United States Patent Application: 0120029095

Folks, it's about time we got real about Carbon Dioxide, ain't it?

It is a valuable raw material resource which we can recover from whatever handy source, whether, as in:

West Virginia Coal Association | WVU March 28, 2013, Economical Harvesting of Flue Gas CO2 | Research & Development; concerning: "United States Patent Application 20130078172 - Layered Solid Sorbents for Carbon Dioxide Capture; 2013; Inventors: Bingyun Li, et. al.; Assignee: West Virginia University Research Corporation, Morgantown; Abstract: A solid sorbent for the capture and the transport of carbon dioxide gas is provided ... . Government Interests: Certain embodiments of this invention were made with Government support in conjunction with the National Energy Technology Laboratory, Pittsburgh, Pa., under RES contract number DE-FE0004000 awarded by the U.S. Department of Energy. The Government may have certain rights in the invention. A method of capturing carbon dioxide from a pollutant source";

from the exhaust gases of industrial processes, or, as in:

West Virginia Coal Association | Columbia University August 2012 Practical CO2 Air Capture | Research & Development; concerning: "United States Patent 8,246,731 - Systems and Methods for Extraction of Carbon Dioxide from Air; 2012; Inventors: Klaus Lackner and Frank Zeman, NY; Assignee: The Trustees of Columbia University in the City of New York; Abstract: The present invention describes methods and systems for extracting, capturing, reducing, storing, sequestering, or disposing of carbon dioxide (CO2), particularly from the air. The CO2 extraction methods and systems involve the use of chemical processes. Methods are also described for extracting and/or capturing CO2 via exposing air containing carbon dioxide to - - a basic solution which absorbs carbon dioxide and produces a carbonate solution. The solution is causticized and the temperature is increased to release carbon dioxide, followed by hydration of solid components to regenerate the base";

from the atmosphere itself; and, then, as explained by our own National Aeronautics and Space Administration, NASA, in:

West Virginia Coal Association | NASA Rocket Fuel from CO2 | Research & Development; wherein we're told, in part, that: "methane can be manufactured ... via the Sabatier process: Mix some carbon dioxide (CO2) with hydrogen (H), then heat the mixture to produce CH4 and H2O - methane and water";

convert, via, as seen in:

Paul Sabatier - Biography of Paul Sabatier; "Sabatier was a French chemist who advanced the understanding of catalysts. He was awarded half the 1912 Nobel Prize in Chemistry (and, is) known for the Sabatier reaction where hydrogen reacts with carbon dioxide under high temperature and pressure to create methane and water using nickel as a catalyst";

the one-century old Sabatier process, into Methane.

Note, that, since NASA is proposing to utilize the Sabatier process to convert Carbon Dioxide into Methane; and, since, as above, the Sabatier process requires elemental, molecular Hydrogen to effect that conversion of Carbon Dioxide, NASA, as seen in:

West Virginia Coal Association | NASA Hydrogen from Water and Sunlight | Research & Development; concerning: "United States Patent 4,045,315 - Solar Photolysis of Water; 1977; Inventors: James Fletcher (pro-forma, we believe), Administrator, NASA; and, Porter R. Ryason; Abstract: Hydrogen is produced by the solar photolysis of water";

has also been at work developing the technology for employing freely-available environmental energy to extract the needed Hydrogen from plain old Water, H2O.

And, herein, we learn that NASA has, as well, through contractors, been further improving the technology, and the apparatus for operating that technology, which converts, through the Sabatier reaction, Carbon Dioxide, as recovered from whatever handy source, into substitute natural gas Methane.

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

"United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction

Patent US20120029095 - Sabatier process and apparatus for controlling exothermic reaction - Google Patents

Sabatier process and apparatus for controlling exothermic reaction - Junaedi, Christian

Date: February 2, 2012

Inventors: Christian Junaedi, et. al., Connecticut

Abstract: A Sabatier process involving contacting carbon dioxide and hydrogen in a first reaction zone with a first catalyst bed at a temperature greater than a first designated temperature; feeding the effluent from the first reaction zone into a second reaction zone, and contacting the effluent with a second catalyst bed at a temperature equal to or less than a second designated temperature, so as to produce a product stream comprising water and methane. The first and second catalyst beds each individually comprise an ultra-short-channel-length metal substrate. An apparatus for controlling temperature in an exothermic reaction, such as the Sabatier reaction, is disclosed.

Government Interests: 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.

