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Our own, US, Department of Defense archives document that Imperial Japan established factories in the Japanese homeland, the Korean peninsula and the Chinese mainland that converted coal into liquid fuel for her military during WWII.
We've reported further that coal-to-liquid technical and industrial development has, more recently, been underway in all three nations. China, especially, has a well-documented, and extensive, coal-to-liquid industrialization program underway.
In this submission, we document that all three of those Asian countries are not only at work developing coal liquefaction industries, but are also further developing the technologies, which we've documented to be feasible and practical, to recycle the Carbon Dioxide co-product of coal use into additional liquid fuels.
Several links and excerpts, with minor editing of obtuse formulaic symbols, follow:
Document title
Hydrogenation of carbon dioxide over Cu-Zn-chromate/zeolite composite catalyst : the effects of reaction behavior of alkenes on hydrocarbon synthesis
Fujiwara M.; Ando H.; Tanaka M.; Souma Y.
Osaka national res. inst., AIST, MITI, Ikeda, Osaka 563, Japon
Abstract
The hydrogenation of carbon dioxide was studied using composite catalysts comprised of Cu-Zn-chromate and HY zeolite. These composite catalysts enabled the reaction combining methanol synthesis and methanol-to-gasoline reaction, and achieved the formation of ethylene and propene as the first example of the composite catalysts. The addition of alkaline metals, especially cesium, to Cu-Zn-chromate enhanced the selectivities of those alkenes. The influences of the reaction pressure and the space velocity on the production of alkenes show that alkanes are obtained by the hydrogenation of the corresponding alkenes. The composite catalysts producing alkenes in high selectivity afforded heavier hydrocarbons preferentially. These results indicate that the hydrogenation of alkenes inhibits the carbon homologation of alkenes to result in the predominant formation of the corresponding lighter alkanes. From these observations, it was found that methanol synthesis catalysts used for the composite catalysts are required to be effective for methanol synthesis at high temperature and to bear the low activity of the hydrogenation of alkenes.
ScienceDirect - Energy Conversion and Management : Catalytic conversion of carbon dioxide into hydrocarbons over zinc promote.
Catalytic conversion of carbon dioxide into hydrocarbons over zinc promoted iron catalysts
Sang-Sung Nam, Soo-Jae Lee, Ho Kim, Ki-Won Jun, Myuong-Jae Choi and Kyu-Wan Lee
KRICT., P.O. Box 107, Yusong, Taejon 305-600, Korea
Abstract
The hydrogenation of carbon dioxide to hydrocarbons over iron catalysts was studied in a fixed bed reactor under pressure of 10 atm and temperature of 573 K. Iron catalysts promoted with V, Cr, Mn and Zn prepared by precipitation method were adopted in the present study. The catalysts were characterized by XRD, carbon dioxide chemisorption and Mössbauer spectroscopy. The hydrocarbons were formed directly from carbon dioxide over iron catalysts. The iron promoted with Cr and Mn improved conversion of carbon dioxide and increased the selectivity of alkenes. Whereas, the Zn promoted iron catalyst showed unusually very high selectivity. With varying Fe:Zn ratio, the smaller ratio of Zn increased the alkene selectivity.
Low-temperature synthesis of DME from CO2/H2 over Pd-modified CuO–ZnO–Al2O3–ZrO2/HZSM-5 catalysts
Kunpeng Sun, Weiwei Lu, Min Wang and Xianlun Xu
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China
Abstract
Three series of Pd-modified HZSM-5 catalysts were prepared and characterized by BET, XRD and TPR analysis. The catalytic system was evaluated in the development of direct synthesis of dimethyl ether (DME) from carbon dioxide hydrogenation at low temperature). The results indicated that the addition of palladium markedly enhanced the DME synthesis and retarded the CO formation. An explanation of this promoting effect of Pd on the DME synthesis could be attributed to the spillover of hydrogen from Pd to the neighboring phase.
