United States Patent: 8138380

We have presented, over the long course of our reportage, numerous examples of the Carbon Dioxide recycling technology that has been, and is being, established at the University of Southern California, by their Nobel Laureate chemist, George Olah, and his USC colleagues.

Their array of CO2 utilization processes is compendious. It is as astounding to us here that just the sheer volume of their work, their productivity, has yet to garner any real public notice, as is the main point which they continue to drive home with such potent persistence, which is:

Carbon Dioxide, as it arises in only a very small way, relative to natural sources of emission, such as volcanoes, from our varied and productive uses of Coal, is a valuable raw material resource.

We can, on a practical basis, reclaim Carbon Dioxide, even from the atmosphere itself, and, then, convert it, just as we can convert our abundant Coal, into anything, quite literally anything, we now enslave ourselves, and economically indenture both our nation and our children's future, to OPEC for the supply of.

Our previous reports concerning the CO2-recycling achievements made at USC include, for a few examples:

West Virginia Coal Association | Southern California Recycles More CO2 | Research & Development; 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; 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 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".

And, since Olah and his colleagues consistently specify that the Carbon Dioxide can be obtained from "varied sources", which include "the atmosphere itself", we've documented that they have also taught us, as seen in our report of:

West Virginia Coal Association | California Captures CO2 for Conversion to Hydrocarbons | Research & Development; 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.; Assignee: University of Southern California;

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 (in a process) 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.";

how to go about efficiently doing that.

In any case, only a little more than two weeks ago, our United States Government again confirmed more details and specifics of USC's overall thesis, which is that we can, indeed, treat Carbon Dioxide as what it truly is: a valuable raw material resource that we can reclaim from whatever source we choose, and, then, efficiently convert into basic hydrocarbons from which we can synthesize anything, almost quite literally anything, we must now rely upon OPEC and Big Oil to provide us.

Comment follows, and is inserted within, excerpts from the initial link in this dispatch to:

"United States Patent 8,138,380 - Electrolysis of Carbon Dioxide ... for Production of Methanol

Date: March 20, 2012

Inventors: George Olah and G.K. Surya Prakash, CA

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 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.

(Note, in the above, that we can actually recycle one byproduct of this process, "oxygen", to help us do a better job of combusting our "fossil fuels in power plants". And, we remind you that this technology already sounds very similar in concept to other CO2-H2O "co-electrolysis" technologies we have made report of, including some developed both by scientists in the employ of our own US Government, as seen, for example, in:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; 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";

and, by others, as seen in:

West Virginia Coal Association | Princeton Scientists Convert More CO2 to Methanol and Ethanol | Research & Development; concerning: "United States Patent Application 20110114502 - Reducing Carbon Dioxide to Products; 2011; Inventors: Emily Barton Cole (and) Andrew Bocarsly, et. al., (Cole and Bocarsly are, or were, with Princeton University); Abstract: A method for reducing carbon dioxide to one or more products is disclosed. The method may include steps (A) to (C). Step (A) may bubble the carbon dioxide into a solution of an electrolyte and a catalyst in a divided electrochemical cell. The divided electrochemical cell may include an anode in a first cell compartment and a cathode in a second cell compartment. The cathode generally reduces the carbon dioxide into the products. Step (B) may vary at least one of (i) which of the products is produced and (ii) a faradaic yield of the products by adjusting one or more of (a) a cathode material and (b) a surface morphology of the cathode. Step (C) may separate the products from the solution. The method ... wherein said products (of the Carbon Dioxide chemical reduction) comprise one or more of acetaldehyde, acetone, carbon, carbon monoxide, carbonates, ethanol, ethylene, formaldehyde, formic acid, glyoxal, glyoxylic acid, graphite, isopropanol, methane, methanol, oxalate, oxalic acid and polymers containing carbon dioxide".

We further note that the full disclosure of our subject herein specifies that this is an improvement on, or advancement of, the CO2-recycling technology disclosed by the above-cited, earlier "United States Patent 7,704,369 - Electrolysis of Carbon Dioxide ... for Production of Methanol".)

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, a metal cathode electrode in a second cell compartment containing an aqueous solution comprising methanol or water, and an anion-conducting membrane in contact with the anode and cathode; recycling carbon dioxide from an existing source into the second cell compartment; electrochemically reducing the recycled carbon dioxide and solution by the cathode in the second cell compartment to produce therein a reaction mixture containing carbon monoxide and hydrogen gas in a ratio of 1:2 to 1:2.1; 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 in a high yield of at least 60% 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 the recited ratio without adding hydrogen from outside of the cell.

(Note that no external source of additional Hydrogen, at additional cost, is required.) 

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. 

The method ... wherein the metal cathode electrode is a gold electrode.

(Sure, gold is expensive. But, we do have plenty; and, it isn't consumed or used up to any appreciable extent in the process. It represents a capital investment, not really an ongoing expense for consumables.)

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.

