Greenhouse Gases to Liquid Fuels

 
 
We've reported that Carbon Dioxide can be reduced and converted, via the Sabatier process, into oxygen, and methane, as is being done on the International Space Station, where the methane produced is dumped overboard as a means to dispose of excess carbon. We submit, and documentation is available, that NASA is studying the prospect of using Sabatier technology to produce fuel for the return leg of a journey to Mars, where the atmosphere is predominantly Carbon Dioxide. At least one of their scenarios proposes, as we've also documented to be feasible, the electrolysis of water to provide needed hydrogen for the methane synthesis.
 
As we've also noted, there are documented processes whereby methane, as could be produced by Sabatier technology, can be used as the basis for synthesis of more complex hydrocarbons, such as methanol.
 
Interestingly such use, the "reforming", of methane, can be designed to actually consume even more Carbon Dioxide, and produce a synthesis gas that is "preferred for the synthesis of valuable oxygenated chemicals and long-chain hydrocarbons". Long-chain hydrocarbons similar to liquid fuels, we presuppose. 
 
The enclosed report is actually just one of many available resources documenting the potential for using additional CO2 to synthesize methane into more complex, and more valuable, hydrocarbons. In other words, the initial recycling of Carbon Dioxide, with methane as a by-product, makes possible the recycling of even more CO2 to create more complex hydrocarbons that could themselves be used to make liquid fuels.
 
The excerpt: 

"Carbon Dioxide Reforming of Methane Over Nickel Supported Mesoporous Material Catalysts with Superior Stability

Dapeng Liu and Yanhui Yang, School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, Singapore

Catalytic reforming of methane with carbon dioxide, also known as dry reforming, has recently attracted considerable attention due to simultaneous utilization and reduction of two types of greenhouse gases, CO2 and CH4. The synthesis gas (syngas) produced has a lower H2/CO ratio than those available from steam reforming and partial oxidation of methane; the lower ratio is preferred for the synthesis of valuable oxygenated chemicals and long-chain hydrocarbons."
 
If we understand this correctly, and other reports seem to confirm it, using Carbon Dioxide to process, to reform, Methane, which itself can be produced from Carbon Dioxide by the Sabatier process, actually results in compounds better-suited for additional synthesis into more useful hydrocarbon products. 
 
Carbon Dioxide is a valuable by-product of our coal use. We shouldn't be trying to legislate the industries that generate it out of existence.

ACS Symposium: CO2 Utilization


 
We reported that a symposium had been held this year, with surprisingly little public notice, given the alarmism that has been fostered about the topic of global warming and the culpability of supposed "greenhouse" gasses in the process, on the recycling and reuse of Carbon Dioxide, which can arise as a much-maligned by-product from our coal-use industries.
 
Such symposia have been held, in near-secrecy it would seem, for quite some time now, as this reference will attest.
 
Some excerpts from the enclosed link:

"ACS Symposium #809: Co2 Conversion and Utilization

Held March, 2000, in San Francisco, CA
Chunshan Song, Editor  

 1. CO2 Conversion and Utilization: An Overview, Chunsan Song

2. CO2 Mitigation and Fuel Production, M. Steinberg

3. CO2 Emission Reductions: An Opportunity for New Catalytic Technology, Leo E. Manzer

Synthesis of Organic Chemicals

 

4. Key Issues in Carbon Dioxide Utilization as a Building Block for Molecular Organic Compounds in the Chemical Industry, Michele Aresta and Angela Dibenedetto

 

5. Selective Conversion of Carbon Dioxide and Methanol to Dimethyl Carbonate Using Phosphoric Acid-Modified Zirconia Catalysts, Yoshiki Ikeda, Yutaka Furusawa, Keiichi Tomishige, and Kaoru Fujimoto

 

6. Utilization of Carbon Dioxide for Direct, Selective Conversion of Methane to Ethane and Ethylene with Calcium-Based Binary Catalysts, Ye Wang and Yasuo Ohtsuka

 

7. Copolymerization of Carbon Dioxide, Propylene Oxide, and Cyclohexene Oxide by an Yttrium-Metal Coordination Catalyst System, Chung-Sung Tan, Char-Fu Chang, and Tsung-Ju Hsu

 

8. The Role of CO2 for the Gas-Phase O2 Oxidation of Alkylaromatics to Aldehydes, Jin S. Yoo

 

9. Effective Conversion of CO2 to Valuable Compounds by Using Multifunctional Catalysts, Tomoyuki Inui

 

