United States Patent: 8771403

We first remind you that our United States Government's Department of Energy, and contractors working for our United States Department of Energy, have repeatedly and officially confirmed, as seen, for just several examples, in our reports of:

USDOE 2009 CO2 to Gasoline | Research & Development | News; which centers on: "United States Patent 7,592,291 - Method of Fabricating a Catalytic Structure; 2009; Assignee: Battelle Energy Alliance, LLC, Idaho Falls, ID (United States Department of Energy Idaho National Laboratory); Abstract: A precursor to a catalytic structure comprising zinc oxide and copper oxide. The zinc oxide has a sheet-like morphology or a spherical morphology and the copper oxide comprises particles of copper oxide. The copper oxide is reduced to copper, producing the catalytic structure. The catalytic structure is fabricated by a hydrothermal process. A reaction mixture comprising a zinc salt, a copper salt, a hydroxyl ion source, and a structure-directing agent is formed. The reaction mixture is heated under confined volume conditions to produce the precursor. The copper oxide in the precursor is reduced to copper. A method of hydrogenating a carbon oxide using the catalytic structure is also disclosed, as is a system that includes the catalytic structure.Government Interests: The United States Government has certain rights in this invention pursuant to Contract No. DE-AC07-05ID14517 between the United States Department of Energy and Battelle Energy Alliance, LLC";

wherein our United States Government repeats several times, that:

"Carbon dioxide gas (CO2) may be converted into liquid fuels such as, for example, hydrocarbon molecules of between about 5 and about 12 carbon atoms per molecule (e.g., gasoline) through multi-step reactions"; and:

USDOE Sunlight Converts CO2 into Methane | Research & Development | News; concerning: "United States Patent Application 20130079577 - Synthesis of Photocatalysts for Solar Fuel Generation; 2013; Assignee: UChicago Argonne, LLC, Chicago, (USDOE Argonne National Laboratory); 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. 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 other hydrocarbon fuels, particularly promoted by sunlight"; and:

USDOE Announces Plastics Made from Carbon Dioxide | Research & Development | News; concerning: "'Recycling Carbon Dioxide to Make Plastics'; May 20, 2013; Novomer’s thermoplastic pellets incorporate waste CO2 into a variety of consumer products. The world’s first successful large-scale production of a polypropylene carbonate (PPC) polymer using waste carbon dioxide (CO2) as a key raw material has resulted from a projected funded in part by the U.S. Department of Energy's Office of Fossil Energy";

that:

Carbon Dioxide is a valuable raw material which can be used and consumed, in processes that can in some cases be powered by freely-available environmental energy, in the synthesis of such seemingly-needed products as fracking-free substitute natural gas Methane, and, OPEC-free Gasoline and Plastics.

Given that Carbon Dioxide is such a valuable, perhaps even precious, raw material resource, we would expect that our United States Department of Energy would also attend to the development of technologies that are capable of efficiently reclaiming Carbon Dioxide from various of it's sources. And, as we've documented in other reports, indeed, they have.

Herein, we present you with yet more Carbon Dioxide recovery technology, developed under the sponsorship of our USDOE; CO2-harvesting technology which might have special interest for, and applicability in, our already economically essential Coal-fired electric power generation facilities.

Comment follows excerpts from the initial link in this dispatch to:

"United States Patent 8,771,403 - Method and System for Capturing Carbon Dioxide and/or Sulfur Dioxide from Gas Streams

Method and system for capturing carbon dioxide and/or sulfur dioxide from gas stream - The Regents of the University of Califo 

Patent US8771403 - Method and system for capturing carbon dioxide and/or sulfur dioxide from ... - Google Patents

Date: July 8, 2014

Inventors: Shih-Ger Chang, et. al., California

Assignee: The Regents of the University of California, Oakland

Abstract: The present invention provides a system for capturing CO2 and/or SO2, comprising:

(a) a CO2 and/or SO2 absorber comprising an amine and/or amino acid salt capable of absorbing the CO2 and/or SO2 to produce a CO2- and/or SO2-containing solution;

(b) an amine regenerator to regenerate the amine and/or amino acid salt; and, when the system captures CO2,

(c) an alkali metal carbonate regenerator comprising an ammonium catalyst capable catalyzing the aqueous alkali metal bicarbonate into the alkali metal carbonate and CO2 gas. The present invention also provides for a system for capturing SO2, comprising: a SO.sub.2 absorber comprising aqueous alkali metal carbonate, wherein the alkali metal carbonate is capable of absorbing the SO2 to produce an alkali metal sulfite/sulfate precipitate and CO2.

