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  • norrishappy norrishappy Mar 5, 2013 2:50 PM Flag

    Japan is Recycling CO2 into Hydrocarbon Syngas

    Wednesday - January 02, 2013
    United States Patent: 6387843
    We regret what you will find to be the cluttered nature of this dispatch. And, we apologize to the exceptional Japanese company, and the accomplished scientists among their number, upon whom our dissertation is centered, for what will be the inadequate attention we will be able to devote herein to their achievements.
    But, there is a lot of ground to cover.
    First, we remind you of three previous reports:
    West Virginia Coal Association | More Japan CO2 + Methane = Hydrocarbon Syngas | Research & Development; concerning: "United States Patent 6,312,660 - Process for Preparing Synthesis Gas; 2001; Assignee: Chiyoda Corporation, Japan";
    West Virginia Coal Association | Japan CO2 + Methane = Hydrocarbon Syngas | Research & Development; "United States Patent 6,340,437 - Preparing Synthesis Gas by Autothermal Reforming; 2002; Assignee: Chiyoda Corporation, Japan; (A) process for producing a synthesis gas by an autothermal reforming method including a step of partially oxidizing a carbon-containing organic compound to produce a high temperature mixed gas, and a synthesis producing step of reacting the unreacted carbon-containing organic compound contained in the high temperature mixed gas with carbon dioxide and/or steam, wherein a catalyst having a considerably suppressed carbon deposition activity is used as a catalyst for the synthesis gas producing step."; and:
    West Virginia Coal Association | Even More Japan CO2 + Methane = Hydrocarbon Syngas | Research & Development; concerning: "US Patent 6,656,978 - Producing Liquid Hydrocarbon Oil from Hydrocarbon Gas and Carbon Dioxide; 2003; Assignee: Chiyoda Corporation, Japan";
    wherein the development of an integrated Carbon Dioxide recycling technology by Japan's Chiyoda Corporation is documented, with Methane being the "carbon-containing organic compound" and the "Hydrocarbon Gas" specified in the full Disclosures.
    The above-cited "United States Patent 6,340,437 - Preparing Synthesis Gas by Autothermal Reforming" is, perhaps, of some special significance, since it demonstrates that, unlike the Carbon Dioxide recycling and conversion technology being employed now in Iceland, as we've reported, for only one example, in:
    West Virginia Coal Association | Iceland Recycles Even More CO2 | Research & Development; concerning: "Carbon Recycling International (CRI) captures carbon dioxide from industrial emissions and converts carbon dioxide into Renewable Methanol (RM). RM is a clean fuel and can be blended at different levels with gasoline to meet renewable energy directives. The capture of carbon dioxide minimizes emissions from energy intensive industries. It is compatible to the existing energy and fuel infrastructure. RM is a drop-in fuel for existing automobiles and hybrid flexible vehicles and can be purchased at existing gasoline stations. The production of RM is feasible in many locations in the world with geothermal, wind, and solar energy sources. CRI plans to build commercial plants for domestic consumption and for export to other European countries";
    wherein nothing else but Water is used as a raw material, Carbon Dioxide, in combination with Methane, can be converted into a hydrocarbon synthesis gas suitable for catalytic chemical condensation into a wide variety of liquid and gaseous hydrocarbons, with very little energy from an external source needed to drive the reaction processes.
    The tradeoff being that some of the raw material Methane is oxidized in the system to generate heat to help drive the process, a technique which generates some of it's own Carbon Dioxide, thus reducing the amount of CO2 which can be imported into the reaction sequence for consumption and utilization - - the net amount of Carbon Dioxide recycled in other words - - while "wasting" some of the raw material Methane.
    However, since, as most recently seen in:

