Research & Development

Australia Recycles CO2

Herein are three links and accompanying excerpts, detailing, first:
 
That zeolites, as used by Exxon-Mobil in their "MTG"(r), methanol-to-gasoline, Process, wherein the methanol is posited to be made from coal, can also be, as we have earlier documented from other sources, used to catalyze the hydrogenation of Carbon Dioxide, as is emitted from a wide variety of natural and human sources, into hydrocarbon gasses and liquids which can then be further synthesized into liquid fuels and plastics manufacturing raw materials, thus recycling and sequestering, in a productive and profitable way, CO2 emissions, whether from natural or artificial sources.
 
And, second:
 
That zeolites can be obtained in abundance from coal combustion ash.
 
Comment follows: 
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J. Am. Chem. Soc., 2006 Apr 26;128(16):5322-3.

Design of effective zeolite catalysts for the complete hydrogenation of CO2.

Chan B., Radom, L.

School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia. This email address is being protected from spambots. You need JavaScript enabled to view it.

Ab initio molecular orbital calculations have been applied to the study of the three-stage zeolite-catalyzed hydrogenation of CO2 to methanol. The results present strong evidence that appropriate chemical modifications to ZSM-5 can lead to significantly lower energy barriers for the three component reactions, that is, hydrogenation of CO2, HCO2H, and CH2O. Zeolites incorporating either Na+ or Ge are more effective catalysts than conventional acidic zeolites for the hydrogenation of CO2 to give HCO2H, but amine-based zeolites do not lead to significantly lower barriers for any of the three hydrogenation reactions. However, we predict that when all three features, namely, Na+, N, and Ge, are incorporated in the zeolite, there is a dramatic improvement in catalytic activity for all three reactions.


J. Am. Chem. Soc., 2008 Jul 30;130(30):9790-9.

Zeolite-catalyzed hydrogenation of carbon dioxide and ethene.

Chan B., Radom, L.

School of Chemistry and Centre of Excellence for Free Radical Chemistry and Biotechnology, University of Sydney, Sydney, NSW 2006, Australia.

Ab initio molecular orbital theory and density functional theory calculations have been used to study the three-stage zeolite-catalyzed hydrogenation of CO2 to methanol and the hydrogenation of C2H 4 to ethane, with the aim of designing an effective zeolite catalyst for these reactions. ... . It is found that appropriately designed zeolites can provide excellent catalysis for these reactions, particularly for the hydrogenation of CO2, HCO2H and CH2O, ... . We propose that alkali metal zeolites ... could be very effective catalysts for hydrogenation processes.

 
Large-scale synthesis of artificial zeolite from coal fly ash
 
Ryo Moriyama, Shohei Takeda, Masaki Onozaki, Yukuo Katayama, Kouji Shiota, Tomoya Fukuda, Hiroaki Sugihara and Yuichi Tani 

The Institute of Applied Energy, Shinbashi SY BLDG. 14-2 Nishishinbashi 1-chome, Minato-ku, Tokyo 105-0003, Japan

The Institute of Applied Energy, 2-17, Tsukisamu-Higashi, Toyohira-ku, Sapporo 062-8517, Japan

Institute of Technology, Penta-Ocean Construction Co., Ltd., 1534-1, Yonku-cho, Nishinasuno-machi, Nasu-gun, Tochigi 329-2746, Japan


February 2005
 
 
A new process for converting coal fly ash to an artificial zeolite is described. The process is comprised of a high-temperature operation and water removal during the operation. Suitable operation parameters of the process were investigated using a test unit, and the optimal conditions were found ... . The zeolites obtained from a pilot plant had a higher cation exchangeable capacity than those from the test unit and were comparable to zeolites prepared using a conventional method."
 
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So, we can use the solid waste of coal combustion to recycle the gaseous waste of coal combustion into liquids of utility and value.

More Coal Conversion Processes

We've documented that multiple processes exist, which would, if we had the will to implement them, allow us to convert our abundant coal into currently-scarce liquid fuels - needed commodities we allow ourselves to be extorted with by folks who might not really have all our best interests at heart.
 
Herein we document, through several enclosed references, yet another route for the indirect conversion of coal into direct replacements for liquid petroleum products. It differs from the others we've so far reported to you, and, through it's differences, illustrates even further that multiple, and practical, processes exist which would enable us to supply much of our liquid fuel and industrial organic chemical needs through complete utilization of our most abundant natural resource.
 
First, we remind you of the volatile gas, acetylene, which should be familiar to any country boy who's ever had to use a "blue wrench", an oxy-acetylene torch, in the repair of a rusty pick-up truck's exhaust system.
 