(Note: We couldn't find record of the specific contract identified above. However, as can be learned from our Government's Small Business Innovations office, via:

Novel Catalytic Reactor for CO2 Reduction via Sabatier Process | SBIR.gov; "Fiscal Year 2011; Novel Catalytic Reactor for CO2 Reduction via Sabatier Process; Agency: NASA; Contract: NNX11CC05C; Principal Investigator: Christian Junaedi; Precision Combustion, Inc., CT; A novel short contact time Microlith Sabatier reactor system for CO2 reduction offers a significant advance in support of manned spaceflight. Compared to current and prospective alternatives (including microchannels), the reactor will be much smaller and lighter, more energy and resource efficient, and more durable. Precision Combustion, Inc. (PCI) proposes to build on Phase 1 proof of concept success to develop, demonstrate, and deliver an integrated ... test Sabatier reactor Development Unit (SDU) for CO2 reduction ... . The SDU will convert CO2 and H2 to methane and water, achieving close-to-equilibrium CO2 conversions at high throughputs and at low operating temperatures";

the company involved is:

Precision Combustion, Inc. Catalytic Reactor; Combustion Products for the Energy Sector; "Precision Combustion, Inc. (PCI) is a clean energy technology company developing and manufacturing advanced catalytic devices and systems for energy sector applications.".)

Claims: . A process of converting a mixture of carbon dioxide and hydrogen into a mixture of water and methane, comprising: (a) contacting a mixture of carbon dioxide and hydrogen in a first reaction zone in the presence of a first catalyst bed comprising at least one layer of ultra-short-channel-length metal substrate, the contacting occurring at a temperature greater than a first designated temperature, so as to produce an effluent comprising water and methane and unconverted carbon dioxide and hydrogen; and (b) contacting the effluent from step (a) in a second reaction zone with a second catalyst bed comprising at least one layer of ultra-short-channel-length metal substrate, the contacting occurring at a temperature equal to or less than a second designated temperature, so as to produce a product comprising water and methane with a carbon dioxide conversion greater than about 80 percent of an equilibrium carbon dioxide conversion under isothermal process conditions.

The process ... wherein the carbon dioxide is obtained from ... byproducts of industrial processes, oxidation processes, Earth's atmosphere, ... or a combination thereof.

The process ... wherein the hydrogen is obtained from (for example) electrolysis of water ... .

The process ... wherein the hydrogen and carbon dioxide are fed to the first reaction zone in an inlet H2/CO2 mole ratio ranging from 2/1 to 6/1. 

The process ... wherein the first and second reaction zones are maintained each individually at a pressure ranging from 0.5 atm ... to 10 atm. 

The process ... wherein the first and second catalyst beds each individually comprise an ultra-short-channel-length metal mesh substrate having deposited thereon one or more Group VIII metals. 

The process ...  wherein the first reaction zone is maintained at a first designated temperature greater than 240 C and the second reaction zone is maintained at a second designated temperature equal to or less than 400 C. 

The process ... wherein the conversion of carbon dioxide is greater than 80 mole percent, based on the moles of carbon dioxide fed to the first reaction zone.

The process ... wherein the selectivity to methane and water are each individually greater than 80 mole percent, based on the moles of carbon dioxide converted to products.

(In other words, better than 80 percent of the CO2 fed into this thing will be converted into Methane.)

The process ... wherein the methane produced is converted to methanol.

(The above conversion of Methane, as synthesized herein from CO2,  into Methanol might be accomplished  via a process like that disclosed in our report of:

West Virginia Coal Association | California Converts Even More CO2 into Methanol | Research & Development; concerning: "United States Patent Application 20120115965 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane; 2012; Inventors: George Olah and G. K. Surya Prakash; Assignee: University of Southern California; Abstract: (A) method of forming methanol by combining a mixture of methane, water and carbon dioxide under specific reaction conditions sufficient to form a mixture of hydrogen and carbon monoxide which are then reacted under conditions sufficient to form methanol";

by reacting that CO2-based Methane with even more Carbon Dioxide.)

An apparatus for use in an exothermic reaction, the apparatus comprising: (a) a first reaction zone comprising a first catalyst bed comprising at least one layer of ultra-short-channel-length metal substrate; (b) a second reaction zone in fluid communication with and downstream from said first reaction zone, the second reaction zone comprising a second catalyst bed comprising at least one layer of ultra-short-channel-length metal substrate; (c) at least one inlet for feeding one or more reactants into the first reaction zone; (d) an outlet for exiting a product stream from said second reaction zone; (e) a means for removing heat from said first reaction zone so as to maintain a temperature in said first reaction zone less than a maximum temperature suitable for materials of construction but greater than a first designated temperature; and (f) a means for removing heat from said second reaction zone so as to maintain a temperature in said second reaction zone equal to or less than a second designated temperature.

(As we've previously documented, the Sabatier reaction, that converts CO2 into Methane, is exothermic; it generates at least a small amount of heat energy which can be reclaimed and recycled into other reactions and processes supportive of the process.)

