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US Lab Recycles CO2 to Fuel

 
This report, from our own, United States, Idaho National Laboratory, is notable in one very key respect, relative to the many international and domestic reports we've so far cited, demonstrating that Carbon Dioxide, as arises from our use of coal, is a valuable raw material resource from which we can manufacture needed liquid fuels and chemicals.
 
Explanatory comment follows the excerpt, which includes an unfortunately somewhat dense Abstract, from which we have edited some over-long discussion:
 
"Hybrid Heterogeneous Catalysts for Hydrogenation of Carbon Dioxide
 
Authors: L.M. Petkovic; H.W. Rollins; D.M. Ginosar; K.C. Burch; Idaho National Laboratory
 
DOE Contract Number: DE-AC07-99ID-13727
 
Conference: 232nd - ACS National Meeting & Exposition,San Francisco, CA,09/10/2006,09/14/2006
 
Abstract:
 
Anthropogenic emissions of carbon dioxide, a gas often associated with global warming, have increased considerably since the beginning of the industrial age. In the U.S., stationary CO2 sources, such as electricity generation plants, produce about one-third of the anthropogenic CO2 generation. Reports indicate that the power required to recover 90% of the CO2 from an integrated coal-fired power-plant is about 10% of the power-plant capacity. This energy requirement can be reduced to less than 1% if the recovered CO2 is applied to the production of synthetic fuels. However, the lack of efficient catalysts along with the costs of energy and hydrogen has prevented the development of technologies for direct hydrogenation of CO2. Although the cost of hydrogen for hydrogenating CO2 is not economically attractive at present, the future production of hydrogen by nuclear power sources could completely change this scenario. Still, an efficient catalyst will be essential for commercial application of those processes. The objective of the work presented here was the development of hybrid catalysts for one-step carbon dioxide hydrogenation to liquid fuels. The hybrid catalysts, which were prepared by two novel techniques, included a copper/zinc oxide catalytic function distributed within an acidic zeolitic matrix. Results of catalyst activity and selectivity studies at atmospheric pressure are presented in this contribution. ... One hundred milligrams of a commercial syngas-to-methanol catalyst along with the same amount of a commercial zeolite catalyst was utilized under the same reaction conditions for comparison purposes."
 
The rather tiresome, tire-rut thinking embodied in "the cost of hydrogen for hydrogenating CO2 is not economically attractive at present, the future production of hydrogen by nuclear power sources could completely change this scenario" is, as we have in other reports documented, being dispelled by research leading to the use of environmental energies to obtain the needed hydrogen, and/or the use of various hydrogen-donor materials, perhaps derived from biological sources, as co-feeds in the CO2 hydrogenation process. 
 
We think the key point, out of all of this, is: The energy needed to capture a power plant's CO2, which just might be ultimately required by law, "can be reduced to less than 1% (in energy equivalents of the plant's capacity) if the recovered CO2 is applied to the production of synthetic fuels."
 
That doesn't state the entire economic case. There will be NO costs incurred by coal-use industries to geologically sequester the CO2 in service to Big Oil's petroleum reservoir scavenging efforts. And, all the money spent on CO2 recycling into fuels stays in the US, rather than being sent to OPEC for their petroleum fuels, and all the concomitant, costly military imbroglios our co-dependent relationships with them seem to entail. Plus, the environment gets cleaned a little, whether or not it needs it, and money thus isn't squandered by various ideological camps in unproductive and conflicting propaganda campaigns about the dangers of CO2 emissions from coal-fired power plants. 
 
It's another coal-based win-win for the US, for all of us.
 

Switzerland Recycles CO2 to Fuel


Landlocked Switzerland's Alpine geologic terrain contains no oil or commercial reserves of coal.
 
They have, however, like our own US Navy, and the DOD's defense contractors, as affirmed in their several patents for CO2 recycling, copies of which we sent you, figured out how to drill for oil in the, for the Swiss, very thin air.
 
The Swiss, like Japan, Korea, China, Singapore and South Africa's coal liquefaction giant, Sasol, have realized the importance behind Sabatier's Nobel-winning technology for reclaiming Carbon Dioxide, from coal plant emissions and from the atmosphere, and converting it into liquid hydrocarbon fuels.
 
