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Since we've presented evidence that makes it appear China is attempting to hijack the patent rights to WVU's "West Virginia Process" for direct coal liquefaction, we wanted to show you that they have at least given some thought as to how the by-products of that conversion process can be profitably employed.
In this case, they suggest that tar-like residues left behind by direct coal liquefaction can be employed as a paving and road-repair material, very much like the natural petroleum asphalt we're all familiar with.
The excerpt, with additional comment following:
"Novel Use of Residue from Direct Coal Liquefaction Process
Jianli Yang, Zhaixia Wang, Zhenyu Liu and Yuzhen Zhang
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, P.R. China, State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P.R. China, and State Key Laboratory of Heavy Oil Processing, Petroleum University, Dongying 257061, P.R. China
Abstract
Direct coal liquefaction residue (DCLR) is, commonly, designed to be used as a feed stock for gasification or combustion. Use of DCLR as a value added product is very important for improving overall economy of direct coal liquefaction processes. This study shows that the DCLR may be used as a pavement asphalt modifier. The modification ability is similar to that of Trinidad Lake Asphalt (TLA), a superior commercial modifier. Asphalts modified by two DCLRs meet the specifications of ASTM D5710 and BSI BS-3690 designated for the TLA-modified asphalts. The required addition amount for the DCLRs tested is less than that for TLA due possibly to the high content of asphaltene in DCLRs. Different compatibility was observed for the asphalts with the same penetration grade but from the different origin. Different components in the DCLR play different roles in the modification. Positive synergetic effects among the fractions were observed, which may due to the formation of the stable colloid structure. Unlike polymer-type modifier, the structure of asphalt-type modifier has a similarity with petroleum asphalts which favors the formation of a stable dispersed polar fluid (DPF) colloid structure and improves the performance of pavement asphalt."
So, residue left behind by a direct coal liquefaction process very similar to, or exactly the same as, WVU's West Virginia coal conversion Process is a superior additive for asphalt used in road paving. Now, in a state, like West Virginia, where the State Seal was once believed to incorporate the image of road worker, in silhouette, leaning into his shovel at the edge of a pothole, wouldn't a by-product of converting their most abundant resource into desperately-needed liquid fuels that would reduce the need for placing such road repair signs be a "good thing"?
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You will recall that Chunshan Song appeared prominently in one of the recent Carbon Dioxide Utilization symposia we informed you of. Since Penn State is a relatively local institution, and readily accessible for further investigation, of you're so inclined, we wanted to send you one of Dr. Song's individual works on the recycling of the Carbon Dioxide by-product of our coal-use industries.
Excerpt as follows:
"Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing"
Chunshan Song
Clean Fuels and Catalysis Program, The Energy Institute, and Department of Energy & Geo-Environmental Engineering, The Pennsylvania State University 209 Academic Projects Building, University Park, PA 16802, USA
Abstract
Utilization of carbon dioxide (CO2) has become an important global issue due to the significant and continuous rise in atmospheric CO2 concentrations, accelerated growth in the consumption of carbon-based energy worldwide, depletion of carbon-based energy resources, and low efficiency in current energy systems. The barriers for CO2 utilization include: (1) costs of CO22 chemical conversion (plus source and cost of co-reactants); (3) market size limitations, little investment-incentives and lack of industrial commitments for enhancing CO2-based chemicals; and (4) the lack of socio-economical driving forces. The strategic objectives may include: (1) use CO2 for environmentally-benign physical and chemical processing that adds value to the process; (2) use CO2 to produce industrially useful chemicals and materials that adds value to the products; (3) use CO2 as a beneficial fluid for processing or as a medium for energy recovery and emission reduction; and (4) use CO2 recycling involving renewable sources of energy to conserve carbon resources for sustainable development. The approaches for enhancing CO2 utilization may include one or more of the following: (1) for applications that do not require pure CO2, develop effective processes for using the CO2-concentrated flue gas from industrial plants or CO2-rich resources without CO2 separation; (2) for applications that need pure CO2, develop more efficient and less-energy intensive processes for separation of CO2 selectively without the negative impacts of co-existing gases such as H2O, O2, and N2; (3) replace a hazardous or less-effective substance in existing processes with CO2 as an alternate medium or solvent or co-reactant or a combination of them; (4) make use of CO2 based on the unique physical properties as supercritical fluid or as either solvent or anti-solvent; (5) use CO2 based on the unique chemical properties for CO2 to be incorporated with high ‘atom efficiency’ such as carboxylation and carbonate synthesis; (6) produce useful chemicals and materials using CO2 as a reactant or feedstock; (7) use CO2 for energy recovery while reducing its emissions to the atmosphere by sequestration; (8) recycle CO2 as C-source for chemicals and fuels using renewable sources of energy; and (9) convert CO2 under either bio-chemical or geologic-formation conditions into “new fossil” energies. Several cases are discussed in more detail. The first example is tri-reforming of methane versus the well-known CO2 reforming over transition metal catalysts such as supported Ni catalysts. Using CO2 along with H2O and O2 in flue gases of power plants without separation, tri-reforming is a synergetic combination of CO2 reforming, steam reforming and partial oxidation and it can eliminate carbon deposition problem and produces syngas with desired H2/CO ratios for industrial applications. The second example is a CO2 “molecular basket” as CO2-selective high-capacity adsorbent which was developed using mesoporous molecular sieve MCM-41 and polyethylenimine (PEI). The MCM41-PEI adsorbent has higher adsorption capacity than either PEI or MCM-41 alone and can be used as highly CO2-selective adsorbent for gas mixtures without the pre-removal of moisture because it even enhances CO2 adsorption capacity. The third example is synthesis of dimethyl carbonate using CO2 and methanol, which demonstrates the environmental benefit of avoiding toxic phosgene and a processing advantage. The fourth example is the application of supercritical CO2 for extraction and for chemical processing where CO2 is either a solvent or a co-reactant, or both. The CO2 utilization contributes to enhancing sustainability, since various chemicals, materials, and fuels can be synthesized using CO2, which should be a sustainable way in the long term when renewable sources of energy are used as energy input." capture, separation, purification, and transportation to user site; (2) energy requirements of CO
Admittedly a rather dense synopsis. But, the detail should be affirmation that, although it hasn't for whatever perverse reason been publicized and popularized, the potential to recover and recycle the CO2 by-product of our coal use industries is quite real. It could make our use of coal, whether we generate electricity or synthesize liquid fuels with it, even more valuable and essential to us than it now is.
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We reported that a symposium had been held this year, with surprisingly little public notice, given the alarmism that has been fostered about the topic of global warming and the culpability of supposed "greenhouse" gasses in the process, on the recycling and reuse of Carbon Dioxide, which can arise as a much-maligned by-product from our coal-use industries.
Such symposia have been held, in near-secrecy it would seem, for quite some time now, as this reference will attest.
Some excerpts from the enclosed link:
"ACS Symposium #809: Co2 Conversion and Utilization
Held March, 2000, in San Francisco, CA
Chunshan Song, Editor
1. CO2 Conversion and Utilization: An Overview, Chunsan Song
2. CO2 Mitigation and Fuel Production, M. Steinberg
3. CO2 Emission Reductions: An Opportunity for New Catalytic Technology, Leo E. Manzer
Synthesis of Organic Chemicals
4. Key Issues in Carbon Dioxide Utilization as a Building Block for Molecular Organic Compounds in the Chemical Industry, Michele Aresta and Angela Dibenedetto
5. Selective Conversion of Carbon Dioxide and Methanol to Dimethyl Carbonate Using Phosphoric Acid-Modified Zirconia Catalysts, Yoshiki Ikeda, Yutaka Furusawa, Keiichi Tomishige, and Kaoru Fujimoto
6. Utilization of Carbon Dioxide for Direct, Selective Conversion of Methane to Ethane and Ethylene with Calcium-Based Binary Catalysts, Ye Wang and Yasuo Ohtsuka
7. Copolymerization of Carbon Dioxide, Propylene Oxide, and Cyclohexene Oxide by an Yttrium-Metal Coordination Catalyst System, Chung-Sung Tan, Char-Fu Chang, and Tsung-Ju Hsu
