We have a lot of closely-related ground concerning the productive collection and recycling of Carbon Dioxide we want to cover in this dispatch, so please forgive any stylistic lapses in our narrative. We'll need to condense things as much as possible.
We've made, over the long course of our reportage, numerous reports of, and allusions to, the extraordinary body of Carbon Dioxide recycling and utilization technology that has been, and is being, developed at Penn State University.
Of particular note should be the pending United States Patent Application we reported in:
West Virginia Coal Association | Penn State Seeks CO2 Recycling Patent | Research & Development; concerning: "United States Patent Application 20100213046 - Nanotube ... Photocatalytic Conversion of Carbon Dioxide; 2010; Inventors: Craig Grimes, et. al., PA; The Penn State Research Foundation; Abstract: Nitrogen-doped titania nanotubes exhibiting catalytic activity on exposure to any one or more of ultraviolet, visible, and/or infrared radiation, or combinations thereof are disclosed. The nanotube arrays may be co-doped with one or more nonmetals and may further include co-catalyst nanoparticles. Also, methods are disclosed for use of nitrogen-doped titania nanotubes in catalytic conversion of carbon dioxide alone or in admixture with hydrogen-containing gases such as water vapor and/or other reactants as may be present or desirable into products such as hydrocarbons and hydrocarbon-containing products, hydrogen and hydrogen-containing products, carbon monoxide and other carbon-containing products, or combinations thereof.Claims: A method for photocatalytically converting carbon dioxide into reaction products comprising any one or more of hydrocarbons and hydrocarbon-containing products, hydrogen and hydrogen-containing products, carbon monoxide and other carbon-containing products, or combinations thereof ...".
One of the "hydrocarbons" which Penn State is capable of producing by "photocatalytically converting carbon dioxide" is, as seen in:
West Virginia Coal Association | Penn State Solar CO2 + H2O = Methane | Research & Development; concerning: "High-Rate Solar Photocatalytic Conversion of CO2 and Water Vapor to Hydrocarbon Fuels; Oomman K. Varghese, Maggie Paulose, Thomas J. LaTempa, and Craig A. Grimes; The Pennsylvania State University; 2009; Efficient solar conversion of carbon dioxide and water vapor to methane";
plainly, Methane; and, which Methane can then be employed, as explained in:
West Virginia Coal Association | More Penn State CO2 Recycling with Methane | Research & Development; concerning, in part: "Tri-reforming of methane: a novel concept for catalytic production of industrially useful synthesis gas with desired H2/CO ratios; Authors: Chunsan Song; Wei Pan; Pennsylvania State University;
Abstract: A novel process concept called tri-reforming of methane has been proposed in our laboratory using CO2 in the flue gases from fossil fuel-based power plants without CO2 separation... . The proposed tri-reforming process is a synergetic combination of CO2 reforming, steam reforming, and partial oxidation of methane in a single reactor for effective production of industrially useful synthesis gas (syngas)";
in reactions with even more Carbon Dioxide, wherein both are converted into "synthesis gas", a blend of Carbon Monoxide and Hydrogen, "with desired H2/CO ratios", which can be catalytically condensed, as via the almost generic Fischer-Tropsch process into various hydrocarbons.
The above "Tri-reforming of methane" with Carbon Dioxide, and H2O, to form hydrocarbon synthesis gas, is well-known in certain circles, as we've documented; and, some others have actually done a better job of publicly disclosing the process technology than has Penn State University, as can be seen, for one example, in the full Disclosure of:
West Virginia Coal Association | Exxon 2010 CO2 + Methane = Liquid Hydrocarbons | Research & Development; concerning: "United States Patent 7,772,447 - Production of Liquid Hydrocarbons from Methane; 2010; Assignee: ExxonMobil; Abstract: (A) process for converting methane to liquid hydrocarbons ... , ... the process comprising: contacting a feed containing methane and ... H2O (and) CO2 with a (specified) catalyst".
In point of fact, as study of the literature reveals, Penn State posits that, once you have the Methane, preferably, we submit, as synthesized from Carbon Dioxide, the subsequent "reforming" of more Carbon Dioxide with the Methane can be accomplished without first separating the Carbon Dioxide from the flue gas.
