https://ebims.net/bims/bi_
In light of some recently-published confirmations of technical achievements, which we'll be making report of in coming days, we wanted to reintroduce a subject we had begun to treat in a few previous dispatches.
Right up front, though, we'll tell you what the gist of it all will be:
Carbon Dioxide, as is emitted in only a small way, relative to some uncontrollable and un-taxable sources of emission, such as the Earth's inexorable processes of planetary volcanism, from our essential use of Coal in the generation of truly abundant and truly affordable electric power, is a valuable raw material resource.
As seen in our reports, for instance, of:
West Virginia Coal Association | USDOE Says CO2 is a 'Vast Natural Resource' | Research & Development; concerning: "US Patent 4,197,421 - Synthetic Carbonaceous Fuels and Feedstocks; 1980; Inventor: Meyer Steinberg; Assignee: The United States of America; Abstract: This invention relates to the use of a three compartment electrolytic cell in the production of synthetic carbonaceous fuels and chemical feedstocks such as gasoline, methane and methanol by electrolyzing an aqueous ... solution, obtained from scrubbing atmospheric carbon dioxide with an aqueous sodium hydroxide solution, whereby the hydrogen generated at the cathode and the carbon dioxide liberated in the center compartment are combined thermocatalytically into methanol and gasoline blends"; and:
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; (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 of at a temperature sufficient to catalyze reduction of carbon dioxide to a hydrocarbon ... . This invention relates to the energy efficient photocatalytic conversion of carbon dioxide gas and water vapor to methane ... promoted by sunlight (referred to herein as "solar-derived fuel" or "solar fuel")";our United States Department of Energy has been at work, unbeknownst to all of us under-informed troglodytes in United States Coal Country, for multiple decades on the development of technologies for the electro-chemical and photo-chemical conversion, the recycling, of Carbon Dioxide in the synthesis of both liquid and gaseous hydrocarbon fuels.
And, as we've seen, for one example, in our report of:
West Virginia Coal Association | USDOE Hydrocarbon Syngas from CO2 and H2O | Research & Development; concerning: "United States Patent 4,313,925 - Thermochemical Cyclic System for Decomposing H2O and/or CO2 by Means of Cerium-Titanium-Sodium-Oxygen Compounds; 1982; Assignee: The USA as Represented by the USDOE; Abstract: A thermochemical closed cyclic process for the decomposition of water and/or carbon dioxide to hydrogen and/or carbon monoxide begins with the reaction of ceric oxide (CeO2), titanium dioxide (TiO2) and sodium titanate (Na2TiO3) to form sodium cerous titanate (NaCeTi2O6) and oxygen. Sodium cerous titanate (NaCeTi2O6) reacted with sodium carbonate (Na2CO3) in the presence of steam, produces hydrogen. The same reaction, in the absence of steam, produces carbon monoxide. The products, ceric oxide and sodium titanate, obtained in either case, are treated with carbon dioxide and water to produce ceric oxide, titanium dioxide, sodium titanate, and sodium bicarbonate. After dissolving sodium bicarbonate from the mixture in water, the remaining insoluble compounds are used as starting materials for a subsequent cycle. The sodium bicarbonate can be converted to sodium carbonate by heating and returned to the cycle";
the USDOE has, as well, been at work for some time on the thermo-chemical conversion of Carbon Dioxide, in conjunction with Water, into hydrocarbons, via the initial production of a synthesis gas blend of Carbon Monoxide and Hydrogen; in processes wherein simple heat energy is the driver of the needed reactions.
And, it is that general technology for the use of heat to drive CO2 recycling processes - - no matter what thermal energy source we derive it from, although, as we will see in reports to follow, Solar seems to be preferred among the organizations developing that type of Carbon Dioxide utilization technology, and auxiliary technologies have been developed to support the chemical processes, and to supply them with Solar-derived heat - - that form the basis of our report herein, and of some reports to follow documenting more recent achievements.
