WV Coal Member Meeting 2024 1240x200 1 1

Denmark 2015 CO2 + H2O = Hydrocarbons

United States Patent Application: 0150118592

We've already made many reports on other versions of the core technology recorded herein, disclosed in a document published by the United States Government just yesterday, for the electrochemical conversion of Carbon Dioxide, as reclaimed from whatever handy source, and Water, H2O, into both simple hydrocarbon fuels and/or a synthesis gas blend of Carbon Monoxide and Hydrogen, which "syngas" can be catalytically, chemically condensed, as via for one example the nearly-ancient Fischer-Tropsch process, into various hydrocarbon fuels and chemicals.

The United States Department of Energy and their contractors have been at work developing such technology for a number of years, as seen in our reports of:  

USDOE Converts CO2 into Methane via "Syntrolysis" | Research & Development | News; concerning: "Results of Recent High Temperature Co-Electrolysis Studies at the Idaho National Laboratory; 2007; For the past several years, the Idaho National Laboratory (INL) and subcontractor Ceramatec, Inc. have been studying the ... high temperature coelectrolysis of steam/CO2 mixtures to produce syngas: the raw material for synthetic fuels production. The INL and Ceramatec have been conducting experiments to characterize the electrochemical performance of coelectrolysis, as well as validate INL- developed computer models. An inline methanation reactor has also been tested to study direct methane production from coelectrolysis products. It is also feasible to produce syngas by separately electrolyzing steam and CO2. There are, however, significant advantages to electrolyzing steam and CO2 simultaneously, the primary one of which is electrical efficiency. For a given solid oxide electrolysis cell, pure CO2 electrolysis will exhibit a higher area specific resistance (ASR) than steam electrolysis. This is due to the slower overall kinetics of CO2 electrolysis and the higher overpotentials required. In coelectrolysis, the reverse gas shift reaction is relied upon for most of the CO production and therefore the overall electrical requirement is less. ... The Idaho National Laboratory has demonstrated the feasibility of using high temperature solid oxide cells to coelectrolyze H2O and CO2 simultaneously to produce syngas (and, the) concept of directing coelectrolysis products through a methanation reactor was tested, with yields of 40-50 volume % methane being produced. Overall, the coelectrolysis process appears to be a promising technique for large-scale syngas production"; and:

Utah Recycles CO2 | Research & Development | Newsconcerning: "Co-Electrolysis of Steam and Carbon Dioxide as Feed to a Methanation Reaction; Lyman Frost, Joseph Hartvigsen and S. Elangovan; Ceramatec, Inc, Salt Lake City, UT; Abstract: Solid oxide fuel cells can be operated in reverse by applying an electric potential across the fuel cells and forcing the oxygen ion to flow in the opposite direction from the fuel cell mode. If a mixture of high temperature steam and carbon dioxide are fed to a fuel cell stack operating in this electrolysis mode, the result will be a mixture of carbon monoxide and hydrogen. By adjusting the input ratios of steam and carbon dioxide, the output of the electrolysis system can be modified to be in the proper ratio for the formation of a number of different hydrocarbons by catalytic process through either Fischer Tropsch or methanation reactions. This paper will report on work being done at Ceramatec on use of proprietary Ceramatec solid oxide fuel cell materials operating in a high temperature electrolysis mode. The paper will report on the durability of the materials in this endothermic mode of operation and will provide data on the variation in percentages of output gases (synthesis gas) dependent on the input gas stream. The operation of a small methanation reactor on the synthesis gas will be described and the reaction results will be documented and reported".

Other nations of the world, as well, have been at work developing such "co-electrolysis" technology, sometimes called "syntrolysis"; and, the European country which is featured in our report today, Denmark, has, as seen in:

Denmark Recycles CO2 via Syntrolysis | Research & Development | News; concerning:  "Co-electrolysis of CO2 and H2O in Solid Oxide Fuel Cells; 2010; Authors: Christopher Graves, et. al.; Affiliations: National Laboratory for Sustainable Energy, Denmark; and, Columbia University, NY; Abstract: This study examines the initial performance and durability of a solid oxide cell applied for co-electrolysis of CO2 and H2O. Such a cell, when powered by renewable/nuclear energy, could be used to recycle CO2 into sustainable hydrocarbon fuels";

already been documented to be developing those more advanced CO2-to-fuel processes. And, in Denmark, as seen in:

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";

current developments in syntrolysis technology might be seen as having grown out of earlier corporate research into related Carbon Dioxide utilization processes.

