Keep in mind that Carbon Dioxide, as is co-produced in relatively small amounts, compared to some natural sources of CO2 emissions, such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of abundant and reliable, and affordable, electricity, can be and should be treated as a valuable raw material resource.
As seen for example in:
West Virginia Coal Association | USDOE 1976 Atmospheric CO2 to Methanol | Research & Development; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Assignee: The USA as represented by the USDOE; Abstract: A method and system for synthesizing methanol from the CO2 in air using electric power (and) 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";
our US Government recognized long ago that Carbon Dioxide could be utilized and consumed in the synthesis of valuable fuels and organic chemicals.
And, more lately, as seen in:
West Virginia Coal Association | USDOE Sunlight Converts CO2 into Methane | Research & Development; concerning: "US Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; 2013; Assignee: UChicago Argonne, LLC, Chicago; ("Argonne National Laboratory ...is one of the U.S. Department of Energy's largest national laboratories for scientific and engineering research.) Abstract: In one preferred embodiment, a photocatalyst for conversion of carbon dioxide and water to a hydrocarbon and oxygen ... . Government Interests: The United States Government has rights in this invention pursuant to Contract No. DE-AC02-06CH11357 between the United States Government and UChicago Argonne, LLC representing Argonne National Laboratory. Claims: A photocatalyst for conversion of carbon dioxide and water into a hydrocarbon and oxygen ... . A method of converting carbon dioxide and water into a hydrocarbon and oxygen comprising exposing a gaseous mixture of carbon dioxide and water to sun light in the presence of a photocatalyst ... . This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane"; and, in:
West Virginia Coal Association | Saudi Arabia 4th of July CO2 to Hydrocarbons | Research & Development; concerning: "US Patent Application 20130168966 - Method for Conversion of Carbon Dioxide into Hydrocarbons; Date: July 4, 2013; Inventors: Mazen Abdullah Ba-Abbad, et. al., Riyadh, Saudi Arabia; Assignee: King Saud University, Riyadh; Abstract: The present invention relates to a method for converting carbon dioxide into hydrocarbons by reacting magnesium with carbon dioxide to obtain magnesium oxide and carbon, reacting the carbon with hot water steam to obtain hydrogen (H2) and carbon monoxide, reacting hydrogen and carbon monoxide according to the Fischer-Tropsch method, or reacting the carbon obtained with earth alkaline metal oxide to obtain earth alkaline metal carbide and carbon monoxide, wherein the earth alkaline metal carbide is then reacted with water to obtain acetylene";
entities far removed both geographically and ideologically have reaffirmed that value of Carbon Dioxide, as a raw material resource from which any and all sorts of gaseous and, via the "Fischer-Tropsch method", liquid hydrocarbons can be ultimately synthesized.
Given that Carbon Dioxide is a valuable raw material, and, that, as in the above-cited "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2", our United States Department of Energy and it's precedent agencies have known that to be true since at least 1976, it's not surprising, that, as seen in:
West Virginia Coal Association | USDOE Pays for Conoco CO2 Acceptor to Clean Coal Syngas | Research & Development; concerning: "United States Patent 4,191,538 - Synthetic CO2 Acceptor and Gasification Process Therewith; 1980; Inventor: Everett Gorin; Assignee: Continental Oil Company; This invention resulted from work done pursuant to a contract with the Energy Research and Development Administration (now Department of Energy). Abstract: A synthetic CO2 acceptor comprising at least one compound selected from the group consisting of calcium oxide and calcium carbonate supported in a refractory carrier matrix of the general formula 3CaO(SiO2)x (Al2O3)x wherein x is from about 0 to about 1.0. Claims: A synthetic CO2 acceptor consisting essentially of at least one chemically uncombined calcium compound selected from the group consisting of calcium oxide and calcium carbonate supported in a refractory carrier matrix ... . In a process for producing a synthesis gas by reacting a carbonaceous feedstock with water in the presence of a carbon dioxide acceptor to produce a synthesis gas rich in hydrogen with at least a portion of the carbon dioxide so produced being reacted with said calcium oxide to produce calcium