Research & Development

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?

India Recycles CO2 with CoalTL Technology

 
We earlier suggested that some types of biomass, specifically cellulose derived from various botanical sources, such as pulpwood, and the cell walls of algae, which have been proposed to be grown in "bioreactors", attached to the exhaust flues of coal power plants to take advantage of the more concentrated Carbon Dioxide content, could be liquefied along with coal to provide hydrogen to help with the "hydrogenation" of primarily carbonaceous coal into liquid hydrocarbon fuels.
 
Researchers in India have now proposed that biomass, which naturally recycles Carbon Dioxide in any case, but which is Hydrogen-rich, can be gasified, combined with additional Carbon Dioxide to enrich the synthesis gas, and then catalyzed into liquid hydrocarbons, i.e. liquid fuels.
 

"Title: Fischer-Tropsch synthesis using bio-syngas and CO2
Authors: Srinivas, S.; Malik, Ranjan Kumar; Mahajani, Sanjay; Indian Institute of Technology - Bombay
Citation: Energy For Sustainable Development; Elsevier, 2007
Abstract:
While Fischer-Tropsch synthesis (FTS) using coal and natural gas in conventional reactors is an almost well-established technology, the production of liquid hydrocarbons from syngas obtained from biomass is in its preliminary stages of commercialization in countries like Germany. With concerns about global warming and ways of disposing of CO2 being searched for, CO2 hydrogenation using FTS to liquid hydrocarbons can act as a CO2 sink. A brief review of FTS using CO2-rich syngas is given in this paper, looking at FTS as a technology that can help reduce global warming and as a process integration alternative. The reverse water gas shift (r-WGS) reaction is vital for CO2 hydrogenation. We have studied the effect of this using an FT kinetic model and have proposed a new flow sheet alternative for FTS using CO2-rich syngas. Simulations suggested that this new process gives better conversion of CO2. The product selectivity and yields from an FT plant are vital to make the process viable economically."
 
The key excerpt here might be: "CO2 hydrogenation using FTS (Fischer-Tropsch Synthesis - JtM) to liquid hydrocarbons can act as a CO2 sink. A brief review of FTS using CO2-rich syngas is given in this paper, looking at FTS as a technology that can help reduce global warming."
 
So, a technology developed to convert coal into liquid hydrocarbon fuels can be used, as we have earlier suggested, and documented to be feasible, for "CO2 hydrogenation" to create "liquid hydrocarbons" that serve as a "CO2 sink", or channel of CO2 recycling, and can thereby "help reduce global warming".
 
It is yet another coal-based solution to both the problem of liquid fuel shortages, and the possible hazard of greenhouse gas emissions, and it bears repetition:
 
Coal-to-Liquid conversion technology can "help reduce global warming".
 
And, another thing: These Indian researchers refer to Fischer-Tropsch coal conversion as being "an almost well-established technology".
 
Not, sadly, in Coal Country, where it should long ago have been.

OPEC to Recycle CO2

 
We're tempted to say that we, all of us, in Coal Country, in the US, have our heads stuck in the sand when it comes to the potentials for converting our abundant coal into liquid fuels, and for recycling the Carbon Dioxide by-product of our coal use into even more liquid fuels.
 
Sadly, we're forced to conclude that we have our heads stuck somewhere even darker and less pleasant.
 
And, unless we put an end to the compulsive practice of contemplating the inner walls of our colons, and get to work converting our abundant coal and recycling Carbon Dioxide, into the liquid fuels and chemical manufacturing raw materials we need, we are going to wind up even further behind, and in even deeper bondage to, some people with whom we don't enjoy the warmest of relations.
 
As documented herein, OPEC is making ready to recycle Carbon Dioxide into hydrocarbon products, so that they can continue to extort us after the deserts run as dry of oil as they are of water.
 
The portentous excerpt:
 
"MHI to License Flue Gas Carbon Dioxide Recovery Technology To GPIC in Bahrain -- World-class Recovery Capacity of 450 Tons/Day 
 
Article Excerpt
Tokyo, Japan, Dec 20, 2007 - (JCN Newswire) - Mitsubishi Heavy Industries, Ltd. (MHI) has singed a license agreement for carbon dioxide (CO2) recovery technology with Gulf Petrochemical Industries Company (GPIC), a manufacturer of fertilizers and petrochemicals in Bahrain.

GPIC will use the technology to recover CO2 from flue gas emitted at its existing petrochemical plant and utilize the captured CO2 to increase urea and methanol production. The recovery units can capture 450 metric tons of CO2 per day, one of the world's largest capacities for the chemical application."
 
We shouldn't by now have to explain the utility of methanol.
 
When those of us in Coal Country, in the United States, finally wake up and pull our heads out of whatever dark place it is we have them stuck, and realize that we're paying a sheik's ransom to OPEC for a liquid fuel they're making out of the primary by-product of our coal use, that stuff we'll be wiping out of our eyes and combing out of our hair won't be some of OPEC's desert sand.

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.

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.

  1. Ethanol from Coal - in Louisiana
  2. USAF & Morgantown/Pittsburgh DOE Convert Coal & Bio
  3. National Mining Association & CoalTL
  4. CO2 + Iceland = New Kuwait

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