(As seen in a related process about which we earlier reported, as accessible via:

Standard Oil Electrolyzes CO2 to Carbon Monoxide | Research & Development; 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";

not a lot of electric power, expressed at least in terms of voltage, is required to effect the electrolysis of Carbon Dioxide in aqueous solutions, if the right kinds of metal, or other, compounds are dissolved in the water with the CO2, or, otherwise used as components of the processing equipment. These can, thus, apparently, be relatively low-energy demand processes.)

The method ... wherein the existing source of carbon dioxide is an exhaust stream from a fossil fuel burning power or industrial plant, a source accompanying natural gas, or a source from geothermal wells, or the carbon dioxide is obtained from the natural gas or geothermal well source. 

The method ... wherein the existing source of carbon dioxide 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.

(That, as seen in our introductory reference to "United States Patent 7,795,175 - Absorbents for the Separation of CO2 from Gas Mixtures Including the Air". See also:

West Virginia Coal Association | US Navy and Columbia University Recycle Atmospheric CO2 | Research & Development; concerning, in part: "United States Patent 7,833,328 - Scrubber for Capturing Carbon Dioxide from Air; 2010; Assignee: Columbia University; Abstract: The present invention is directed to methods for carbon dioxide from air, which comprises exposing solvent covered surfaces to air streams where the airflow is kept laminar (and) also provides for an apparatus, which is a laminar scrubber, comprising solvent covered surfaces situated such that they can be exposed to air streams such that the airflow is kept laminar. An apparatus ... wherein the solvent is adapted to remove carbon dioxide from open air under ambient conditions (and) wherein the solvent is a hydroxide solution.  The present invention relates to carbon dioxide (CO2) removal under ambient conditions from the open air without heating or cooling the air".)

The method ... wherein the adsorbent is treated by sufficient heating or by subjecting the adsorbent to sufficient reduced pressure to release the adsorbed carbon dioxide. 

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.

(Those potentials are available to us in US Coal Country. See, for example:

http://hydropower.inl.gov/resourceassessment/pdfs/states/wv.pdf; concerning: the "U.S. Hydropower Resource Assessment for West Virginia; (USOE)", which specifies more than "37 identified sites" in the "Ohio Main Stream (and) Kanawha River basin"s that are suitable for the generation of significant amounts of hydroelectric power;

and:

Wind Powering America: Pennsylvania 50-Meter Wind Map; which informs that: "The U.S. Department of Energy's Wind Program and the National Renewable Energy Laboratory (NREL) published a wind resource map for the state of Pennsylvania. This map indicates that Pennsylvania has wind resources consistent with community-scale production. The good-to-excellent wind resource areas are concentrated on ridge crests in the southwestern part of Pennsylvania, located southwest of Altoona and southeast of Pittsburgh";

with additional info concerning such potentials, and their relation to the recycling of CO2, to follow in coming, future reports.)

The method ... wherein the direct reaction ... produced methanol in a yield of about 85 to 95%. 

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, a metal cathode electrode in a second cell compartment containing an aqueous solution comprising methanol or water, and an anion-conducting membrane in contact with the anode and cathode; recycling carbon dioxide from an existing source into the second cell compartment; electrochemically reducing the recycled carbon dioxide and solution by the cathode in the second cell compartment to produce therein a reaction mixture containing carbon monoxide and hydrogen gas in a ratio of 1:2 to 1:2.1; obtaining the carbon monoxide and hydrogen gas of the reaction mixture from the second cell compartment; directly reacting the reaction mixture in the presence of a catalyst to produce methanol in a high yield of at least 60% while also producing oxygen in the first cell compartment at the anode; and obtaining the oxygen produced at the anode and forwarding it for more efficient combustion of fossil fuels in power plants to exclusively produce clean CO2 exhausts to benefit the environment by reducing atmospheric carbon dioxide. 

The method ... which further comprises capturing the CO2 exhausts and recycling the captured CO2 exhausts as the existing source of CO2 for the cell.

(Although we might balk at the thought of capturing the CO2 on-site, at our Coal-fired power stations or natural gas stripping and pumping facilities, it can be done with some efficiency and economy. See, for example:

West Virginia Coal Association | Efficient Power Plant CO2 Capture for CO2-to-Fuel Conversion | Research & Development; concerning: "Development of an Economic Post-Combustion Carbon Capture Process;  2008; Siemens AG and EON Energie AG, Germany; Siemens develops an improved CO2 capture process with minimized energy demand, optimized for integration in conventional coal-fired power plants.

Further, the implication made by Olah, et. al., in the above, is that use of the co-product Oxygen to support combustion in fossil fuel power plants will result in a purer exhaust stream, i.e., less contaminated with stuff like oxides of Nitrogen, from which it might be more efficient to extract the CO2.)

The method ... wherein the anion-conducting membrane is sandwiched between the anode and cathode in a membrane electrode assembly (and) wherein the membrane is an anion-conducting polymer electrolyte based on polymeric amines.

(Yes, such "anion-conducting membrane"s are known, understood, available and being utilized. See:

http://www.electrochem.org/dl/interface/sum/sum10/sum10_p031-035.pdf ; concerning: "Anion Exchange Membrane Fuel Cells".)

