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We have thoroughly documented that the technology exists, as explained by Penn State University, and others, which would enable us to recycle the Carbon Dioxide co-product of our coal use by converting it into valuable hydrocarbons.
Penn State's "Tri-reforming" technology posits the use of Methane as a raw material to be combined with Carbon Dioxide to effect that transmutation.
As we have earlier documented, Methane, through established technologies, such as the Sabatier process now being employed by NASA, can itself be synthesized from Carbon Dioxide.
As we have also documented, including in one US study from the 1950's, the Methane required for Carbon Dioxide recycling can also be synthesized from coal.
Herein, Southern Illinois University, in research funded by Japan, confirms that fact, and reports improvements in the process which make it more efficient.
In comments following the excerpt, we emphasize what should be an important point:
"LOW TEMPERATURE STEAM-COAL GASIFICATION CATALYSTS
Edwin J. Hippo and Deepak Tandon
Department of Mechanical Engineering and Energy Processes
Southern Illinois University
Carbondale, IL 62901
Department of Mechanical Engineering and Energy Processes
Southern Illinois University
Carbondale, IL 62901
INTRODUCTION
Shrinking domestic supplies and larger dependence on foreign sources have made an assortment of fossil fuels attractive as possible energy sources. The high sulfur and mineral coals of Illinois would be an ideal candidate as possible gasification feedstock.
Large reserves of coal as fossil fuel source and a projected shortage of natural gas (methane) in the US, have made development of technology for commercial production of high Btu pipeline gases from coal of interest. Several coal gasification processes exist, but incentives remain for the development of processes that would significantly increase efficiency and lower cost. A major problem in coal gasification is the heat required which make the process energy intensive. Hence, there is a need for an efficient and thermally neutral gasification process.
At the present time, natural gas (methane) reserves are sufficient to meet the demands but projections indicate a dwindling supply in the future. There is a need to develop an economical process for production of methane to ensure a steady supply. Direct methanation of high sulfur and mineral coals would not only utilize this important fossil fuel feedstock but would also be inexpensive as compared to other energy intensive gasification processes.
Catalytic steam methanation of coal is an almost thermoneutral process.
("Thermoneutral", i.e., low energy input is needed to drive the process. - JtM)
The role of the catalyst in coal gasification has been to reduce the reaction temperature and increase the rate of reaction.
Catalytic gasification of coal has attracted much attention recently. ... Catalyst(s) that are active at low temperatures would favor the process of direct gasification for methane production, since low temperature and high pressure favors the formation of methane.
Various oxides, halides and carbonates of both alkali and alkaline earth metals, along with transition metals have been surveyed as possible char gasification catalysts.
Some of the general conclusions drawn are as follows:
(1) Catalytic effect decreases with increasing temperature;
(2) Catalysts are more effective in gasification processes if steam is present in the gasification gases;
(3) There usually is an optimum catalyst loading
(4) Relative effects of catalysts can differ under different reaction conditions;
(5) Gasification reactivity can be effected significantly by the method /condition of catalyst impregnation; and (6) Catalyst impregnation is more effective than physical mixing with the carbon.
(2) Catalysts are more effective in gasification processes if steam is present in the gasification gases;
(3) There usually is an optimum catalyst loading
(4) Relative effects of catalysts can differ under different reaction conditions;
(5) Gasification reactivity can be effected significantly by the method /condition of catalyst impregnation; and (6) Catalyst impregnation is more effective than physical mixing with the carbon.
... incentives exist to explore the thermoneutral catalytic steam methanation of coals to produce methane economically and in a single reaction.
Catalytic effects on gasification of carbon materials have been studied for last several decades. ... The main objective of these studies have been to improve the process for production of water gas or producer gas. Outside of the work at Exxon, these work, have little qualitative value in assessing the catalytic effects on coal/char gasification for production of methane from steam.
It was the aim of this research to study the catalytic steam gasification of high sulfur, high mineral, agglomerating coals at elevated pressures and lower temperatures for production of methane.
The ultimate goal of this research was to develop a low temperature sulfur resistant catalyst system that would not only be efficient. and economic but would also produce methane in a single step. ... At low temperature operations, interaction of catalyst with the coal mineral phases are less likely.
Exxon catalytic gasification process produces substitute natural gas (SNG) by catalytic steam gasification of coal ... .