Government Interests: The invention was made with government support under Contract No. DE-AC02-05CH11231 awarded by the U.S. Department of Energy. The government has certain rights in the invention.

Claims: A system for capturing CO2, comprising:

(a) a first chemical reaction vessel comprising an amine and/or amino acid salt, for absorbing the CO2 to produce an amine-COO compound and/or amino acid-COO compound in a CO2-containing solution;

(b) a second chemical reaction vessel comprising an aqueous alkali metal carbonate for extracting the CO2 from the amine-COO compound and/or amino acid-COO compound in the CO2-containing solution to form an alkali metal bicarbonate solid and regenerate the amine and/or amino acid salt; and:

(c) a third chemical reaction vessel for thermally regenerating the alkali metal carbonate from the alkali metal bicarbonate. 

(As above, the "thermally regenerating the alkali metal carbonate from the alkali metal bicarbonate" also releases a nearly pure stream of Carbon Dioxide, thus making the CO2 available for use in processes like those discussed in our introductory comments and others, perhaps like that disclosed in our report of:

More USDOE CO2 "Syntrolysis" | Research & Development | News; 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. ... Syngas, a mixture of hydrogen and carbon monoxide, can be used for the production of synthetic liquid fuels via Fischer-Tropsch processes".

Also note, that, as we have previously documented to be feasible, though we can't at the moment track down reference links, but as will be made clear further on, the chemical transfer of the captured CO2 from the amine initial absorbent to the metal carbonate/bicarbonate enables lower temperatures to be use in the concurrent/subsequent thermal recovery of the CO2 and the regeneration of the metal carbonate. This is, overall, a much more energy-efficient CO2 recovery process; and, it will minimize, perhaps nearly eliminate, either parasitic drains on the electriciy being produced by the power plant or the necessity of importing supplemental energy from some external source.)

The system ... wherein the third chemical reaction vessel further comprises an ammonium catalyst for catalyzing the aqueous alkali metal bicarbonate into the alkali metal carbonate and CO2 gas (and) wherein the ammonium catalyst comprises ammonium carbonate, ammonium bicarbonate, ammonium hydroxide, or ammonium carbamate, or a mixture thereof. 

(The above inexpensive ammonia-derived catalysts lower the temperature, the energy, needed to regenerate the "alkali metal carbonate" and release the "CO2". And, we remind you, that, as seen in our report of:

New Jersey Converts CO2 and Nitrogen Oxides into Fertilizer | Research & Development | News; concerning: "United States Patent 8,524,066 - Electrochemical Production of Urea from NOx and Carbon Dioxide; 2013; Assignee: Liquid Light Inc., NJ; Abstract: Methods and systems for electrochemical production of urea are disclosed. A method may include, but is not limited to, steps (A) to (B). Step (A) may introduce carbon dioxide and NOx to a solution of an electrolyte and a heterocyclic catalyst in an 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 may reduce the carbon dioxide and the NOx into a first sub-product and a second sub-product, respectively. Step (B) may combine the first sub-product and the second sub-product to produce urea. ... The method ... wherein said first sub-product is at least one of carbon monoxide or a reduced CO2 intermediate species, and wherein said second sub-product is at least one of ammonia or an ammonia-related intermediate compound';

it is conceivable that we could make those ammonia compounds, as well, from the components of Coal-fired power plant exhaust streams.)

The system ... wherein the third chemical reaction vessel comprises low pressure steam for stripping the CO2 gas and regenerating the solvent (and) further comprising a heat exchanger for facilitating energy transfer from high temperature lean solvent to low temperature rich solvent.