In this dispatch, we learn that a very significant institution of higher learning in Denmark has continued to develop and advance the technology for co-electrolyzing Carbon Dioxide and Water, with the result being the publication, again just yesterday, of:

"United States Patent Application 20150118592 - High-Performance Reversible Electrochemical Cell for H2O Electrolysis or Conversion of CO2 and H2O to Fuel


Date: April 30, 2015

Inventors: Frank Allebrod, et. al., Denmark

Assignee: Danmarks Tekniske Universitet

(About DTU - Technical University of Denmark; "For almost two centuries DTU, Technical University of Denmark, has been dedicated to fulfilling the vision of H.C. Orsted - who founded the university in 1829 to develop and create value using the natural sciences and the technical sciences to benefit society. Today, DTU is ranked as one of the foremost technical universities in Europe".

Technical University of Denmark - Wikipedia, the free encyclopedia; "The Technical University of Denmark (DanishDanmarks Tekniske Universitet), often simply referred to as DTU, is a university in Kongens Lyngby, just north of Copenhagen, Denmark. It ... is today ranked among Europe's leading engineering institutions, and the best engineering university in the Nordic countries".)

Abstract: The present invention relates to a reversible electrochemical cell, such as an electrolysis cell for water splitting or for conversion of carbon dioxide and water into fuel. The present invention relates also to an electrochemical cell that when operated in reverse performs as a fuel cell. The electrochemical cell comprises gas diffusion electrodes and a porous layer made of materials and having a structure adapted to allow for a temperature range of operation between 100-374 C and in a pressure range between 3-200 bars.

(Concerning the above, the USDOE syntrolysis technology is often described, as we have reported, as like a fuel cell operated in reverse. Thus, when a syntrolysis, or co-electrolysis, cell is "operated in reverse" it could, conceptually, work like "a fuel cell". If you're not familiar with what a fuel cell is, see:

Fuel cell - Wikipedia, the free encyclopedia; wherein, in a detailed article, we're told, in part: Fuel cells come in many varieties; however, they all work in the same general manner. They are made up of three adjacent segments: the anode, theelectrolyte, and the cathode. Two chemical reactions occur at the interfaces of the three different segments. The net result of the two reactions is that fuel is consumed, water or carbon dioxide is created, and an electric current is created, which can be used to power electrical devices".

When operated in reverse, as in the technology disclosed herein, "electric current" is used to convert the products of combustion, "water" and "carbon dioxide", back into Hydrogen, Carbon Monoxide, and Oxygen. If you've no idea what a "gas diffusion electrode" might be, see:

Gas diffusion electrode - Wikipedia, the free encyclopedia; "Gas diffusion electrodes (GDE) are  electrodes with a conjunction of a solid, liquid and gaseous interface, and an electrical conducting  catalystsupporting an electrochemical reaction between the liquid and the gaseous phase".)

Claims: An electrochemical cell comprising: at least two porous gas diffusion electrodes, wherein said at least one of said at least two porous gas diffusion electrodes comprises doped strontium titanate; a ceramic porous layer, wherein said porous layer is located in between said at least two porous gas diffusion electrodes and wherein said ceramic porous layer comprises an aqueous electrolyte immobilized in said ceramic porous layer, wherein said ceramic porous layer has (a structure as specified) and ... the formula (comprising) a combination of the elements Calcium, Strontium, and Barium; (and) Titanium, Zirconium, Hafnium and Cerium (combined with) lanthanide elements (as specified); or wherein said ceramic porous layer is an alkaline earth metal titanate; or wherein said ceramic porous layer is a metal carbide; or wherein said porous layer is a metal nitride; whereby said electrochemical cell withstands a temperature range between 100-374 C and a pressure range between 3-200 bars, allowing for said electrochemical cell to operate within that temperature and pressure range (and) wherein said aqueous electrolyte is an aqueous solution of (Hydrogen, Lithium, Sodium, Potassium, Rubidium, or Cesium - Chloride, Bromide or Iodide).