RESULTS AND DISCUSSION
When potassium hydroxide was used with transition metals significant increases in the conversions were obtained and also the concentration of the methane in the product gas increased substantially.
ACKNOWLEDGMENTS
This work was supported by a grant supplied by the New Energy Development Organization (NEDO) through the International Cooperative Research Program of Japan. Coal samples were provided by the ... Illinois State Geological Survey."
This work was supported by a grant supplied by the New Energy Development Organization (NEDO) through the International Cooperative Research Program of Japan. Coal samples were provided by the ... Illinois State Geological Survey."
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Again, we can use Methane, as herein made from Coal at "lower temperatures for production of methane", to recycle Carbon Dioxide, via Penn State University's Tri-reforming technology, into valuable hydrocarbons.
And, we think significantly, this was research focused on refining the technology to make Methane from Coal, since, as in "Exxon ... produces substitute natural gas ... (from) ... coal", some people already knew, and still no doubt know, how to do it.
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We earlier documented Israel's and Switzerland's cooperative development of Carbon Dioxide recycling technology. We submit herein further report of their research into the "Tri-reforming" process, similar to that explained by Penn State University scientists, wherein not only can the CO2 in flue gas be reclaimed and recycled, but other valuable products can be generated concurrently.
Comment follows the brief excerpt:
"Title: Fuel saving, carbon dioxide emission avoidance, and syngas production by tri-reforming of flue gases from coal and gas-fired power stations, and by the carbothermic reduction of iron oxide
Authors: Halmann, M.; Steinfeld, A.
Affiliations:
Weizmann Institute of Science, Department of Environmental Sciences and Energy Research; Israel
ETH-Zurich, Department of Mechanical and Process Engineering; Zurich, Switzerland
Solar Technology Laboratory, Paul Scherrer Institute; Villigen, Switzerland
Abstract: Flue gases from coal, gas, or oil-fired power stations, as well as from several heavy industries, such as the production of iron, lime and cement, are major anthropogenic sources of global CO2 emissions. The newly proposed process for syngas production based on the tri-reforming of such flue gases with natural gas could be an important route for CO2 emission avoidance. In addition, by combining the carbothermic reduction of iron oxide with the partial oxidation of the carbon source, an overall thermoneutral process can be designed for the co-production of iron and syngas rich in CO. Water-gas shift (WGS) of CO to H2 enables the production of useful syngas. The reaction process heat, or the conditions for thermoneutrality, are derived by thermochemical equilibrium calculations. The thermodynamic constraints are determined for the production of syngas suitable for methanol, hydrogen, or ammonia synthesis. The environmental and economic consequences are assessed for large-scale commercial production of these chemical commodities. Preliminary evaluations with natural gas, coke, or coal as carbon source indicate that such combined processes should be economically competitive, as well as promising significant fuel saving and CO2 emission avoidance. The production of ammonia in the above processes seems particularly attractive, as it consumes the nitrogen in the flue gases."
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Please note: Israel and Switzerland are not just "avoiding" CO2 emissions. They are using CO2 emissions, as per the "tri-reforming" process, elsewhere explained by Penn State University, both to make "syngas", for liquid fuel production, and to refine iron ore - in a process, which we have earlier documented, that is exothermic and generates heat from the chemical reactions involved. That heat can be harnessed and used to drive the entire system, thus making this recycling of Carbon Dioxide, into valuable hydrocarbons, and this refining of iron ore, into steel, "an overall thermoneutral process".
So, without using much external energy input, we can make liquid fuels from Carbon Dioxide and steel from iron ore.
Note: The tri-reforming process, as specified herein, as with Penn State's descriptions, uses natural gas to convert Carbon Dioxide into hydrocarbons. As we have amply documented, such "natural" gas can be generated through coal coking or gasification processes; or, through Sabatier and similar technologies, synthesized from Carbon Dioxide itself.
And, as a bonus, we get fertilizer in the bargain, as in: "The production of ammonia in the above processes seems particularly attractive, as it consumes the nitrogen in the flue gases."
What more, seriously, do we want our coal, and the co-products of it's use, to do for us?
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We earlier cited these Swiss and Israeli scientists, and documented how flue gas Carbon Dioxide could be recycled into liquid fuels, in a lower-energy requirement, "thermo-neutral", process, to make both liquid fuels and, as a by-product, ammonia fertilizer.
As it happens, yet another commercial by-product, as well, can be manufactured from the process: Cement.
