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Japan Recycles CO2 with Methane

 
We continue to follow up on our assertions that both CO2 and Methane, rather than being dangerous greenhouse gasses, are, instead, valuable raw material resources; both of which can be co-produced as useful "side benefits" of our coal use and coal extraction industries.
 
Herein, The University of Tokyo confirms the validity of developments reported by Penn State University, whereby the supposed greenhouse pollutants, Methane and Carbon Dioxide, can be combined and, in catalyzed reactions, produce for us more complex, and more useful, hydrocarbons.
 
The Abstract is sparse, and we submit this report only to confirm that development is ongoing, and process improvements are being made, that will enable us to profitably recycle both Carbon Dioxide and Methane.
 
Brief comment follows:
 
"Effective methane reforming with CO2 and O2  ... using NiO–MgO and fluidized bed reactor 

Keiichi Tomishige, Yuichi Matsuo, Yasushi Sekine and Kaoru Fujimoto

Department of Applied Chemistry, School of Engineering, The University of Tokyo, Japan

November 2000
 

Abstract

"Circulation of NiMgO catalyst particles in the fluidized bed reactor gave much higher CH4 conversion in methane reforming with CO2 and O2 under pressurized condition than the case of the catalyst without moving in the fixed bed reactor. In addition, circulation of the catalyst particles in the fluidized bed reactor inhibited carbon deposition which is the serious problem in methane reforming."

Interestingly, they don't specify what products arise from this technique. But, a safe bet is that, as in Penn State's "Tri-reforming", they are higher hydrocarbons that can serve quite useful purposes.

The real point is: Carbon Dioxide and Methane aren't worthless pollutants we have to waste time and money on trying to get rid of. They are, instead, like Coal, quite valuable, even precious, raw material resources we should invest time and money into figuring out how to use more wisely, more profitably.

These Japanese researchers herein, through report of their efforts, confirm their knowledge of that fact.

Others, too, recognize the value of Methane and, as we continue to document, have been, and are continuing, to refine methods for producing it directly from both Coal and Carbon Dioxide.

More Israel & Switzerland CO2 Recycling


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?

Israel & Switzerland Recycle CO2

 
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?

Illinois & Japan Convert Coal to Methane

 
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

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.

... 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."
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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.

China Improves CO2 & Methane Conversion

 
We have been documenting China's accomplishments in the field of "carbon conversion", which include coal conversion technology developed along the lines of WVU's "West Virginia Process" for direct coal liquefaction, as well as technology for the recycling of Carbon Dioxide, into liquid hydrocarbon fuels, which we perceive to be similar to Penn State University's "Tri-reforming" Process, for CO2 and Methane conversion, which, as we have documented, has been published by PSU's Chunsan Song and Craig Grimes. 
 
Herein, via the attached link and enclosed document, Chinese researchers report improvements in the catalysis of the reaction between Carbon Dioxide and Methane, to synthesize the liquid fuel, and gasoline and plastics raw material, Methanol.
 
Some brief excerpts:
 
"Studies in Preparation of Gas for Methanol Synthesis by Methane Reforming with Steam and CO2
 
Tang, Song-Bai, et. al.
 
The Laboratory of Natural Gas Chemistry; Chengdu Inst. of Organic Chem.; Chinese Academy of Sciences
 
1996
 
Abstract
 
An experimental preparation of feedstock gas for methanol synthesis by methane reforming with steam and CO2 has been investigated with (a) newly prepared ... nickel-based catalyst ... (which) ... had excellent activity ... .  ... methane conversion reached 95% ... (with) ... no carbon deposition.
 
Conclusion
 
... A methane conversion of 95% was achieved. The synthesis gas for methanol production in industry can be produced (from CO2, methane and steam). ... The structure and properties of SYM 1 catalyst remained unchanged ... (and) SYM 1 catalyst may be used in industry."
 
As we have elsewhere documented, Methane can be manufactured from either Coal or, using the Sabatier or similar processes, Carbon Dioxide. Then, by using even more Carbon Dioxide, that methane can be synthesized into the liquid fuel and, as per the ExxonMobil MTG(r) Process, gasoline raw material, Methanol.