WV Coal Member Meeting 2024 1240x200 1 1

Stanford University Solar CO2 to Hydrocarbon Fuels


In our prior report of:

Stanford Converts CO2 to Methane | Research & Development | News; concerning the technical paper:

"Electrocatalytic conversion of carbon dioxide to methane and oxygen with an oxygen ion-conducting electrolyte; Authors: Gurt, T.M.; Wise, H.; Huggins, R.A.; Affiliation: Stanford University; Dept. of Materials Science Engineering; Stanford, CA; Publication: Journal of Catalysis, 1991, vol. 129, pp. 216-224; Abstract: The performance characteristics of a solid-state electrochemical cell have been examined for the catalytic conversion of carbon dioxide and hydrogen to methane and oxygen. The electrolyte, made up of yttria-stabilized zirconia (YSZ), served the dual function of (a) a support material for the platinum catalyst, and (b) an oxygen ion-conducting membrane for the removal of surface oxygen formed during the reaction. The results indicate a linear increase in reaction rate with DC bias applied across the solid electrolyte. The reaction proceeds by way of a stepwise abstraction of oxygen atoms from carbon dioxide and hydrogenation of surface carbon to methane";

we documented, that, very nearly one-quarter of a century ago, California's prestigious Stanford University had been at work establishing and reporting on technology whereby Carbon Dioxide, as harvested from whatever convenient source, could be directly and efficiently used and consumed as the key, basic raw material in the industrial synthesis of substitute, fracking-free natural gas Methane.

Further, as seen in our additional report of:

Stanford University Converts CO2 to Methane | Research & Development | News; concerning: "United States Patent 4,404,068 - Solid State Method for Synthesis Reactions; 1983; Inventors: Robert Huggins and Turgut Gur, California; Assignee: Stanford University; Abstract: A method for synthesizing reaction products, such as hydrocarbons, from fluid reactants is provided by use of a solid state electrochemical cell. A preferred embodiment may be used to produce methane at a substantially enhanced, controllable rate. Claims: A method for synthesizing a reaction product comprising the steps of: providing an electrochemical cell having a first electrode, a second electrode, and a solid state electrolyte intercommunicating said first and second electrodes, said electrolyte adapted to permit ions to flow there-across; (And) contacting a first fluid reactant with said first electrode, ... (and) forming a reaction product at said first electrode in the presence of at least a second fluid reactant, said reaction product derived from said first reactant residue and at least said second reactant. (And) wherein reactants are in gaseous form. (And) wherein: said first reactant is CO or CO2 and said second reactant is H2. 
(And) wherein: said reaction product is methane";

Stanford University had clearly been at work developing processes for the conversion of Carbon Dioxide into substitute natural gas Methane for at least a decade prior to their open publication of  the paper: "Electrocatalytic conversion of carbon dioxide to methane and oxygen with an oxygen ion-conducting electrolyte".

And, although we haven't done as good a job of documenting the fact as perhaps we should have, Stanford University has continued to remain involved in the development of what we might now more consistently label as processes of "artificial photosynthesis", wherein solar light energy, or the low-grade and intermittent electrical power that can be generated via solar photovoltaic technology, provides sufficient energy to drive the conversion of Carbon Dioxide, in combination with Water, H2O, into a full range of hydrocarbon fuels and related products.

Another organization involved in the development of catalytic technologies for the productive use and consumption of Carbon Dioxide is, as seen for one example in our report of:

Denmark Converts CO2 to Methane and Carbon Monoxide | Research & Development | News; concerning: "United States Patent 5,496,530 - Process for the Preparation of Carbon Monoxide Rich Gas; 1996; Inventors: Rickard Vannby and Charlotte Nielsen, Denmark; Assignee: Haldor Topsoe, Denmark; Abstract: Process for the preparation of carbon monoxide rich gas comprising reacting a mixed gas of hydrogen and carbon dioxide in the presence of a conversion catalyst to carbon monoxide rich gas, which process further comprises reacting part of the carbon dioxide and hydrogen in the gas feed exothermically to methane simultaneously with the carbon monoxide producing reaction and carrying out both reactions under adiabatic conditions, so that the exothermical methane producing reaction provides necessary heat for the endothermic carbon monoxide producing reaction";

the major Danish chemical technology company, Haldor Topsoe, of which additional information included in the above report says: "Haldor Topsoe is a Danish catalyst company ... founded in 1940. The company ...  develops process technology for petroleum refining, ammonia production, methanol production, and other industries. Haldor Topsoe specialises in the production of heterogeneous catalysts and the design of process plants based on catalytic processes. Focus areas include the fertiliser industry, chemical and petrochemical industries, and the energy sector (refineries and power plants)".