8. The Role of CO2 for the Gas-Phase O2 Oxidation of Alkylaromatics to Aldehydes, Jin S. Yoo
9. Effective Conversion of CO2 to Valuable Compounds by Using Multifunctional Catalysts, Tomoyuki Inui
10. Supported Copper and Manganese Catalysts for Methanol Synthesis from CO2-Containing Syngas, K. Omata, G. Ishiguro, K. Ushizaki, and M. Yamada
11. Catalytic Reduction of CO2 into Liquid Fuels: Simulating Reactions under Geologic Formation Conditions, D. Mahajan, C. Song, and A. W. Scaroni
12. Methane Dry Reforming over Carbide, Nickel-Based, and Noble Metal Catalysts, Abolghasem Shamsi
13. A Highly Active and Carbon-Resistant Catalyst for CH4 Reforming with CO2: Nickel Supported on an Ultra-Fine ZrO2, Jun-Mei Wei, Bo-Qing Xu, Jin-Lu Li, Zhen-Xing Cheng, and Qi-Ming Zhu
14. CO2 Reforming of Methane over Ru-Loaded Lanthanoid Oxide Catalyst, Kiyoharu Nakagawa, Shigeo Hideshima, Noriyasu Akamatsu, Na-oko Matsui, Na-oki Ikenaga, and Toshimitsu Suzuki
15. CO2 Reforming and Simultaneous CO2 and Steam Reforming of Methane to Syngas over CoxNi1-xO Supported on Macroporous Silica-Alumina Precoated with MgO, V. R. Choudhary, A. S. Mamman, B. S. Uphade, and R. E. Babcock
16. Low-Temperature CH4 Decomposition on High-Surface Area Carbon Supported Co Catalysts, Z.-G. Zhang, K. Haraguchi, and T. Yoshida
17. Effects of Pressure on CO2 Reforming of CH4 over Ni/Na-Y and Ni/Al2O3 Catalysts, Chunshan Song, Srinivas T. Srimat, Satoru Murata, Wei Pan, Lu Sun, Alan W. Scaroni, and John N. Armor
18. A Comparative Study on CH4-CO2 Reforming over Ni/SiO2-MgO Catalyst Using Fluidized-and Fixed-Bed Reactors, A. Effendi, Z.-G. Zhang, and T. Yoshida
19. Effects of Pressure on CO2 Reforming of CH4 over Rh/Na-Y and Rh/Al2O3 Catalysts, Srinivas T. Srimat and Chunshan Song
20. Methane Reforming with Carbon Dioxide and Oxygen under Atmospheric and Pressurized Conditions Using Fixed- and Fluidized-Bed Reactors, Keiichi Tomishige, Yuichi Matsuo, Mohammad Asadullah, Yusuke Yoshinaga, Yasushi Sekine, and Kaoru Fujimoto
21. Computational Analysis of Energy Aspects of CO2 Reforming and Oxy-CO2 Reforming of Methane at Different Pressures, Wei Pan and Chunshan Song
22. Photocatalytic Reduction of CO2 with H2O on Various Titanium Oxide Catalysts, Hiromi Yamashita, Keita Ikeue, and Masakazu Anpo
23. Electrochemical Reduction of CO2 with Gas-Diffusion Electrodes Fabricated Using Metal and Polymer-Confined Nets, K. Ogura, H. Yano, and M. Nakayama".
We'll presume some of the more technical phrases, and their significance, such as "Reforming" and "Methanol Synthesis", to be familiar by now from our earlier posts, and will not explicate them herein.
There is more, but these selections should illustrate the, apparently well-known in certain circles, potential that exists to utilize the Carbon Dioxide which arises from our coal use in valuable and profitable ways.
Just like the liquid fuel, petroleum, "shortage", which could be profitably resolved by converting our abundant coal into liquid fuels, and leveraging coal conversion technology to begin employing biological feed stocks, the Carbon Dioxide "danger" is a false belief artificially fostered by special interests who would be somehow served by a reduction in coal's use and perceived importance.
There is no real Carbon Dioxide "problem". There is, however, a great CO2 opportunity. Carbon Dioxide is a valuable by-product of our coal-use industries. We should reward and encourage those enterprises which make it for us
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We've reported that Carbon Dioxide can be reduced and converted, via the Sabatier process, into oxygen, and methane, as is being done on the International Space Station, where the methane produced is dumped overboard as a means to dispose of excess carbon. We submit, and documentation is available, that NASA is studying the prospect of using Sabatier technology to produce fuel for the return leg of a journey to Mars, where the atmosphere is predominantly Carbon Dioxide. At least one of their scenarios proposes, as we've also documented to be feasible, the electrolysis of water to provide needed hydrogen for the methane synthesis.
As we've also noted, there are documented processes whereby methane, as could be produced by Sabatier technology, can be used as the basis for synthesis of more complex hydrocarbons, such as methanol.
Interestingly such use, the "reforming", of methane, can be designed to actually consume even more Carbon Dioxide, and produce a synthesis gas that is "preferred for the synthesis of valuable oxygenated chemicals and long-chain hydrocarbons". Long-chain hydrocarbons similar to liquid fuels, we presuppose.