    SortNewest  |  Oldest  |  Most Replied Expand all replies
    • Patent 6,312,660 - Process for Preparing Synthesis Gas; 2001; Assignee: Chiyoda Corporation, Japan";
      West Virginia Coal Association | Japan CO2 + Methane = Hydrocarbon Syngas | Research & Development; "United States Patent 6,340,437 - Preparing Synthesis Gas by Autothermal Reforming; 2002; Assignee: Chiyoda Corporation, Japan; (A) process for producing a synthesis gas by an autothermal reforming method including a step of partially oxidizing a carbon-containing organic compound to produce a high temperature mixed gas, and a synthesis producing step of reacting the unreacted carbon-containing organic compound contained in the high temperature mixed gas with carbon dioxide and/or steam, wherein a catalyst having a considerably suppressed carbon deposition activity is used as a catalyst for the synthesis gas producing step."; and:
      rporation, Japan";
      wherein the development of an integrated Carbon Dioxide recycling technology by Japan's Chiyoda Corporation is documented, with Methane being the "carbon-containing organic compound" and the "Hydrocarbon Gas" specified in the full Disclosures.
      TheWest Virginia Coal Association | Even More Japan CO2 + Methane = Hydrocarbon Syngas | Research & Development; concerning: "US Patent 6,656,978 - Producing Liquid Hydrocarbon Oil from Hydrocarbon Gas and Carbon Dioxide; 2003; Assignee: Chiyoda Co above-cited "United States Patent 6,340,437 - Preparing Synthesis Gas by Autothermal Reforming" is, perhaps, of some special significance, since it demonstrates that, unlike the Carbon Dioxide recycling and conversion technology being employed now in Iceland, as we've reported, for only one example, in:
      West Virginia Coal Association | Iceland Recycles Even More CO2 | Research & Development; concerning: "Carbon Recycling International (CRI) captures carbon dioxide from industrial emissions and converts carbon dioxide into Renewable Methanol (RM). RM is a clean fuel and can be blended at different levels with gasoline to meet renewable energy directives. The capture of carbon dioxide minimizes emissions from energy intensive industries. It is compatible to the existing energy and fuel infrastructure. RM is a drop-in fuel for existing automobiles and hybrid flexible vehicles and can be purchased at existing gasoline stations. The production of RM is feasible in many locations in the world with geothermal, wind, and solar energy sources. CRI plans to build commercial plants for domestic consumption and for export to other European countries";
      wherein nothing else but Water is used as a raw material, Carbon Dioxide, in combination with Methane, can be converted into a hydrocarbon synthesis gas suitable for catalytic chemical condensation into a wide variety of liquid and gaseous hydrocarbons, with very little energy from an external source needed to drive the reaction processes.
      The tradeoff being that some of the raw material Methane is oxidized in the system to generate heat to help drive the process, a technique which generates some of it's own Carbon Dioxide, thus reducing the amount of CO2 which can be imported into the reaction sequence for consumption and utilization - - the net amount of Carbon Dioxide recycled in other words - - while "wasting" some of the raw material Methane.
      However, since, as most recently seen in:
      West Virginia Coal Association | Japan Converts CO2 into Lower-Cost Methane | Research & Development
      "United States Patent Application 20120018311 - Carbon Dioxide Reduction Method; 2012; Assignee: Panasonic Corporation, (Japan); (The) method and the device of the present invention achieve reduction of carbon dioxide to carbon monoxide, formic acid, methane, etc. and provide these substances with less energy and at lower cost. The present embodiment can also be applied to more environmentally-friendly methods and devices. For example, it can be applied to the use of a solar cell as an external power supply, and to a catalyst for solar energy reduction by combination with a photocatalyst. The present invention not only can provide carbon monoxide, formic acid, methane, etc. obtained by reducing carbon dioxide with less energy and at lower cost, but also can be used as a technique for reducing the amount of carbon dioxide";
      it is known, in Japan, that the needed Methane can itself be synthesized in the first place, "at lower cost", using freely available "solar energy", from Carbon Dioxide, it's hard to see why that would matter so much.
      But, returning to Chiyoda Corporation, here's some background:
      Brief History of CHIYODA Corporation | About Chiyoda | CHIYODA CORPORATION; "CHIYODA Corporation was created by the enthusiasm of Mr. Akiyoshi Tamaki, who had been a manager of the construction division at Mitsubishi Oil Co., Ltd. (currently NIPPON OIL & Energy). Mr. Tamaki, in anticipation of the resumption of the petroleum refining business in postwar days, committed himself to the creation of an advanced engineering company specializing in industrial facilities, and retained some of the engineers in Mitsubishi Oil, which had been substantively liquidated just after World War II. With the support of the senior executives of Mitsubishi Oil, he established CHIYODA Corporation in January 1948, two years after the war, with 25 employees".
      And, here is, in part, what their current President and CEO, Takashi Kubota, has to say about Chiyoda, and the essence of their guiding business principle, "Energy and Environment in Harmony":