An apparatus for use in an exothermic process, comprising: (a) two concentric tubes, such that an inner tube of a specified diameter is positioned within an outer tube of a larger diameter; the outer tube comprising a housing; the inner tube comprising a reactor section; and the annular space bounded by the inner tube and the outer tube comprising a heat exchange section; (b) the reactor section comprising a first catalyst bed, and a second catalyst bed downstream and in fluid communication with the first catalyst bed; the first and second catalyst beds each individually comprising at least one layer of ultra-short-channel-length metal mesh substrate having one or more Group VIII metals deposited thereon; (c) at least one inlet for feeding one or more reactants into the first catalyst bed; (d) an outlet for removing a product stream from the second catalyst bed; (e) at least one inlet for feeding a heat exchange fluid into the annular space between the inner tube and the outer tube, the inlet being coincident with the second catalyst bed; and (f) at least one outlet for removing the heat exchange fluid from the annular space between the inner tube and the outer tube, the outlet being coincident with the first catalyst bed.

Background and Field: In one aspect, this invention pertains to a process of converting a mixture of carbon dioxide and hydrogen into a product mixture comprising water and methane (hereinafter "the process"). In the art the process is known as the "Sabatier process" or the "Sabatier reaction" or the "carbon dioxide methanation reaction." In another aspect, this invention pertains to an apparatus that finds use as a reactor for an exothermic process, for example, the Sabatier reaction.

Summary: In one aspect, this invention pertains to a novel two-stage Sabatier process of converting carbon dioxide into a mixture of water and methane.

The novel Sabatier process comprises:

(a) contacting a mixture of carbon dioxide and hydrogen in a first reaction zone in the presence of a first catalyst bed comprising at least one layer of ultra-short-channel-length metal substrate, the contacting occurring at a temperature greater than a first designated temperature, so as to produce an effluent comprising water and methane and unconverted carbon dioxide and hydrogen; and:

(b) contacting the effluent from step (a) in a second reaction zone with a second catalyst bed comprising at least one layer of ultra-short-channel-length metal substrate, the contacting occurring at a temperature equal to or less than a second designated temperature, so as to produce a product comprising water and methane with a carbon dioxide conversion greater than about 80 percent of an equilibrium carbon dioxide conversion under isothermal process conditions.

For the purposes of this invention, the term "carbon dioxide conversion" is defined as the moles of carbon dioxide changed to products in the overall two-stage process divided by the moles of carbon dioxide fed to the first reaction zone, on a percentage basis."

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We'll leave our excerpts at that. This device will convert fully eighty percent of the Carbon Dioxide fed into it into Methane. Although Water, as well, is co-produced, only the Methane incorporates the Carbon in the Carbon Dioxide into it's molecule.

You'll find that the design of this Sabatier reactor is intended for use in smaller-scale reactors with provision made to limit the rate of reaction and the amount of exothermic reaction heat that has to be dealt with.

We submit that it could be made much larger, and faster, with provision made, instead, to collect, remove and productively utilize the by-product heat energy, perhaps, as seen in:

West Virginia Coal Association | USDOE 1976 Thermochemical Hydrogen from Water | Research & Development; concerning: "United States Patent 3,996,343 - Process for Thermochemically Producing Hydrogen; 1976; Inventors: Carlos Bamberger and Donald Richardson, Oak Ridge, TN; Assignee: The United States of America; Abstract: Hydrogen is produced by the reaction of water with chromium sesquioxide and strontium oxide. The hydrogen producing reaction is combined with other reactions to produce a closed chemical cycle for the thermal decomposition of water";

to help, through "the thermal decomposition of" perhaps already-heated "water" co-produced with Methane in the Sabatier reactor, generate the Hydrogen needed to convert Carbon Dioxide, via the process disclosed by our subject herein, "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction", into, primarily, Methane.

Which Methane, we remind you, once it has been synthesized as herein from Carbon Dioxide, can then, as seen for only one out of now many examples in our report of:

West Virginia Coal Association | Exxon 2010 CO2 + Methane = Liquid Hydrocarbons | Research & Development; concerning: "United States Patent 7,772,447 - Production of Liquid Hydrocarbons from Methane; 2010; Assignee: ExxonMobil; Abstract: (A) process for converting methane to liquid hydrocarbons ... , including benzene and/or naphthalene, and produce a first effluent stream comprising hydrogen ... . A process for converting methane to higher hydrocarbons, the process comprising: (a) contacting a feed containing methane and ...  H2O (and) CO2 with a (specified) catalyst under conditions effective to convert said methane to aromatic hydrocarbons, including benzene and naphthalene, and produce a first effluent stream comprising aromatic hydrocarbons and hydrogen";

be reacted with even more Carbon Dioxide, with both the CO2-derived Methane and the additional Carbon Dioxide being converted through such reaction into various "liquid hydrocarbons" - plus some "hydrogen", which could be sent back for use in the process of our subject herein, "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction", to help in converting even more Carbon Dioxide into even more Methane.

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