That doesn't seem to be the case in other CO2-Methane reforming technologies, such as ExxonMobil's above process of "United States Patent 7,772,447"; and, purer, more concentrated Carbon Dioxide does seem required by Penn State's own process of the above "United States Patent Application 20100213046 - Nanotube ... Photocatalytic Conversion of Carbon Dioxide", to synthesize the Methane in the first place.
But, the Pennsylvania State University does have that base covered.
If we do need more concentrated Carbon Dioxide to, first, synthesize the Methane; and, then, to react with that Methane to form hydrocarbon synthesis gas, Penn State, with support from the United States Department of Energy, has devised a technology that would, if implemented, enable us to efficiently collect that Carbon Dioxide from the exhaust gases of Coal-fired power plants.
As briefly introduced in excerpts, with additional links and excerpts appended, from the initial link in this dispatch to:
"Penn State EMS Energy Institute: CO2 Capture from Flue Gas Using Solid Molecular Basket Sorbents
DOE NETL Award No. DE-FE0000458; Chunshan Song (et. al.); DOE Project Manager: Andrew O'Palko
2011 NETL CO2 Capture Technology Meeting; Pittsburgh, August 22-26, 2011
Research at Song's Group: CO2 Capture; CO2 to Chemicals; CO2 to Fuels: CH4 & CO2 to Syngas
Project Objective: To develop a new generation of solid and regenerable polymeric 'molecular basket' sorbent (MBS for more efficient capture and separation of CO2 from flue gas of coal-fired power plants."
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The above should give you the flavor of the thing. The full presentation is much more detailed and informative, but its graphic nature doesn't lend itself well to textural summary. More specific information can be learned via the USDOE National Energy Technology Laboratory's summary fact sheet on the project, accessible via:
http://www.netl.doe.gov/
"CO2 Capture from Flue Gas Using Solid Molecular Basket Sorbents; January, 2012
Background: The mission of the U.S. Department of Energy/National Energy Technology Laboratory
(DOE/NETL) Existing Plants, Emissions & Capture (EPEC) Research & Development (R&D) Program is to develop innovative environmental control technologies to enable full use of the nation’s vast coal reserves, while at the same time allowing the current fleet of coal fired power plants to comply with existing and emerging environmental regulations.
The EPEC R&D Program portfolio of post- and oxy-combustion carbon dioxide (CO2) emissions control technologies and CO2 compression is focused on advancing technological options for the existing fleet of coal-fired power plants in the event of carbon constraints. Pulverized coal plants burn coal in air to produce steam and comprise 99 percent of all coal-fired power plants in the United States. CO2 is exhausted in the flue gas at atmospheric pressure and a concentration of 10–15 percent by volume. Post-combustion separation and capture of CO2 is a challenging application due to the low pressure and dilute concentration of CO2 in the waste stream, trace impurities in the flue gas (nitrogen oxides, sulfur oxides, and particulate matter) that affect removal processes, and the parasitic energy cost associated with the capture and compression of CO2. An effective post-combustion CO2 control technology being investigated for the capture of CO2 from flue gas is the use of novel nanoporous polymer-based sorbents with high CO2 adsorption capacities for application to existing and future power plants.
Project Description: Pennsylvania State University (PSU) will develop a new generation of solid polymer-based sorbents for more efficient capture and separation of CO2 from flue gas of coal-fired power plants. The project is based on the concept of a molecular basket sorbent (MBS), which was invented and developed at PSU. The idea of MBS development is to load CO2-philic polymers onto high surface area nanoporous materials. This process increases the number of approachable sorption sites on/in the sorbent and enhances the sorption/desorption rate by increasing the gas-sorbent contacting interface and by improving the mass transfer in the sorption/desorption process. The expected result of this project will be a concentrated CO2 stream that can be directed to CO2 sequestration or CO2 utilization.
(Nuts, of course, to "CO2 sequestration"; but, that "CO2 utilization" is another thing, entirely.)
Development of the new generation of MBS involves the selection of the best performing, most cost-effective CO2-philic polymer and nanoporous materials. Different types of nanoporous materials will be purchased as support materials. A series of polymers will be immobilized in the nanoporous materials to prepare different sorbents. The prepared sorbents will be tested and evaluated for CO2 capture in a fixed-bed flow system. The promising MBSs will be further characterized to determine their structure; surface properties; thermal, physical, and chemical properties; and CO2-sorption/desorption properties. Advanced molecular modeling will be used to facilitate the screening of the polymer sorbents and the design of novel polymers.
