United States Patent Application: 0130237618
About three and half years ago, back in April of 2010, in our report of:
West Virginia Coal Association | Japan's Mitsui Recycles CO2 | Research & Development; concerning the article: "'Establishing an Innovative Technology to Synthesize Methanol from CO2'; On May 23, 2009, a pilot plant at the Mitsui Chemicals Osaka Works became the first site in the world to synthesize methanol from it's carbon dioxide (CO2) exhaust. Methanol can be used to make the raw materials for plastics";
we documented that Japan's Mitsui Chemicals company was developing the technology to convert Carbon Dioxide, as recovered from whatever handy source, into Methanol, a fuel alcohol which can, as Mitsui noted in the above report, be used and consumed in the synthesis of certain plastics, wherein the CO2 consumed in the synthesis of the Methanol would be chemically, productively, and permanently "sequestered".
That Carbon Dioxide can be so productively utilized in the synthesis of Methanol shouldn't be a surprise to anyone who actually follows news originating from places in the world outside the sheltered confines of US Coal Country, since, as seen in our report of:
West Virginia Coal Association | Sweden Makes Public Report of CO2 to Motor Fuel Recycling | Research & Development; concerning the Swedish newspaper article: "'Iceland As A Green Saudi Arabia'; March 12, 2013; Recently, they shipped the first load to oil company Argos in Holland, for low level blending in gasoline. Vulcanol is just a name for methanol, regular wood spirit. It is the production method which makes this fuel especially interesting. It is made using renewable electricity, water and captured CO2 from the nearby geothermal power plant HS Orka";
Carbon Dioxide is being converted into Methanol on a commercial basis, and that fact is being reported on in the public press, in other parts of the world far removed from the US and it's spendthrift thirst for Cap & Trade carbon taxes.
In any case, Mitsui, as in our 2010 report, continued their work in developing an efficient, innovative way to convert Carbon Dioxide into Methanol, and, that has resulted in, as excerpted from the initial link in this dispatch, the recently published:
"United States Patent Application 20130237618 - Process for Producing Methanol
Patent US20130237618 - Process for producing methanol - Google Patents
PROCESS FOR PRODUCING METHANOL - MITSUI CHEMICALS, INC.
September 12, 2013
Inventors: Tatsumi Matsushita, et. al., Japan
Assignee: Mitsui Chemicals, Inc., Tokyo
(Even though perhaps unfamiliar to most of us, as can be learned via:
Mitsui Chemicals - Wikipedia, the free encyclopedia; "Mitsui Chemicals ... is a Japanese Chemicals company listed on the Nikkei. It is a part of the Mitsui conglomerate. The company has a turnover of around 15 billion USD and has business interests in Japan, Europe, China, Southeast Asia and the USA. It employs approximately 13,000 people worldwide. The company mainly deals in performance materials, petro and basic chemicals and functional polymeric materials"; and:
Mitsui - Wikipedia, the free encyclopedia; "Mitsui Group ... is one of the largest corporate conglomerates (keiretsu) in Japan and one of the largest publicly traded companies in the world";
Mitsui Chemicals Incorporated is a very significant company with a global reach.)
Abstract: An object of the invention is to provide a methanol production process which can efficiently produce methanol from carbon dioxide and hydrogen while suppressing loads to the global environment. The process for producing methanol of the invention includes a step (a) of reacting hydrogen and carbon dioxide with each other in a reactor in the presence of a copper-containing catalyst to produce a reaction mixture containing methanol; a step (b) of circulating part or all of the reaction mixture to the step (a); a step (c1) of combusting part of the reaction mixture to produce a combustion product and energy, and a step (c2) of circulating part or all of the combustion product to the step (a), the step (c1) and the step (c2) being performed when the reaction mixture contains a compound (p) containing carbon and hydrogen except methanol at not less than 0.1 mol % (wherein all components of the reaction mixture excluding methanol and water represent 100 mol %); and a step (d) of separating a component including methanol from the reaction mixture.
