We've reported many times on various "reforming" technologies, wherein Carbon Dioxide, CO2, is reacted with Methane, CH4, and/or Water, and is made thereby to form a hydrocarbon synthesis gas suitable for catalytic condensation into liquid hydrocarbons via what are, in some circles at least, well-known processes.
From an historical perspective, those CO2-CH4 reforming technologies seem to have been discovered, or development of them first got underway, during the WWII era, as witness, for just one example, our report:
More Standard Oil 1944 CO2 + CH4 = Hydrocarbons | Research & Development; concerning: "United States Patent 2.347.682 - Hydrocarbon Synthesis; 1944; Assignee: Standard Oil Company of Indiana; Abstract: This invention relates to an improved method and means for effecting the synthesis of hydrocarbons from carbon monoxide and hydrogen (made by a fully-specified and described) reforming operation (which converts a) methane-carbon dioxide-steam mixture into a gas consisting chiefly of hydrogen and carbon monoxide ... hereinafter referred to as ... 'synthesis' gas."
The CO2-recycling principles behind the process of Standard Oil's US Patent 2.347.682, and a surprising number of others similar originating in the same general time frame, wasn't lost on our later United States Department of Energy, who further refined the technology, and developed innovative ways of supplying the energy needed to drive the chemical reactions required by it, as seen in:
USDOE 1990 Solar CO2-Methane Recycling-Reforming | Research & Development; which reports: "Solar Reforming of Methane; 1990; Sandia National Labs; DOE Contract: AC04-76DP00789; The concept of solar driven chemical reactions in a commercial-scale ... was successfully demonstrated. Solar reforming of methane (CH4) with carbon dioxide (CO2) was achieved".
And, the USDOE does have some ideas about where the Methane, needed for such reforming reactions with Carbon Dioxide, could come from.
They believe that the needed Methane could itself be made from Carbon Dioxide, as seen, for just one example, which explains just one potential way of accomplishing the CO2-to-CH4 transmutation, in:
USDOE Converts Sequestered CO2 to Methane | Research & Development; wherein is disclosed: "Biogenic Methane: A Long-Term CO2 Recycle Concept; U.S. Department of Energy; This paper explores some of these opportunities (for Carbon Dioxide "sequestration' through reuse), and focuses on one “value-added” concept (i.e.,) biogenic methane. (That) concept is the geologic storage of CO2 in depleting and depleted oil and gas reservoirs, with subsequent conversion of the CO2 to CH4 via designer microbes or biomimetic systems that operate either below or above ground."
And, again, once the USDOE has the Methane, made, perhaps, as immediately above, from Carbon Dioxide, they posit that such CO2-derived Methane can be reacted with even more Carbon Dioxide; and, be made thereby to form hydrocarbon synthesis gas, as further witnessed by our excerpts, with additional comment appended, from the initial link in this dispatch to:
"United States Patent 6,187,226 - Method for Production of Carbon Monoxide and Hydrogen
Date: February, 2001
Inventors: Brent Detering and Peter Kong, Idaho
Assignee: Bechtel BWXT Idaho, LLC, Idaho Falls
(We must, unfortunately, interrupt here to explain the assignment of rights. As we once reported, our United States Government, in it's wisdom, has seen fit to start "farming out" the management of our critical USDOE National Laboratories to consortiums of private and semi-private corporate and institutional entities; which entities are not only paid to manage the laboratories, but, who are as well entitled to assume ownership of inventions developed by US Government-employed, tax dollar-paid scientists working in US Government-owned, tax dollar-financed facilities. At the time the subject US Patent of this dispatch was issued, the USDOE's Idaho National Laboratory was under the management of the above-named "Bechtel BWXT Idaho, LLC"; and, the best description of who and what "Bechtel BWXT" was and did we were able to find is accessible on the web site of one of the former partners, Babcock and Wilcox, a long-time military contractor, via:
Babcock & Wilcox Technical Services Group, Inc.: Locations - Business Units - B&W.
However, subsequent to issuance of our subject "United States Patent 6,187,226", the USDOE reassigned management of the Idaho Lab, as in:
Idaho National Laboratory Management for Nuclear Research, Development & Demonstration Laboratory
"In 2005, Battelle Energy Alliance assumed the management and operational responsibility for the newly named Idaho National Laboratory. The Battelle-led team was selected to transform INL into the nation’s pre-eminent nuclear research, development, and demonstration laboratory. As the leader of a national renaissance in nuclear energy, INL will chart the course for the next generation of nuclear power systems to develop Generation-IV reactor technologies, advanced fuel cycles, space nuclear power systems, and approaches to more efficiently produce hydrogen."
