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Japan Converts CO2 to Fuel

 
We have cited other Japanese research efforts in the arena of Carbon Dioxide recycling, in addition to their well-documented conversion of coal into liquid fuels for their military during WWII, a major undertaking with coal conversion plants in Japan itself, and on mainland China and the Korean peninsula.
 
But, herein, we are able to document what seems to be the ongoing development of Carbon Dioxide conversion technology, conducted by a group of researchers whose sequential results are being published, for whatever reason, in  separate journals.
 
These Japanese researchers confirm that Carbon Dioxide can be reclaimed and recycled into the valuable liquid fuels, methanol and dimethyl ether (DME). Both can be further processed to manufacture gasoline, though DME is, by reports, a quite serviceable diesel fuel as is. Both compounds are also useful as raw materials for the manufacture of plastics and other products.
 
The excerpts, and an additional link, with some editing to minimize formatting differences between the two  sources and to clarify chemical formulae, as follows:
 
"Title: Dimethyl ether synthesis from carbon dioxide by catalytic hydrogenation (Part 1) activities of methanol dehydration catalysts
 
Authors: Hirano Masaki; Imai Tetsuya; Yasutake Toshinobu; Kuroda Kennosuke
 
Technical Research Center, The Kansai Electric Power Co., Inc
Hiroshima Research & Development Center, Mitsubishi Heavy Industries, Ltd
Engineering & Construction Center, Mitsubishi Heavy Industries, Ltd 
 
Journal Title: Journal of the Japan Petroleum Institute
 
Abstract:
 
The authors have developed (Copper-Zinc-Aluminum-Gallium- Magnesium Oxide - JtM) catalyst for methanol synthesis from CO2 and H2, and have been studying a technology for the direct synthesis of dimethyl ether (DME) from CO2 and H2 using the combination of the methanol synthesis catalyst above mentioned and a methanol dehydration catalyst. In the present study, the catalytic activities of three types of (Aluminum Oxides) with different specific surface areas, four types of compound oxides (Zirconium, Silicon, Aluminum, Titaniu) and a ZSM-5 zeolite (the same one specified by Exxon-Mobil in their "MTG", methanol-to-gasoline, Process) for DME synthesis by methanol dehydration were tested. DME synthesis activity increased with higher specific surface area of Aluminum Oxide catalyst. Compound oxide catalysts containing (Aluminum Oxide) showed higher DME synthesis activity than catalysts without (Aluminum Oxide), and (Zirconium-Aluminum Oxide), the best compound oxide, showed higher DME synthesis activity. Addition of a metal oxide as the promoter is effective for improving the DME synthesis activity. ZSM-5 zeolite produced more olefins rather than DME. The presence of water in the methanol feed suppressed the DME synthesis reaction by methanol dehydration.  
 
 
 
Dimethyl Ether Synthesis from Carbon Dioxide by Catalytic Hydrogenation (Part 2) Hybrid Catalyst Consisting of Methanol Synthesis and Methanol Dehydration Catalysts
 
Authors: Hirano Masaki; Imai Tetsuya; Yasutake Toshinobu; Kuroda Kennosuke
 
Technical Research Center, The Kansai Electric Power Co., Inc
Hiroshima Research & Development Center, Mitsubishi Heavy Industries, Ltd
Engineering & Construction Center, Mitsubishi Heavy Industries, Ltd 
 
Direct DME synthesis from Carbon Dioxide and Hydrogen was carried out using hybrid catalysts consisting of a methanol synthesis catalyst (Copper-Zinc-Aluminum-Gallium- Magnesium Oxide) and a methanol dehydration catalyst (Zirconium-Aluminum Oxide). The effects of the compositions of the two catalysts on methanol + DME yield, DME selectivity and durability of the hybrid catalysts were investigated. The optimum mixing ratio of the methanol synthesis catalyst to the methanol dehydration catalyst in a hybrid catalyst was 50 : 50 weight percent. In the DME direct synthesis from Carbon Dioxide and Hydrogen, the methanol + DME yield and the DME selectivity increased with higher temperature. However, after the methanol yield reached the equilibrium, the methanol + DME yield declined with higher temperature. ... A two-layer structure consisting of an upper layer of methanol synthesis catalyst and a lower layer of a mixture of the methanol synthesis catalyst and the methanol dehydration catalyst was the most effective. The hybrid catalyst with the two-layer structure also showed better durability than catalysts with other structures." 
 
We know the foregoing is some pretty dense stuff. We don't pretend to understand much of it, nor do we expect many of our readers to be able to. What we do understand, though, and it should be clear to our readers, is that the knowledge exists to convert, to recycle, the Carbon Dioxide by-product of our coal use industries into valuable liquid fuels and plastics manufacturing raw materials, just as the knowledge exists to transmute coal itself into those same fuels and chemicals. The knowledge is consistent, and it has been independently and publicly verified by scientists in many nations around the world.
 
When will that knowledge be publicly verified in the Coal Country of the United States of America, where it needs most to be heard, and where it could be put to the best use and be of the greatest benefit for the most people, the most important people - the citizens of Coal Country, of the United States of America?