(Keep in mind that we could get some "low pressure steam", as above, from the exhaust of the electric power generation turbines.) 

The system ... wherein the first chemical reaction vessel further comprises a water-soluble polymer (and) wherein the water soluble polymer is PEG (polyethylene glycol).

(The above "PEG (polyethylene glycol)" useful in this process belongs to a class of chemicals known generically as "polyols", which, interestingly enough, as seen in our report of:

Bayer Is Converting Coal Power Plant CO2 Into Plastics | Research & Development | News; concerning:

"'Bayer Material Science CO2-to-Plastics Pilot Plant, Germany'; In February 2011, Bayer MaterialScience started a new pilot plant (in   the) North Rhine-Westphalia state of Germany for producing plastics from carbon dioxide (CO2). It will be used to develop polyurethanes from the waste gas released during power generation. The Leverkusen pilot plant will test a new   process technology on technical scale for producing raw material of   polyurethane. ... Bayer aims to use CO2 as an alternative to production of polymer materials from   fossil fuels. ... The CO2 thus acts   as a substitute for the petroleum production of plastics. 

Polyurethanes are used to produce a wide range of everyday applications. When they are used for the insulation of buildings, the polyurethane saves about 80% more energy than it consumes during production.   Light weight polymers are used in the automotive industry, upholstered   furniture and mattress manufacturing. Polyurethanes are formed by reacting two monomer units of isocyanates (polymerics isocyanate or diisocyanates) and polyols. The reaction takes place in the presence of specific quantities of catalyst and  additives under predetermined conditions. The waste carbon dioxide gas is recycled and used   as a raw material in the pilot plant. It produces polyether polycarbonate polyols (PPPs), the chemical precursor which is processed into polyurethanes";

can themselves in some cases be synthesized from Carbon Dioxide.)

The system ... wherein the first chemical reaction vessel further comprises a water wash system and a condense system, for collection of amine and water from a treated gas stream (and) wherein the second chemical reaction vessel operates at a temperature in the range of 20 C (to)100 C. 

The system ... wherein the second chemical reaction vessel further comprises apparatus selected from the group consisting of a unit of a rotating filter, a stationary filter, a cyclone, a hydrocyclone, and a sedimentation equipment for separation of the alkali metal bicarbonate (and) wherein the system is configured such that slurry coming from the second chemical reaction vessel is pumped by a peristaltic slurry pump, or a centrifugal slurry pump (and) wherein the second reaction vessel is placed right above the third chemical reaction vessel for slurry transfer to the third chemical reaction vessel by gravity. 

The system ...wherein the third chemical reaction vessel produces concentrated alkali metal carbonate solution for amine and/or amino acid regeneration (and) wherein the third chemical reaction vessel produces alkali metal carbonate solid, which is used for amine and/or amino acid regeneration (and) wherein the third chemical reaction vessel comprises a heat exchanger. 

The system ... wherein the system is further for capturing SO2. 

The system ... further comprising: a SO2 absorber comprising an amine and/or amino acid salt, wherein the amine and/or amino acid salt is capable of absorbing the SO2 to produce a SO2-containing solution; and an amine regenerator comprising an aqueous alkali metal carbonate capable of forming an alkali metal sulfite/sulfate precipitate and regenerating the amine and/or amino acid salt. 

The system ... further comprising: a fourth chemical reaction vessel comprising aqueous alkali metal carbonate, wherein the alkali metal carbonate is capable of absorbing the SO2 to produce an alkali metal sulfite/sulfate precipitate and CO2. 

(Nearly-pure CO2 is also extracted from the absorbent by another step in the overall process.)

The system ... wherein two immiscible liquid phases form in the second chemical reaction vessel, an upper phase comprising amine solvent and a lower phase comprising alkali metal carbonate solvent. 

The system ...  wherein the amine and/or amino acid salt is sterically hindered amine (as specified and described, and) wherein the secondary amine is selected from the group (specified and defined). 