And, more concerning the management change can be learned via:
Master Government List of Federally Funded Research and Development Centers; wherein it's revealed:
"On February 1, 2005, the Idaho National Engineering and Environmental Laboratory was renamed the Idaho National Laboratory (INL). Also, INL's administrator has changed from Bechtel BWXT Idaho, LLC to Battelle Energy Alliance, LLC."
We regret the need for that lengthy interruption; but, not as much as we regret the fact that such questionable twists and turns have actually been allowed and enabled by the supposedly-representative managers of both our public wealth and our public interests.
But, we return to the technical specifics of our subject "United States Patent 6,187,226", as follows:)
Abstract: Carbon monoxide is produced in a fast quench reactor. The production of carbon monoxide includes injecting carbon dioxide and some air into a reactor chamber having a high temperature at its inlet and a rapidly expanding a reactant stream, such as a restrictive convergent-divergent nozzle at its outlet end. Carbon dioxide and other reactants such as methane ... are injected into the reactor chamber. Other gas may be added at different stages in the process to form a desired end product and prevent back reactions. The resulting heated gaseous stream is then rapidly cooled by expansion of the gaseous stream.
The United States Government has rights in this invention pursuant to Contract No. DE-AC07-941D13223 between the United States Department of Energy and Lockheed Martin Idaho Technologies Company.
(Again, yet another private corporation is seen to be sharing in this publicly-funded prize. - JtM)
Claims: A method for thermally converting one or more carbon-containing reactants in a thermodynamically stable high temperature gaseous stream to at least one reaction product, comprising the following steps:
(And) introducing a reactant stream that provides a source of carbon atoms and a source of oxygen atoms at one axial end of a reaction chamber containing an ionized gas, the reaction chamber comprising an inlet end and an outlet end;
(And) heating the reactant stream in the reaction chamber to form a carbon monoxide containing reaction product stream; and collecting the reaction product.
The method ... wherein ... the reactant stream further comprising methane.
The method ... wherein the reactant stream contains carbon dioxide.
The method ... (wherein) the reactant stream further (comprises) methane and carbon dioxide ... in a methane to carbon dioxide ratio of about 1:1 (and/or) greater than 1:1.
The method ... wherein heating is accomplished by introducing a stream of plasma arc gas to a plasma torch at the one axial end of the reaction chamber to produce a plasma within the reaction chamber which extends toward its remaining axial end.
The method ... wherein the reaction product includes a product ratio of about 1.75 mole carbon monoxide, to about 0.1 mole carbon dioxide, to about 1.5 mole diatomic hydrogen, to about 0.2 mole water, and the balance impurities.
(The co-produced Water and the passed-through Carbon Dioxide are, in other words, negligible. - JtM)
A method for thermal conversion of a carbon atom source in a thermodynamically stable high temperature gaseous stream to carbon monoxide ... wherein the carbon atom source comprises carbon dioxide.
A method for thermal conversion of a carbon atom source in a thermodynamically stable high temperature gaseous stream to carbon monoxide ... wherein the carbon atom source includes a light hydrocarbon selected from the group consisting of methane, ethane, propane, and butane.
A method for thermal conversion of a carbon atom source in a thermodynamically stable high temperature gaseous stream to carbon monoxide ... wherein the oxygen atom source is carbon dioxide.
A method for thermal conversion of a carbon atom source in a thermodynamically stable high temperature gaseous stream to carbon monoxide ... wherein the carbon atom source is carbon dioxide and methane in a molar ratio of about 1:1 (or) in a molar ratio of more methane than carbon dioxide.
Background and Field: This present invention relates to equipment for thermal conversion of a source of carbon atoms and a source of oxygen atoms and other reactants such as methane to desired end products, particularly carbon monoxide and hydrogen.
Carbon dioxide is a generally inert gas that is produced in abundance by combustion processes (such as) slash and burn deforesting that occurs in developing countries (and) carbon dioxide is constantly being produced.
(Pay heed to the following, Marcellus Shale fans:)
Carbon dioxide is also often found in natural gas. As a natural gas component, carbon dioxide is a contaminant that lowers the burn efficiency of the natural gas. Natural gases that are being extracted from the North Slopes of Alaska may contain up to 20% carbon dioxide or more. At any amount, carbon dioxide acts as a contaminant for specific volume energy output.
Additionally, in petroleum refining operations, natural gas is often flared and carbon dioxide is present in abundance in the combustion products.