10. Supported Copper and Manganese Catalysts for Methanol Synthesis from CO2-Containing Syngas, K. Omata, G. Ishiguro, K. Ushizaki, and M. Yamada

 

11. Catalytic Reduction of CO2 into Liquid Fuels: Simulating Reactions under Geologic Formation Conditions, D. Mahajan, C. Song, and A. W. Scaroni

 

12. Methane Dry Reforming over Carbide, Nickel-Based, and Noble Metal Catalysts, Abolghasem Shamsi

 

13. A Highly Active and Carbon-Resistant Catalyst for CH4 Reforming with CO2: Nickel Supported on an Ultra-Fine ZrO2, Jun-Mei Wei, Bo-Qing Xu, Jin-Lu Li, Zhen-Xing Cheng, and Qi-Ming Zhu

 

14. CO2 Reforming of Methane over Ru-Loaded Lanthanoid Oxide Catalyst, Kiyoharu Nakagawa, Shigeo Hideshima, Noriyasu Akamatsu, Na-oko Matsui, Na-oki Ikenaga, and Toshimitsu Suzuki

 

15. CO2 Reforming and Simultaneous CO2 and Steam Reforming of Methane to Syngas over CoxNi1-xO Supported on Macroporous Silica-Alumina Precoated with MgO, V. R. Choudhary, A. S. Mamman, B. S. Uphade, and R. E. Babcock

 

16. Low-Temperature CH4 Decomposition on High-Surface Area Carbon Supported Co Catalysts, Z.-G. Zhang, K. Haraguchi, and T. Yoshida

 

17. Effects of Pressure on CO2 Reforming of CH4 over Ni/Na-Y and Ni/Al2O3 Catalysts, Chunshan Song, Srinivas T. Srimat, Satoru Murata, Wei Pan, Lu Sun, Alan W. Scaroni, and John N. Armor

 

18. A Comparative Study on CH4-CO2 Reforming over Ni/SiO2-MgO Catalyst Using Fluidized-and Fixed-Bed Reactors, A. Effendi, Z.-G. Zhang, and T. Yoshida

 

19. Effects of Pressure on CO2 Reforming of CH4 over Rh/Na-Y and Rh/Al2O3 Catalysts, Srinivas T. Srimat and Chunshan Song

 

20. Methane Reforming with Carbon Dioxide and Oxygen under Atmospheric and Pressurized Conditions Using Fixed- and Fluidized-Bed Reactors, Keiichi Tomishige, Yuichi Matsuo, Mohammad Asadullah, Yusuke Yoshinaga, Yasushi Sekine, and Kaoru Fujimoto

 

21. Computational Analysis of Energy Aspects of CO2 Reforming and Oxy-CO2 Reforming of Methane at Different Pressures, Wei Pan and Chunshan Song

 

22. Photocatalytic Reduction of CO2 with H2O on Various Titanium Oxide Catalysts, Hiromi Yamashita, Keita Ikeue, and Masakazu Anpo

 

23. Electrochemical Reduction of CO2 with Gas-Diffusion Electrodes Fabricated Using Metal and Polymer-Confined Nets, K. Ogura, H. Yano, and M. Nakayama".

We'll presume some of the more technical phrases, and their significance, such as "Reforming" and "Methanol Synthesis", to be familiar by now from our earlier posts, and will not explicate them herein.

There is more, but these selections should illustrate the, apparently well-known in certain circles, potential that exists to utilize the Carbon Dioxide which arises from our coal use in valuable and profitable ways.

Just like the liquid fuel, petroleum, "shortage", which could be profitably resolved by converting our abundant coal into liquid fuels, and leveraging coal conversion technology to begin employing biological feed stocks,  the Carbon Dioxide "danger" is a false belief artificially fostered by special interests who would be somehow served by a reduction in coal's use and perceived importance.  

There is no real Carbon Dioxide "problem". There is, however, a great CO2 opportunity. Carbon Dioxide is a valuable by-product of our coal-use industries. We should reward and encourage those enterprises which make it for us

Recycle CO2 - Penn State

 
You will recall that Chunshan Song appeared prominently in one of the recent Carbon Dioxide Utilization symposia we informed you of. Since Penn State is a relatively local institution, and readily accessible for further investigation, of you're so inclined, we wanted to send you one of Dr. Song's individual works on the recycling of the Carbon Dioxide by-product of our coal-use industries.
 