(Sounds sort of complicated, we know; but, they are generating some of the energy needed for the process by combusting a portion of the product, which, as we will see, is byproduct Methane; and, are recycling the combustion products back into the process. There would be some limiting factors inherent in that scheme; and, somewhere along the line energy has to be added from an external source to prevent the system's combustion byproducts from meeting, then exceeding, the system's requirement for raw material CO2 from an external source. Other factors figure in to the picture, though, as will be seen.)
Claims: A process for producing methanol (as stated in the Abstract) wherein the compound (p) is inert to the copper-containing catalyst (and) wherein at least a part of the compound (p) is a hydrocarbon (and) wherein the compound (p) is methane (and) wherein the reaction mixture contains the compound (p) at 0.1 to 50 mol %.
(Thus, a little, almost none, or a relative lot, up to "50 mol %", of Methane can be used to react with the Carbon Dioxide, and with the Hydrogen, although excess byproduct Methane is extracted from the Methanol final product and may be combusted to generate thermal energy for use in driving the total process. And, we remind you, that, as seen for just two examples in our reports of:
West Virginia Coal Association | Panasonic High-Efficiency Hydrogen from H2O | Research & Development; concerning: "US Patent Application 20120285823 - Hydrogen Generation Device; 2012; Assignee: Panasonic Corporation, Osaka; Abstract: A hydrogen generation device of the present invention includes: a transparent substrate; a photocatalytic electrode formed of a transparent conductive layer and a photocatalytic layer disposed on the transparent substrate; a counter electrode connected electrically to the transparent conductive layer; a water-containing electrolyte solution"; and:
West Virginia Coal Association | Japan Maximizes Hydrogen Production from Wind Power | Research & Development; concerning: "US Patent 7,667,343 - Hydrogen Production System Using Wind Turbine Generator; 2010; Assignee: Hitachi, Ltd., Tokyo; Abstract: A wind turbine-driven hydrogen production system"; and:
West Virginia Coal Association | Japan Improves CO2 to Methane Catalysis | Research & Development; concerning: "US Patent Application 20090042998 - Catalyst for Methanation of Carbon Oxides; 2009; Assignee: Daiki Ataka Engineering Company, Tokyo; Abstract: Disclosed is a catalyst for methanation reaction producing methane with high conversion by reaction of hydrogen with carbon dioxide";
they know, in Japan, how to generate the needed Hydrogen from Water via processes powered by renewable energy, and, using some of that Hydrogen, how then to generate any desired Methane from CO2. -
The process for producing methanol ... wherein the copper-containing catalyst is a catalyst containing copper, zinc, aluminum and silicon.
(Nothing too exotic, or expensive, is required. The remaining claims explain how thermal energy produced in exothermic reactions in one step of the process can be used to help drive endothermic reactions in another step )
Background and Field: The present invention relates to a process for producing methanol from carbon dioxide and hydrogen as materials.
Methanol is used as a material for products such as dimethyl ether, MTBE (methyl tertiary butyl ether) and petrochemical intermediates, and also as a fuel.
A known ... technique is to synthesize methanol from CO2 and hydrogen as materials.
Due to the thermodynamic equilibrium of the reaction as well as because the reaction is inhibited by water that is by-produced together with methanol, synthesizing methanol from a material gas with a high carbon dioxide content requires a catalyst exhibiting a higher activity and a higher durability than in the methanol synthesis from a syngas.
With such needs, copper-containing multicomponent catalysts such as copper/zinc oxide/aluminum oxide/zirconium oxide and copper/zinc oxide/aluminum oxide/zirconium oxide/gallium oxide have been developed (and, because) these catalysts are solid catalysts, the methanol synthesis reaction is generally carried out with a fixed-bed reactor.
In general, the reactor may be a multitubular reactor. In general, the reaction mode may be batchwise.