carbonate, the improvement wherein, said CO2 acceptor consists essentially of at least one chemically uncombined calcium compound selected from the group consisting essentially of calcium oxide and calcium carbonate supported in a refractory carrier matrix ... .The improvement ... wherein said acceptor is contacted with steam at a pressure (and) a temperature (as specified) after at least a portion of said calcium oxide has reacted to produce calcium carbonate. The improvement ... wherein said acceptor is regenerated by heating said acceptor to a temperature in excess of 1800 F thereby converting said calcium carbonate to calcium oxide. In accordance with the present invention, a synthetic acceptor is provided. The synthetic acceptor of the present invention comprises, in essence, a thermally stable inert matrix which is a porous refractory carrier which is substantially inert to lime and the high temperature steam environments encountered in the (Coal gasification) process ... . ... The reaction of the calcium carbonate and carbon dioxide liberates substantial quantities of heat which is required to sustain the reaction of carbon with steam. Since substantial quantities of carbon dioxide are removed from the reaction zone, the synthesis gas mixture so produced is rich in methane and, particularly, is rich in hydrogen since the removal of the CO2 tends to result in a substantial shifting of the equilibrium composition to hydrogen";
the USDOE has, over the decades, devoted, through contractors, some effort and expense to establishing the means by which Carbon Dioxide could be collected from industrial exhaust gas streams.
As an aside, note that the inventor, Everett Gorin, of the above USDOE-sponsored "United States Patent 4,191,538 - Synthetic CO2 Acceptor and Gasification Process Therewith", as seen for one example in:
West Virginia Coal Association | Consol 14-cent Gasoline from Coal | Research & Development; concerning the deceptively-titled: "US Patent 3,188,179 - Producing High-Purity Hydrogen from Hydrocarbon Gas and Steam; 1965; Inventor: Everett Gorin, Pittsburgh; Assignee: Consolidation Coal Company, PA; Abstract: This invention relates to a process for the conversion of coal to hydrocarbonaceous products. More particularly, this invention relates to a process for the conversion of coal to hydrocarbonaceous liquids suitable for conversion to gasoline in a conventional gasoline refining plant. As a result of my research I have now developed an economic process for the conversion of coal to gasoline. Via the process of my invention, gasoline may be obtained from coal at a cost of less than about 14 cents per gallon";was at one time employed by Consol, in Pittsburgh, where he developed an impressive suite of Coal conversion technologies, including some, as seen in:
West Virginia Coal Association | Consol 1954 Coal Steam Gasification | Research & Development; concerning: "United States Patent 2,682,455 - Gasification of Carbonaceous Solid Fuels; 1954; Inventor: Everett Gorin, Pittsburgh; Assignee: Consolidation Coal Company, Pennsylvania; Abstract: This invention relates to the gasification of carbonaceous solid fuels and, more particularly, to methods of and apparatus for reacting carbonaceous solid fuels with steam. The primary object of this invention is to provide an improved process for converting carbonaceous solid fuels into a gaseous product by reaction with steam ... under such conditions that no heat need be added to the system, i.e., under thermoneutral conditions.
Still another object of this invention is to provide an improved method for converting carbonaceous solid fuels into a gas which is rich in hydrogen";
which did employ indirect processes, wherein Coal is first gasified to form a hydrocarbon synthesis gas consisting of Hydrogen and Carbon Monoxide and suitable for, as in the above-cited Saudi Arabian process of "US Patent Application 20130168966 - Method for Conversion of Carbon Dioxide into Hydrocarbons", catalytic, chemical condensation into hydrocarbons via "the Fischer-Tropsch method"; and which syngas would be appropriate for processing and Carbon Dioxide removal via Gorin's process of "United States Patent 4,191,538 - Synthetic CO2 Acceptor and Gasification Process Therewith"
And, herein we see that the United States Department of Energy followed up directly on further development of the process embodied in the earlier, USDOE-sponsored process of Everett Gorin's US Patent 4,191,538, establishing more advanced CO2-acceptor technology that requires less energy for the regeneration of the absorbent and the release of the captured Carbon Dioxide.
