal; but, it represents a capital investment since it isn't used up or consumed in the Carbon Dioxide reduction process.)

The method ... wherein the electrochemical reduction includes applying a voltage of from -1.5 to -4 V with respect to a Ag/AgCl reference electrode.

(Note that not a lot of voltage is required to operate this CO2-to-syngas process. In later claims and extended exposition, Olah and Prakash specify that a variety of environmental sources of energy will be sufficient to generate the low-voltage electricity required by this Carbon Dioxide utilization process.)

The method ... wherein the existing source is an exhaust stream from a fossil fuel burning power or industrial plant ... and wherein the carbon dioxide is obtained from such existing source.

The method ... wherein the existing source is the atmosphere and which further comprises obtaining the carbon dioxide from such existing source by absorbing atmospheric carbon dioxide onto a suitable adsorbent followed by treating the adsorbent to release the adsorbed carbon dioxide therefrom.

(Concerning the above capture of Carbon Dioxide for utilization purposes, see George Olah's and the University of Southern California's own:

California Captures CO2 for Conversion to Hydrocarbons | Research & Development | News; concerning: "United States Patent 7,795,175 - Absorbents for the Separation of CO2 from Gas Mixtures Including the Air; 2010; Inventors: George Olah, et. al., CA; Assignee: University of Southern California, Los Angeles; Abstract: The invention relates to regenerative, supported amine sorbents that includes an amine or an amine/polyol composition deposited on a nano-structured support such as nanosilica. The sorbent provides structural integrity, as well as high selectivity and increased capacity for efficiently capturing carbon dioxide from gas mixtures, including the air. The sorbent is regenerative, and can be used through multiple operations of absorption-desorption cycles. ... The sorbent ... which releases absorbed carbon dioxide when treated for regeneration. ... The sorbent ... wherein the sorbent is treated with sufficient heat, reduced pressure, vacuum, gas purge, or a combination thereof to release a substantial amount or all the absorbed carbon dioxide. A method for continuously capturing and separating carbon dioxide from a gas mixture with a sorbent, which comprises exposing the sorbent (as described and specified herein) to the gas mixture to effect absorption of carbon dioxide by the sorbent and treating the sorbent that contains absorbed or entrapped carbon dioxide to release a substantial amount or all the absorbed carbon dioxide. The method ... which further comprises reacting the released carbon dioxide to form useful products. The method ... wherein carbon dioxide is used to produce methanol by (a) electrochemical reduction of carbon dioxide in water or (b) reducing carbon dioxide under conditions sufficient to produce an intermediate compound and catalytically hydrogenating the intermediate compound with hydrogen under conditions sufficient to form methanol".)

The method ... wherein electrical energy for the electrochemical reduction of the carbon dioxide is provided from an energy source based on ... hydroelectric, wind, geothermal or solar power.

(Concerning the above mention of "geothermal ... power", one little secret the proponents of "green" energy fail to make note of when promoting geothermal as a somehow "green" alternative is the fact that geothermal hot water is often loaded with dissolved, naturally-occurring Carbon Dioxide as it resides, pressurized, in the Earth's subsurface. When such geothermal hot water is brought to the surface for use in "environmentally responsible" power generation, when the pressure on that hot water is relieved when it passes through turbines or heat exchangers, that dissolved Carbon Dioxide off-gases. And, it is quite possible that geothermal power generators could emit as much, perhaps more, Carbon Dioxide per unit of electricity generated as do Coal-fired electric power plants. Not to worry. As seen separately in:

http://www.freepatentsonline.com/8791166.html: "United States Patent 8,791,166 - Producing Methanol and its Products Exclusively from Geothermal Sources and Their Energy; July 29, 2014; Inventors: George Olah and Surya Prakash; Assignee: University of Southern California";

Nobel Prize winner Olah and his worthy USC colleague Prakash have that covered, as well.).