Excerpt as follows:
 
"Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing"
 
Chunshan Song

Clean Fuels and Catalysis Program, The Energy Institute, and Department of Energy & Geo-Environmental Engineering, The Pennsylvania State University 209 Academic Projects Building, University Park, PA 16802, USA

Abstract

Utilization of carbon dioxide (CO2) has become an important global issue due to the significant and continuous rise in atmospheric CO2 concentrations, accelerated growth in the consumption of carbon-based energy worldwide, depletion of carbon-based energy resources, and low efficiency in current energy systems. The barriers for CO2 utilization include: (1) costs of CO22 chemical conversion (plus source and cost of co-reactants); (3) market size limitations, little investment-incentives and lack of industrial commitments for enhancing CO2-based chemicals; and (4) the lack of socio-economical driving forces. The strategic objectives may include: (1) use CO2 for environmentally-benign physical and chemical processing that adds value to the process; (2) use CO2 to produce industrially useful chemicals and materials that adds value to the products; (3) use CO2 as a beneficial fluid for processing or as a medium for energy recovery and emission reduction; and (4) use CO2 recycling involving renewable sources of energy to conserve carbon resources for sustainable development. The approaches for enhancing CO2 utilization may include one or more of the following: (1) for applications that do not require pure CO2, develop effective processes for using the CO2-concentrated flue gas from industrial plants or CO2-rich resources without CO2 separation; (2) for applications that need pure CO2, develop more efficient and less-energy intensive processes for separation of CO2 selectively without the negative impacts of co-existing gases such as H2O, O2, and N2; (3) 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; (4) make use of CO2 based on the unique physical properties as supercritical fluid or as either solvent or anti-solvent; (5) use CO2 based on the unique chemical properties for CO2 to be incorporated with high ‘atom efficiency’ such as carboxylation and carbonate synthesis; (6) produce useful chemicals and materials using CO2 as a reactant or feedstock; (7) use CO2 for energy recovery while reducing its emissions to the atmosphere by sequestration; (8) recycle CO2 as C-source for chemicals and fuels using renewable sources of energy; and (9) convert CO2 under either bio-chemical or geologic-formation conditions into “new fossil” energies. Several cases are discussed in more detail. The first example is tri-reforming of methane versus the well-known CO2 reforming over transition metal catalysts such as supported Ni catalysts. Using CO2 along with H2O and O2 in flue gases of power plants without separation, tri-reforming is a synergetic combination of CO2 reforming, steam reforming and partial oxidation and it can eliminate carbon deposition problem and produces syngas with desired H2/CO ratios for industrial applications. The second example is a CO2 “molecular basket” as CO2-selective high-capacity adsorbent which was developed using mesoporous molecular sieve MCM-41 and polyethylenimine (PEI). The MCM41-PEI adsorbent has higher adsorption capacity than either PEI or MCM-41 alone and can be used as highly CO2-selective adsorbent for gas mixtures without the pre-removal of moisture because it even enhances CO2 adsorption capacity. The third example is synthesis of dimethyl carbonate using CO2 and methanol, which demonstrates the environmental benefit of avoiding toxic phosgene and a processing advantage. The fourth example is the application of supercritical CO2 for extraction and for chemical processing where CO2 is either a solvent or a co-reactant, or both. The CO2 utilization contributes to enhancing sustainability, since various chemicals, materials, and fuels can be synthesized using CO2, which should be a sustainable way in the long term when renewable sources of energy are used as energy input." capture, separation, purification, and transportation to user site; (2) energy requirements of CO

Admittedly a rather dense synopsis. But, the detail should be affirmation that, although it hasn't for whatever perverse reason been publicized and popularized, the potential to recover and recycle the CO2 by-product of our coal use industries is quite real. It could make our use of coal, whether we generate electricity or synthesize liquid fuels with it, even more valuable and essential to us than it now is.

CoalTL By-Product Use

 
 
Since we've presented evidence that makes it appear China is attempting to hijack the patent rights to WVU's "West Virginia Process" for direct coal liquefaction, we wanted to show you that they have at least given some thought as to how the by-products of that conversion process can be profitably employed.
 
In this case, they suggest that tar-like residues left behind by direct coal liquefaction can be employed as a paving and road-repair material, very much like the natural petroleum asphalt we're all familiar with.
 