The excerpt, with a, perhaps pertinent, comment, and a question, appended: 

"Document title

Hydrogenation of carbon dioxide to methanol with a discharge-activated catalyst

Authors

ELIASSON B.; KOGELSCHATZ U. ; BINGZHANG XUE ; ZHOU L.-M.

Affiliations

ABB Corporate Research Ltd., 5405 Baden, SUISSE

Abstract

To mitigate greenhouse gas CO2 emissions and recycle its carbon source, one possible approach would be to separate CO2 from the flue gases of power plants and to convert it to a liquid fuel, e.g., methanol. Hydrogenation of CO2 to methanol is investigated in a dielectric-barrier discharge (DBD) with and without the presence of a catalyst. Comparison of experiments shows that this nonequilibrium discharge can effectively lower the temperature range of optimum catalyst performance. The simultaneous presence of the discharge shifts the temperature region of maximum catalyst activity from 220 to 100°C, a much more desirable temperature range. The presence of the catalyst, on the other hand, increases the methanol yield and selectivity by more than a factor of 10 in the discharge. Experiment and numerical simulation show that methane formation is the major competitive reaction for methanol formation in the discharge. In the case of low electric power and high pressure, methanol formation can surpass methanation in the process.

Journal Title

Industrial & engineering chemistry research   ISSN 0888-885  CODEN IECRED; 1998, vol. 37, no8, pp. 3350-3357 (32 ref.)

Publisher

American Chemical Society, Washington, DC, ETATS-UNIS  (1987) (Revue)"
 
This article, on recycling the Carbon Dioxide arising from our coal-use industries, and converting it into a valuable alcohol, methanol, which is an excellent liquid fuel and plastics manufacturing raw material; which can also be converted, through at least one commercial technology, our oft-mentioned Exxon-Mobil "MTG"(r), Methanol-to-Gasoline process, into the standard-issue gasoline we're all familiar with; and, which can also be with great alacrity synthesized from coal and renewable cellulose, was written by Swiss power company researchers, including, it would appear, some Chinese nationals. However, it was published more than 20 years ago, in English and by the American Chemical Society.
 
Why, then, have we American Coal Country citizens not been informed of these developments and potentials at some point during those two decades: those twenty years we've been sending our young people to die in OPEC wars; those twenty years we've been allowing our vital coal industries to shrivel under the attacks of, perhaps well-meaning, environmentalists; those twenty years we've allowed our hard-working and patriotic coal people to languish at the precipice of poverty; those twenty years we have financed and defended the lavish lifestyles of oil sheiks and oil company robber barons?

CTL Giant Sasol to Recycle CO2

 
We reported some months ago on the Singapore CO2 recycling development, as briefly mentioned below. Our account of it lies in the archives of the WV Coal Association's R&D Blog.
 
However, the importance of this submission is that South Africa's Sasol, the world's leader in converting coal into liquid fuels, is now making ready to commercialize one of the several technologies that do exist for recycling Carbon Dioxide - into more liquid fuels and chemical feed stocks for plastics manufacturing.
 
A brief excerpt: 

"JOHANNESBURG (miningweekly.com) – South Africa's coal-to-liquids company Sasol is studying the conversion of carbon dioxide (CO2) into fuel.

Engineers and scientists in Sasol's technology division are working on algaeic forms of methanol production and Singapore's Institute of Bioengineering and Nanotechnology reported a CO2-to-methanol breakthrough earlier this year."

As we've said before: Carbon Dioxide, as arises from our use of coal, isn't a pollutant, but a raw material resource of great potential value.

The Orient Recycles CO2 to Fuel

Our own, US, Department of Defense archives document that Imperial Japan established factories in the Japanese homeland, the Korean peninsula and the Chinese mainland that converted coal into liquid fuel for her military during WWII.
 
We've reported further that coal-to-liquid technical and industrial development has, more recently, been underway in all three nations. China, especially, has a well-documented, and extensive, coal-to-liquid industrialization program underway.
 
In this submission, we document that all three of those Asian countries are not only at work developing coal liquefaction industries, but are also further developing the technologies, which we've documented to be feasible and practical, to recycle the Carbon Dioxide co-product of coal use into additional liquid fuels.
 
Several links and excerpts, with minor editing of obtuse formulaic symbols, follow: 
 

Document title

Hydrogenation of carbon dioxide over Cu-Zn-chromate/zeolite composite catalyst : the effects of reaction behavior of alkenes on hydrocarbon synthesis
 
Fujiwara M.; Ando H.; Tanaka M.; Souma Y.
 