Further: We are making report of this technology now since it is apparently viewed as an important milestone by those working to establish the technical bases for a Carbon Dioxide recycling industry; it is, as we will point out in a few reports to follow, often cited by developers of CO2-recycling art, as a viable source of Carbon Dioxide, as a potentially economical way to extract CO2 from industrial exhaust in order to make the CO2 available for conversion into hydrocarbon fuels and chemicals.
Comment follows excerpts from the initial link in this dispatch to:
"United States Patent 6,387,337 - Carbon Dioxide Capture Process with Regenerable Sorbents
Patent US6387337 - Carbon dioxide capture process with regenerable sorbents - Google Patents
May 14, 2002
Inventor: Henry Pennline and James Hoffman, PA
Assignee: The United States of America as represented by the US Department of Energy
Abstract: A process to remove carbon dioxide from a gas stream using a cross-flow, or a moving-bed reactor. In the reactor the gas contacts an active material that is an alkali-metal compound, such as an alkali-metal carbonate, alkali-metal oxide, or alkali-metal hydroxide; or in the alternative, an alkaline-earth metal compound, such as an alkaline-earth metal carbonate, alkaline-earth metal oxide, or alkaline-earth metal hydroxide. The active material can be used by itself or supported on a substrate of carbon, alumina, silica, titania or aluminosilicate. When the active material is an alkali-metal compound, the carbon-dioxide reacts with the metal compound to generate bicarbonate. When the active material is an alkaline-earth metal, the carbon dioxide reacts with the metal compound to generate carbonate. Spent sorbent containing the bicarbonate or carbonate is moved to a second reactor where it is heated or treated with a reducing agent such as ... hydrogen, or a synthesis gas comprising of a combination of carbon monoxide and hydrogen. The heat or reducing agent releases carbon dioxide gas and regenerates the active material for use as the sorbent material in the first reactor. New sorbent may be added to the regenerated sorbent prior to subsequent passes in the carbon dioxide removal reactor.
(The above use of "synthesis gas" as one of the agents of extraction is intriguing. But, note that "hydrogen" as well can be used to extract CO2 from the absorbent, which fact leads, in some subsequent technologies, to the starting mixture for use in CO2-to-hydrocarbon conversion technologies, much as that seen in our report of:
West Virginia Coal Association | NASA Improves CO2 to Methane Conversion | Research & Development; concerning: "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2012; Inventors: Christian Junaedi, et. al., Connecticut; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen in a first reaction zone with a first catalyst bed at a temperature greater than a first designated temperature; feeding the effluent from the first reaction zone into a second reaction zone, and contacting the effluent with a second catalyst bed at a temperature equal to or less than a second designated temperature, so as to produce a product stream comprising water and methane".)Government Interests: The United States Government has rights in this invention pursuant to the employer-employee relationship of the Government to the inventors as U.S. Department of Energy employees at the National Energy Technology Laboratory.
Claims: A method for removing carbon dioxide from a gas stream, comprising the step of:
- continuously moving a dry, solid sorbent, comprised of an active material, vertically through a first moving-bed reactor;
- directing materially unaltered stream of gas containing carbon dioxide from a source to said first moving bed reactor;
- flowing said unaltered stream of gas containing carbon dioxide through a bed of said sorbent perpendicular to the movement of said sorbent;
- regulating a speed of said sorbent movement through said first moving-bed reactor relative to a flow rate of said gas such that the carbon dioxide reacts with the active material to remove the carbon dioxide from the gas;
- continuously removing a spent sorbent from said first moving-bed reactor and moving said spent sorbent to a second reactor;
- processing said spent sorbent in said second reactor so as to liberate a stream of carbon dioxide and produce a regenerated sorbent; and
- recycling said regenerated sorbent to the first moving-bed reactor.
The method ... wherein said active material is selected from the group consisting of alkali metal carbonates, alkali-metal oxides, alkali-metal hydroxides, alkaline-earth metal carbonates, alkaline-earth metal oxides, or alkaline-earth metal hydroxides.