      • 1 Reply to norrishappy
      • CO2 Reforming Process | Technology | CHIYODA CORPORATION; "CO2 Reforming Process: Chiyoda has developed the CO2/Steam Reforming Process, which ... reuses efficiently CO2 emitted from various industrial processes. This reforming process can produce synthesis gases (H2 and CO) more efficiently than conventional steam-reforming process. Synthesis gases are used as raw materials for producing liquid fuels (GTL, DME, etc.) and various chemicals. The produced liquid fuels contain no sulfuric and nitrogenous compounds, so that exhausted gases after combustion become extremely clean. This process uses CO2 as a raw material and uses Chiyoda’s unique reforming catalyst, thereby achieving high energy efficiency. Therefore, this reforming process is an environmentally-friendly technology due to significant reduction of carbon dioxide emissions."
        We can't reproduce them in our excerpts, but the page accessible via the above link presents a schematic of their "CO2-Steam Reforming Process", and a photograph of a chemical plant labeled as the "Japan GTL Demonstration Plant, which operates the CO2-reforming process"; and, which is capable pf the "Direct Production of Synthesis Gases with a Wide Range of H2/CO Ratios" by that "CO2-Steam Reforming Process".
        All of that said, following are two more United States Patents issued to Chiyoda Corporation, for additional components of an overall Carbon Dioxide recycling technology, which might well be that being operated at the "Japan GTL Demonstration Plant".
        First, as excerpted from the initial link in this dispatch, we have:
        "United States Patent 6,387,843 - Method of Preparing Rh- and/or Ru-catalyst Supported on MgO Carrier and Reforming Process Using the Catalyst
        Method of preparing Rh- and/or Ru-catalyst supported on MgO carrier and reforming process using the catalyst - Chiyoda Corpora
        Date: May 14, 2002
        Inventors: Fuyuki Yagi, et. al., Japan
        Assignee: Chiyoda Corporation
        Abstract: A method of preparing a catalyst, including molding a mixture of magnesium oxide with a binder selected from carbon, fatty acids having 12-22 carbon atoms, magnesium salts of fatty acids having 12-22 carbon atoms, carboxymethyl cellulose, a magnesium salt of carboxymethyl cellulose and polyvinyl alcohol and calcining the molded mixture to obtain a carrier having a specific surface area (as specified). The carrier is impregnated with an aqueous solution containing Rhodium and/or Ruthenium compounds for loading a catalytic metal component and then dried and calcined.
        The catalyst is used for reforming a lower hydrocarbon gas with steam and carbon dioxide or with carbon dioxide to produce a synthesis gas.
        Background and Field: This invention relates to a method of preparing a catalyst containing Rh and/or Ru supported on a Magnesium Oxide carrier and to a process of producing a synthesis gas ... a mixed gas containing hydrogen and carbon monoxide ... used as a raw material for the synthesis of ammonia, methanol, acetic acid, etc. Such a synthesis gas may be produced by reforming a hydrocarbon with steam and/or carbon dioxide in the presence of a catalyst such as Ni or other transition metals. In the reforming reaction, however, carbon deposition occurs as a result of side reactions to cause a problem of catalyst poisoning.
        Summary: The production of a synthesis gas may be performed by reacting a hydrocarbon feed with steam and/or carbon dioxide (CO2) in the presence of a catalyst prepared by the (method of the invention). As the hydrocarbon feed, a lower hydrocarbon such as methane ... is preferred. In the case of a method of reacting methane with carbon dioxide (CO2) (reforming with CO2), the reaction is as follows:

        CH4 + CO2 = 2H2 +2CO,"
        ----------------------
        And, in addition, Chiyoda has developed:
        "United States Patent: 6806296 - Hydrocarbon Oil ... from Lower Hydrocarbon Gas (and) Carbon Dioxide
        Process of producing liquid hydrocarbon oil or dimethyl ether from lower hydrocarbon gas containing carbon dioxide - Chiyoda C
        Date: October 19, 2004
        Inventors: Yoshimo Shiroto, et. al., Japan
        Assignee: Chiyoda Corporation
        Abstract: A process for the production of a liquid hydrocarbon oil from a gas feed containing a lower hydrocarbon and CO2, wherein

 
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