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Note, in the above, the mention of Iron-group metals and zeolite (HZSM-5) catalysts used in the liquefaction of Carbon Dioxide. Those catalysts are at the core of at least two "indirect" coal-to-liquid technologies, the Fischer-Tropsch method employed by Germany in WWII, and the more current Exxon-Mobil "MTG" (r), or methanol-to-gasoline, Process, wherein the methanol is posited to be made from coal. "DME", or dimethyl ether, mentioned above, is a useful liquid, diesel-type, fuel and chemical synthesis raw material in it's own right, and can be converted into diesel and gasoline.
This work in China, Japan and Korea is in addition to other Asian CO2-recycling accomplishments, in Singapore, which we've earlier brought to your attention.
Recycling Carbon Dioxide is feasible. And, it sounds a lot more promising and profitable than strangling our coal-use industries through Cap&Trade legislation, or drafting them into the expensive service of Big Oil through enforced geologic sequestration, doesn't it?
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We reported some months ago on the Singapore CO2 recycling development, as briefly mentioned below. Our account of it lies in the archives of the WV Coal Association's R&D Blog.
However, the importance of this submission is that South Africa's Sasol, the world's leader in converting coal into liquid fuels, is now making ready to commercialize one of the several technologies that do exist for recycling Carbon Dioxide - into more liquid fuels and chemical feed stocks for plastics manufacturing.
A brief excerpt:
"JOHANNESBURG (miningweekly.com) – South Africa's coal-to-liquids company Sasol is studying the conversion of carbon dioxide (CO2) into fuel.
Engineers and scientists in Sasol's technology division are working on algaeic forms of methanol production and Singapore's Institute of Bioengineering and Nanotechnology reported a CO2-to-methanol breakthrough earlier this year."
As we've said before: Carbon Dioxide, as arises from our use of coal, isn't a pollutant, but a raw material resource of great potential value.
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Landlocked Switzerland's Alpine geologic terrain contains no oil or commercial reserves of coal.They have, however, like our own US Navy, and the DOD's defense contractors, as affirmed in their several patents for CO2 recycling, copies of which we sent you, figured out how to drill for oil in the, for the Swiss, very thin air.The Swiss, like Japan, Korea, China, Singapore and South Africa's coal liquefaction giant, Sasol, have realized the importance behind Sabatier's Nobel-winning technology for reclaiming Carbon Dioxide, from coal plant emissions and from the atmosphere, and converting it into liquid hydrocarbon fuels.The excerpt, with a, perhaps pertinent, comment, and a question, appended:"Document title
Hydrogenation of carbon dioxide to methanol with a discharge-activated catalystAuthors
ELIASSON B.; KOGELSCHATZ U. ; BINGZHANG XUE ; ZHOU L.-M.Affiliations
ABB Corporate Research Ltd., 5405 Baden, SUISSE
Abstract
To mitigate greenhouse gas CO2 emissions and recycle its carbon source, one possible approach would be to separate CO2 from the flue gases of power plants and to convert it to a liquid fuel, e.g., methanol. Hydrogenation of CO2 to methanol is investigated in a dielectric-barrier discharge (DBD) with and without the presence of a catalyst. Comparison of experiments shows that this nonequilibrium discharge can effectively lower the temperature range of optimum catalyst performance. The simultaneous presence of the discharge shifts the temperature region of maximum catalyst activity from 220 to 100°C, a much more desirable temperature range. The presence of the catalyst, on the other hand, increases the methanol yield and selectivity by more than a factor of 10 in the discharge. Experiment and numerical simulation show that methane formation is the major competitive reaction for methanol formation in the discharge. In the case of low electric power and high pressure, methanol formation can surpass methanation in the process.Journal Title
Industrial & engineering chemistry research ISSN 0888-885 CODEN IECRED; 1998, vol. 37, no8, pp. 3350-3357 (32 ref.)