The method ... wherein said active material is a molecular sieve (and) wherein the substrate is selected from the group consisting of carbon, alumina, silica, titania, and aluminosilicates (and) has a surface area such that the active material deposited thereon is available to react with said gas.
The method ... wherein the sorbent regeneration step comprises heating the sorbent to a temperature sufficient to liberate the carbon dioxide.
(Later technologies involve a lower temperature, and thus a lower energy, with implied economies, for releasing the CO2 and regenerating the absorbent. Although, as seen in following claims, there are more intriguing options.)
The method ... wherein the sorbent regeneration step comprises chemically treating the spent sorbent to liberate the carbon dioxide (and) wherein said step of chemically treating the sorbent to liberate the carbon dioxide is accomplished by exposing the spent sorbent to a regeneration gas that is selected from the group consisting of ... methane, carbon monoxide, hydrogen, and a synthesis gas comprising a combination of carbon monoxide and hydrogen.
(Keep in mind the potentials, if the Carbon Dioxide is extracted with "methane", for a follow-on process like that seen in our report of:
West Virginia Coal Association | Saudia Arabia CO2 + Methane = Hydrocarbons + Syngas | Research & Development; concerning: "United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas; 2008; Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: Process for producing benzene, ethylene and synthesis gas, comprising the steps of: i) introducing a starting gas flow comprising methane and carbon dioxide into a reactor (and) removing a product gas flow comprising benzene, ethylene and synthesis gas from the reactor".)The method ... further comprising the step of maintaining an approximately constant temperature in the first reactor in the range of between about 200 and about 2000 degrees F (and) of maintaining an approximately constant temperature in the second reactor in the range of between about 200 and about 2000 degrees F.
Description and Background: The process described here can be installed at new facilities or can be retrofitted into an existing producer of CO2 -containing gases, e.g. a utility or industrial boiler. Depending upon the optimum temperature of CO2 absorption with the sorbent, the absorber could be placed anywhere along the gas stream that may have been or will be treated with another scrubbing process to remove other pollutants. The process may be installed anywhere along the gas path of new advanced power systems such as Integrated Gasification Combined Cycle (IGCC), Low-Emissions Boiler Systems (LEBS), High Performance Power Systems (HIPPS), and Pressurized Fluid Bed Combustors (PFB).
In addition, the process may be utilized with any system that produces CO2 either as a product, by-product, waste, or in any system where the objective is to concentrate CO2.
Objects and Summary: The primary objective of this invention is to provide a continuous ab/adsorption process for removing carbon dioxide from a gas stream with the active material being an alkali-metal compound or alkaline-earth metal compound. Another objective of this invention is to provide a process for regenerating and reusing the active material used to remove carbon dioxide from the gas stream.
A carbon dioxide-laden gas stream enters a moving-bed reactor and contacts an active material that is an alkali-metal compound or alkaline-earth metal compound by itself or supported on a substrate of carbon, alumina, silica, titania or aluminosilicate. The carbon dioxide reacts with the metal compound to generate bicarbonate when the active material is an alkali-metal compound or carbonate when the active material is an alkaline-earth metal compound.
The spent sorbent containing the bicarbonate or carbonate is moved through a second reactor where it is heated or treated with a reducing agent to release concentrated carbon dioxide gas and thereby regenerating the active material for reuse as the sorbent material in the first reactor".
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We apologize for the extended excerpts and the rather dry technical exposition.
However, keep the main points in mind:
This technology has been improved upon to reduce the energy requirements and, thus, the costs of extracting, in a cyclic process, "concentrated carbon dioxide gas" from an exhaust gas, or perhaps a synthesis gas, stream.
And, since the Carbon Dioxide can be extracted from the absorbent by "a reducing agent" which, as earlier specified, can be "methane" or "hydrogen", which would result in blends of CO2 and Hydrogen, or CO2 and Methane, that leads to, as we will see more fully explained in reports to follow, some seemingly profound potentials, as already exemplified in our above-cited reports concerning "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction" and "United States Patent 7,355,088 - Process for Producing Benzene, Ethylene and Synthesis Gas".