By their recent issuance of the United States Patent we enclose in this dispatch, our United States Government confirms one key conclusion arrived at by the inventors, all accomplished scientists, as excerpted from the "Results" section, near the end of the full Disclosure, after exposition of extensive experimental data:
"In comparison to conventional CO2 capture strategies based on removing CO2 from high temperature flue gas, adsorptive fixation of CO2 from the ambient air is an improvement in that it can be a carbon-negative technology that can actually reduce the current CO2 level in the atmosphere."
In other words, if we feel compelled to capture Carbon Dioxide, for whatever purpose, then it makes more sense to extract it directly from the atmosphere than to saddle our various productive industries that might generate CO2 as a byproduct with parasitic, site-specific CO2 capture devices.
And, one key United States Patent cited by the inventors as precedent and foundational art, is one about which we previously reported via:
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., 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";
and which report, we remind you, also contained a link to:
"United States Patent 7,608,743 - Efficient ... Recycling of Carbon Dioxide to Methanol; 2009; Inventors: George Olah and Surya Prakash, CA; Assignee: University of Southern California, Los Angeles; Abstract: An efficient and environmentally beneficial method of recycling and producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by chemical or electrochemical reduction secondary treatment to produce essentially methanol, dimethyl ether and derived products";
which sort of explains why one might wish to effect the "Separation of CO2 from ... the Air" in the first place.
And, to confirm and affirm the practicality and importance of recovering Carbon Dioxide from the atmosphere, as opposed to saddling our vital Coal-fired power generation facilities with expensive and parasitic CO2 capture equipment, a group of accomplished scientists from around the country teamed up to devise the process, as excerpted from the initial link in this dispatch, of:
"United States Patent 8,491,705 - Application of Amine-tethered Absorbents to CO2 Fixation from Air
Application of amine-tethered solid sorbents to CO2 fixation from air - Choi, Sunho
Date: July 23, 2013
Inventors: Sunho Choi, (Department of Chemical Engineering, Northeastern University; Boston); Jeffrey Drese, (Now employed by Phillips 66); Ron Chance,(formerly of ExxonMobil); Peter Eisenberger, (Columbia University); Christopher W. Jones, (Georgia Tech University).
(Note that, in this case, we reproduce the names all of the inventors, and list their current affiliations as determined from web-based references. There seems, as yet, to be no official "Assignee of Rights" to this US Patent. An official Assignment of Rights document has not yet been created, or at least made web-accessible, by the US Patent and Trademark Office; and, the official patent document only lists "Applicants". However, all the inventors, with the exception of Eisenberger, who is at Columbia University and is affiliated with the company "Global Thermostat", seem to have either past or current affiliations with Georgia Tech University. That said, note that, as in:
West Virginia Coal Association | New York City Reclaims and Recycles Carbon Dioxide | Research & Development; concerning: "United States Patent Application 20110011945A1 - System and Method for Removing CO2 from an Atmosphere; 2011; Inventors: Peter Eisenberger, NJ, and Graciela Chichilnisky, NY; Abstract: A system for removing carbon dioxide from an atmosphere to reduce global warming including an air extraction system that collects carbon dioxide from the atmosphere through a medium and removes carbon dioxide from the medium; a sequestration system that isolates the removed carbon dioxide to a location for ... generation of a renewable carbon fuel";
we have cited Eisenberger previously; and, we thought that we had made report of one or two of Ron Chance's CO2-capture innovations while he was with ExxonMobil, but cannot at this time find evidence that we did so. Further report on his work will follow in future dispatches, although, like Eisenberger, he is associated with the company Global Thermostat, as is co-inventor and Georgia Tech professor Christopher Jones. More can be learned via:
front-page | GlobalThermostat; "Global Thermostat (GT) offers low-cost solutions to capture CO2 promoting sustainable and harmonious use of the earth's resources. It utilizes low-cost process heat left over in a range of industrial activities to capture carbon from air"; and:
Team | GlobalThermostat; "Global Thermostat has assembled a brain trust of leading experts in the energy, sciences and climate policy fields as well as engineers, clean-tech entrepreneurs and business leaders".
The point is, all of these cats are pretty accomplished scientists, regardless of who they're now working for. And, maybe we should be paying attention to what they have to say.)