Now, Solar-powered processes, especially high-temperature Solar processes, might not do us poor old hillbillies all that much good right here in the often-cloudy heart of US Coal Country. But, there are places in the USA not too far away from Coal Country where Solar thermal energy could be viable; and, we don't know about you, but, if we had our druthers, we would a lot druther buy Gasoline made from recycled Carbon Dioxide at a plant in South Carolina than Gasoline made from recycled Carbon Dioxide at a plant, as suggested in our report of:
West Virginia Coal Association | Saudi Arabia and Texas CO2 to Hydrocarbon Syngas | Research & Development; "United States Patent 8,288,446 - Catalytic Hydrogenation of CO2 into Syngas Mixture; 2012;
Assignee: Saudi Basic Industries Corporation, Riyadh; Abstract: The invention relates to a process of making a syngas mixture containing hydrogen, carbon monoxide and carbon dioxide, comprising a step of contacting a gaseous feed mixture containing carbon dioxide and hydrogen with a catalyst, wherein the catalyst substantially consists of chromia/alumina. This process enables hydrogenation of carbon dioxide into carbon monoxide with high selectivity, and good catalyst stability over time and under variations in processing conditions. The process can be applied separately, but can also be combined with other processes, for example up-stream with other synthesis processes for making products like aliphatic oxygenates, olefins or aromatics";
in Saudi Arabia.
That said, in excerpts from the initial and one following links in this dispatch, we learn how the USDOE, via it's western US National Laboratories, has been fostering and promoting the development of thermally-driven processes for the conversion of Carbon Dioxide and Water into Carbon Monoxide and Hydrogen, and, thence, into hydrocarbons:
"Solar Fuel Production Through The Thermochemical Decomposition of Carbon Dioxide
Nathan P. Siegel, et. al., Sandia National Laboratories, Albuquerque, NM USA
Abstract: Solar energy systems based on an intermittent resource benefit from an energy storage mechanism that decouples the solar resource from the load, enabling operation when the resource is unavailable. For utility scale power plants this is achieved with thermal energy storage (TES) systems incorporating significant volumes (some larger than 106 liters) of inorganic salts.
Storing solar energy in the form of chemical fuels offers another more energy dense storage mechanism that enables the utilization of solar energy to address the energy needs of the transportation sector.
Concentrating solar power (CSP) systems are capable of operating at the elevated temperatures needed to drive thermochemical reactions that convert the stable combustion products, carbon dioxide and water, first into synthesis gas, a mixture of carbon monoxide and hydrogen, and then into liquid hydrocarbon fuels such as methanol, gasoline, and jet fuel.
Sandia National Laboratories (SNL) is developing a process called Sunshine to Petrol, or S2P, in which a two-step thermochemical cycle is used to produce synthesis gas via H2O and/or CO2 decomposition that may then be converted into a liquid hydrocarbon fuel. The specific thermochemical cycles that are currently under investigation are based on ferrite or ceria compounds. These compounds must meet certain criteria related to mechanical and chemical stability as well as thermochemical performance in order to be suitable for solar fuel production. In this paper we discuss some of the development of candidate materials and also present results from on sun testing of ferrite compounds over successive CO2 splitting cycles during which we measure carbon monoxide production. We have found that CO production improves as the reaction temperature is increased up to 1200 C despite being thermodynamically more favorable at lower temperatures.
(Note, in the above, mention of the use of "ceria compounds", as in the earlier, above-cited USDOE 1982 "United States Patent 4,313,925 - Thermochemical Cyclic System for Decomposing H2O and/or CO2 by Means of Cerium-Titanium-Sodium-Oxygen Compounds". As we will see in this and reports to follow, the element Cerium is of great utility in these heat-driven CO2 reduction/conversion technologies.)
There are several routes that can be taken to produce liquid fuels using chemical feed stocks and solar energy. One option uses CO2 and H2O, stable combustion products, which are first reenergized via a two-step thermochemical process to produce synthesis gas1 that is then further processed to produce methanol, a precursor to the production of other fuels such as gasoline.
We call this methodology “Sunshine to Petrol” or S2P. A schematic of the process configured for the solar thermochemical production of CO is shown in Figure 1. Other configurations are possible, e.g. solar thermochemical production of both CO and H2 or solar thermochemical production of H2 followed by a reverse water-gas shift reaction to produce CO.
(We have seen the label "Sunshine to Petrol", "S2P", previously in our studies of these USDOE Carbon Dioxide utilization technologies, but don't think we've repeated it in any of our reports. That "Petrol" thing, though strictly speaking accurate, sounds a little too "continental" to be comfortable for us old Coal mining hillbillies.).