More about them can be learned via the link to their company web site:

Haldor Topsoe .

And, herein we find, that, at a European conference sponsored by Haldor Topsoe, convened in Denmark in August of 2011, and devoted to the exposition of advanced catalytic chemical technology, Stanford University disclosed further advances they've made in the technology for using and consuming Carbon Dioxide as the basic raw material in the synthesis of simple hydrocarbons, and other products, in processes which have energy demands low enough that they can be driven by "solar power".

Comment follows and is inserted within excerpts from the initial link in this dispatch to:

"Semiconductors and Catalysts for the Production of Solar Fuels


(We're including a separate, somewhat different link to the presentation. Both the initial link in this dispatch and the one immediately above function at the time of this writing.)

Prof. Thomas F. Jaramillo, Kendra Kuhl, Etosha Cave, David Abram

Dept. of Chemical Engineering; Stanford University

Topsoe Catalysis Forum; Munkerupgaard, Denmark

Jaramillo Research Group: Reactions of Interest: CO2 + nH+ + ne (=) CxHy + CaHbOH + cH2O

(The above "CxHy + CaHbOH", we are told, represent general formulas for, or generic representations of, hydrocarbons and alcohols. That is further confirmed in following slides; and, the remainder of our excerpts represent only a minor portion of the full presentation.)

Fuel Production From Renewable Resources: nCO2 + m(H+ + e) = alcohols + hydrocarbons + H2O

(Accompanying illustrations suggest the use of solar and wind energy to drive the "electroreduction" of Carbon Dioxide and Water into "Fuel", i.e., "alcohols + hydrocarbons". One technical note: Stanford refers to the process of extracting the needed Hydrogen, "H+", from Water, H2O, as the "Oxygen evolution" reaction, or process.)

(Slide 5):  The importance of PEC H2 production: DOE Hydrogen Production Roadmap; “Technoeconomic Analysis of Photoelectrochemical (PEC) Hydrogen Production,” DOE Contract # GS10F009J.

(Slide 9): CO2 + 2H+ + 2e = CO + H2O; CO2 + 8H+ + 8e = CH4 + 2H2O; 2CO2 + 12H+ + 12e =  C2H4 + 4H2O; 2CO2 + 12H+ + 12e = C2H5OH + 3H2O; 3CO2 + 18H+ + 18e = C3H7OH + 5H2O

(The above confusing string is more intelligibly presented on the slide itself. The various products of Carbon Dioxide/H2O electroreduction/conversion, such as, for example, "CH4", i.e., Methane, and "C2H4", Ethylene, can, as seen for just a few examples in our reports of:

Columbia University Converts CO2 to Ethylene | Research & Development | News; concerning: "US Patent Application 20130048506 - Electrodes for High Efficiency Aqueous Reduction of CO2; 2013; Inventor: Ed Chen, NY; Assignee: The Trustees of Columbia University in the City of New York; Abstract: An electrolytic cell system to convert carbon dioxide to a hydrocarbon that includes a first electrode including a substrate having a metal porous dendritic structure applied thereon; a second electrode, and an electrical input adapted for coupling to a source of electricity, for applying a voltage across the first electrode and the second electrode. The electrolytic cell system ... wherein the metal is copper. ... A method of converting carbon dioxide to a hydrocarbon comprising: providing an electrolytic cell that includes (a) a first electrode including a substrate having a metal porous dendritic structure applied thereon; (b) a second electrode, and (c) an electrical input adapted for coupling to a source of electricity, for applying a voltage across the first electrode and the second electrode; introducing a source of carbon dioxide to the electrolytic cell; and applying the voltage across the first electrode and the second electrode. ... The method ... wherein the carbon dioxide is obtained from an air stream, a combustion exhaust stream, or a pre-existing carbon dioxide source. 
The method ... wherein the hydrocarbon
(produced) is ethylene"; and:

