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.