The enclosed report is actually just one of many available resources documenting the potential for using additional CO2 to synthesize methane into more complex, and more valuable, hydrocarbons. In other words, the initial recycling of Carbon Dioxide, with methane as a by-product, makes possible the recycling of even more CO2 to create more complex hydrocarbons that could themselves be used to make liquid fuels.
The excerpt:
"Carbon Dioxide Reforming of Methane Over Nickel Supported Mesoporous Material Catalysts with Superior Stability
Dapeng Liu and Yanhui Yang, School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, Singapore
Catalytic reforming of methane with carbon dioxide, also known as dry reforming, has recently attracted considerable attention due to simultaneous utilization and reduction of two types of greenhouse gases, CO2 and CH4. The synthesis gas (syngas) produced has a lower H2/CO ratio than those available from steam reforming and partial oxidation of methane; the lower ratio is preferred for the synthesis of valuable oxygenated chemicals and long-chain hydrocarbons."
If we understand this correctly, and other reports seem to confirm it, using Carbon Dioxide to process, to reform, Methane, which itself can be produced from Carbon Dioxide by the Sabatier process, actually results in compounds better-suited for additional synthesis into more useful hydrocarbon products.
Carbon Dioxide is a valuable by-product of our coal use. We shouldn't be trying to legislate the industries that generate it out of existence.
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We have reported on demonstrated technologies, wherein coal conversion and bio-fuel production could be combined in comprehensive and synergistic ways to provide both a domestic, US, source of renewable liquid fuels, and an inherent method of recycling Carbon Dioxide.
Much has been made, in the United States, of ethanol, derived from corn and other agricultural, renewable and carbon-consuming, sources as a pollution-reducing liquid fuel. Some gasoline vendors blend a small percentage of it into some of their products.
Ethanol alone isn't all that compatible with our current liquid fuel infrastructure, or automotive engine designs, and it really doesn't have the energy density to serve, unblended, as a satisfactory liquid transportation fuel.
It could, however, serve our liquid fuel needs in another way.
Coal that is converted into liquid fuels must be somehow enriched with Hydrogen to form liquid hydrocarbons similar to those that power our current transportation fleet.
A number of supplemental Hydrogen sources have been proposed, and utilized, over the many decades that coal has been converted into liquid transportation fuels: in wartime Germany and Japan, in contemporary South Africa, and in WVU's West Virginia CTL Process, for instance.
As it happens, renewable and CO2-recycling Ethanol can serve as the Hydrogen donor in coal conversion processes, as follows:
"Title
Iron/sulfur-catalyzed coal liquefaction in the presence of alcohol and carbon monoxideAuthors
HATA K.-A.; KAWASAKI N.-A ; FUJI N.; NAKAGAWA Y. ; HAYASHI J.-I; WATANABE Y.; WADA K.; MITSUDO T.-A.Affiliation
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Japan
Abstract
The activities of several iron-based catalyst precursors towards the liquefaction of various kinds of coals, ranging from brown to bituminous, were examined in alcohol-carbon monoxide systems. Pentacarbonyliron (Fe(CO)5) with or without sulfur, or synthetic pyrite were found to be excellent catalyst precursors. Primary alcohols (ethanol and 1-propanol)-CO acted as an effective hydrogen source, whereas branched alcohols were less effective. In the Fe(CO)5/sulfur catalyzed liquefaction of Yallourn coal at 375°C for 120 min, a high conversion (99.5%) was achieved in the presence of ethanol and CO (7.0 MPa/cold). The two-staged reaction (375°C, 60 min + 425°C, 60 min) further improved the oil yield to 59.1% with a slight decrease in the coal conversion. The uptake of alcohol into asphaltene and preasphaltene fractions was distinctly observed, especially for Illinois No. 6 coal. The infrared analyses of the asphaltene fractions from each coal showed absorption at around 1705 cm-', characteristic for those obtained in the linear alcohol-CO systems. According to the characterization of the products by NMR and the preliminary study using a model compound, alkylation as well as the hydrogenolysis seem to contribute to the dissolution of coals."So, Ethanol provides needed Hydrogen and enables a nearly 100% conversion of coal, as in "a high conversion (99.5%) was achieved in the presence of ethanol", into liquid fuels compatible with our current transportation fleet, while helping to recycle Carbon Dioxide.
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