Acetylene is yet another hydrocarbon gas that can be made from coal. And, it can be made from coal both indirectly, and directly. 
 
Some old coal miners might still be around who remember the use of "Carbide" lamps underground, wherein water was added to lumps of calcium carbide, resulting in the generation of acetylene, which was ignited by a spark wheel on the lamp's reflector.
 
Calcium carbide, which, when combined with water, generates acetylene, is made from coal and limestone, both of which WV is blessed with in abundance, as in the following reference:
 
 
Herein, we learn that:

"Calcium carbide is produced industrially in an electric arc furnace from a mixture of lime and coke at approximately 2000 °C. This method has not changed since its invention in 1888."

We, of course, get the lime from limestone and the coke from coal, as confirmed in:

 
"The principal raw materials for acetylene manufacture are ... limestone ... and coal" ... via the manufacture of calcium carbide and it's subsequent reaction with water." 

But, technology moves on, and we can now produce all the acetylene we need directly from coal, as follows:

 
"Plasma process for coal-based acetylene production replaces calcium carbide process.
 
China Chemical Reporter | June 26, 2005 | COPYRIGHT 2005 China National Chemical Information Center. This material is published under license from the publisher through the Gale Group, Farmington Hills, Michigan.  All inquiries regarding rights should be directed to the Gale Group
 
A series of breakthroughs have been achieved in the plasma process for the acetylene production through coal conversion. Taiyuan University of Technology has established the first lab for the acetylene production through the plasma pyrolysis of coal in China. A lab for the acetylene production through the plasma pyrolysis of coal with the largest power in the world has also been established in the Institute of Plasma and Physics of CAS (IPP). The acetylene production will hopefully no longer use the calcium carbide process in future."
 
We shouldn't need to point out, but we will, since this horse apparently needs flogged until it moves, that China has been intensively developing coal conversion technologies, even to the point of, it seems, the attempted theft, through the international patent filings we've documented for you, of WVU's "West Virginia Process" for the direct liquefaction of coal, using the hydrogen-donor solvent, tetralin.
 
In any case, they have developed the technology to obtain acetylene directly from coal.
 
And, once acetylene is produced from coal, it can be further processed into liquid hydrocarbons, as in:
 
 
"Title: Catalyzed conversion of acetylene to higher hydrocarbons
 
Author: He, Y., Jang, W.L., Timmons, R.B., (Univ. of Texas, Arlington (United States))
 
Publication: Energy and Fuels; (United States); Journal Volume: 5:4
 
Abstract: The continuous catalyzed conversion of acetylene to higher hydrocarbons has been the subject of numerous studies. Interest in this process reflects the fact that a successful conversion of this type could serve as a possible alternative source of synthetic fuel. The synthetic fuel possibility is centered on the fact that acetylene is obtainable in industrial quantities from coal and methane. However, as noted explicitly by previous workers, the unavailability of an effective catalyst for continuous C{sub 2}H{sub 2} conversion has prevented development of this alternative fuel route. The present report communicates a dramatically improved continuous flow catalyzed conversion of C{sub 2}H{sub 2} to higher hydrocarbons. This conversion is achieved by using a modified H-ZSM5 zeolite catalyst and a reactant gas feed consisting solely of C{sub 2}H{sub 2} plus water. Using this combination, the authors have demonstrated efficient continuous 100% conversion of C{sub 2}H{sub 2} to higher hydrocarbons for over 24 h at a C{sub 2}H{sub 2} space velocity of 2.1 {times} 10{sup 3} h{sup {minus}1} and a reaction temperature of only 623 K."
 
So successful is the conversion of acetylene, as can be made from coal, into "higher hydrocarbons", that a US Patent has been issued on the process:
 
 
(Note, in light of the above technical report, the "Inventors", and, the "Assignee":)
 
"Inventors: Timmons, Richard B.; He, Yigong; Jang, Wen-Long
 
Assignee: Board of Regents, The University of Texas System 
 
1. Field of the Invention

The invention relates to a process for the continuous conversion of alkynes to mixtures of aromatics, olefins and paraffins useful as fuels or fuel additives. The process utilizes a shape selective zeolite, modified with a metal such as nickel or cobalt, and requires the addition of a hydrogen containing co-reactant in order to achieve continuous single-step conversion of alkynes to higher hydrocarbon product mixtures
 
2. Description of Related Art

The continuous catalyzed conversion of acetylene to higher hydrocarbons has been the subject of numerous studies (Tsai, P. and Anderson, 1983; Allenger, Fairbridge et al, 1987; Allenger, McLean et al, 1987; Allenger, Brown et al, 1988). Interest in this process reflects the fact that successful conversion of this type could serve as a possible source of synthetic fuel (Tsai and Anderson, 1983; Allenger, Fairbridge et al, 1987; Allenger, McLean et al, 1987). The synthetic fuel possibility is centered on the fact that acetylene is obtainable in industrial quantities from coal and methane (Tedeschi, 1982). However, as noted explicitly by previous workers, the unavailability of an effective catalyst for continuous acetylene conversion has prevented development of this alternative fuel route (Tsai and Anderson, 1983; Allenger, Fairbridge et al, 1987; Allenger, McLean et al, 1987)."
 