Comment follows the:
"Production of lime, hydrogen, and methanol by the thermo-neutral combined calcination of limestone with partial oxidation of natural gas or coal
M. Halmann and A. Steinfeld
Department of Environmental Sciences and Energy Research, Weizmann Institute of Science, 76100 Rehovot, Israel
Department of Mechanical and Process Engineering, ETH-Swiss Federal Institute of Technology, 8092 Zurich, Switzerland
July 2005
Abstract
The cement and lime industries are major contributors to the anthropogenic CO2 emissions to the atmosphere. By combining the CO2-releasing calcination of CaCO3 with the CO2-consuming dry-reforming of CH4, and by further combining these endothermic reactions with the exothermic partial oxidation of CH4, a single thermo-neutral process can be designed for co-producing CaO and syngas in an authothermal reactor. Syngas can be further processed to H2, methanol, or Fischer–Tropsch chemicals. The conditions for thermo-neutrality are determined by thermo chemical equilibrium calculations. Such combined processes could achieve considerable CO2 emission avoidance as well as fuel saving relative to the conventional production of CaO and syngas. A preliminary evaluation indicates favorable economics for the co-production of CaO and hydrogen or methanol from CaCO3+O2+H2O and natural gas (NG) or coal."
Again: The "CH4" for "CO2-consuming" can be obtained via coal gasification or Sabatier CO2 recycling.
We submit that, if we have "H2", we can further hydrogenate crude coal liquids into more entertaining products.
But, aside from that, combining "CH4" with "CO2" yields "Fischer–Tropsch chemicals", which, if you've been following our posts, you know to include liquids that can be refined into diesel and gasoline.
And, these authors specify that this "thermo-neutral" technology does produce "methanol", which ExxonMobil can, through their "MTG(r)" process, convert into gasoline for us. It's also a good starting point for a few valuable plastics manufacturing processes, as well.
Finally, this whole scenario is presented as a solution to the CO2 emissions of the "cement and lime industries". They do need a CO2 solution as much as, or more than, coal-fired power plants do. So, this sounds like a win-win for all concerned.
Be real nice to have a "win" in Coal Country, wouldn't it?
Don't forget: In addition to fuel and fertilizer, we get more cement, too, out of it all, for those Mountain State road repairs.
These Swiss and Israeli scientists conclude with: An "evaluation indicates favorable economics for the co-production of CaO (i.e., cement) and ... methanol from ... coal."
Really: How good does it have to get?
- Details
We know that we're being, and have been, redundant to the point of burden. But, until the facts we are attempting to drive home are acknowledged openly, to the broader Coal Country public, we will keep drilling the face.
Herein, from China, we have even more confirmation of the truth that Carbon Dioxide can be used to "reform" Methane into "higher" hydrocarbons suitable for further processing, refining, into liquid fuels; and, into chemical manufacturing feed stocks for such important economic sectors as our plastics industry.
Comment follows:
"Effective reforming of methane with CO2 and O2 to low H2/CO ratio syngas over Ni/MgO–SiO2 using fluidized bed reactor
Q. S. Jing, J. H. Fei, H. Lou, L. Y. Mo and X. M. Zheng
Institute of Catalysis, Zhejiang University, Hangzhou, Zhejiang 310028, PR China
Chemistry Department, Xinyang Normal University, Xinyang 464000, PR China
February 2004
Abstract
Reforming of methane with CO2 and oxygen was used to produce low H2/CO ratio syngas over a Ni/MgO–SiO2 catalyst under certain reaction conditions. The effects of the reaction temperature, space velocity and feed gas composition were evaluated. The effect of catalyst fluidization on the conversion of methane was investigated over Ni/MgO–SiO2 and Pt–Ni/MgO–SiO2 catalysts. Circulation of Ni/MgO–SiO2 particles in the fluidized bed reactor gave much higher CH4 conversion than the case without circulation in the fixed bed reactor. This reactor effect was dependent on the catalyst properties. In addition, carbon deposition was inhibited in the fluidized bed reactor."
Seems like a lot of niggling detail, doesn't it?
That's one key point. They know how to combine Carbon Dioxide and Methane to make syngas - from which we already know, and have known since before WWII, how to make such interesting things as diesel fuel and gasoline. They are making this already-known technology, for combining methane and carbon dioxide to synthesize hydrocarbons, better. They know it can be done. They are at work on the details to make the doing of it more profitable.