California Liquefies Coal, Recycles CO2

 
We have thoroughly documented the Carbon Dioxide recycling achievements of the University of Southern California and their Nobel Laureate, George Olah.
 
We have also thoroughly documented the very real, commercial technology developed by UOP-Honeywell to convert Appalachian coal into valuable organic chemicals.
 
The two entities are now combining their skills and knowledge base to commercialize some of the very real coal conversion and Carbon Dioxide recycling technologies we have already reported to you.
 
The excerpt: 

"UOP LLC, a Honeywell company, announced that it will partner with the USC Loker Hydrocarbon Research Institute to develop and commercialize new technology to transform carbon dioxide into clean-burning alternative fuels.

USC developed fundamental chemistry to transform carbon dioxide to methanol or dimethyl ether, two potentially cleaner-burning alternatives to traditional transportation fuels, thereby reducing emissions of carbon dioxide, a gas known to contribute to global warming.

Nobel Laureate and USC College Distinguished Professor George Olah, director of the Loker Hydrocarbon Research Institute, his colleague G.K. Surya Prakesh and their team of researchers have developed fundamental chemistry that could aid in the improved production of methanol and/or dimethyl ether from a variety of sources such as natural gas, coal and carbon dioxide."

To repeat: California researchers developed technology to improve the "production of methanol and ... dimethyl ether from ... coal and carbon dioxide".

Not that we couldn't do that previously, mind you, but, the technology to convert Coal and Carbon Dioxide into liquid fuels is being improved - in California!

China & Japan: CO2 Improves CoalTL

 
In confirmation of the US Department of Energy project we just reported to you, wherein the addition of flue gas Carbon Dioxide actually improved the production of liquid fuels from coal-derived synthesis gas, we are able to submit a report of work performed in China and Japan, and published very recently by the American Chemical Society.
 
These Chinese and Japanese researchers, too, acknowledge that the Carbon Dioxide by-product of coal use can improve the production of liquid fuels from synthesis gas extracted from coal.
 
The excerpt: 
 
"Researching Fe Catalyst Suitable for CO2-Containing Syngas for Fischer−Tropsch Synthesis
 
Wensheng Ning, Naoto Koizumi and Muneyoshi Yamada
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Chaowang Road No. 18, Hangzhou 310032, China
Department of Applied Chemistry, Graduate School of Engineering, Tohoku University, Aoba 6-6-07, Aramaki, Aoba-ku, Sendai 980-8579, Japan
Energy Fuels, 2009, 23 (9), pp 4696–4700
DOI: 10.1021/ef900428t
Publication Date (Web): August 19, 2009
Copyright © 2009 American Chemical Society 

Abstract

Fischer−Tropsch (FT) synthesis is a technology to produce liquid fuels from coal, natural gas, and biomass as an alternate to crude oil. However, the quantity of emitted CO2 from the FT process consisting of syngas preparation, FT synthesis, and product workup is one of the serious disadvantages of FT process. The conversion of CO2 into hydrocarbons is one of the promising methods to decrease CO2 emissions. Effects of promoter addition on the activity of precipitated Fe catalysts for the conversion of CO22 and CO2-containing syngas feeds. The results suggested that CO2 can be activated by suitable promoter(s) for hydrocarbon synthesis at low temperature. Low K content is suitable for increasing hydrocarbon yield. The Fe catalysts promoted by equal Zn and Cu have higher CO and CO2 conversion and decreased CH4 selectivity." were studied using pure CO

So, even though CO2 is generated both by coal combustion for power generation and by some indirect processes of coal liquefaction, "CO2 can be activated by suitable promoter(s) for hydrocarbon synthesis at low temperature".

In other words, Carbon Dioxide, wherever we get it, can be converted into hydrocarbons, such as liquid fuels, in a low energy, "low temperature", process. 

And, note: Even though the work was performed in China and Japan, it was reported by the American Chemical Society.

This process of coal conversion and CO2 recycling might be "low temperature", but it's way past time for our Coal Country journalists to start turning up the heat on the topic of coal conversion and CO2 recycling, isn't it?

CO2 Improves Fuel Synthesis - Japan

 
We regret the technically-dense language of this Abstract. We have edited it somewhat for clarity and concision, and will append some explanatory comment, following:
 
"Co-methanation of carbon monoxide and carbon dioxide on supported nickel and cobalt catalysts prepared from amorphous alloys
 
Hiroki Habazaki, Michiaki Yamasaki, Bo-Ping Zhang, Asahi Kawashima, Shunpei Kohno, Takuro Takai and Koji Hashimoto

Institute for Materials Research, Tohoku University Sendai 980-8577 Japan

Engineering Department, Ishii Iron Works Co. Ltd., 6-5-1 Higashi-kojiya, Ohta-ku Tokyo Japan

Production Engineering Laboratory, Technology Research Center, Japan National Oil Corporation, 1-2-2 Hamada, Mihama-ku Chiba, 261-0025 Japan; 

September 1998.