Publisher
American Chemical Society, Washington, DC, ETATS-UNIS (1987) (Revue)"This article, on recycling the Carbon Dioxide arising from our coal-use industries, and converting it into a valuable alcohol, methanol, which is an excellent liquid fuel and plastics manufacturing raw material; which can also be converted, through at least one commercial technology, our oft-mentioned Exxon-Mobil "MTG"(r), Methanol-to-Gasoline process, into the standard-issue gasoline we're all familiar with; and, which can also be with great alacrity synthesized from coal and renewable cellulose, was written by Swiss power company researchers, including, it would appear, some Chinese nationals. However, it was published more than 20 years ago, in English and by the American Chemical Society.Why, then, have we American Coal Country citizens not been informed of these developments and potentials at some point during those two decades: those twenty years we've been sending our young people to die in OPEC wars; those twenty years we've been allowing our vital coal industries to shrivel under the attacks of, perhaps well-meaning, environmentalists; those twenty years we've allowed our hard-working and patriotic coal people to languish at the precipice of poverty; those twenty years we have financed and defended the lavish lifestyles of oil sheiks and oil company robber barons?
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We won't even attempt editing the following excerpts from the two links above, or adding much comment, except:
Our own US DOE has developed coal-to-liquid fuel technology with a variety of independent corporate contractors. These are not the only projects "out there".
Where are the reports of all this work? What is the status? Where are we headed now?
This is the US GUV at work, and they work for us, or are supposed to.
Way past time our employees delivered all of us, especially those of us in Coal Country, a progress report, don't you think?
There are some contact names, telephone numbers and emails included in the excerpts below. It's time, way past time, the bosses checked up to see what their employees have been up to lately.
Excerpts as follows:
| United States Department of Energy | |
| Office of Fossil Energy | |
| Project Fact Sheet | |
| | |
| Project Information | |
| Project ID: | DE-FC26-06NT42449 |
| Project Title: | Production of High-Hydrogen Content Coal-Derived Liquids |
| FE Program: | Coal Fuels - Liquid Fuels |
| Research Type: | Engineering Development |
| Funding Memorandum: | Cooperative Agree't (nonCCT) - Tech R&D |
| Project Performer | |
| Performer Type: | For-profit Organization |
| Performer: | Integrated Concepts & Research Corporation 41150 Technology Park Drive Suite 103 |
| Project Team Members: | |
| Project Location | |
| City: | Sterling Heights |
| State: | Michigan |
| Zip Code: | 48314-4156 |
| Congressional District: | 10 |
| Responsible FE Site: | NETL |
| Project Point of Contact | |
| Name: | Bergin, Steve P. |
| Telephone: | (586) 799-1780 |
| Fax Number: | (586) 991-0950 |
| Email Address: | |
| Fossil Energy Point of Contact | |
| Name: | Driscoll, Daniel J. |
| Telephone: | (304) 285-4717 |
| Location: | NETL |
| Email Address: | |
| Project Dates | |
| Start Date: | 07/01/2005 |
| End Date: | 06/30/2010 |
| Contract Specialist | |
| Name: | Harshman, Angela (Delmastro) |
| Telephone: | (412) 386-5038 |
| Cost & Funding Information | |
| Total Est. Cost: | $3,477,494 |
| DOE Share: | $2,779,168 |
| Non DOE Share: | $698,326 |
| Project Description | |
| The objective of this project is to evaluate and compare intrinsic differences between cobalt (Co) and iron (Fe) catalysts for Fischer-Tropsch (F-T) synthesis utilizing coal-derived synthesis gas. Specific parameters to be evaluated include: the effect of contaminants contained in coal-derived syngas on catalyst activity and lifetime, the required H2/CO ratios for efficient conversion, the required level of syngas cleanup to maintain catalyst reactivity and raw product upgrading requirements to produce high-hydrogen content coal-derived liquids. | |
| Project Background | |