(Are such "petroleum refining operations", and Natural Gas producers, to be as punished and hobbled as Coal-fired electric utilities by pending Cap & Trade taxation; and, by the mandated Geologic Sequestration of CO2 in leaky old oil wells, for the purposes of subsidized secondary petroleum recovery?)
Carbon monoxide is a valuable intermediate for many industries. The prior technology for production of carbon monoxide involved steam and/or catalytic reforming of natural gas to form the products of carbon monoxide and diatomic hydrogen.
It would be an improvement in the art to utilize the abundant carbon dioxide, that is produced by the large number of operations around the globe, to generate the valuable intermediate of carbon monoxide.
Summary: The present invention relates to the formation of carbon monoxide and hydrogen from feed stocks containing carbon, oxygen, and simple hydrocarbons such as methane.
The present invention converts a predominantly carbon dioxide stream to carbon monoxide with minor amounts of impurities. The present invention also converts a carbon dioxide-rich hydrocarbon stream into carbon monoxide, diatomic hydrogen, and minor impurities including elemental carbon.
(Deeper in the bowels of the highly-technical Disclosure, the inventors reveal that such "elemental carbon" can be recycled back into the system and made to form more Carbon Monoxide.)
The present reactor and method are directed toward high temperature reactions that decompose sources of carbon and oxygen as well as hydrocarbons such as methane into thermodynamically stable compounds of carbon monoxide and diatomic hydrogen ... .
Another source of carbon atoms is pure carbon such as carbon black and the like. In its simplest form, production of carbon monoxide may be carried out using pure carbon and carbon dioxide according to the following equation: (CO2 + C = 2CO).
(As in now many of our previous reports documenting the fact, CO2 can be converted into the reactive and valuable Carbon Monoxide by simply mixing CO2 with red-hot Carbon; and, if preferable, incandescent Coal dust will work just fine as the Carbon source. However, this also admits of the fact that the "minor impurities including elemental carbon" which are co-produced by this system can be recycled back into the system, for further reactions with more Carbon Dioxide, and subsequent production of more Carbon Monoxide)
Carbon monoxide and diatomic hydrogen are especially preferred products made according to this invention."
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And, CO and H2 are the "especially preferred products made according to this invention", because, although the Idaho Lab doesn't come right out and say so, since, as seen in:
Syngas - Wikipedia, the free encyclopedia - "Syngas (from "synthetic gas" or "synthesis gas") is the name given to a gas mixture that contains varying amounts of carbon monoxide and hydrogen. Examples of production methods include ... the gasification of coal. The name comes from (it's) use as (an) intermediate in creating synthetic natural gas (SNG)[and for producing ... methanol. Syngas is also used (to produce)
synthetic petroleum for use as a fuel or lubricant via the Fischer-Tropsch process (and related technology)";
and, in:
Syngas as fuel - What is syngas - Synthesis gas - "As its unabbreviated name implies, Synthesis gas is mainly used as an intermediary building block for the final production (synthesis) of various fuels such as synthetic natural gas, methanol and synthetic petroleum fuel (i.e.,) synthesized gasoline and diesel fuel";
such "Carbon monoxide and diatomic hydrogen" can be catalytically converted into hydrocarbon fuels.
Once again, this USDOE Carbon Dioxide recycling technology is derivative of many similar that have been developed over the course of many decades; and, which development continues, unheralded, within the petroleum industry itself, as seen, for another instance, in:
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 ... (that is, a) process for converting methane to higher hydrocarbons (by) 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".
Finally, to belabor the point, we can obtain such valuable Methane, CH4, which can be so utilized in converting Carbon Dioxide, reclaimed from whatever handy source, perhaps a brewery, into the "thermodynamically stable compounds of carbon monoxide and diatomic hydrogen" which can then be converted into "liquid hydrocarbons", either, as in:
Exxon Converts 99% of Coal to Methane | Research & Development; which makes report of: "United States Patent 4,077,778 - Process for the Catalytic Gasification of Coal; 1978; Assignee: Exxon Research and Engineering Company; Abstract: A process for the production of synthetic natural gas from ... coal";
by the appropriate conversion of some of our abundant Coal; or, as seen in:
NASA Recycles CO2 to Methane at Room Temp | Research & Development | News; concerning the: "Electrocatalytic Reduction of Carbon Dioxide to Methane; Lyndon B. Johnson Space Center; 2008;
(An) electrocatalytic process that effects the overall chemical reaction CO2 + 2H2O = CH4 + 2O2";
by the appropriate recycling of Carbon Dioxide itself.