Research & Development

USDOD Converts CO2 to Methane

 
As we have amply documented, Penn State University has developed "tri-reforming" technology which enables us to convert, through reactions with the gas, Methane, the valuable Carbon Dioxide by-product of our coal-use industries into liquid fuels and chemicals.
 
With the attached and enclosed document, which, if you open and examine it, you will discover to be more than three decades old, we confirm that the needed Methane can, itself, be synthesized from Carbon Dioxide.
 
As reported to the United States Department of Defense by one of their major contractors, with advance regrets for the stridency of our comments and questions, which follow our excerpts from:
 
"KINETICS OF CARBON DIOXIDE METHANATION ON A RUTHENIUM CATALYST

Peter J. Lunde and Frank L. Kester
 
Hamilton Standard Division,
United Aircraft Corporation
Windsor Locks, Connecticut, 06096
 
INTRODUCTION
 
The catalytic hydrogenation of carbon dioxide to methane is often called the Sabatier reaction, after the Belgian chemist who investigated the hydrogenation of hydrocarbons using a nickel catalyst. The Sabatier reaction is becoming of commercial interest for the manufacture of natural gas from the products of coal gasification. The reverse reaction, of course, is called steam reformation and is a commercial method for hydrogen manufacture.
 
This paper developed from work performed under contract to NASA to investigate the Sabatier reaction as a step in reclaiming oxygen within closed cycle life support systems. Carbon dioxide from the cabin atmosphere is thus changed into water vapor which is electrolyzed to provide oxygen for the cabin plus one-half the hydrogen required for the Sabatier reaction. The rest of the hydrogen is provided from the electrolysis of stored water, which produces breathing oxygen as a by-product, reducing the proportion of available carbon dioxide which must be reacted and assuring excess carbon dioxide in the feed mixture.
 
The Sabatier reaction is a reversible, highly exothermic reaction which proceeds at a useful rate at the low temperatures required for high yields only when a catalyst is used. Dew, White, and Sliepcevitch (1)studied this reaction using a nickel catalyst. This paper examines the kinetics of the reaction using a Ruthenium catalyst ... .
 
(Note: As we have earlier reported, a portion of the CO2 recycling process is exothermic, and, if the heat generated were to be harnessed, it could, in part, be self-sustaining, with resultant economies. - JtM)
 
... Thompson (3) conducted a Sabatier catalyst screening program for the US Air Force.

Ruthenium and nickel were found to be appreciably more active catalysts for promoting the Sabatier reaction. Nickel, however, presented several operating problems.
 
Ruthenium had ... (no problems as with nickel) ... and was somewhat more active than the nickel as a catalyst. Furthermore, there was a potential for even more activity if heavier loadings of the metal on the substrate are used.
 
Consequently a 0.5% ruthenium catalyst on 118 in x 118 cylindrical alumina pellets was selected for further investigation. The prepared catalyst, Englehard type “E”, was purchased from
 
Englehard Industries Division
Englehard Minerals and Chemicals Corp.
113 Aster Street
Newark, N. J.
 
(So, at least one of the critical components of the process is already commercially available. - JtM)

Feed flow ratios ...  were investigated. Temperatures  ...  were ...  low enough to allow virtually complete conversion of the feed in a practical reactor. 
 
(The "feed" - Carbon Dioxide - underwent "virtually complete conversion" into Methane. - JtM) 
 
Complete raw data is given in Reference 5, which is the NASA report of this work.
 
(Might be nice to have a copy of "the NASA report of this work". - JtM) 
 
References (Selected - JtM)
 
1. Dew, J. M., White, R. R. and Sliepcevitch, C. M. "Hydrogenation of Carbon Dioxide on Nickel ...". IEC V 47, _1, Jan. 1955
 
2. Wagman, D. D., et a1 "Heats, Free Energies, and Equilibrium Constants of Some Reactions involving 02, H2, H20, C, CO, CO2, and CH4". Research Paper Rp 1634, J. Res. Nat. Bu. of Std., V 34, Feb. 1945, p. 143-161.