It will also be preferable to adopt a continuous reaction mode in which part or all of unreacted materials (including carbon dioxide and hydrogen) are recovered from the reaction mixture containing methanol formed, and the unreacted material components are circulated back to the material introduction step.
In order to separate the reaction mixture into methanol and the unreacted gas, techniques such as distillation and separation with a gas-liquid separator are known).
Summary: According to studies carried out by the present inventors, methanol production from carbon dioxide and hydrogen has suffered a decrease in reaction efficiency with time when unreacted materials are recovered and reused as materials. It has been found that the above phenomenon is ascribed partly to the degradation of the catalyst with time but is attributed largely to the fact that the proportion of components which are present in small amounts in the reaction materials and do not react with the catalyst of the present application (hereinafter, sometimes referred to as inert components) is increased with time with the result that carbon dioxide and hydrogen to be reacted with each other under catalysis of the catalyst come to represent a smaller proportion relative to the materials supplied to the reactor.
It has been further found that the inert components include compounds containing carbon and hydrogen, such as methane. Furthermore, the present inventors have found that hydrogen and carbon dioxide used as materials contain such inert components in small amounts. That is, the progress of the methanol production reaction is accompanied by an increasing proportion of the inert components and a consequent decreasing concentration of the materials, thus leading to a decrease in reaction efficiency. A possible approach to remedy this decrease in reaction efficiency is to clear the reactor system of part or all of the unreacted materials that have come to have a larger proportion of the inert components. However, such an approach causes a risk that the inert components such as methane are released into the atmosphere. Methane is known to have a greenhouse effect. Thus, this approach can adversely affect the global environment.
Accordingly, it is important that a methanol production process be provided which can efficiently produce methanol from carbon dioxide and hydrogen while suppressing loads to the global environment. The present invention has been made in order to address this problem.
(The) present inventors have ... have found that methanol can be produced with good efficiency and the above problem can be solved by providing a step in which part or all of unreacted materials containing the inert components are combusted to produce a combustion product and energy such as thermal energy, and a step in which the combustion product from the above step which contains carbon oxides such as carbon monoxide and carbon dioxide is circulated again as a material. The present invention has been completed based on this finding.
A process for producing methanol according to the present invention comprises a step (a) of reacting hydrogen and carbon dioxide with each other in a reactor in the presence of a copper-containing catalyst to produce a reaction mixture containing methanol."
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So, it is again confirmed that we can synthesize Methanol from Carbon Dioxide.
And, we remind you, that, as seen in our report of:
West Virginia Coal Association | ExxonMobil Coal to Methanol to Gasoline | Research & Development; concerning both: "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification; 1982; Assignee: Exxon Research and Engineering Company; A process for the production of methanol from a carbonaceous feed material (which) comprises coal. This invention provides a process for producing methanol by the substantially thermoneutral reaction of steam with coal"; and: "United States Patent 4,035,430 - Conversion of Methanol to Gasoline; 1977; Assignee: Mobil Oil Corporation; The conversion of methanol to gasoline";
once we have the Methanol, no matter which of our precious natural resources we make it from, whether, as in the above Exxon technology of "United States Patent 4,348,486 - Production of Methanol via Catalytic Coal Gasification", from Coal, or, as in the process of our subject herein, the Mitsui Chemicals technology of
"United States Patent Application 20130237618 - Process for Producing Methanol", from Carbon Dioxide, we can then convert that Methanol into something we seem willing to mortgage our grandchildren's economic future to the alien, often inimical nations of OPEC to keep ourselves supplied with in the here and now.