The excerpt, with additional comment following:
 
"Novel Use of Residue from Direct Coal Liquefaction Process
 
Jianli Yang, Zhaixia Wang, Zhenyu Liu and Yuzhen Zhang
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, P.R. China, State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P.R. China, and State Key Laboratory of Heavy Oil Processing, Petroleum University, Dongying 257061, P.R. China 

Abstract

Direct coal liquefaction residue (DCLR) is, commonly, designed to be used as a feed stock for gasification or combustion. Use of DCLR as a value added product is very important for improving overall economy of direct coal liquefaction processes. This study shows that the DCLR may be used as a pavement asphalt modifier. The modification ability is similar to that of Trinidad Lake Asphalt (TLA), a superior commercial modifier. Asphalts modified by two DCLRs meet the specifications of ASTM D5710 and BSI BS-3690 designated for the TLA-modified asphalts. The required addition amount for the DCLRs tested is less than that for TLA due possibly to the high content of asphaltene in DCLRs. Different compatibility was observed for the asphalts with the same penetration grade but from the different origin. Different components in the DCLR play different roles in the modification. Positive synergetic effects among the fractions were observed, which may due to the formation of the stable colloid structure. Unlike polymer-type modifier, the structure of asphalt-type modifier has a similarity with petroleum asphalts which favors the formation of a stable dispersed polar fluid (DPF) colloid structure and improves the performance of pavement asphalt."

So, residue left behind by a direct coal liquefaction process very similar to, or exactly the same as, WVU's West Virginia coal conversion Process is a superior additive for asphalt used in road paving. Now, in a state, like West Virginia, where the State Seal was once believed to incorporate the image of road worker, in silhouette, leaning into his shovel at the edge of a pothole, wouldn't a by-product of converting their most abundant resource into desperately-needed liquid fuels that would reduce the need for placing such road repair signs be a "good thing"?

Recycle CO2 - US Navy

 
Interestingly enough, there have been a number of other CO2 Conversion and Utilization Conferences sponsored by the American Chemical Society.
 
But, the latest one was held just this month, and we're left wondering why we didn't hear anything about it - much as we didn't hear anything in the popular media about the multiple Coal-to-Liquid conferences that have taken place in the past year.
 
In any case, we find it doubly interesting that our own, US, Navy is promoting and sponsoring this effort, just as the US Air Force is promoting and sponsoring, as we've documented, efforts to refine the process of converting coal into liquid jet fuel at, among other places, the University of Dayton.
 
The excerpt, with some comments interspersed:  

"ACS Meeting Symposium Focuses on Conversion and Utilization of CO2 for Fuels and Chemicals

16 August 2009

Researchers at the US Naval Research Laboratory (NRL) led off a day-long symposium on advances in CO2 conversion and utilization being held at the 238th American Chemical Society (ACS) national meeting, which began today in Washington, DC. The NRL researchers presented their progress in hydrogenating CO2 to jet fuel via a two-stage, high-yield and highly selective synthesis process."

("Hydrogenating CO2 to ... fuel". Remember, Sabatier won the Nobel Prize for demonstrating the feasibility of this technology almost one hundred years ago. And, we're still trying to tax our coal industries out of existence for generating this valuable raw material as a by-product.)

"Robert Dorner and his colleagues are looking at converting CO2 and hydrogen (both won from sea-water) over catalysts, using the CO2 as a building block to form synthetic fuel. This reaction is energetically not favored and thus a catalyst is needed, which will lower the energy barrier of the reaction and increase the rate at which it occurs. The energy utilized to convert CO2 and hydrogen is also harvested from the ocean, by taking advantage of the temperature gradient of the water with increasing depth, making the fuel CO2-neutral.

'CO2 conversion to hydrocarbons over catalysts has been known for several decades but has been shown very little research and development attention, as other technologies have been much cheaper and efficient in yielding cheap oil. However, with the increasing awareness of the impact CO2 has on the environment more and more attention is being directed at how to mitigate the effects CO2 has as a greenhouse gas. Most research to date however is focusing on the sequestration of CO2 in underground reservoirs.

Our research proposes the utilization of CO2 into fuel, recycling the gas and using it as a raw material rather than a waste product. In light of dwindling oil resources and the looming presence of peak oil, alternative fuels that are environmentally friendly and enhance energy security are of mounting importance. Our research is aiming at increasing productivity and selectivity of the desired products formed; thus reducing unwanted side-products and lowering costs, making this technology more economically feasible.'

—Robert Dorner"

("Our research proposes the utilization of CO2 into fuel, recycling the gas and using it as a raw material rather than a waste product." - We know it can be done. NASA is doing it now - using Sabatier's century-old technology.)

"The electrochemical reduction of carbon dioxide. The NRL work was followed by a presentation of work being done at the University of Liverpool (UK) on the electrochemical reduction of CO2, focused on surface structures of copper electrodes and the role of solution-based copper species for their catalytic effect on the reaction.