A method of capturing CO2 from a stream of flue gas, comprising:

(a) reacting CO2 with an amine and/or amino acid salt to produce an amine-COO and/or amino acid-COO compound in a CO2 containing solution without forming precipitate;

(b) reacting the amine-COO and/or amino acid-COO compound with an alkali metal carbonate to thereby form an alkali metal bicarbonate precipitate and regenerate the amine and/or amino acid salt in a two-immiscible-aqueous-phase system; and:

(c) reacting the alkali metal bicarbonate precipitate in a thermal regeneration reaction to thereby regenerate the alkali metal carbonate and release CO2. 

The system further comprising a fourth reaction vessel for precipitating out the alkali metal sulfite/sulfate precipitate (and) wherein the upper amine solvent phase is fed to the first chemical reaction vessel, and the lower alkali metal carbonate solvent phase is fed to a fourth chemical reaction vessel for absorbing SO2 to produce an alkali metal sulfite/sulfate precipitate and CO2.

(Purified CO2, as above, is, again, recovered in multiple stages.)

The present invention also provides a system for capturing SO2, comprising: a SO2 absorber comprising an amine and/or amino acid salt, wherein the amine and/or amino acid salt is capable of absorbing the SO2 to produce a SO2-containing solution; and (b) an amine regenerator comprising an aqueous alkali metal carbonate capable of forming an alkali metal sulfite/sulfate precipitate and regenerating the amine and/or amino acid salt. The amine and/or amino acid salt can be in an aqueous solution or an organic solution. The present invention also provides for a system comprising both the system for capturing CO2 and the system for capturing SO2. The amine regenerator and SO2 absorber can be separate or they can be the same.

The CO2 absorber and SO2 absorber can be separate absorbers or they can be the same absorber.

The present invention also provides a system for capturing SO2, comprising: (a) a SO absorber comprising aqueous alkali metal carbonate, wherein the alkali metal carbonate is capable of absorbing the SO2 to produce an alkali metal sulfite/sulfate precipitate and CO2. The present invention also provides for a system comprising both the system for capturing CO2 and the system for capturing SO2. The amine regenerator and SO2 absorber can be separate or they can be the same reaction mixture, or reaction chamber or vessel. In some embodiments of the invention, the alkali metal sulfite/sulfate precipitate can be optionally separated, and further converted to ammonium sulfite/sulfate which is a commercially valuable product. 

(http://en.wikipedia.org/wiki/Ammonium_sulfitehttp://en.wikipedia.org/wiki/Ammonium_sulfate; The commercial value is real, though it might seem modest.)

In some embodiments of the invention, the CO2 and/or SO2 captured are from or in a gas stream or flue gas. In some embodiments of the invention, the alkali metal is potassium, sodium or lithium. Each reaction takes place in a reaction mixture which can be in a reaction chamber or vessel. 

The heat to facilitate the ammonium species, such as NH4HCO3, decomposition can be from any suitable source, such as waste heat (which) can come from a boiler (tail end) or a flue gas. ... Therefore, low pressure steam consumption could be reduced because of the utilization of the waste heat from flue gas. 

The CO2 and/or SO2 containing flue gas can be from any suitable source, such as fossil fuel power plants (coal, oil, or gas fired), steel, chemical, or cement plants. 

The absorber employs an aqueous solution of amine with or without an absorption rate promoter to capture CO2 from flue gas. The promoter is selected from amines or amino acids such that it can effectively release the absorbed CO2 to K2CO3, resulting in the production of KHCO3 precipitates. Subsequently, KHCO3 is converted, by reacting with a regeneration rate promoter (such as NH2CO2NH4), to K2CO3 and NH4HCO3. Herein the regeneration rate promoter is an ammonium species catalyst.

NH4HCO3 decomposes at low temperature (60C); consequently, waste heat from power plants may be employed.

The system can substantially reduce the energy demand for solvent regeneration because it deals with aqueous slurries of KHCO3 and NH4HCO3, and thus largely reduce the sensible and latent heat consumed by water in the stripping process of a conventional solvent system. Also, CO2 is produced from the thermal decomposition of NH4HCO3, which occurs more readily than the thermal decomposition of KHCO3 or amine carbamate, thus further decreases the sensible heat consumption".

