United States Patent: 8596047

We first noticed the exposition of Saudi Arabian CO2-to-fuel technology we bring to you herein back when it was "just" a United States Patent Application.

And, even though, as seen for one example in:

 

: Saudi Arabia and CO2: The Rich Get Richer | Research & Development | News; concerning; "'SABIC Unit Plans World’s Largest CO2 Purification Plant'; United Jubail Petrochemical Company, an affiliate of Saudi’s SABIC, has awarded a construction contract for the plant to Germany’s Linde Group. By Aarti Nagraj, August 21, 2013; An affiliate of Saudi Basic Industries Corporation (SABIC) announced that it has awarded a construction contract to build the world’s largest carbon dioxide (CO2) purification and liquefaction plant in the Kingdom. United Jubail Petrochemical Company (United), a manufacturing unit of SABIC, has given the engineering, procurement and construction contract for the project to Germany’s The Linde Group, it said in a statement. ... The plant will be designed to compress and purify about 1,500 tons per day of raw carbon dioxide coming from ethylene glycol plants. The purified gaseous CO2 will then be supplied through pipes to three SABIC-affiliated companies for enhanced methanol and urea production, the statement said. Methanol is a basic commodity for the chemical industry, and urea is used for fertilizer production. The plant will help save an estimated 500,000 tons of CO2 emissions each year, SABIC stated. Yousef Al-Zamel, SABIC executive vice president, Chemicals Strategic Business Unit, said: “It will add to SABIC’s business portfolio of industrial gas products.This is the first of many other similar projects to be executed next year;

it is becoming clear that Saudi Arabia has been getting pretty serious about treating Carbon Dioxide for what it truly is, i.e., a valuable and freely-available raw material resource, we held off on making report of it to you because of some doubts we had about it's technical viability.

We have a better handle on it now, and, so do the technical experts in our United States Patent and Trademark Office, who recently confirmed it's validity via issuance of, as excerpted from the initial link in this dispatch:

"United States Patent 8,596,047 - Vehicle Electrocatalyzer for Recycling Carbon Dioxide to Fuel Hydrocarbons

Saudi Arabia Improves CO2-to-Hydrocarbon Catalysis | Research & Development | News

Patent US8596047 - Vehicle electrocatalyzer for recycling carbon dioxide to fuel hydrocarbons - Google Patents

December 3, 2013

Inventors: R. A. K. Shawabkeh, et. al., Saudi Arabia 

Assignees: King Fahd University of Petroleum and Minerals and King Abdulaziz City for Science and Technology

Abstract: The vehicle electrocatalyzer for recycling carbon dioxide to fuel hydrocarbons includes a main tubular member having a plurality of tubular catalytic cells, electrically connected in series disposed inside and separated from one another by semipermeable membranes allowing the passage of fluids, but not solids. The electrocatalyzer can be attached in the exhaust system where hydrogen could be generated by the electrolysis of water. Metallic copper, iron, carbonaceous materials (such as activated carbon, carbon nanomaterials, or graphite), metal oxides, or metal-supported catalysts may be used in each catalytic cell. A DC current connected across the cells is used to initiate reaction of the carbon dioxide with hydrogen gas. The resulting hydrocarbons are recycled back to the vehicle engine and used as a makeup fuel.

Claims: A vehicle electrocatalyzer for recycling carbon dioxide to fuel hydrocarbons, comprising: a hollow outer shell adapted for mounting in an exhaust system of a vehicle; a plurality of multistage anodic and cathodic electrocatalytic cell modules electrically connected together and spaced at intervals, wherein adjacent cell modules have opposite polarities inside the hollow outer shell, each of the cell modules including a plurality of members having a nanoparticle coating, the nanoparticle coating being selected from the group consisting of metallic copper, iron, carbonaceous materials, metal oxides, and metal-supported catalysts; gas manifolds having a gas-out conduit and a gas-in conduit attached to respective opposing ends of the hollow outer shell to allow carbon dioxide gas flow through the electrocatalyzer; fluid manifolds having a fluid-out conduit and a fluid-in conduit attached to respective opposing ends of the hollow outer shell to allow electrolytic fluid flow through the electrocatalyzer; and gas-fluid permeable isolation membranes disposed between the electrocatalytic cell modules; and wherein, when the gas manifold is connected in a feedback loop to a vehicle exhaust system and the fluid manifold is connected to cycle electrolyte through the electrocatalyzer and the cells are subjected to voltage across the cells while maintaining the opposing polarities of adjacent cell modules, carbon dioxide flowing through the electrocatalyzer is converted to selected hydrocarbon fuels based on the nanoparticle coating of each of the electrocatalytic cell modules, the hydrocarbon fuel being adapted for recycling to fuel a combustion engine of the vehicle. 