| BACKGROUND F-T plants that have used coal as their feedstock have virtually all used iron catalyst systems for F-T synthesis. When coal is gasified, it produces syngas that has a much lower hydrogen content than syngas obtained by reforming other hydrocarbons. For example, methane typically produces syngas with a H2/CO ratio of ~2, or about double that typically obtained with coal. Iron F-T catalyst systems are generally considered to be much more tolerant of syngas with coal's low H2/CO ratios because the iron system can catalyze a significant amount of water-gas shift, and thus increase the effective H2/CO ratio at essentially the same time as it catalyzes F-T synthesis. This means that the raw F-T products synthesized from coal-derived syngas using iron catalysts need not be as deficient in hydrogen as might be implied by the initial H2/CO ratio of the syngas. Cobalt F-T catalyst systems need their incoming syngas to have a H2/CO ratio of about two to produce the highest quality products. If coal is the feedstock, the H2/CO ratio of the syngas must be increased for a cobalt catalyst system. This adds cost and complexity, but the cobalt catalyst system may (or may not) provide other advantages that more than compensate overall. This project provides the unique opportunity for combining and evaluating, in a single R&D project, real-world, in-depth studies of all the primary or core elements required for the integration of the full-range of F-T synthesis technologies (with both cobalt and iron catalyst systems) using coal-derived syngas. The work will provide a detailed comparison between cobalt and iron catalysts, evaluate the catalysts sensitivity to various contaminants and poisons, assess possible gas cleanup scenarios, and produce and test experimental quantities of coal-derived F-T liquid fuels. | |
| Project Milestones | |
| This information is currently unavailable. | |
| Project Accomplishments | |
| Title: | Revised Agreement |
| Date: | 09/19/2008 |
| Description | A revised agreement with a modified SOW was put in place on July 10, 2008. |
| Title: | Status/Accomplishments |
| Date: | 04/01/2006 |
| Description | A Cooperative Agreement was awarded to Integrated Concepts and Research Corporation on March 30, 2006. |
| United States Department of Energy | |
| Office of Fossil Energy | |
| Project Fact Sheet | |
| | |
| Project Information | |
| Project ID: | DE-FC26-05NT42448 |
| Project Title: | Production and Optimization of Coal-Derived, High-Hydrogen Content Fischer-Tropsch Liquids |
| FE Program: | Coal Fuels - Liquid Fuels |
| Research Type: | Engineering Development |
| Funding Memorandum: | Cooperative Agree't (nonCCT) - Tech R&D |
| Project Performer | |
| Performer Type: | Large Business |
| Performer: | Headwaters Technology Innovation Group 1501 New York Avenue |
| Project Team Members: | |
| Project Location | |
| City: | Lawrenceville |
| State: | New Jersey |
| Zip Code: | 08648-4635 |
| Congressional District: | 12 |
| Responsible FE Site: | NETL |
| Project Point of Contact | |
| Name: | Lee, Theo L.K. |
| Telephone: | (609) 394-3102 ext. 262 |
| Fax Number: | (609) 394-1278 |
| Email Address: | |
| Fossil Energy Point of Contact | |
| Name: | Driscoll, Daniel J. |
| Telephone: | (304) 285-4717 |
| Location: | NETL |
| Email Address: | |
| Project Dates | |
| Start Date: | 07/01/2005 |
| End Date: | 04/15/2010 |
| Contract Specialist | |
| Name: | Reese (formerly Sheehan), Dona |
| Telephone: | (412) 386-5918 |
| Cost & Funding Information | |
| Total Est. Cost: | $1,396,485 |
| DOE Share: | $1,100,000 |
| Non DOE Share: | $296,485 |
| Project Description | |
| The primary objective of this project is to investigate the production of barrel quantities of high-hydrogen content, coal-derived liquids using iron-based Fischer-Tropsch (FT) synthesis in a process development unit (PDU)-scale reactor. Tests conducted in the PDU-scale reactor will be based on optimization studies conducted in bench-scale reactor systems. The bench-scale reactor systems will evaluate two iron-based FT catalysts - a high alpha catalyst in a slurry bubble column and a medium alpha catalyst in an ebullated-bed mode of operation. The catalyst holding the most promise for future commercial application will be recommended for PDU-scale reactor testing and the production of barrel quantities of high-hydrogen content, coal-derived FT liquids. In support of the primary objective, the project will also investigate primary and secondary wax/catalyst