The ultimate viability of the S2P concept is tied to the fuel production efficiency which is, to a large extent, determined by the most energy intensive step in the process: the conversion of the stable combustion products CO2 and H2O into synthesis gas. The degree to which this step can be performed efficiently and in a practical manner is largely dependent on the reactive materials themselves with respect to their physical and thermodynamic behavior. The design and operation of the solar reactor are also important considerations that we have discussed previously. Although the focus of this work is on the development of reactive materials suitable for use in such a reactor, the
characteristics of these materials and the manner in which they are evaluated are influenced by the reactor configuration.
The reactor configuration that we are using for solar fuels production, the counter-rotating-ringreceiver/
reactor/recuperator (CR5), is a rotary reactor built for a parabolic dish platform that requires the use of
monolithic reactive structures.
(We've actually made a few prior reports concerning the "CR5" CO2-recycling "solar fuels" production device, invented/developed primarily it seems by one Rich Diver. We can't at this time locate our prior reports in the West Virginia Coal Association R&D archives; but, for some additional background and overview, have a look at:
http://tri-lab.lanl.gov/index.
and, even, from National Geographic Magazine a few years ago:
http://news.
These structures must absorb incident solar energy and support thermochemical reactions with minimal loss in performance over thousands of cycles. In addition, each reaction ... is allowed between one to two minutes to reach completion. Our performance target is to achieve an overall reaction extent of 25% in this time. The current material design methodology is to mix a reactive component, such as ferrite, with an inert ceramic such as yttria stabilized zirconia (YSZ). This process ... allows successive thermochemical cycles to be performed without deactivation due to agglomeration of the reactive material. We have developed several techniques for producing reactive structures that are relatively open, facilitating direct volumetric solar absorption, while maintaining sufficient geometric surface area to support chemical reactions.
(The paper then goes on to provide illustrations of the configuration and process, and experimental results.)
The thermodynamic argument for efficient solar fuel production via thermochemistry is contingent on the ability to provide nearly all of the energy required to convert CO2 and H2O into fuel in the form of heat as opposed to first converting the heat to work and then cracking those materials using, for example, an electrochemical process; Minimizing the number of energy conversion steps improves the overall energy efficiency potential of the process.
Thermochemical fuel production from CO2 and H2O using solar energy is contingent on developing the materials that can be used to effectively carry out the required reactions."
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Well, the fact is, that, they have developed "the materials that can be used to effectively carry out the required reactions", as we will eventually see. And, as might be indicated in another report available from the USDOE concerning "S2P":
http://prod.sandia.gov/
"SANDIA REPORT: SAND2012-0307;
Printed January 2012; Final Report
Reimagining Liquid Transportation Fuels: Sunshine to Petrol
James E. Miller, Mark D. Allendorf, Andrea Ambrosini, Ken S. Chen, Eric N. Coker, Daniel E. Dedrick, Richard B. Diver, Roy E. Hogan, Ivan Ermanoski, Terry A. Johnson, Gary L. Kellogg, Anthony H. McDaniel, Nathan P. Siegel, Chad L. Staiger, and Ellen B. Stechel
(Note the above authors. A number of them will be featured in reports to follow.)
Prepared by Sandia National Laboratories Albuquerque, New Mexico 87185 and Livermore, California 94550; Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Two of the most daunting problems facing humankind in the twenty‐first century are energy security and climate change. This report summarizes work accomplished towards addressing these problems through the execution of a Grand Challenge LDRD project (FY09‐11). The vision of Sunshine to Petrol is captured in one deceptively simple chemical equation:
Solar Energy + xCO2 + (x+1) H2O = CxH2x+2 (liquid (hydrocarbon) fuel) + (1.5x+.5) O2
Practical implementation of this equation may seem far‐fetched, since it effectively describes the use of solar energy to reverse combustion. However, it is also representative of the photosynthetic processes responsible for much of life on earth and, as such, summarizes the biomass approach to fuels production. It is our contention that an alternative approach, one that is not limited by efficiency of photosynthesis and more directly leads to a liquid fuel, is desirable. The development of a process that efficiently, cost effectively, and sustainably reenergizes thermodynamically spent feedstocks to create reactive fuel intermediates would be an unparalleled achievement and is the key challenge that must be surmounted to solve the intertwined problems of accelerating energy demand and climate change. We proposed that the direct thermochemical conversion of CO2 and H2O to CO and H2, which are the universal building blocks for synthetic fuels, serve as the basis for this revolutionary process. To realize this concept, we addressed complex chemical, materials science, and engineering problems associated with thermochemical heat engines and the crucial metal‐oxide working‐materials deployed therein. By project’s end, we had demonstrated solar‐driven conversion of CO2 to CO, a key energetic synthetic fuel intermediate, at 1.7% efficiency.