3. Thompson, Edward B. Jr. Technical Documentary Report No. FDLTDR-64-22; "Investigations of Catalytic Reactions for CO2 Reduction". Parts I -V, 1964 -67. Published by: Air Force Flight Dynamics Laboratory; Research and Technology Division; Air Force Systems Command; Wright-Patterson Air Force Base, Ohio
  
5. Baum, R. A., Kester, F. L. and Lunde', P. J. "Computerized Analytical Technique for Design and Analysis of a Sabatier Reactor Subsystem", Hamilton Standard report No. SVHSER 5082, (1970), prepared on NASA contract 9-9844. Available through Nat. Tech. Service Publications. Document No. 71-26295."
 
-------- 
 
Note the references: Carbon Dioxide recycling technical data from 1945, 1955, 1967, and 1970.
 
And: Our US Air Force developed Carbon recycling technology for years, as in "Investigations of Catalytic Reactions for CO2 Reduction". Parts I -V, 1964 -67". 
 
Why haven't we US citizens, especially we US citizens of US Coal Country, who paid the taxes that paid for this research, been informed of any of it?
 
Why have we not been told that coal can be converted, on a practical, well-established basis, into the liquid fuels we've been, over the course of decades, extorted for the supply of?
 
Why have we not been told that the most publicly objectionable by-product of our coal use, Carbon Dioxide, can itself be recycled into even more of those liquid fuels?

Use CO2 - Penn State

 
As noted in our most recent dispatch concerning Penn State University's Craig Grimes, and his public urging, in a Texas newspaper, that we recycle the carbon dioxide by-product of our coal-use industries, rather than, for suspect purposes and with doubtful effectiveness, spend a lot of money trying to shove it all down leaky geologic storage rat holes, another Penn State scientist, Chunsan Song, has also been urging, and helping to develop the technologies for, the conversion, the recycling, of carbon dioxide into products of value.
 
We ask you to recall that we have previously cited Dr. Song in this regard. The paper:
 
"Tri-reforming: A New Process Concept for Conversion and Utilization of CO2 in Flue Gas"
Chunshan Song
Department of Energy & Geo-Environmental Engineering
Pennsylvania State University
University Park, PA, USA "
 
has been referenced by us in our dispatches to the West Virginia Coal Association; and, we have cited other sources on the "tri-reforming of methane", through reactions that consume carbon dioxide, to produce liquid fuels and other useful organic chemicals of direct commercial value.
 
Herein, we present - - and, the three of us confess, after much debate among us, great puzzlement as to why this seemingly-important exposition, made in one of the capitals of US Coal Country, wasn't, apparently, taken notice of by the Coal Country press - - a link to, and edited excerpts from, the presentation:
 
"Chemical Conversion and Utilization of CO2 from Fossil Fuel Combustion

Chunshan Song

Department of Energy & Geo-Environmental Engineering, and Clean Fuels Program, The Energy Institute,
Pennsylvania State University, University Park, PA 16802, USA
 
DOE NETL Workshop on Carbon Sequestration Science

May 22-24, 2001, Pittsburgh, PA, USA

Objectives of CO2 Conversion & Utilization:

Use CO2 for environmentally-benign physical and chemical processing
 
Use CO2 to produce industrially useful chemicals and materials
 
Use CO2 to recover energy and reduce its emission to the atmosphere

Use CO2 recycling to conserve carbon resources for sustainable development
 
Critical R&D Issues of CO2 Conversion & Utilization:
 
To make use of CO2 based on the unique physical or chemical properties of CO2
 
To produce useful chemicals and materials using CO2 as a reactant or feedstock
 
To replace a hazardous or less-effective substance in existing processes with CO2 as an alternate medium
or solvent or co-reactant or a combination of them
 
Barriers & Challenges for Promoting CO2 Conv & Uilization
 
Costs of CO2 capture, separation, purification, and transportation to user site.
 