Osaka national res. inst., AIST, MITI, Ikeda, Osaka 563, Japon

Abstract

The hydrogenation of carbon dioxide was studied using composite catalysts comprised of Cu-Zn-chromate and HY zeolite. These composite catalysts enabled the reaction combining methanol synthesis and methanol-to-gasoline reaction, and achieved the formation of ethylene and propene as the first example of the composite catalysts. The addition of alkaline metals, especially cesium, to Cu-Zn-chromate enhanced the selectivities of those alkenes. The influences of the reaction pressure and the space velocity on the production of alkenes show that alkanes are obtained by the hydrogenation of the corresponding alkenes. The composite catalysts producing alkenes in high selectivity afforded heavier hydrocarbons preferentially. These results indicate that the hydrogenation of alkenes inhibits the carbon homologation of alkenes to result in the predominant formation of the corresponding lighter alkanes. From these observations, it was found that methanol synthesis catalysts used for the composite catalysts are required to be effective for methanol synthesis at high temperature and to bear the low activity of the hydrogenation of alkenes.

ScienceDirect - Energy Conversion and Management : Catalytic conversion of carbon dioxide into hydrocarbons over zinc promote.

 
Catalytic conversion of carbon dioxide into hydrocarbons over zinc promoted iron catalysts

Sang-Sung Nam, Soo-Jae Lee, Ho Kim, Ki-Won Jun, Myuong-Jae Choi and Kyu-Wan Lee

KRICT., P.O. Box 107, Yusong, Taejon 305-600, Korea

Abstract

The hydrogenation of carbon dioxide to hydrocarbons over iron catalysts was studied in a fixed bed reactor under pressure of 10 atm and temperature of 573 K. Iron catalysts promoted with V, Cr, Mn and Zn prepared by precipitation method were adopted in the present study. The catalysts were characterized by XRD, carbon dioxide chemisorption and Mössbauer spectroscopy. The hydrocarbons were formed directly from carbon dioxide over iron catalysts. The iron promoted with Cr and Mn improved conversion of carbon dioxide and increased the selectivity of alkenes. Whereas, the Zn promoted iron catalyst showed unusually very high selectivity. With varying Fe:Zn ratio, the smaller ratio of Zn increased the alkene selectivity.

 
Low-temperature synthesis of DME from CO2/H2 over Pd-modified CuO–ZnO–Al2O3–ZrO2/HZSM-5 catalysts 

Kunpeng Sun, Weiwei Lu, Min Wang and Xianlun Xu

State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China 

Abstract

Three series of Pd-modified HZSM-5 catalysts were prepared and characterized by BET, XRD and TPR analysis. The catalytic system was evaluated in the development of direct synthesis of dimethyl ether (DME) from carbon dioxide hydrogenation at low temperature). The results indicated that the addition of palladium markedly enhanced the DME synthesis and retarded the CO formation. An explanation of this promoting effect of Pd on the DME synthesis could be attributed to the spillover of hydrogen from Pd to the neighboring phase.

---------------

Note, in the above, the mention of Iron-group metals and zeolite (HZSM-5) catalysts used in the liquefaction of Carbon Dioxide. Those catalysts are at the core of at least two "indirect" coal-to-liquid technologies, the Fischer-Tropsch method employed by Germany in WWII, and the more current Exxon-Mobil "MTG" (r), or methanol-to-gasoline, Process, wherein the methanol is posited to be made from coal. "DME", or dimethyl ether, mentioned above, is a useful liquid, diesel-type, fuel and chemical synthesis raw material in it's own right, and can be converted into diesel and gasoline.

This work in China, Japan and Korea is in addition to other Asian CO2-recycling accomplishments, in Singapore, which we've earlier brought to your attention.

Recycling Carbon Dioxide is feasible. And, it sounds a lot more promising and profitable than strangling our coal-use industries through Cap&Trade legislation, or drafting them into the expensive service of Big Oil through enforced geologic sequestration, doesn't it? 

US National Lab Liquefies Coal

 
To further support our contention that there is much, much more to the story of how technology is available, and how that technology is being further refined, that would allow us, the United States, to convert abundant coal and CO2-recycling renewable biomass into the liquid fuels we need, liquid fuels that we are led to believe we're short of and that we must import, through bloated oil companies and from hostile OPEC nations, we submit the enclosed selection of works from one of our premier National Laboratories, Sandia.
 