We suppose it is, by now, truly gratuitous to note that zeolite catalysts are at the heart of Exxon-Mobil's "MTG"(r), methanol-to-gasoline, process, wherein the methanol is to be, and in China is being, synthesized from coal; and, that zeolites can be harvested in abundance from coal plant fly ash.
 
They've figured it all out in China and Texas, it seems. When, do you suppose, the news will reach the people who most deserve to know, and to have something done, about it - the citizens of West Virginia and Pennsylvania, and the rest of US Coal Country?

Japan Improves CO2 Recycling

 
We haven't yet been able to find out much more about this very recent development. But, the gist of it seems to be that Japanese researchers have dramatically lowered the energy needed to "break open", as it were, the Carbon Dioxide molecule, and thus make it's components available for recombination with other elements for more efficient recycling.
 
We've no idea what the genuine utility of potassium formate - formic acid - as below, might be, although quick searches reveal that it is employed in the manufacture of vinyl, and there seems to be a significant international trade in it, with most suppliers seemingly based in China. But, we are including an additional link and excerpt, following, from the international chemical giant, BASF, detailing some of formic acid's uses, one of which is somewhat interesting.
 
As follows:
 
"Catalytic hydrogenation of carbon dioxide using Ir(III)-pincer complexes.
 
Tanaka, R.; Yamashita, M.; Nozaki, K. 
 
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.

Journal of the American Chemical Society, 2009 Oct 14;131(40):14168-9.

Catalytic hydrogenation of carbon dioxide in aqueous potassium hydroxide was performed using a newly synthesized isopropyl-substituted PNP-pincer iridium trihydride complex as a catalyst. Potassium formate was obtained with turnover numbers up to 3,500,000 and a turnover frequency of 150,000 h(-1), both of which are the highest values reported to date."

And, herein are some of formic acid's current commercial applications:


 
Worldwide Applications
From the traditional pickling of leather to highly advanced pharmaceutical syntheses, BASF formic acid is indispensable in numerous applications.
 
Chemical Intermediate
Formic acid is an intermediate in the production of various chemicals and pharmaceuticals such as caffeine, enzymes, antibiotics, artificial sweeteners, plant protection agents, PVC-plasticizers and rubber antioxidants.
 
Dyeing/Pickling
In the dyeing of natural and synthetic fibers, formic acid regulates the pH and is also used to help waterproof textiles. In the leather industry, formic acid is used in the dyeing process, for pickling, deliming and as an auxiliary in the tanning process.
 
Silage
Formic acid is used in the preservation of green feed/fodder
 
Cleaning/Disinfection
Formic acid is used as an active ingredient in commercial cleaning products such as descalers, rust removers, multipurpose cleaners, degreasers and institutional laundry products. In addition, formic acid is used in the disinfection of wood barrels for wine and beer due to its bactericidal properties.
 
Flue Gas Desulfurization
An application for formic acid is pH regulation in the Saarberg-Hoelter-Umwelttechnik (SHU) flue gas desulfurization process. Most fossil fuels contain sulfur, which release sulfur dioxide into the air when burned. The SHU process captures this sulfur dioxide by passing the flue gas through an aqueous limestone slurry containing formic acid. The sulfur dioxide reacts with the limestone to form gypsum (calcium sulfate).
 
Coagulation of Rubber
One of the traditional uses of formic acid is in the coagulation of natural rubber, which is primarily produced in southeast Asia. Latex milk is tapped from rubber trees and is mixed with formic acid to produce the coagulated rubber that is further processed into tires and numerous other rubber products."
 
We submit this information in further support of our thesis that the CO2 co-product of our coal use technologies is a raw material whose true, and significant, value we are only beginning to understand. This documented use of it, please keep in mind, is in addition to the Nobel Prize-winning and US Department of Defense-patented technologies, wherein CO2 can be reclaimed and recycled into liquid fuels and chemicals; most especially, methanol: a material of extraordinary value, both in it's own right as a liquid fuel, and, as a starting point from which other fuels, including gasoline, and very useful, and carbon-sequestering, plastics can be manufactured.
 