An environmentally beneficial method of producing methanol by recycling and reductive conversion of any available source of carbon dioxide (and) wherein the existing source is an exhaust stream from a fossil fuel burning power or industrial plant, ... and providing electrical energy for the electrochemical reduction from an energy source based on ...hydroelectric, wind, geothermal or solar power thus providing environmental benefits (and) wherein the carbon monoxide and hydrogen gas are present in the reaction mixture in a ratio of 1:2 to 1:2.1, the metal cathode electrode is a gold electrode, and a voltage is applied in a range from -1.5 to -4 V with respect to a Ag/AgCl reference electrode.

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.

Methanol is not only a convenient and safe way to store energy. Methanol either can be blended with gasoline or diesel and used as fuels, for example in internal combustion engines ... .

Closely related to and derived from methanol, and also a desirable alternative fuel is dimethyl ether. Dimethyl ether is easily obtained by methanol dehydration. Dimethyl ether (DME, CH3OCH3), 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 has a boiling point of -25 C, and is a gas under ambient conditions. DME has no propensity to form peroxides unlike higher homologous ethers. 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.

In addition to use 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 formaldehyde, ... as well as various polymers, paints, adhesives, construction materials, and others.  ... 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; MDI foam is used as insulation in refrigerators, doors, and in car dashboards and bumpers). Formaldehyde resins are predominantly employed as an adhesive in a wide variety of applications, e.g., manufacture of particle boards, plywood and other wood panels.

In producing basic chemicals, raw material feedstock constitutes typically up to 60-70% of the manufacturing costs. The cost of feedstock therefore plays a significant economic role. Because of its lower cost, methanol is considered a potential feedstock for processes currently utilizing more expensive feedstocks such as ethylene and propylene, to produce chemicals including acetic acid, acetaldehyde, ethanol, ethylene glycol, styrene, and ethylbenzene, and various synthetic hydrocarbon products. For example, direct conversion of methanol to ethanol can be achieved using a rhodium-based catalyst, which has been found to promote the reductive carbonylation of methanol to acetaldehyde with selectivity close to 90%, and a ruthenium catalyst, which further reduces acetaldehyde to ethanol. The possibility of producing ethylene glycol via methanol oxidative coupling instead of the usual process using ethylene as feedstock is also pursued, and significant advances for synthesizing ethylene glycol from dimethyl ether, obtained by methanol dehydration, have also been made.

Conversion of methanol to olefins such as ethylene and propylene, also known as methanol to olefin (MTO) technology, is particularly promising considering the high demand for olefin materials, especially in polyolefin production.

(Note, in the above discussion, the rather immense array of polymers and plastics, and raw materials for polymers and plastics, that can be made from Methanol. Keep in mind that such applications for the Carbon Dioxide-derived Methanol would displace raw materials ordinarily and currently derived from OPEC petroleum; and, that, the CO2 consumed in the original synthesis of the Methanol would remain forever "sequestered" in those plastics and polymers.)

There is also a methanol to gasoline (MTG) process, in which medium-pore zeolites with considerable acidity, e.g., ZSM-5, are used as catalysts. In this process, methanol is first dehydrated to an equilibrium mixture of dimethyl ether, methanol and water over a catalyst, and this mixture is then converted to light olefins, primarily ethylene and propylene. The light olefins can undergo further transformations to higher olefins, C3-C6 alkanes, and C6-C10 aromatics such as toluene, xylenes, and trimethylbenzene.

(Concerning the above "methanol to gasoline (MTG) process" with "ZSM-5" zeolite catalysis, that is as in, or is intrinsically related to, our introductory comments concerning our prior reports of: "United States Patent 4,025,575 - Process for Manufacturing Olefins" and "United States Patent 4,447,310 - Production of Distillates through Methanol to Gasoline".