Energy requirements of CO2 chemical conversion (plus source & cost of H2 if involved).
 
Market size limitations, and lack of investment-incentives for CO2-based chemicals.
 
Socio-economical driving forces do not facilitate enhanced CO2 utilization.
 
Chemical Processes for CO2 Conversion; CO2 Conversion Processes:

Chemical/Catalytic
Catalytic-HomogeneusPhotochemical/Catalytic
Bio-chemical/Enzymatic
Electrochemical/Catalytic
Solar-thermal/Catalytic

Strategies for CO2 Conversion & Utilization

Select concentrated CO2 sources for CO2 capture; aim for on-site/nearby uses if possible.
 
Convert CO2 along with other co-reactants into industrially useful chemical products.
 
Take value-added approaches for CO2 sequestration coupled with utilization.
 
Fix CO2 into environmentally-benign organic polymer materials or inorganic materials.
 
Use CO2 to replace a hazardous or less-effective substance in existing chemical processes for making products with significant volumes.
 
Chemical Synthesis Using CO2 Synthesis of Dimethyl Carbonate (Phosgene Substitution)
 
Env. Benefits of Synthesis Using CO2 [Case of Dimethyl Carbonate Synthesis]
 
Env. Benefits of Synthesis Using CO2 [Case of Methanol Synthesis]
 
CO2 Reforming of CH4 - application for F-T & MeOH synthesis. (i.e., Fischer-Tropsch liquid fuel and methanol - JtM)

Some Reviews on Chemical Conversion:
 
Aresta, M.; Dibenedetto, A.; Tommasi, I. Developing Innovative Synthetic Technologies of Industrial Relevance Based on Carbon Dioxide as Raw Material. Energy & Fuels, 15: 269-273, 2001.
 
Halmann, M. M.; Steinberg, M. Greenhouse Gas Carbon Dioxide Mitigation: Science and Technology. Lewis Publishers, Boca Raton, Fl, 1999, 568 pp.
 
Aresta M. Perspectives of Carbon Dioxide Utilisation in the Synthesis of Chemicals. Coupling Chemistry with Biotechnology. STUD SURF SCI CATAL 114: 65-76, 1998
 
Arakawa H. Research and Development on New Synthetic Routes for Basic Chemicals by Catalytic Hydrogenation of CO2. STUD SURF SCI CATAL 114: 19-30, 1998
 
Audus H; Oonk H. An Assessment Procedure for Chemical Utilisation Schemes Intended to Reduce CO2 Emissions to Atmosphere. ENERG CONV MANAGE 38: S409-S414 Suppl. S 1997 

Chemical Conversion and Utilization of CO2 [Some Recent ACS Symps on Chemical Aspects] 

Am. Chem. Soc. Symp. on “Greenhouse Gas Control and Utilization” (Cocahirs: C. Song, M. Aresta, and K. Y. Lee), ACS Spring 2001 National Meeting in San Diego, Published in Am. Chem. Soc. Div. Fuel. Chem.
Prepr., 2001, Vol. 46, No. 1.
 
Am. Chem. Soc. Symp. on “CO2 Conversion and Utilization” (Co-chairs: C. Song, A. M. Gaffney, and K. Fujimoto), ACS Spring 2000 National Meeting in San Francisco, Published in Am. Chem. Soc. Div. Petrol. Chem. Prepr., 2000, Vol. 45, No. 1.

Energy & Fuels April 2001 “CO2 Capture, Utilization and Sequestration” (Co-chairs: R. M. Enick and R. P. warzinski) 2001, Vol. 15, No. 2.
 
Proceedings of International Conference on Carbon Dioxide Utilization (1991- Nagoya, Japan; 1993-Bari, Italy; 1995-Oklahoma, US; 1997-Kyoto, Japan; 
 
U.S. Transportation Fuels Market & Hypothetical Upper Limit of US Demand for CO2-Based Fuels
Source: C. Song. Am. Chem. Soc. Symp. Ser., 2001  

Idea for CO2-Based Tri-generation of Chemicals, Fuels, and Electricity:
 
Can we design a chemical system where the expensive CO 2
pre-separation from flue gases is not necessary?
 