And, please note the synergy, above, wherein the formic acid produced from a coal combustion waste can be used to clean up another coal combustion waste, as per formic acid's use in "Flue Gas Desulfurization".
 

Arkansas, USBM Convert Coal to Methane

 
In the course of our dispatches concerning the real potentials of coal conversion technology, we've noted a few times the potentials for using "bio" technologies to perform, or to enhance, the processes of converting coal into hydrocarbons, and extracting hydrocarbon values from coal wastes. The research into bacteria living in coal mine wastes Joe assisted with at WVU, in the mid-Seventies, and Craig Venter's more recent efforts to isolate carbon-converting microbes resident deep within the earth, which we documented for you, are examples.
 
We've also cited research into the biological conversion of syngas derived from coal, into hydrocarbons, as an alternative to established catalytic methods.
 
Herein is documentation, from a trio of research organizations, that biotechnology can, indeed, assist, if needed, in the transformation of coal into more versatile hydrocarbons.
 
As follows:
 
"Biological production of methane from bituminous coal 

J.C. Volkwein, A.L. Schoeneman, E.G. Clausen, J.L. Gaddy, E.R. Johnson, R. Basu, N. Ju and K.T. Klasson

United States Department of the Interior, Bureau of Mines, P.O. Box 18070, Pittsburgh, PA 15236-0070, USA

University of Arkansas, Department of Chemical Engineering, Fayetteville, AR 72701, USA

Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA


May 1994

Abstract

Biogasification of coal offers significant economic and environmental benefits for the continued utilization of coal resources. Several consortia from various natural sources associated with coal have been shown to produce methane from media containing only coal as the organic carbon source. Methane production of these samples has continued to increase with time. The cultures have remained viable and have continued to produce methane after 5 successive transfers to media containing coal as the sole carbon source. Methane quantities of 4 and 5 volume percent methane have been observed from Pittsburgh and Wyodak coals. Serum tube experiments were scaled to larger column experiments that also indicated that methane is produced from medium containing coal as the only carbon source."

Methane from coal might not sound all that exciting, at first. However, if you recall some of our earlier posts, there exist a number of technological paths which enable the fairly straightforward conversion of methane into more complex, and more valuable, hydrocarbons, including liquid fuels.

Japan Recycles CO2 to Petrochemicals

 
 
Herein, from Japan, we have yet more credible affirmation that Carbon Dioxide, as emitted from various sources, including human agricultural activity and natural volcanism, is a raw material resource of potential value.
 
The excerpt: 

Document title

Reduction of carbon dioxide to petrochemical intermediates

Authors

KANECO S; IIBA K.; OHTA K ; MIZUNO T.

Affiliations

Department of Chemistry for Materials, Faculty of Engineering, Mie University, Tsu, Mie, JAPON

Abstract

The electrochemical reduction of CO2 at the Cu electrode was investigated in methanol-based electrolyte using various cesium supporting salts as the ionophore at an extremely low temperature (243 K). Cesium acetate, chloride, bromide, iodide, and thiocyanate were used as the ionophore. The main products from CO2 by electrochemical reduction were methane, ethylene, ethane, carbon monoxide, and formic acid. In the methanol-based electrolyte using cesium supporting salts, except for acetate, the Faradaic efficiency for ethylene was larger than that for methane. This research can contribute to large-scale manufacturing of petrochemical intermediate products, such as methane and ethylene, from readily available and cheap raw materials; CO2-saturated methanol from industrial absorbers (the Rectisol process). Thus the synthesis of hydrocarbons by the electrochemical reduction of CO2 may be of practical interest for fuel production, storage of solar energy, and production of intermediate materials for the petrochemical industry.

Journal Title

Energy sources; ISSN 0090-8312   CODEN EGYSAO; 2000, vol. 22, n2, pp. 127-135 (12 ref.); Taylor & Francis, Philadelphia, PA, 1973" 
 
So, in 1973, we knew that CO2 had potential use in "the synthesis of hydrocarbons ... and production of intermediate materials for the petrochemical industry".
 
And, we are still trying to either tax our coal-use industries out of existence, through Cap&Trade shell games, or force them to help Big Oil squeeze more of the stuff he extorts us all with out of his nearly-depleted reservoirs, through enforced geologic CO2 sequestration?
 
How much money have we wasted on debating all of that nonsense, over the past 36 years, when we could have been building factories both to convert our abundant domestic coal into the liquid fuels we need and to recycle Carbon Dioxide into other "hydrocarbons ... and ... materials for the petrochemical industry"?
 
  1. Coal Liquefaction Industry Research Info
  2. Belgium & Coal-Methanol-Plastics
  3. Clean Energy from Coal-Derived DME
  4. Pitt Studies Coal Syngas

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