The method ... wherein the direct reaction ... produces methanol in a yield of about 85 to 95%. 

The method ... wherein the membrane is an anion-conducting polymer electrolyte based on polymeric amines.

Background and Description: 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.

Hydrogen is beneficial as a clean fuel, producing only water when combusted. Free hydrogen, however, is not a natural energy source, and its generation from hydrocarbons or water is a highly energy-consuming process. Further, ... Hydrogen 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. Methanol either 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.

(Although Methanol does have some advantages, relative to Gasoline, as a liquid fuel, as the full Disclosure goes on to point out, it does have a significantly lower energy density, and mileage would be terrible. We could, though, instead, simply convert the Methanol, as seen in, for one example:

ExxonMobil Coal to Methanol to Gasoline | Research & Development; concerning: "United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation; Abstract: The conversion of methanol to gasoline";

into Gasoline; and, fill 'er up and go from there.)

Methanol has a latent heat of vaporization of about 3.7 times higher than gasoline, and can absorb a significantly larger amount of heat when passing from liquid to gas state. This helps remove heat away from the engine and enables the use of an air-cooled radiator instead of a heavier water-cooled system. Thus, compared to a gasoline-powered car, a methanol-powered engine provides a smaller, lighter engine block, reduced cooling requirements, and better acceleration and mileage capabilities. Methanol is also more environment-friendly than gasoline, and produces low overall emissions of air pollutants such as hydrocarbons, NOx, SO2 and particulates. 

Methanol also provides an attractive and more environment-friendly alternative to diesel fuel. Methanol does not produce smoke, soot, or particulates when combusted, in contrast to diesel fuel, which generally produces polluting particles during combustion. Methanol also produces very low emissions of NOx because it burns at a lower temperature than diesel. Furthermore, methanol has a significantly higher vapor pressure compared to diesel fuel, and the higher volatility allows easy start even in cold weather, without producing white smoke typical of cold start with a conventional diesel engine. If desired, additives or ignition improvers, such as (specified) can be added to bring methanol's cetane rating to the level closer to diesel. 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 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 (can be) 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 40 million tons of annually produced methanol is used to manufacture a large variety of chemical products and materials, including basic chemicals such as formaldehyde, acetic acid, MTBE (although it is increasingly phased out in the U.S. for environmental reasons), as well as various polymers, paints, adhesives, construction materials, and others. Worldwide, almost 70% of methanol is used to produce formaldehyde (38%), methyl-tent-butyl ether (MTBE, 20%) and acetic acid (11%). 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, silicones, 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; 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. It is considered that methanol is first dehydrated to dimethyl ether (DME), which then reacts to form ethylene and/or propylene.

In addition to being a conveniently storable energy source and fuel, methanol and methanol-derived DME and DMC are useful starting materials for various chemicals such as formaldehyde, acetic acid, and a number of other products including polymers, paints, adhesives, construction materials, synthetic chemicals, pharmaceuticals, and single cell proteins."

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And, in which "ethylene and/or propylene", which can be easily transformed into the plastics polyethylene and polypropylene, and, in the other "polymers, paints, adhesives", and "construction materials", not only would the Carbon Dioxide, collected from "a fossil fuel burning power or industrial plant" or from "natural gas"; or, even, from "the atmosphere itself", be for all practical purposes forever "sequestered"; but, it would be so sequestered in a productive, profitable way that would likely forestall and spare the consumption and use of some natural raw materials; and would, thus, contribute to the conservation of our natural resources and environment.

Far past time we stopped wasting time talking counter-productive nonsense like Cap & Trade taxation and mandated Carbon Dioxide "sequestration" in leaky old, nearly-depleted, natural petroleum reservoirs, to help Big Oil squeeze a few more drops of oil out of the ground, and a few more bucks out of our pockets, ain't it?

Clearly, as demonstrated herein by the University of Southern California, and as confirmed by our own United States Government, Carbon Dioxide can be, and should be, viewed and treated as a valuable raw material resource.

Once we have Carbon Dioxide, collected from whatever handy source, we can convert it, using environmental sources of energy to drive the processes, into Methanol.

And, once we have the Methanol, we can then, as in our above reference to: "United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation", convert that Methanol directly into something we seem desperately to need; so much so that we have indentured ourselves for many, many decades to any number of foreign, we dare say alien, nations to keep ourselves supplied with it.

Further, as explained in the full Disclosure of our subject, "United States Patent 8,138,380 - Electrolysis of Carbon Dioxide ... for Production of Methanol", once we have the Methanol, we can, instead, convert it through known and commercialized processes into a variety of "polymers, paints, adhesives" and "construction materials", wherein the Carbon Dioxide consumed in the original synthesis of the Methanol would not be just "sequestered"; but, like lead transformed by the Philosopher's Stone into gold, would instead be transformed into materials and products of value; in a process and in an industry that, in its entirety, would bring value in terms of greater domestic employment; an improved environment; and, an inspiring, maybe even a patriotic, sense of United States self-sufficiency and independence.


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