Abstract

The activity and durability of the catalysts prepared by the oxidation–reduction treatment of (various percentage blends of Cobalt, Zirconium, and Nickel - JtM) alloys have been investigated for simultaneous methanation of carbon monoxide and carbon dioxide. It has been found that the (Nickel–Zirconium) catalyst shows the highest activity among the catalysts examined, and the activity of the Cobalt–Zirconium catalyst is lower than those of the nickel-based catalysts, in agreement with the activity for the solo methanation of carbon dioxide. On all the catalysts, carbon monoxide reacts preferentially with hydrogen, and is completely converted into methane at and above 523 K. The remaining hydrogen further reacts with carbon dioxide to form methane. The methanation rate in the H2–CO–CO2 mixed gas is higher than that in H2–CO mixed gas without CO2."

There is more technical rhetoric in the unedited Abstract, but the gist of it is: These Japanese researchers discovered that blending Carbon Monoxide, an essential component of coal-derived syngas directed to liquid fuel synthesis, with Carbon Dioxide, in the presence of Hydrogen and certain non-exotic metal catalysts, actually enhanced and increased the conversion of Carbon species into the Hydrocarbon gas, Methane, which, we have documented earlier, from other sources, can be further, and efficiently, synthesized into the liquid fuel and, as it serves in Exxon-Mobil's MTG(r) Process, gasoline precursor, Methanol.

The conclusion, again, is: "The methanation rate in the H2–CO–CO2 mixed gas is higher than that in H2–CO mixed gas without CO2."

Carbon Dioxide improves the conversion process, and it increases the production of fuel from a mixture of Carbon Monoxide and Hydrogen, which is, essentially, "syngas", as can be made, as we have thoroughly documented, from coal.

So, synthesis gas derived from coal can be combined with Carbon Dioxide derived from the combustion of coal to enhance the production of a fuel gas that can, itself, again as we have elsewhere thoroughly documented, be converted into a liquid fuel, gasoline precursor and plastics manufacturing raw material.

We really don't want to be stuffing all of our CO2 down geologic storage rat holes to help Big Oil scrape out a few more drops of petrol to extort us with, or to tax our coal-use industries out of existence through Cap and Trade legislation because of it, do we?

Not when we can recycle CO2 that arises from our coal use, ultimately, into gasoline.

CO2 Recycling in Korea + Russia

 
 
Enclosed is yet more authoritative documentation, affirming the work of at least one Nobel Prize winner, that CO2, as arises from our coal-use industries, can be collected and recycled into liquid fuels.
 
These Korean and Russian scientists have developed their technology for turning CO2 into the valuable liquid fuel, and gasoline and plastics raw material, methanol, to the point where they have actually given it a name.
 
As follows:
 
"Carbon Dioxide Hydrogenation To Form Methanol via a Reverse-Water-Gas-Shift Reaction (the CAMERE Process)
 
Oh-Shim Joo, Kwang-Deog Jung, Il Moon, Alexander Ya. Rozovskii, Galina I. Lin, Sung-Hwan Han, and Sung-Jin Uhm
 
[Unable to display image]Catalysis Laboratory, Korea Institute of Science and Technology
Department of Chemical Engineering, Yonsei University, Seoul, Korea
A.V. Topchiev Institute of Petrochemical Synthesis, Leninsky Prospect, Moscow, Russia
Ind. Eng. Chem. Res., 1999, 38 (5), pp 1808–1812; April 1, 1999
Copyright © 1999 American Chemical Society
 
Abstract

The CAMERE process (carbon dioxide hydrogenation to form methanol via a reverse-water-gas-shift reaction) was developed and evaluated. The reverse-water-gas-shift reactor and the methanol synthesis reactor were serially aligned to form methanol from CO2 hydrogenation. Carbon dioxide was converted to CO and water by the reverse-water-gas-shift reaction (RWReaction) to remove water before methanol was synthesized. With the elimination of water by RWReaction, the purge gas volume was minimized as the recycle gas volume decreased. Because of the minimum purge gas loss by the pretreatment of RWReactor, the overall methanol yield increased up to 89% from 69%. An active and stable catalyst ...  was developed. The system was optimized and compared with the commercial methanol synthesis processes from natural gas and coal."

Aside from the fact that a CO2 recycling system, which could provide us with fuels and a raw material for plastics manufacturing has been developed, and could thus put a stop to the economic threats to our coal industries, and put an end to our OPEC bondage, has been developed, is the sad truth that news of the development was published in the United States, as in "Copyright © 1999 American Chemical Society", but we are all still arguing about coal-crippling issues like Cap&Trade and Sequestration.

Don't our Press and our political office holders owe all of us in Coal Country, all of us in the US, an explanation as to why we have been left to worry about our security and livelihoods, while they waste ink and time on what should be irrelevancies like oil shortages, OPEC hostilities and green house gas emissions?

The very real technologies that exist to, cleanly and profitably, convert our abundant coal into liquid fuels, and to recycle the Carbon Dioxide by-product of coal use into even more liquid fuels and manufacturing raw materials, are established, and, in certain circles, well-known. It is far, far past time they became well-known in some broader circles.