And, as it is further disclosed in our report of:

ExxonMobil Coal to Methanol to Gasoline | Research & Development | News; concerning both: 

"United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982;

Assignee: Exxon Research and Engineering Company, NJ; Abstract: Methanol is produced by gasifying a carbonaceous feed material with steam ... (and) wherein said carbonaceous feed material comprises coal";

and:

"United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation, NY; Abstract: The conversion of methanol to gasoline ... boiling products in a plurality of sequentially arranged catalyst beds comprising a dehydration catalyst followed by a special class of crystalline zeolite conversion catalyst is described wherein the dehydration catalyst life is prolonged";

it is seen to have been originally developed by the companies that became ExxonMobil in order to make, via an intermediate production of synthesis gas, and then, Methanol from that synthesis gas, Gasoline out of our abundant United States Coal.)

With decreasing oil and gas reserves, it is inevitable that synthetic hydrocarbons would play a major role. Thus, methanol-based synthetic hydrocarbons and chemicals available through MTG and MTO processes will assume increasing importance in replacing oil and gas-based materials.

Summary and Description: The invention relates to various embodiments of an environmentally beneficial method for producing methanol by reductive conversion of an available source of carbon dioxide including flue gases of fossil fuel burning power plants, industrial exhaust gases or the atmosphere itself. The method includes electrochemically reducing the carbon dioxide in a divided electrochemical cell that includes an anode in one cell compartment and a metal cathode electrode in another cell compartment that also contains an aqueous solution or aqueous methanolic solution and an electrolyte of one or more alkyl ammonium halides, alkali carbonates or combinations thereof to produce 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.

Advantageously, the carbon dioxide used in the reaction is obtained from an exhaust stream from fossil fuel burning power or industrial plants (or) may also be obtained from the atmosphere ... .

The electrical energy for the electrochemical reducing of carbon dioxide can come from a conventional energy source ... and alternatives (hydroelectric, wind, solar power, geothermal, etc.).

The present invention relates to the simple, efficient, and economical conversion of carbon dioxide from flue gases of fossil fuel burning power plants, industrial exhaust gases, carbon dioxide accompanying natural gas, carbon dioxide accompanying steam from geothermal wells or from the atmosphere itself to methanol, with subsequent application for energy storage and transportation fuels, conversion to synthetic hydrocarbons and its products. The carbon dioxide to methanol conversion is a better alternative to sequestration making it a renewable general carbon source for fuels, synthetic hydrocarbons and their products.

It has now been discovered that the use of electrochemical reduction of carbon dioxide (CO2), tailored over certain cathode electrocatalysts produces carbon monoxide (CO) and hydrogen gas (H2) in a high yielding ratio of approximately 1:2.

It has further been discovered that the electrochemical reduction of CO2 using noble metal, preferentially a gold electrode as a catalyst in aqueous methanol (or in water) with tetrabutylammonium halides and alkali carbonates as electrolytes not only gives CO but also H2 at the cathode, while producing oxygen gas (O2) at the anode.

The CO and H2 produced at the cathode are subsequently reacted over Cu (Copper) and Ni (Nickel) based catalysts to produce high yields of methanol (CH3OH)".

----------------------------- 

The final excerpted passages are of key importance to us at this point.

Although Methanol and it's "derived products", such as Dimethyl Ether, are the subjects of the extended dissertation herein, keep in mind that our subject, "United States Patent 7,704,369 - Electrolysis of Carbon Dioxide in Aqueous Media to Carbon Monoxide and Hydrogen for Production of Methanol", is, at it's core, a relatively low-energy process that requires only "-1.5 to -4" volts of electricity to convert Carbon Dioxide in "an aqueous", i.e., water, "solution" into a blend of "CO and H2", Carbon Monoxide and Hydrogen.

That CO2-derived "CO and H2" are then suggested by Olah and Prakash to be reacted over Copper or Nickel catalysts to produce Methanol.

However, as we will see in reports to follow, as versatile as Methanol might be, as a raw material for both Gasoline and Plastics, there are many other ways to process - - and many other products that can be directly synthesized from - - the blend of "CO and H2", synthesis gas, which, as in the process of our subject, "United States Patent 7,704,369 - Electrolysis of Carbon Dioxide in Aqueous Media to Carbon Monoxide and Hydrogen", can be produced so efficiently, with such a relatively small expenditure of energy, from nothing, in essence, but Water and Carbon Dioxide.


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