Can we use the CO 2 in flue gas along with H2O and O2
directly for producing industrial useful products?
 
Is it possible to use waste heat in power plants for CO2
conversion?

Energetics of CO2 Conversion;Tri-reforming Reactor System at PSU; Tri-reforming: Experimental Work: 

Advantages of Proposed Tri-reforming 
 
- Direct use of CO2 in waste flue gases of power plants without CO2 separation and purification.
- Taking advantage of H2O and O2 impurities in flue gases, for more energy efficient reforming.
- Produces synthesis gas with desired H2/CO ratios. 
- Eliminate or largely reduce coke formation, common in dry reforming, by using O2 and H2O.
- Proactive/advantageous use of greenhouse gas.
- New process concept for large-scale syngas prod.
- Challenges: catalyst, process, E, feed+prod, etc.
 
Advantages of Proposed Tri-Generation 

- Start with synthesis gas from tri-reforming of natural gas using flue gas of power plants.
- Synthesis of chemicals such as alcohol, acetic acid, ether, olefins, and hydrogen, etc.
- Production of ultra-clean hydrocarbon fuels by Fischer-Tropsch method; production of oxygenated fuels such as alcohols and ethers.
- Additional generation of electricity, by using syngas, hydrogen, and waste heat, by gas turbine generator, fuel cells, and others.
 
Challenges: ... paradigm shift"
 
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Well, we think we all now know, and have a much clearer picture of, what some "challenges", standing in the way of recycling the carbon dioxide by-product of our coal use, and, by extension, of fully utilizing our coal resources through the proven technologies of coal liquefaction, are.  Song posits one of the challenges standing in the way of implementing these critical carbon conversion technologies as, simply, "paradigm shift".
 
A paradigm shift in what, exactly, Dr. Song does not specify. But, we submit that a paradigm shift in the public reportage, and resultant public knowledge, on the truths of coal-to-liquid conversion and carbon dioxide recycling technologies sure wouldn't hurt.
 
If we can overcome the primarily psychological challenges, we can start making valuable chemicals, such as "alcohol, acetic acid, ether, olefins", etcetera, and "ultra-clean hydrocarbon fuels" out of both our abundant Coal and our Carbon Dioxide.

Korea Recycles CO2

 

Subsequent to our recent citations of Penn State University's Chunsan Song, and others, revealing the truth that Carbon Dioxide is a valuable by-product of our coal-use industry, we wanted to confirm that the concept of "tri-reforming" CO2, to produce liquid hydrocarbon fuels and valuable industrial chemicals, isn't just some isolated notion cooked up in the academic clouds of Pennsylvania's Happy Valley.
 
Herein, research from Korea affirms that, yes, we certainly can recycle Carbon Dioxide into products of genuine commercial, industrial value, through the tri-reforming process.
 
The excerpt, with brief comment appended: 
"Tri-reforming of CH4 using CO2 for production of synthesis gas to dimethyl ether
 
Seung-Ho Lee, Wonihl Cho, Woo-Sung Ju, Byoung-Hak Cho, Young-Chul Lee and Young-Soon Baek

LNG Technology Research Center, Research and Development Division, Korea Gas Corporation, 973, Dongchun-dong, Yeonsu-gu, Incheon 406-130, South Korea


Abstract

In general, there are three processes for production of synthesis gas; steam reforming, CO2 reforming and partial oxidation of methane or natural gas. In the present work, we refer to tri-reforming of methane to synthesize syngas with desirable H2/CO ratios by simultaneous oxy-CO2-steam reforming of methane. In this study, we report the results obtained on tri-reforming of methane over the Ni/ZrO2 based catalyst in order to restrain the carbon deposition and to evaluate the catalytic performance. Results of tri-reforming of CH4 by three catalysts (Ni/Ce–ZrO2, Ni/ZrO2 and Haldor Topsoe R67-7H) are showed that the coke on the reactor wall and the surface of catalyst were reduced dramatically. It was found that the weak acidic site, basic site and redox ability of Ce–ZrO2 play an important role in tri-reforming of methane conversion. Carbon deposition depends not only on the nature of support, but also on the oxidant as like steam or oxygen. Therefore, the process optimization by reactant ratios is important to manufacture the synthesis gas from natural gas and carbon dioxide."