As acknowledged from the beginning, the ultimate vision for thermochemical fuels was never going to be achievable in a three‐year LDRD Grand Challenge project. Rather we set out to demonstrate a prototype device at a level of maturity that would provide evidence as to the achievability of our ultimate purpose and provide additional support for the credibility of this claim through scientific study and engineering analysis. Furthermore we set out to develop a research community with a “critical mass” of expertise, interest, and passion for this research that would sustain it beyond the three‐year LDRD project limit. It is our contention that we have achieved these broad objectives. In addition we have also created a unique legacy for the laboratory in the form of new experimental and computational tools, capabilities, and expertise. We also believe we have established the laboratory as a national and international leader in the field of thermochemistry.
If thermochemistry is to achieve its promise, much work remains to be done. We propose a path forward that addresses the three principle topics areas: Reactors, Materials, and Systems.
Materials: Current materials are incapable of supporting efficiencies high enough for the thermochemical technology to outpace other approaches (e.g. electrochemistry). However, looking forward, our material efforts have laid the groundwork for a new generation of thermochemical materials.
The three legs of our strategy include: 1) exploring new classes of thermochemical redox systems; 2) building on current knowledge to improve on mixed and composite systems that combine functionalities such as ion transport with a high density of redox centers; and 3) structuring materials so that characteristic dimensions are matched to transport dimensions. This approach is required, yet it is unique in that it will be among the first in this field
to be guided by materials design considerations extending beyond the simplest thermodynamics."
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We know the above-specified "1.7 percent" efficiency with which the Solar-driven CO2-to-fuel conversion process has been demonstrated doesn't sound that great. But, in point of fact, it probably is pretty good, relative to alternatives for the indirect recycling of Carbon Dioxide, via various biomass techniques such as the cultivation, fermentation and distillation of corn ethanol.
And, it has gotten better. We'll be providing documentation of the technical improvements in the US Government's "S2P", solar heat-driven conversion of Carbon Dioxide and Water into hydrocarbon synthesis gas blends of Hydrogen and Carbon Monoxide in some reports to follow; but, for now, as can be learned via an official, and very recent, United States Government solicitation:
"October 29, 2013: Sandia and Sunshine-to-Petrol (TM): Renewable Drop-in Transportation Fuels; Solicitation Number: 14-396; Agency: United States Department of Energy; Sandia National Laboratories (Sandia) is conducting ongoing research and development into solar fuels, the conversion of sunlight, CO2, and H2O into high energy density, gasoline, diesel, and jet fuel pre-cursors. Our solar fuels program, Sunshine to Petrol (S2P), is cost competitive with other renewable transportation fuel options such as biofuels, gas-to-liquid reforming, solar electrolysis and photoelectrocatalysis. In addition to cost competitiveness, the unique value in S2P is the production of fuels other than methanol, ethanol, and hydrogen that can be integrated directly into the existing transportation infrastructure.S2P uses a two-step solar thermochemical cycle. Sandia is the world leader in this technology having developed two engine prototypes, in addition to pioneering the gold standards in redox/catalyst materials, and also completing thorough systems studies and life cycle analysis. Sandia has authored multiple publications and owns a substantial intellectual property (IP) portfolio.
Sandia is seeking a company or companies interested in this unique opportunity which will lead to the demonstration and deployment of this technology. We are seeking a partner interested in Cooperative Research & Development Agreements (CRADAs) or Work for Others agreements (WFOs). Potential partners must have a significant interest in developing this technology to the demonstration and deployment stage. The CRADA or WFO is expected to include funds-in to Sandia from the partner(s). Background IP and new IP developed in the course of the relationship will be available for licensing, up to an exclusive license.
Interested companies are preferred but not required to have experience and expertise in: Commercialization and integration of renewable transportation fuel options into the existing petrochemical/fuel infrastructure."
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the United States Department of Energy is, right now, via it's Sandia National Laboratories, looking for commercial partners to further refine and to reduce "S2P" to industrial practice; to begin converting, using Solar heat energy to drive the process, Carbon Dioxide and Water into "gasoline, diesel and jet fuel ... that can be integrated directly into the existing transportation infrastructure".
Adios, OPEC and Cap & Trade Carbon taxes.
Happy Thanksgiving, United States Coal Country.