(We're condensing and summarizing the chemical formula and specifications in the extreme for clarity in presentation herein. The chemistry, though, is not complex. One of the possible options for making the "aqueous electrolyte" would be "Sodium ... Chloride", i.e., table salt.)

The electrochemical cell ...  wherein said at least one of said at least two porous gas diffusion electrodes comprises Nickel, a Nickel alloy or Nickel--Cobalt (and) wherein said at least one of said at least two porous gas diffusion electrodes comprises a ceramic material.

(The Claims go into some detail concerning specification of the "gas diffusion electrodes". As seen in our report of:

New Jersey Improves CO2 Recycling Technology | Research & Development | News; concerning: "United States Patent Application 20130105304 - High Surface Area Electrodes for the Electrodes for the Electrochemical Reduction of Carbon Dioxide; 2013; Inventors: Jerry Kaczur, et. al., FL, NY, NJ, and CA; Assignee: Liquid Light, Inc., NJ; Abstract: Methods and systems for electrochemical conversion of carbon dioxide to organic products including formate and formic acid are provided. A system may include an electrochemical cell including a cathode compartment containing a high surface area cathode and a bicarbonate-based catholyte saturated with carbon dioxide. The high surface area cathode may include an indium coating and having a void volume of between about 30% to 98. The system may also include an anode compartment containing an anode and an acidic anolyte. The electrochemical cell may be configured to produce a product stream upon application of an electrical potential between the anode and the cathode. Background and Field: The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical reduction of carbon dioxide using high surface area electrodes";

they are known and are being improved upon by various organizations and companies for use in Carbon Dioxide utilization processes like that disclosed herein.)

The electrochemical cell ... wherein at least one of said at least two porous gas diffusion electrodes is loaded with a catalyst. 

A method of using an electrochemical cell ... comprising: providing the electrochemical cell ... and producing hydrogen and oxygen from water with said electrochemical cell (or) producing a synthetic fuel from carbon dioxide and water with said electrochemical cell.

The electrochemical cell ... wherein at least one of said at least two porous gas diffusion electrodes comprises a metal foam.

An electrochemical cell stack, said stack comprising: at least two electrochemical cells ... and a bipolar plate located in between said at least two electrochemical cells, wherein said bipolar plate comprises at least one metal foil located in between at least two sheets of metal foam (and) wherein said at least two sheets of metal foam are Nickel based foam sheets and said at least one metal foil is a dense Ni-foil.

Background and Field: The present invention relates to an electrochemical cell which can perform either water splitting or fuel synthesis. The present invention relates also to an electrochemical cell that when operated in reverse performs as a fuel cell. The invention further relates to a method of producing an electrochemical cell which can perform either water splitting, co-electrolysis of CO2 and water, or fuel synthesis and when operated in reverse can perform as a fuel cell.

Electrolysis can play an important role for energy storage purposes. 

In particular, efficient transformation of excess electricity into fuel, such as hydrocarbons ... may offer a sustainable solution for the energy requirements of the transportation system without the need for a change in transportation technology and infrastructure.

An electrolysis cell is generally characterized by three component parts: an electrolyte and two electrodes, i.e. a cathode and an anode. When driven by an external voltage applied to the electrodes, the electrolyte conducts ions that flow to and from the electrodes, where the reactions take place. The cathode and anode are characterized by the reduction and oxidation of the species that are present in the cell, respectively. For example, in water electrolysis with an aqueous alkaline electrolyte, water is reduced to hydroxide ions and hydrogen gas at the cathode, while hydroxide anions are oxidized to oxygen gas at the anode. Thus, water electrolysis is a method that uses electricity to drive the otherwise non-spontaneous chemical reaction of dissociation of water into oxygen and hydrogen gas.