-------

As with the PSU developments reported by Dr. Song, some of the problems associated with Carbon Dioxide recycling, such as troublesome depositions of "coke" ..."were reduced dramatically", and the process thus made more efficient.

We shouldn't need to, but will, affirm that "synthesis gas", once produced from Coal or CO2, can be used to make a number of useful things, gasoline included. But, once again, dimethyl ether itself is an extremely versatile liquid fuel and organic chemical processing raw material.

And, as NASA is doing aboard the International Space Station, as a function of their air purification system,  if we need additional Methane to react with the Carbon Dioxide, to produce dimethyl ether, we can use Sabatier technology to make that, too, directly out of Carbon Dioxide - or, as we have more-than-thoroughly documented, through gasification processes, directly from Coal.

Conoco Converts More Coal to Methanol

United States Patent: 4430444

In a report not long ago, available as: Conoco Coal to Methanol | Research & Development | News; we introduced United States Patent 4,218,389, from 1980, which is labeled as a "Process for Making Methanol", which was awarded to Oklahoma scientists in the employ of Conoco; and, wherein Coal is identified as the primary raw material for "Making Methanol".

Herein, we see that Conoco continued their development of such technology and were, four years later, awarded yet another United States Patent for improvements on such Coal liquefaction processes.

Read more …

"Burying CO2 Ridiculous" - Penn State University

 
We want to point out, subsequent to our recent exchange of love notes with the Texas Big Oil contingent, that this enclosed item, about an obviously, to us, sensible suggestion made by a Penn State University scientist, was published in a Texas newspaper.
 
We've cited PSU's Craig Grimes, on the subject of CO2 recycling and carbon conversion, previously, as well as a few of his Penn State colleagues, most notably Dr. Chunsan Song. In fact, in following dispatches, we'll document even further some of Dr. Song's sensible presentations on CO2 recycling.
 
But, first, the excerpt from Houston, revealing Penn State's radically sensible stance on the matter of CO2:

"Radical idea: Why not convert carbon dioxide into fuel?

A recent study in the journal Nano Letters  discusses the possibility of using special honeycombs made of nanotubes to capture carbon dioxide and convert it into methane, the primary component in natural gas.

This is what you call making lemonade out of lemons. ... we've got all this extra carbon dioxide coming out of smokestacks. Some researchers are now asking, Hey, maybe this is actually a natural resource that we can put to work for us.

An article in Discovery News quotes the study's lead author, Craig Grimes:

"Right now there is lots of talk about burying carbon dioxide, which is ridiculous," said Craig Grimes of Penn State, who, along with Oomman Varghese, Maggie Paulose and Thomas LaTempa, co-authored a paper on the nanotubes in the journal Nano Letters. "Instead we can collect the waste out of the smoke stack, put it though a converter, and presto, use sunlight to change [CO2] back into fuel.""

When sunlight hits the copper oxide, carbon dioxide is converted into carbon monoxide. When sunlight hits the titanium oxide, water molecules split apart. The hydrogen freed from the water and the carbon freed from CO2 then recombine to create burnable methane, and the spare oxygen atoms pair up to create breathable oxygen.""

Again, in case you missed it: "burying carbon dioxide ... is ridiculous".

  1. Let's Chemically Recycle CO2
  2. USDOE Coal Liquefaction Progress Report
  3. Sequestering CO2 as Liquid Fuel
  4. USDOE Encoal(R) Final Report

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