Chicago Converts CO2 into Methane and Ethylene | Research & Development | News; concerning: "United States Patent 4,897,167 - Electrochemical Reduction of CO2 to CH4 and C2H4; 1990; Inventors: Ronald Cook, et. al., Illinois; Assignee: Gas Research Institute, Chicago; Abstract: A process for electrochemical reduction of CO2 to CH4 (methane) and C2H4 (ethylene) providing both high current densities and high Faradaic efficiencies. The process is carried out in an electrochemical cell wherein copper is electrodeposited in situ on the cathode surface making freshly deposited copper available for the electrochemical reduction. Faradaic efficiencies of about 75 to about 98 percent for production of CH4 and C2H4 are obtained";

be synthesized from Carbon Dioxide and water via a number of similar and related electro-catalytic processes. The quarter-century-old Gas Research Institute process of  the above "United States Patent 4,897,167 - Electrochemical Reduction of CO2 to CH4 and C2H4" is noteworthy, we think, since it clearly demonstrates that CO2 and H2O can be converted into multiple valuable products in catalytic processes that don't seem to require the input of a lot of energy to drive them.)

(Slide 16): Product Distribution (of CO2 aqueous electro-reduction at) 1.05 V: Methane 30.95%; Ethylene 25.84%; Hydrogen 22.64%; (etc.)

(Since elemental, molecular "Hydrogen" is one of the major products, along with substitute shale gas "Methane" and the valuable hydrocarbon "Ethylene", being generated so efficiently from Carbon Dioxide and Water, we remind you, that, as explained for only one example in our report of: 

NASA 2014 CO2 to Methane | Research & Development | News; concerning: "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 2014; Inventors: Christian Junaedi, et. al., CT; Assignee: Precision Combustion, Inc., CT; Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen ... so as to produce a product stream comprising water and methane. ... Government Support: This invention was made with support from the U.S. government under U.S. Contract No. NNX10CF25P sponsored by the National Aeronautics and Space Administration. The U.S. Government holds certain rights in this invention";

such co-product Hydrogen can then, if wanted, be directly and efficiently reacted with even more Carbon Dioxide, with both the H2 and the CO2 then being converted into even more synthetic natural gas Methane.)

(Slide 17): Products (of CO2 aqueous electro-reduction on Copper electrode): Carbon Monoxide, Methanol, Methane, Ethylene, Ethylene Glycol, Ethanol, Propanol, (etc.)

(Note, again, that, valuable liquid fuels, such as "Methanol" and "Ethanol", too, can be directly produced via the "electro-reduction" of Carbon Dioxide and Water - - a fact which, as seen in our report of:

USDOE 1976 Atmospheric CO2 to Methanol | Research & Development | News; concerning: "United States Patent 3,959,094 - Electrolytic Synthesis of Methanol from CO2; 1976; Inventor: Meyer Steinberg, NY; Assignee: The USA as represented by the USDOE";

our United States Government formally established four decades ago.),

(Slide 23): (A) variety of metals can ... reduce CO2 to hydrocarbons and alcohols (and) H2 and CO are major reaction products.

(Keep in mind that the "H2 and CO", Hydrogen and Carbon Monoxide, taken together, comprise a hydrocarbon synthesis gas, or "syngas", which can as well be chemically, catalytically condensed, as via the now nearly-ancient Fischer-Tropsch process, into a full range of both gaseous and liquid hydrocarbons.)

(Slide 26): Metal chemistry is very rich for the electroreduction of CO2 to fuels."


We'll close our excerpts there. Slides don't lend themselves to piecemeal extraction of information; and, the presentation was no doubt made personally by one of Stanford University's named investigators, i.e., "Prof. Thomas F. Jaramillo, Kendra Kuhl, Etosha Cave, David Abram", who would have no doubt more fully explained the information as it was presented and then been available to answer questions.

That Stanford team, however, has continued to work on the development of technology for the productive utilization of Carbon Dioxide, as illustrated in our subject, "Semiconductors and Catalysts for the Production of Solar Fuels", and, we will be following up on their further achievements in that arena in future reports.

But, be assured:

We can, if we really and honestly do want to wake up to - and openly acknowledge - the fact, use and consume nothing but water and solar energy to convert "CO2 to fuels".