separation, hydrotreating and hydrocracking of neat FT liquid products, and hydrogen yield from product reforming. The products made will be high-hydrogen content, coal-derived liquid types suitable for additional research and testing in a variety of applications, including distributed hydrogen generation. Data from these tasks will be employed in the development of a conceptual coal-to-liquids plant design and system analysis. The potential benefit of this work is expected to result in the development of a more reliable, economic, and efficient coal-based system for producing FT liquids to meet the long-term goals of the U.S. Department of Energy's (DOE's) Coal-to-Hydrogen Program. The successful development of these technologies will also provide scientific data which will help in accelerating the future commercialization of coal-to-liquids technology in the energy industry. | |
| Project Background | |
| Increased oil prices, political instability in oil rich countries, and environmental concerns have sparked renewed interest in coal-based Fischer-Tropsch (FT) technology as a means of reducing the United States' dependence on foreign oil. Integrated coal gasification, combined cycle, and FT technology holds the potential to provide clean, domestic sources of electricity, liquid fuels, hydrogen, and commodity chemicals. The technical and economical feasibility of coal gasification and FT technologies have been enhanced by recent improvements in coal gasification for clean power generation and in natural gas-to-liquid technologies for monetizing remote gas reserves. However, a different catalysis system is required for coal-derived synthesis gas and numerous integration issues between the coal gasifier and the FT synthesis reactor must be investigated before commercialization can occur. The goal of the proposed work is to accelerate the commercialization of coal-to-liquids technology. | |
| Project Milestones | |
| This information is currently unavailable. | |
| Project Accomplishments | |
| Title: | Status/Accomplishments |
| Date: | 09/30/2005 |
| Description | A Cooperative Agreement was awarded to Headwaters Technology Innovations Group on May 24, 2005. |
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We submit herein yet another web-accessible "textbook" on the conversion of coal - and CO2-recycling biomass - into liquid transportation fuels.
Coal is secondary in this treatment of the subject. Though currently abundant, coal, we must all acknowledge, is ultimately a finite resource. It will, eventually and sadly, run out.
But, it represents, right now, a more concentrated source of carbon compounds from which more valuable organic products can be manufactured as our dwindling supply of petroleum-based chemicals, along with petroleum fuels, grows ever smaller and dwindles, at last, away.
We will want our coal for things more lastingly useful than gasoline.
However, here and now, coal's abundance and the established technologies that exist to convert it into liquid fuels, and plastics manufacturing raw materials, would enable us to establish a liquid fuel production industry starting with coal, and then to use increasing amounts of biomass that can be processed into liquid fuels using the same facilities.
Coal could thus be somewhat conserved for more valuable applications, and a foundation of sustainability thereby established.
All of that would be in addition, of course, to the direct recycling of Carbon Dioxide, via Sabatier, Carnol and other technologies, which we have thoroughly documented, into hydrocarbon fuels and chemicals.
That said, following is the table of contents of the enclosed book; yet more evidence that the technologies do exist to enable both our full employment of coal to supply our current liquid fuel needs and our use of coal to lead us into a future era of true economic, and environmental, sustainability:
Sadly, they do make reference to what we believe should be the outdated, and summarily discarded, concept of expensive and wasteful "carbon storage".
With Sabatier, Carnol and Bio- technologies, we could, and should, start thinking, and planning, in terms of "carbon recycling" to make the fullest use possible of our coal resources, and of our coal-use byproducts.
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