And, following is independent confirmation of that straightforward fact, fittingly from Japan; and, one with explanation of an added benefit that we have discussed in prior reports concerning the ExxonMobil "MTG"(r) methanol-to-gasoline process, i.e.: The conversion of Methanol into Gasoline is an exothermic reaction which generates significant heat energy, and, that heat can be recovered and used to generate electricity; which electricity, we suggest, could be used in a process like that in our above-referenced report concerning "United States Patent 7,667,343 - Hydrogen Production System Using Wind Turbine Generator; 2010; Assignee: Hitachi, Ltd., Tokyo"; to supplement wind-generated electricity in the electrolytic extraction of the Hydrogen required by the process of our primary subject, "United States Patent Application 20130237618 - Process for Producing Methanol", to make Methanol from Carbon Dioxide:
"United States Patent Application: 0130014430 - Method for Generating Electricity and for Producing Gasoline from Methanol and System Therefore
January 17, 2013
Inventor: Masaki Iijima, Japan
Assignee: Mitsubishi Heavy Industries, Ltd., Tokyo
(We remind you, that, as seen for one example in our report of:
West Virginia Coal Association | Japan Helps Iceland Convert CO2 into Liquid Hydrocarbon Fuels | Research & Development; concerning: "Dimethyl Ether Production from Carbon Dioxide and Hydrogen; 2010; Abstract: The chemical recycling of carbon dioxide to methanol and dimethyl ether (DME) provides a renewable, carbon-neutral, source for efficient transportation fuels. DME can be used in diesel engine, although some modifications of the engine are required. The Icelandic government has established a long term vision for zero percent hydrocarbon fuel emissions, and has been working to increase the use of renewable energy. So, Mitsubishi Heavy Industries (MHI) is planning to open a DME plant in 2014, in Iceland. A two step process is adopted to produce DME, via methanol, produced from carbon dioxide and hydrogen";Mitsubishi have their own processes for converting CO2 into the needed Methanol, and are participating in the Renewable Methanol, CO2-to-Methanol revolution taking place now in Iceland, as per our above-cited earlier report concerning: "Iceland As A Green Saudi Arabia".)
Abstract: A method for generating electric power and for producing gasoline from methanol, includes the steps of: synthesizing gasoline by reacting methanol under a catalyst; recovering heat generated from the gasoline synthetic reaction of methanol by cooling the reaction with coolant to vaporize the coolant; and generating electric power by using the coolant vapor produced in the heat recovery. The power generation step may include generating electric power with a plurality of steam turbines in series, e.g., a high-pressure turbine, a medium-pressure turbine, and a low-pressure turbine.
Claims: A method for generating electric power and for producing gasoline from methanol".
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The Abstract sums it all up pretty well, so we'll keep our excerpts brief.
Again, the electricity co-generated during the conversion of Methanol, as synthesized from Coal or Carbon Dioxide, into Gasoline, could be used to help electrolyze Water, to obtain the Hydrogen needed to synthesize the Methanol from the Carbon Dioxide, as per the process of our primary subject, published by our US Government just a little more than two months ago: "US Patent Application 20130237618 - Process for Producing Methanol".
It all serves to confirm an assertion we've made many times over the past going-on half-dozen years:
Carbon Dioxide, as it arises in only a small way relative to some all-natural and un-taxable processes, such as the Earth's inexorable processes of planetary volcanism, from our essential use of Coal in the generation of truly abundant and truly affordable electric power, is a valuable raw material resource.
According herein to some impeccable Japanese corporations of global scale, we can reclaim Carbon Dioxide from whatever convenient source, and then convert that Carbon Dioxide into, first, the valuable fuel Alcohol and plastics manufacturing raw material, Methanol, and, then, through Methanol, into Gasoline, with electric energy as a potential byproduct.
Now, with the obvious potentials for reducing our national exposure to OPEC; for obviating any purported need for Cap & Trade taxes; for improving our environment, at least as far a the rate of CO2 accumulation in the atmosphere goes; and, for putting more US Coal Country citizens to work in good-paying jobs, is there any reason, any credible reason, we all shouldn't be fully and openly educated about these technical innovations, and empowered to use them to create a better and stronger nation, and a better world, for ourselves and for our grandchildren?