The vehicle electrocatalyzer ... further comprising a DC voltages source applying a direct current to the cell modules (and) further comprising an AC voltage source applying an alternating current to the cell modules. 

The vehicle electrocatalyzer ... further comprising means for generating hydrogen by electrolysis of water (as disclosed and described in continuing claims). 

A vehicle electrocatalyzer for recycling carbon dioxide to fuel hydrocarbons, comprising: a hollow outer shell; a plurality of multistage anodic and cathodic electrocatalytic cell modules electrically connected and spaced at intervals, wherein adjacent cell modules have opposite polarities inside the hollow outer shell, each of the cell modules including a plurality of members having a nanoparticle coating, the nanoparticle coating being selected from the group consisting of metallic copper, iron, carbonaceous materials, metal oxides, and metal-supported catalysts; gas manifolds having a gas-out conduit and a gas-in conduit attached to respective opposing ends of said hollow outer shell to allow carbon dioxide gas flow through the electrocatalyzer; and gas permeable isolation membranes disposed between the electrocatalytic cell modules; wherein, when the gas manifold is connected in a feedback loop to a vehicle exhaust system and the cells are subjected to voltage across the cells maintaining the opposing polarities of adjacent cell modules, carbon dioxide flowing through the electrocatalyzer is converted to selective hydrocarbon fuels based on the nanoparticle coating of each of the plurality of electrocatalytic cell modules, the hydrocarbon fuels being adapted for recycling to fuel a combustion engine of the vehicle.

(Regarding the above "metal-supported catalysts", we remind you of a report we made just this past Halloween, concerning the Saudi development of such catalysts:

Saudi Arabia Improves CO2-to-Hydrocarbon Catalysis | Research & Development | News; which was intended to center on: "United States Patent Application 20130256123 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide".

Unfortunately, as too-often happens because of our current isolated living circumstances and the frequent technical difficulties that arise in our communication facilities because of that isolation, the full text of our dissertation concerning that patent application, and all of our excerpts from it, didn't make it through during transmission. If you read that dispatch, and were somewhat puzzled by it's apparent lack of focus, that might be why. In any case, it did concern:

"'United States Patent Application: 0130256123 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide'; October 3, 2013; Inventors: Saleem Ur Rahman, et. al., Saudi Arabia and India; Assignees: King Abdulaziz City for Science and Technology and King Fahd University of Petroleum and Minerals; Saudi Arabia; Abstract: An electrocatalyst for the electrochemical conversion of carbon dioxide to hydrocarbons is provided. The electrocatalyst for the electrochemical conversion of carbon dioxide includes copper material supported on carbon nanotubes. The copper material may be pure copper, copper and ruthenium, copper and iron, or copper and palladium supported on the carbon nanotubes. The electrocatalyst is prepared by dissolving copper nitrate trihydrate in deionized water to form a salt solution. Carbon nanotubes are then added to the salt solution to form a suspension, which is then heated. A urea solution is added to the suspension to form the electrocatalyst in solution. The electrocatalyst is then removed from the solution. In addition to dissolving the copper nitrate trihydrate in the deionized water, either iron nitrate monohydrate, ruthenium chloride or palladium chloride may also be dissolved in the deionized water to form the salt solution. Claims: An electrocatalyst for electrochemical conversion of carbon dioxide, comprising a copper catalyst material supported on carbon nanotubes. Background and Field: The present invention relates to electrochemical catalysts, and particularly to an electrocatalyst for the electrochemical conversion of carbon dioxide to hydrocarbons, such as methanol and methane";

and, it appears to us to be specification of the, or one of the,  "metal-supported catalysts" designated by our subject herein, "United States Patent 8,596,047 - Vehicle Electrocatalyzer for Recycling Carbon Dioxide to Fuel Hydrocarbons", which was also developed by and at King Abdulaziz City for Science and Technology and King Fahd University of Petroleum and Minerals.