Abstract: A method for capturing CO2 from the ambient air by the use of solid tethered amine adsorbents, where the amine adsorbents are tethered to a substrate selected from the group of silica, metal oxides and polymer resins. The tethered amines are joined to the substrate by covalent bonding, achieved either by the ring-opening polymerization of aziridine on porous and non-porous supports, or by the reaction of mono-, di-, or tri-aminosilanes, with silica or a metal oxide having hydroxyl surface groups. The method includes the adsorption of CO2 from ambient air, the regeneration of the adsorbent at elevated temperatures not above 120 C and the separation of purified CO2, followed by recycling of the regenerated tethered adsorbent for further adsorption of CO2 from the ambient atmosphere.
(Our excerpts will repeat some of the no-doubt unfamiliar terms, such as the above "aziridine" and "aminosilanes". All of them, however, are known, and for the most part commercially available, products. We won't, in the interests of space, document and footnote all of them; but see, by way of supporting example:
Aziridine - Wikipedia, the free encyclopedia and Full Range of Silanes - Organosilane, Chlorosilane, Aminosilane and More - Dow Corning;"Dow Corning offers a full range of silanes including organosilanes and chlorosilanes for applications such as adhesion promotion, crosslinking agents, coupling agents (etc). Aminosilane: Adhesion promoter, coupling agent, and resin additive; Improves chemical bonding of resins to inorganic fillers and reinforcing materials; Used for epoxies, phenolics, melamines, nylons, PVC, acrylics, polyolefins, polyurethanes, and nitrile rubbers".)US Patent Document References: United States Patent 7,795,175 (as noted in introductory comments)
Claims: A method for the capture of CO2 from dilute gas streams in a cyclical manner, the concentration of CO2 in the gas stream being in the range of from 1-1000 ppm; the process comprising passing the dilute-CO2 gas stream over a solid adsorbent at a substantially ambient temperature of not greater than 120 C, the solid adsorbent comprising an amine adsorbent tethered to a substrate, the tethered amine being selected from the group consisting of hyperbranched aminopolymers tethered to a substrate selected from the group consisting of a metal oxide, a porous silica and a porous hydrocarbon-based solid polymer support structure, wherein the amine is tethered to the substrate by covalent bonds; and a tethered amine prepared by the reaction of a silyl amine with an oxide substrate; and regenerating the solid adsorbent at a temperature of not substantially greater than about 120 C, to obtain a substantially concentrated CO2 gas stream and a regenerated adsorbent; and repeating the cycle.
Background and Field: One approach to capture CO2 from fossil fuel combustion is to trap CO2 at large point sources such as electricity generating power plants. However, roughly 1/3 of global carbon emissions are associated with distributed sources such as transportation fuels. Thus, large-scale deployment of carbon capture ... technologies at various point sources can at best slow the rate of increase of the atmospheric CO2 concentration. What is needed is a carbon-negative technology, one that actually reduces the concentration of CO2 in the atmosphere. Here, building on the limited existing work, we propose the direct capture of carbon dioxide from the ambient air using solid adsorbents specifically designed for this task as a new approach for reducing the concentration of CO2 in the ambient air. The captured CO2 could be ... used in a beneficial application, such as a feedstock for algae-based biofuels production.
(Although we prefer more direct chemical recycling methods for the utilization of Carbon Dioxide, perhaps as so efficiently captured from the air around us by the process of our subject herein, "United States Patent 8,491,705 - Application of Amine-tethered Absorbents to CO2 Fixation from Air", such as seen for one example in our report of:
West Virginia Coal Association | US Navy 2008 CO2 to Synfuel | Research & Development; concerning:
"United States Patent 7,420,004 - Producing Synthetic Liquid Hydrocarbon Fuels; 2008; Assignee: The USA, as represented by the Secretary of the Navy; Abstract: A process for producing synthetic hydrocarbons that reacts carbon dioxide, obtained from seawater or air, and hydrogen obtained from water, with a catalyst in a chemical process such as reverse water gas shift combined with Fischer Tropsch synthesis. The hydrogen is produced by ... ocean thermal energy conversion, or any other source that is fossil fuel-free, such as wind or wave energy. The process can be either land based or sea based";
it could also, we admit, as seen for one example in our report of:
West Virginia Coal Association | USDOE Algae Recycle More CO2 and Produce Ethanol | Research & Development; concerning: "US Patent 7,973,214 - Designer Organisms for Photosynthetic Production of Ethanol from CO2 and Water; 2011; Inventor: James Weifu Lee, TN; Assignee: UT-Battelle, LLC, (Oak Ridge National Laboratory/USDOE) Abstract: The present invention provides a revolutionary photosynthetic ethanol production technology based on designer transgenic plants, algae, or plant cells. The designer plants, designer algae, and designer plant cells are created such that the endogenous photosynthesis regulation mechanism is tamed, and the reducing power and energy acquired from the photosynthetic (processes) are used for immediate synthesis of ethanol directly from carbon dioxide and water";
be worthwhile using, as "United States Patent 8,491,705" suggests, the captured CO2 "for algae-based biofuels production"; especially since, as seen in: .