Computational results will be utilized to guide project experimental approaches. A techno-economic analysis will also be performed on the new MBSs and CO2 capture process. The analysis will focus on energy consumption and the cost of the sorbents in comparison to a conventional post-combustion CO2 capture process.
The project goal is to develop a new generation of solid polymer-based sorbents that can be used to capture and separate CO2 from coal-fired power plant flue gas in an energy-efficient, economical, and environmentally-friendly manner.
The project objectives are to develop Molecular Basket Sorbents that have regenerable working sorption capacities higher than 70 milligrams of CO2 per gram of sorbent, and to lower the sorbent preparation cost by 30 percent compared to the first and second generations of MBSs.
Penn State University will develop sorbent formulations, test developed MBSs, and analyze the effect of physical and chemical properties of the sorbents on the CO2 sorption performance.
Specific activities include:
Optimizing the combination of CO2-philic polymers and nanoporous materials to further enhance CO2 sorption capacity.
Researching inexpensive and commercially available materials for preparation of the new generation of MBS to significantly reduce the sorbent cost.
Evaluating the sorption performance of the developed MBSs in a laboratory-scale fixed-bed sorption system, including the capacity, selectivity, regenerability, and stability; and determining the best conditions for sorption and desorption.
Improving the thermal stability of the developed MBSs through the cross-linking method.
Conducting a computational chemistry approach to estimate the heats of sorption of CO2 on different MBSs and the kinetic barriers for the diffusion of CO2 sorbate in the bulk of the sorbent for fundamental understanding of the sorption mechanism, which can benefit the development, design, and modification of the sorbents and the process.
On the basis of the experimental data, conducting a preliminary technical and economic analysis of the developed sorbent and process.
Accomplishments: Four types of nanoporous materials were selected for evaluation: silica gels, mesocellular silica foam (MCF), nanostructured fumed silica (FS), and hexagonal mesoporous silica (HMS).
Several samples of each type of material were examined to determine the effect of various parameters, including pore size and particle size, and the molecular weight and loading of the polymer sorbent utilized (polyethylenimine [PEI]) on the sorption performance.
For each material type the most favorable samples were selected and the best PEI molecular weight and PEI loading were determined for preparation of the MBSs for testing.
Each prepared MBS was evaluated in a fixed-bed sorption system using simulated flue gas to obtain CO2 sorption breakthrough curves, and measure CO2 sorption breakthrough capacity and saturation capacity.
Benefits: This project will provide valuable data on new material synthesis and preparation, novel process and operational experience on CO2 capture, and processes of interest for application to large scale power plant flue gas control systems. The optimization of molecular basket sorbent performance to increase post-combustion CO2 capture while significantly lowering costs can benefit both existing and new coal-fired power plants. Additionally, cost effective CO2 capture will significantly contribute to the viability of power generation from the nation’s abundant supplies of coal, thus enhancing U.S. energy security."
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Now, keep in mind that we won't, by such "cost effective CO2 capture" be "enhancing U.S. energy security" just by contributing "to the viability of power generation from the nation’s abundant supplies of coal", as noble and desirable as that might be.
We will actually be harvesting a valuable raw material, Carbon Dioxide, that, to beat it to death, can, as in:
NASA Recycles CO2 to Methane at Room Temp | Research & Development | News; concerning the: Electrocatalytic Reduction of Carbon Dioxide to Methane; Lyndon B. Johnson Space Center; 2008; A room-temperature electrocatalytic process that effects the overall chemical reaction: CO2 + 2H2O = CH4 + 2O2 has been investigated";
be converted into Methane with a high degree of efficiency; and, which Methane can then, as in:
More Standard Oil 1944 CO2 + CH4 = Hydrocarbons | Research & Development; concerning: "United States Patent 2.347.682 - Hydrocarbon Synthesis; 1944; Assignee: Standard Oil Company of Indiana; Abstract: This invention relates to an improved method and means for effecting the synthesis of hydrocarbons from carbon monoxide and hydrogen (by) a reforming operation converts the methane-carbon dioxide-steam mixture into a gas consisting chiefly of hydrogen and carbon monoxide ... hereinafter referred to as ... 'synthesis' gas";
be reacted with Steam and more Carbon Dioxide to form a gas mixture of "hydrogen and carbon monoxide" suitable "for effecting the synthesis of hydrocarbons".