We'll readdress "US Patent Application 20130256123 - Electrocatalyst for Electrochemical Conversion of Carbon Dioxide" with a more coherent dissertation when and if it finally transitions to an issued US Patent.)

Background and Field: The present invention relates to devices for controlling motor vehicle emissions, and particularly to a vehicle electrocatalyzer for recycling carbon dioxide to fuel hydrocarbons. 

Catalytic converters are devices used to reduce the toxicity of exhaust emissions from an internal combustion engine. Inside a catalytic converter, a catalyst stimulates a chemical reaction in which noxious byproducts of combustion (such as carbon monoxide, unburned hydrocarbons, and oxides of nitrogen) are converted to less-toxic or inert substances, such as carbon dioxide, hydrogen, nitrogen and oxygen. These devices, however, fail to deal with carbon dioxide (CO2) ... (and) with the ever rising gas prices there is a push to increase fuel economy. Thus, at least the two aforementioned concerns have not adequately been dealt with until now. 

Thus, a vehicle electrocatalyzer for recycling carbon dioxide to fuel hydrocarbons solving the aforementioned problems is desired.

Summary: The vehicle electrocatalyzer for recycling carbon dioxide to fuel hydrocarbons includes a tubular member having a plurality of catalytic cells electrically connected in series and separated from one another by semipermeable membranes that allow the passage of fluids, but not solids. The electrocatalyzer can be attached in the vehicle's exhaust system, where hydrogen could be generated by the electrolysis of water. Metallic copper, iron, carbonaceous materials (such as activated carbon, carbon nano-materials, or graphite), metal oxides, or metal-supported catalysts may be used in each catalytic cell. A DC current connected across the cells is used to initiate reaction of the CO2 with hydrogen gas. The resulting hydrocarbons are recycled back to the vehicle engine and used as a makeup fuel. The electrocatalyzer will decrease the total fuel consumption in the vehicle and will be an environmentally friendly device.

One of the main products from a direct reaction of carbon dioxide with hydrogen using this system is, but is not limited to, ethylene.

Thus, there is no need to convert the CO2 to CO by a reverse water shift reaction. Therefore, the system  does not target only methanol or methane.

Moreover, the electrocatalyzer can be used to recycle CO2 from vehicles and/or power plants. 

The electrocatalyzer converts carbon dioxide to a selected hydrocarbon, such as ethylene, by combining the effects of absorption and adsorption, where CO2 is absorbed by electrolytic solution, then gets adsorbed on the surface of a nanocatalyst for higher yield and conversion. The nanocatalyst provides enhanced selectivity of the target hydrocarbon for conversion of CO2 to hydrocarbons. For different nanocatalysts, each catalyst will yield a selective product, such as C1-C6 hydrocarbons, alcohols, ethers, or carboxylic acids.

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Note that this technology can, as well, serve to recycle "CO2 from ... power plants", with some obvious, and perhaps more valuable, implications. It isn't just for application to "vehicles" and the CO2 emissions from internal combustion engines; the title, "United States Patent 8,596,047 - Vehicle Electrocatalyzer for Recycling Carbon Dioxide to Fuel Hydrocarbons", notwithstanding. 

Note, further, that the water which is to be electrolyzed, to render the needed Hydrogen, is, as is CO2, a component of automotive exhaust.