Moreover, they seem to be refining an already-known catalyst for these reactions to make it more efficient. The various "SiO2" catalysts they name are, we believe, all zeolites, as is the key element in ExxonMobil's "MTG"(r), methanol-to-gasoline, Process, now being reduced to industrial practice in China, where the methanol, from which gasoline is made, is synthesized directly from coal.
And, as we have documented: Methane, too, can be generated from coal; unless we want to employ NASA's advanced Sabatier technology and make some of it, as well, from Carbon Dioxide.
Coal and Carbon Dioxide are connected by reflex in the minds of the American public. We don't think of one without thinking of the other. And, although that fact has, until now, caused everyone on both sides of the fence a lot of indigestion, it actually could be a good thing when everyone comes to realize that, when we do burn coal to generate the electricity we have to have to keep our homes bright and warm, we are creating a by-product, CO2, that, with a little tweaking, will let us keep our cars full of gasoline in the bargain.
All of that is, of course, on top of the fact that the technology is based on what could - if we were smart enough to put it to work - be 100% domestic, all-American resources; and, could thus, conceivably, help to keep 100% of all Americans employed.
- Details
We long ago cited a number of very specific reports, from very credible sources, that the gas arising from the production of coke, from coal, could be captured and converted into liquid fuels.
We reminded you that coke oven gas is flammable, as should have been obvious to any older native West Virginian who would have seen the vented gas being flared at night on the dark hills.
Coke oven gas is flammable because the coal is being transformed not just into coke for steel furnaces, but into a number of hydrocarbon gasses, as well; notably Methane.
As in Penn State University's Tri-reforming Process, as explained by Song and Grimes, Methane can be combined with Carbon Dioxide to make Syngas, from which liquid fuels and valuable organic chemicals can then be synthesized via long-established technologies such as the Fischer-Tropsch process.
Herein, China affirms that the needed Methane, for the reformation, the recycling, of Carbon Dioxide into liquid fuels can itself be obtained from coal via the coking process.
The excerpt:
"CO2 reforming of CH4 in coke oven gas to syngas over coal char catalyst Guojie Zhang, Yue Dong, Meirong Feng, Yongfa Zhang, Wei Zhao and Hongcheng Cao
Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, 030024, Taiyuan, China
Taiyuan Heavy Machinery Technical Center, Taiyuan, China
Taiyuan Science & Technology Enducation Center, Taiyuan, China
Lu’ an Group, Changzhi, China
September 2008
Abstract
The CO2 reforming of methane (in coke oven gas) on the coal char catalyst was performed in a fixed bed reactor at temperatures between 800 and 1200 C under normal pressure. The effects of the coal char catalyst pretreatment and the ratio of CO2/CH4 were studied. Experimental results showed that the coal char was an effective catalyst for production of syngas, and addition of CO2 did not enhance the CH4 reforming to H2. It was also found that the product gas ratio of H2/CO is strongly influenced by the feed ratio of CO2/CH4. The modified coal char catalyst was more active during the CO2–CH4 reforming than the coal char catalyst based on the catalyst volume, furthermore the modified catalyst exhibited high activity in CO2–CH4 reforming to syngas. The conversion of methane can be divided into two stages. In the first stage, the conversion of CH4 gradually decreased. In the second stage, the conversion of methane maintained nearly constant. The conversion of CO2 decreased slightly during the overall reactions in CO2–CH4 reforming. The coal char catalyst is a highly promising catalyst for the CO2 reforming of methane to syngas."
It might be gratuitous to note, but we have, as well, earlier provided substantial documentation of the fact that coke, after it has been made from coal, can itself be liquefied with hydrogen donor solvents to produce even more hydrocarbon liquids amenable to refining into fuels and chemicals.
And, if you don't by now know what we can make from "syngas", once we've generated it from coal, and/or carbon dioxide, then you haven't been paying attention.
Germany and Japan used it to make liquid fuels for their armies during WWII. It certainly seemed to work for them.
One somewhat intriguing point of this Chinese research: They used a catalyst made from coal, "char", to promote the reaction of a coal combustion product, CO2, with the by-product of coal coking process, Methane, to make syngas, which can then be condensed into liquid fuels.
Seriously: Just how good does this have to get before we just start doing it, and thereby start putting an end to our unhealthy reliance on non-domestic sources of liquid fuels?
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