West Virginia Coal Association | Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development; concerning: "United States Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass; 2010; Assignee: ExxonMobil Research and Engineering Company; Abstract: A process for the co-gasification of carbonaceous solids (coal) and biomass in which the biomass material is pyrolyzed to provide a biomass pyrolysis oil and biomass char or coke which are then mixed with the carbonaceous solid to form a slurry. This slurry is then heated if necessary to achieve a viscosity which can be processed conveniently in the gasifier. The heat required for pyrolyzing the biomass can conveniently be obtained from the heat exchanger used to cool the hot synthesis gas product emerging from the gasifier.
The process ... wherein the solid carbonaceous particles comprise coal (and) wherein the biomass comprises biological matter selected from wood, plant matter, municipal waste, green waste, byproducts of farming or food processing waste, sewage sludge, black liquor from wood pulp, and algae. ... One established route to the production of hydrocarbon liquids is the gasification of carbonaceous materials followed by the conversion of the produced synthesis gas to form liquids by processes such as Fischer-Tropsch and its variants. In this way, solid fuels such as coal and coke may be converted to liquids";
any overgrowth of Algae biomass could then be blended with Coal for "Co-gasification" and consequent conversion into liquid hydrocarbon fuels via the "Fischer-Tropsch" method "and its variants".)
Summary: We have now found that solid substrate-tethered amine adsorbents are useful for the capture of CO2 from the ambient air, where the substrates include silica and other metal oxide substrates and solid hydrocarbon polymer substrates, preferably where the substrate is porous, so that the amine is tethered to the interior pore surfaces as well as to the outer surface. Our results demonstrate that such supported amine sorbents are able to capture considerable amounts of CO2 from dilute sources. In accordance with the present invention, direct CO2 capture from ambient air is achieved by adsorptive fixation on hybrid adsorbents comprising hyperbranched aminopolymers supported on various substrates including mesoporous silica, other porous silica, and metal oxides having surface hydroxide groups, and solid hydrocarbon polymers, under ambient conditions. This invention further provides for the direct CO2 capture from ambient air, and the like, using a ... supported amine adsorbent tethered to silica or a metal oxide or tethered to a polymer resin (preferably a hydrocarbon polymer), or supported amines ... tethered to a metal oxide substrate through a silyl group. In these adsorbents, there is covalent tethering of the amine sorbent to the substrate.
The method of this invention further provides for the desorption of CO2, and regeneration of the tethered adsorbent as the CO2 is desorbed, at temperatures not greater than about 120 C, followed by recycling of the regenerated tethered adsorbent for further adsorption from the ambient atmosphere.
Substantially any metal oxide having surface hydroxyl groups can be used as the substrate ... . Such oxides include the oxides of transition metals (such as Iron, Titanium, Vanadium, Zirconium, Manganese, Niobium, Hafnium, Tantalum, Chromium. Molybdenum, Cobalt, Zinc, Copper), base metal oxides (such as Aluminum, Silicon, Germanium, Boron, Indium, Tin, Lead), as well as other common metal oxides such as those based on Calcium, Barium, Magnesium, Strontium, Cerium, or mixtures of any of these metal oxides.
Hyperbranched aminopolymers can be prepared by the ring-opening polymerization of aziridine on porous and non-porous supports, in which the amine functionalities provide the CO2 capture capability of the supported adsorbents on the several substrates.