Even further, this is a technology much like that seen to have been developed by our United States Department of Energy and it's contractors as, for one example, seen in:

USDOE 2013 Solar CO2 + H2O = Methanol + Methane | Research & Development | News; concerning: "United States Patent Application 20130256147 - Solar Fuels Generator; Date: October 3, 2013;  Inventors: Nathan S. Lewis and Joshua Spurgeon, CA (California Institute of Technology); Abstract: The solar fuels generator ... . Government Interests: This invention was made with government support under DE-SC000493/T-105066 awarded by the Department of Energy. The government has certain rights in the invention. (In some embodiments) CO2 serves as the reactant that is delivered to the photocathodes. Examples of the fuels that can be produced using this reaction in combination with the disclosed solar fuels generator include ... methanol, methane, ethanol";

wherein hydrocarbons and fuel alcohols are synthesized rather directly from Carbon Dioxide and Hydrogen, as extracted from water, as opposed to "syntrolysis"-type processes, like that disclosed in:

USDOE Converts More CO2 into Hydrocarbon Syngas | Research & Development | News;

concerning: "'United States Patent 7,951,283 - High Temperature Electrolysis for Syngas Production'; Date: May 31, 2011; Inventor: Carl Stoots, et. al., Idaho; Assignee: Battelle Energy Alliance (Idaho National Laboratory; USDOE); Abstract: Syngas components hydrogen and carbon monoxide may be formed by the decomposition of carbon dioxide and water or steam by a solid-oxide electrolysis cell to form carbon monoxide and hydrogen, a portion of which may be reacted with carbon dioxide to form carbon monoxide ... . Government Interests: This invention was made with government support under DE-AC07-05ID14517 awarded by the United States Department of Energy. The government has certain rights in the invention. Claims: A method for producing at least one syngas component (from) water and carbon dioxide (in a) solid-oxide electrolysis cell (and) further comprising routing the hydrogen and the carbon monoxide to a synfuel production process";

wherein Carbon Dioxide and Water and first separated into Carbon Monoxide and Hydrogen, or synthesis gas, which "syngas" is then, separately, catalytically condensed, as via, for just one example, the nearly ancient Fischer-Tropsch process, into hydrocarbons.

Some obvious objections will be made that, given energy balances, this process likely couldn't recycle all of the CO2 produced by a vehicle, or completely replace an external fuel supply, and, that, some additional source of energy, in addition to the exhaust gas heat which is specified for use, would be needed.

Both objections are correct, and, the Saudi inventors state in the full Disclosure that the recycled Carbon Dioxide, or the hydrocarbons synthesized from it, would serve only as a supplement to externally-derived fuel, thus increasing the vehicle's gas mileage and economy.

Further, and we might eventually get around to making report of it, Saudi Arabian scientists are among those who have been working diligently to improve solar energy conversion technology, and, they have designed automobiles, and built and operated prototypes, which are, in essence, just big, hollow photovoltaic cells on wheels. And, such technology could no doubt be applied in concert with the process of our subject, "United States Patent 8,596,047 - Vehicle Electrocatalyzer for Recycling Carbon Dioxide to Fuel Hydrocarbons".

If the Saudi technology disclosed herein were to be installed, as they suggest, at "power plants", other supplemental forms of energy, like wind or hydro, might be available; and, instead of fuels like "C1-C6 hydrocarbons", products like the specified alternatives "alcohols, ethers, or carboxylic acids", could be made from the exhaust gas Carbon Dioxide, and subsequently consumed in the synthesis of a variety of plastics and polymers, wherein the initial raw material CO2 would remain, chemically and permanently, and productively and profitably, "sequestered"; and, which CO2-based plastics and polymers would enable us to reduce even further our imports of OPEC, Saudi Arabian, petroleum to be used as raw material for the synthesis of those polymers.

As we'll see in reports to follow, as we've seen in others prior, the United States and it's allies and partners have been at work developing Carbon Dioxide utilization processes similar to that devised and herein disclosed by Saudi Arabia. And, we better get off our dead cans insofar as it comes to educating ourselves, or being educated, about those CO2-utilization processes and putting them to work.

Otherwise, all of us poor folks resident in US Coal Country will wind up being too impoverished from buying Carbon-taxed electricity to be able to afford to buy any of those hydrocarbon fuels and plastics Saudi Arabia will be wanting to export to us; hydrocarbon fuels and plastics made, as herein, from Carbon Dioxide.


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