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There is quite a lot more to it. The disclosure of the process can be difficult to understand, although our take on it is, that, since the necessary reactions can proceed sequentially and/or concurrently, the physical design of the thing itself wouldn't need to be that complicated.

And, it is in fact conceptually related to other flue gas CO2 capture technologies we've made report of, as in, for one example: 

2011 Efficient Extraction of Flue Gas CO2 | Research & Development | News; concerning: "United States Patent 7,927, 572 - Purifying Carbon Dioxide and Producing Acid; 2011; Praxair Technology, Inc, CT; Abstract: Carbon dioxide is purified by processes employing NOx-rich sulfuric acid that can be formed by removal of SO2 from the carbon dioxide. Claims: A process for treating gaseous carbon dioxide, comprising:(A) providing a gaseous feed stream of carbon dioxide that also comprises NOx (i.e., various Nitrogen Oxides, as might be co-produced when plain Air is used for the gasification of Coal) and sulfur dioxide; (B) contacting NOx-rich sulfuric acid with said gaseous feed stream and with NO2 desorbed in step: (C) to strip NOx from said NOx-rich sulfuric acid and form NOx-reduced sulfuric acid and NOx-augmented gaseous carbon dioxide that (also contains) SO2 and NO2; (and) converting NO in said NOx-reduced sulfuric acid to NO2, and desorbing said NO2 from said NOx-reduced sulfuric acid to form NOx-lean sulfuric acid and desorbed NO2; and: (D) controlling the amount of desorbed NO2 contacted with NOx-rich sulfuric acid in step (B) by converting desorbed NO2 to nitric acid and NO, and recovering said nitric acid (and) further comprising recovering product sulfuric acid from said NOx-lean sulfuric acid. A process ... wherein said gaseous feed stream of carbon dioxide is formed by combustion. A process ... further comprising recovering product sulfuric acid";

wherein, in addition to recovering a stream of purified Carbon Dioxide, associated Sulfur Oxides are recovered as well, and transformed into another commodity commercial chemical with established markets and value.

Again, note that the CO2 capture process of our subject, "United States Patent 8,771,403 - Method and System for Capturing Carbon Dioxide and/or Sulfur Dioxide from Gas Streams", seems capable of extracting Carbon Dioxide from flue gas, and of then producing a relatively pure Carbon Dioxide product gas, in several different streams, when powered by little more than "waste heat (which) can come from a boiler (tail end) or a flue gas"

Most of the chemical reagents can, if wanted, be regenerated, so make-up chemical costs could be minimized.

And, yet again, the Carbon Dioxide has great value as a raw material. As seen once more in our recent report of:

Stack Gas" Carbon Dioxide to High-Octane Gasoline | Research & Development | News; concerning:   "United States Patent 8,506,910 - Process and System for Producing Liquid Fuel from Carbon Dioxide and Water; 2013; Assignee: CRI (Carbon Recycling International) EHF, Iceland; Abstract: A process and system for producing high octane fuel from carbon dioxide and water is disclosed. The feedstock for the production line is industrial carbon dioxide and water, which may be of lower quality. The end product can be high octane gasoline";

the technologies for converting Carbon Dioxide, as recovered from whatever handy source and by whatever technical method, into Gasoline, as officially confirmed by our United States Government, are proliferating and being improved upon in a number of places around the globe.

Using technology developed, as herein, by contractors working for our United States Government, we can efficiently recover Carbon Dioxide from the exhaust gases of our Coal-fired power plants.

As per our reports, as cited above, concerning: "United States Patent 7,592,291 - Method of Fabricating a Catalytic Structure", and, "United States Patent 8,506,910 - Process and System for Producing Liquid Fuel from Carbon Dioxide and Water", we can then make stuff like "high octane gasoline" from that recovered flue gas Carbon Dioxide.

Would anyone out there care to speculate on how many Coal Country jobs such a CO2-to-Gasoline industry could create?

Would anyone out there care to speculate how much money the entire United States of America could save by not having to purchase Gasoline, or the petroleum from which we make Gasoline, from the alien, and often inimical, nations of OPEC?

Isn't it time someone out there crunched the numbers and gave us, openly and publicly, the answers to those questions?


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