In comparison to the previously mentioned techniques, this solid adsorbent system is easy to make, environmentally friendly, and potentially cost-effective, while providing considerable CO2 capture performance from dilute sources, such as the atmosphere.
(Recorded experiments and their results demonstrate) that the hybrid adsorbents present effective adsorption performance even from diluted gas sources similar to those found in ambient air. The experiments show that, although reduced and slower to some extent, the adsorption capacity and kinetics of this adsorbent are not reduced equivalently, i.e., by a factor of 10 instead of a factor of 250, i.e., the huge CO2 feed concentration decrease. Instead, the adsorbent can still effectively capture considerable amounts of CO2 at an adequate adsorption rate from a gas mixture simulating the ambient air.
In comparison to conventional CO2 capture strategies based on removing CO2 from high temperature flue gas, adsorptive fixation of CO2 from the ambient air is an improvement in that it can be a carbon-negative technology that can actually reduce the current CO2 level in the atmosphere. Different types of solid adsorbents were prepared, including representative examples of two of the classes of supported amine adsorbents, following a synthesis route of amine grafting (class ii) and hyperbranching polymerization (class iii) onto various support materials, such as hydrocarbon polymers, metal oxides, amorphous silica, and a mesoporous silica with one-dimensional channels.
In accordance with this invention, amines tethered to a variety of substrates were found to be useful for adsorbing CO2 from ambient air, over repeated cycles, and without being assisted by supplementary processes or devices. ... Based on these advantages of adequate capacity, regenerability, and tunable performance, these hybrid adsorbents can be positioned as promising materials for atmospheric CO2 capture applications from the ambient air."
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We note that the CO2 is released from the absorbent, as in "this invention further provides for the desorption of CO2, and regeneration of the tethered adsorbent as the CO2 is desorbed, at temperatures not greater than about 120 C, followed by recycling of the regenerated tethered adsorbent for further adsorption from the ambient atmosphere", by a relatively low-level heat treatment; and, concerning where we might get such a source of heat, we remind you of our report:
West Virginia Coal Association | Another Energy Bonanza for Coal Country | Research & Development; concerning, in part, an article from the Beckley, WV, Register-Herald: "West Virginia Looks Good for Geothermal Energy Production; October 11, 2010; A new study suggests some areas of West Virginia may be a rich source of renewable energy ... . Scientists at Southern Methodist University’s Geothermal Laboratory discovered that the temperature of the Earth beneath certain areas of the state is much higher than previous estimates. The hottest areas - below Tucker, Randolph, Pocahontas, and Greenbrier counties - show potential for use as a commercial baseload of geothermal energy production".
The full Disclosure details that only air heated to the specified temperature is needed to release the Carbon Dioxide from the absorbent. However, at that temperature, "120 C", the released CO2 could be blended with Steam; and, consequently, we remind you of, for just two examples, our reports of:
West Virginia Coal Association | More USDOE CO2 "Syntrolysis" | Research & Development; concerning: "Co-Electrolysis of Steam and Carbon Dioxide for Production of Syngas; 2007; J.E. O'Brien, C.M. Stoots, et. al.; Idaho National Laboratory (INL), 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"; and:West Virginia Coal Association | Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; 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";
wherein, at the temperatures specified for release of the CO2 and the regeneration of the absorbent, the CO2 extracted from the atmosphere by the absorbent and process disclosed herein by our subject, "United States Patent 8,491,705 - Application of Amine-tethered Absorbents to CO2 Fixation from Air", can be blended with Steam, with the resulting blend of the two gases then being subjected to "coelectrolysis" in "oxide electrolysis cells", wherein they are converted into "synthesis gas", or "syngas", that is, "a mixture of hydrogen and carbon monoxide" which "can be used for the production of synthetic liquid fuels" as also specified in our above reference to our report concerning "United States Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass", "via Fischer-Tropsch processes".
Once again, it is confirmed: Carbon Dioxide, as it arises in only a small way, relative to some natural, and non-taxable, sources of emission, such as the Earth's inexorable processes of planetary volcanism, from our economically essential use of Coal in the generation of truly abundant and truly affordable electric power, can be seen as a valuable, natural raw material resource; a natural resource which we can actually productively "mine", as it were, from the very atmosphere around us via the process of our subject herein, "United States Patent 8,491,705 - Application of Amine-tethered Absorbents to CO2 Fixation from Air".