Some excerpts, comment follows:

"Fine particle catalyst testing

Sponsor: DOE/FE

Contact: Fran Stohl

The goal of Sandia's Testing of Fine-Particle Catalysts project is to evaluate the fine-particle size unsupported catalysts that are being developed for coal liquefaction. It is difficult to compare catalytic testing results from different researchers because of the variety of testing procedures used. Sandia has developed a standard test procedure that can be applied to all these catalysts so the best catalysts can be identified. This testing is performed in small batch microautoclaves. Additional efforts include developing procedures to coprocess waste materials (such as plastics or heavy resid) with coal in coal liquefaction reactions.

Direct coal liquefaction

Sponsor: DOE/FE

Contact: Tim Gardner

Sandia has been involved in the direct liquefaction of coal and the upgrading of coal-derived liquids for over ten years. Catalysts based on sulfided NiMo phases supported on silica-doped hydrous titanium oxide (HTO:Si) have been developed which offer distinct advantages over similar catalysts utilizing commercial alumina supports. These advantages are related to the very high dispersion of the catalytic active phase on the HTO:Si supports and the ability to synthesize the catalyst in either a bulk or a coated form. Superior results have been obtained for the HTO:Si-supported NiMo catalysts relative to commercial alumina-supported NiMo catalysts in model reactions (pyrene hydrogenation [see Figure 2] and dibenzothiophene hydrodesulfurization), as well as for actual pilot scale direct coal liquefaction tests and continuous hydrotreatment of coal- or petroleum-derived liquids.

Novel catalysts can enhance the efficiency of coal liquefaction processes through improvements in catalyst activity, selectivity, and life. A viable coal liquefaction process can improve U.S. economic competitiveness by offering an alternative to imported oil and thereby keeping an economic cap on the cost of imported oil. These new catalyst materials may also find important applications in the efficient upgrading of heavy oils, bitumens, and petroleum residues, which are becoming increasingly important as the world's supply of light crude oil is depleted.

The primary goal for the Advanced Direct Liquefaction Concepts for Improved Efficiency and Economics project (Contact: Fran Stohl) is to evaluate new concepts for producing coal liquids that will enable coal-derived liquids to be obtained cost effectively. Sandia's experimental work is aimed at optimizing coal liquefaction processing conditions for various portions of the coal liquids by using continuous operation reactors that can be run unattended. This project is a joint effort with the University of Kentucky Center for Applied Energy Research, CONSOL Inc., and LDP Associates.

The Refining of Coal Liquids project (Contact: Fran Stohl) involves hydrotreating various distillate cuts of the final coal-derived liquid product to determine how best to introduce these liquids into an existing refinery. This project also uses Sandia's continuous operation reactors. This project is a joint effort with Bechtel, Southwest Research Institute, Amoco Oil Co., and M.W. Kellogg.

Indirect coal liquefaction

Sponsor: DOE/FE

Contact: Nancy Jackson

Fossil fuel/waste coprocessing

Sponsor: DOE/FE and DOE/EE

Contact: Anthony Martino

Under Construction

Feedstocks and fuels

Sponsor: LDRD (internal Sandia R&D support)

Contact: Nancy Jackson"

Allow us to recap some of what's going on at Sandia, in addition to the work on CO2 recycling we documented for you quite some time ago. They are/have been:

- developing technology "for coal liquefaction" and "procedures to coprocess waste materials (such as plastics or heavy resid) with coal in coal liquefaction reactions."

- "involved in the direct liquefaction of coal and the upgrading of coal-derived liquids for over ten years."

- working on "novel catalysts" that "can enhance the efficiency of coal liquefaction processes through improvements in catalyst activity, selectivity, and life."

- evaluating "new concepts for producing coal liquids that will enable coal-derived liquids to be obtained cost effectively."

They note that "A viable coal liquefaction process can improve U.S. economic competitiveness by offering an alternative to imported oil and thereby keeping an economic cap on the cost of imported oil."

We'll note, again, that we've also reported on advanced work at Sandia which focuses on the recycling of Carbon Dioxide.

It all sounds good. Where are the results and why haven't they been made public, or publicized, especially in Coal Country? Some contact names and links are included in this dispatch. About time some Coal Country journalists started following up, isn't it? Don't Coal Country people have a right to know?