More on Penn State's efficient CO2 capture technology can be learned via:
http://www.netl.doe.gov/
"CO2 Capture from Flue Gas Using Solid Molecular Basket Sorbents
National Energy Technology Laboratory: Primary Project Goals: Pennsylvania State University (PSU) is developing a new generation of solid and regenerable polymeric molecular basket sorbent (MBS) for more cost-efficient capture and separation of carbon dioxide (CO2) from flue gas of coal-fired power plants.
The current state-of-the-art post-combustion capture technology, aqueous amine scrubbing, is a highly energy-intensive process estimated to increase the cost of electricity (COE) by about 75–85%, according to U.S. Department of Energy (DOE) reports.
The goal of DOE’s Existing Plants, Emissions, and Capture (EPEC) Research and Development (R&D) Program is to achieve 90% CO2 capture with an increase in COE less than 35%. Therefore, it is important to develop inexpensive, effective, and robust materials and technologies that can reduce CO2 emission and are suitable for installation in power plants to maintain the cost-effectiveness of U.S. coal-fired power plants."
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We'll abbreviate our excerpts there, but the full presentation is worth some study; especially for it's list of references concerning the available technology for capturing and recycling Carbon Dioxide.
We do note that an increase in the "cost of electricity", i.e., "COE", of anything like "35%", as above, would still be a little hard to swallow.However, keep in mind that would represent the cost of the raw material Carbon Dioxide itself, which, if subsequently utilized in a process such as that disclosed in:
Chicago Converts CO2 to Methane | Research & Development; concerning: "US Patent 3,766,027 - Method and Apparatus for CO2 Conversion to Methane; 1973; Assignee: Institute of Gas Technology, Chicago; Abstract: A process of fixation and conversion of carbon dioxide from the atmosphere or other sources to produce methane and oxygen. Carbon dioxide is scrubbed from a CO2 -containing source and separated by process of chemical concentration. A special cell is provided in which hydrogen is produced and reacted with the separated CO2 at methanation conditions to produce methane";
to make Methane, and, then, more of the Carbon Dioxide were combined with that Methane, as in:
Standard Oil 1987 CO2 + CH4 = Syngas | Research & Development; concerning: "United States Patent 4,690,777 - Production of Synthesis Gas; 1987; Assignee: The Standard Oil Company, Cleveland;
Abstract: Gas mixtures containing at least hydrogen and carbon monoxide are prepared by reforming hydrocarbons in the presence of a catalyst impregnated on a specially prepared porous catalyst support. In one embodiment of the present invention, methane is reformed in a process to produce a product gas mixture containing carbon monoxide and hydrogen ... . A process for reforming light hydrocarbons ... comprising contacting the light hydrocarbons with carbon dioxide ... (and) wherein the light hydrocarbon is methane. (Gas) mixtures containing carbon monoxide/hydrogen ratios of 1/1 or 1/2 are particularly useful as feed gases in processes for producing higher hydrocarbons and oxygenated derivatives, such as Fischer-Tropsch and alcohol synthesis processes";
to produce "gas mixtures containing carbon monoxide (and) hydrogen (which) are particularly useful as feed gases in processes for producing higher hydrocarbons", then the increased "COE" might be more than offset by the subsequent profits from the sale of "higher hydrocarbons and ... alcohol".
All of which would, of course, lead to fuller employment and greater overall prosperity in United States Coal Country; and, since we'll be making such "higher hydrocarbons and ... alcohol" out of our by-product CO2, a certain amount of heartburn in Big Oil board rooms and OPEC throne chambers.
That, not to mention the avoidance of the costs of Cap and Trade taxation, or, more onerous, the costs of mandated Geologic Sequestration to subsidize Big Oil's secondary petroleum scrounging in nearly-depleted natural reservoirs, and subsequent profits; all of which would show up in our electric bills in any case.
Instead of being coerced into doing something negative with our by-product Carbon Dioxide, we do have herein, via Penn State's efficient CO2 capture technologies, and the subsequent options for converting our captured CO2 into "methane" and "hydrocarbons and alcohol", the alternative of doing something productive and profitable with that CO2 for United States Coal Country.
Why, we are once again compelled to ask, aren't those options being publicly disseminated and discussed?