'The scientific community has known for several decades the ability of certain metals, particularly copper, to convert carbon dioxide into small organic molecules by using electricity as an energy source. This conversion of carbon dioxide occurs only at the interface between the metal surface and carbon dioxide gas. Studying such interfaces is challenging and presents novel research opportunities because the region where the chemistry occurs is of only nanometer dimensions, and therefore identifying specific reactions is like searching for a needle in a very large haystack.

Our work is unique in that we are creating highly controlled reaction environments and using advanced spectroscopic techniques that could, in the needle-in-haystack analogy, provide us an extremely powerful metal detector. This provides an excellent opportunity to study exactly how carbon dioxide transforms into useful, carbon-based, products.'

—Scott Shaw

The University of Liverpool work received support from the European Union ELCAT (Electrocatalytic gas-phase conversion of CO2 in confined catalysts) project. 

Other papers presented in the symposium included:

  • Methane-carbon dioxide reforming over Ni/CaO-ZrO2 catalyst.2 Researchers from the Chinese Academy of Sciences are investigating the carbon dioxide reforming of methane over an Ni/CaO-ZrO catalyst derived from co-precipitation method. The catalyst shows both high catalytic activity and stability at the methane and carbon dioxide ratio of 1:1. The characterization confirms that the nano-porous framework of as-prepared support together with the Ni-support interaction enhances the dispersion of Ni, and then promotes the resistance to sintering under reaction condition. As a result, carbon deposition is prevented, which is important for the catalyst stability. (We'll suppose them to be "reforming" methane, with CO2, to produce methanol and other higher hydrocarbons, as we've documented to be feasible.)

  • Ni-based nanocomposite catalysts for energy-saving syngas and hydrogen production from CH4/CO2 and CH4/CO2/H2O.2, MgO and Al2O3) catalysts as nanocomposites consisting of comparably sized metallic Ni nanocrystals and nanoparticles of “support” oxides. Compared with the conventional oxide-supported Ni catalysts, the nanocomposite catalysts are found extremely stable in catalyzing the methane reforming reactions using stoichiometric CO2 and methane as well as steam (H2O) and methane. (Keep in mind that "Syngas", as above, can also be generated from coal. And, the use of CO2 to both make methane (CH4), and then to "reform" it, into the syngas precursor of liquid fuels, has also been previously documented.) Researchers from Tsinghua University (China) are investigating energy-saving catalysts for natural gas conversion. They developed nanostructured Ni-oxide (oxide = ZrO

  • Photoreduction of CO2 to CO in the presence of H2 over various basic metal oxide photocatalysts. Researchers at Kyoto University (Japan) are exploring the chemical fixation of CO2 in the presence of a heterogeneous photocatalyst as a method for converting it into other carbon sources such as carbon monoxide (CO), formaldehyde (HCHO), formic acid (HCOOH), methanol (CH3OH), and methane (CH4). (The Japanese researchers, and others, are, as we've documented, developing an artificial and industrial-scale photosynthetic process.) 

  • Synthesis and characterization of ferrite materials for thermochemical CO2 splitting using concentrated solar energy. Researchers at Sandia National Laboratories are investigating the use of concentrated solar power to convert carbon dioxide and water to precursors for liquid hydrocarbon fuels (Sunshine to Petrol) using concentrated solar power. (We have previously documented for you this work at Sandia.)


  • Conversion of CO2 into methanol in a novel two-stage catalyst bed concept. Researchers from Shiraz University (Iran) are investigating a two-stage catalyst bed concept for conversion of CO2 to methanol. (Well, we really want an OPEC power to be getting the jump on us with this, don't we? Remember, once we have methanol, we can convert it to gasoline, as per Exxon-Mobil and their "MTG"(r) process, et. al.)



  • A number of other papers presented during the symposium focused on novel methods for carbon dioxide capture or adsorption of CO2 on a catalyst as a key step of the catalytic conversion of CO2 to liquid fuels."


The final phrase sums up the entire focus: "the catalytic conversion of CO2 to liquid fuels". And, the title of the conference should provide a catch phrase for all of us: Convert and utilize CO2. 

Don't tax the producers of CO2 out of existence through Cap & Trade shell games; and, don't waste CO2 by pumping it all down geologic sequestration rat holes. Carbon Dioxide is a valuable by-product of our coal use, whether we employ our coal to generate electricity or, as we should, convert our coal into the liquid fuels and chemical manufacturing raw materials we desperately need.