Co-electrolysis is a method that uses electricity to drive the otherwise non-spontaneous chemical reaction of producing hydrocarbons or syngas by electrolysis of carbon dioxide and water.

(An) improved electrochemical cell would be advantageous, and in particular a more efficient and/or reliable electrochemical cell that is able to operate within intermediate-low temperatures would be advantageous.

Further, an improved electrolysis and co-electrolysis cell that can reversibly operate as a fuel cell would be advantageous.

Summary (Line Items 97-99): (In) some embodiments water electrolysis produces hydrogen gas at the cathode, the cathode being further loaded with a catalyst that can produce synthetic hydrocarbon fuel when fed with carbon dioxide that reacting with the H2 produces synthetic hydrocarbon fuel under the cell operating conditions.

In some other embodiments, co-electrolysis of carbon dioxide and water leads to carbon monoxide and hydrogen gas at the cathode upon reduction; the cathode being further loaded with a catalyst that can produce synthetic hydrocarbon fuel when CO and H2 react under the cell operating conditions.

In some further embodiments, reduction of CO2 leads to CO formation at the cathode; the cathode being further loaded with a catalyst that can produce synthetic hydrocarbon fuel when fed with water that together with the produced CO produces synthetic hydrocarbon fuel under the cell operating conditions. When the electrochemical cell is a co-electrolysis cell the cathode may comprise the catalyst.

This process produces hydrocarbons, such as methanol, CH3OH, from CO2 and water.

Other examples of producible hydrocarbons include methane, ethane, propane, ethylene, propene, ethanol, propanol, dimethylether and formaldehyde".


In sum, this another "co-electrolysis cell" in concept much like that seen for one example in our report of:

West Virginia Coal Association | Utah 2011 CO2 + H2O = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 8,075,746 - Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water; 2011; Assignee: Ceramatec, Inc.; Abstract: A method is provided for synthesizing synthesis gas from carbon dioxide obtained from atmospheric air or other available carbon dioxide source and water using a sodium-conducting electrochemical cell. Synthesis gas is also produced by the coelectrolysis of carbon dioxide and steam in a solid oxide fuel cell or solid oxide electrolytic cell. The synthesis gas produced may then be further processed and eventually converted into a liquid fuel suitable for transportation or other applications".

And, as we take it, the Technical University of Denmark proposes integrating the co-electrolysis cell components with catalysts that facilitate, in one combined process, the synthesis of stuff like "methane, ethane, propane, ethylene", etc., that is, "synthetic hydrocarbon fuel", in a combined, contiguous process from the synthesis gas formed "from CO2 and water".

Truth to tell, the full Disclosure of our subject, "United States Patent Application 20150118592 - High-Performance Reversible Electrochemical Cell for H2O Electrolysis or Conversion of CO2 and H2O to Fuel", is lengthy and detailed, there are some nuances to it beyond those we've included in our excerpts, and it would take someone well-educated in chemistry/electro-chemistry to fully explain it and to explain it well.

However, the sum of it is clear:

Carbon Dioxide, as we might conveniently harvest from the exhaust gases co-produced by our economically essential use of Coal in the generation of abundant, reliable and truly affordable electric power, can be seen and treated as a valuable raw material resource.

Carbon Dioxide can, in combination with plain old Water as the only other raw material needed, be used and consumed as the key raw material in the synthesis of a wide variety of hydrocarbon fuels and chemicals now derived from increasing scarce and increasingly expensive conventional sources.

Those hydrocarbons include the immensely valuable fuel alcohols "methanol" and "ethanol", both of which can, in known processes such as ExxonMobil's "MTG"(r), methanol-to-gasoline technology, be further converted into Gasoline; and, other hydrocarbons such as "formaldehyde", which has wide utility in the further synthesis of a range of plastics, or polymers, in which the Carbon Dioxide consumed in the synthesis of the formaldehyde would remain forever, chemically and profitably, through the creation of new US Coal Country industries and new US Coal Country jobs,"sequestered".