United States Patent: 8710106

We've written many times about the 1912 Nobel Prize-winning Sabatier process, wherein Carbon Dioxide is converted directly into substitute natural gas Methane with, as the inventor of the technology, Paul Sabatier, put it in his Nobel Prize acceptance speech: "the greatest ease".

For more details, see our report of:

CO2 Solution Wins Nobel Prize - in 1912 | Research & Development | News.

The Sabatier process, as succinctly explained separately, by the National Aeronautics and Space Administration, NASA, and it's contractors, via:

 

http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/20120016419.pdf ; concerning:

"'Compact and Lightweight Sabatier Reactor for Carbon Dioxide Reduction'; Christian Junaedi, et. al., Precision Combustion, Inc., North Haven, CT,and NASA George C. Marshall Space Flight Center, Huntsville, AL; The utilization of CO2 to produce life support consumables, such as O2 and H2O, via the Sabatier reaction is an important aspect of NASA’s cabin Atmosphere Revitalization System and In-Situ Resource Utilization architectures for both low-earth orbit and long-term manned space missions. In the current International Space Station (ISS) and other low orbit missions, metabolically-generated CO2 is removed from the cabin air and vented into space, resulting in a net loss of O2. This requires a continuous resupply of O2 via water electrolysis, and thus highlights the need for large water storage capacity. For long-duration space
missions, the amount of life support consumables is limited and resupply options are practically nonexistent, thus atmosphere resource management and recycle becomes crucial to significantly reduce necessary O2 and H2O storage. Additionally, the potential use of the Martian CO2-rich atmosphere and Lunar regolith to generate life support consumables and propellant fuels is of interest to NASA. Precision Combustion, Inc. (PCI) has developed a compact, lightweight Microlith(r)-based Sabatier (CO2 methanation) reactor which
demonstrates the capability of achieving high CO2 conversion and near 100% CH4 selectivity ... . The combination of the Microlith(r) substrates and durable, novel catalyst coating permitted efficient Sabatier reactor operation that favors high reactant conversion, high selectivity, and long-term durability. This paper presents the reactor development and performance results at various operating conditions. Additionally,
results from 100-hr durability tests and mechanical vibration tests are discussed. The Sabatier process is an exothermic reaction and is limited by the thermodynamic equilibrium. Lower operating temperatures, typically around 250-400 C, are desirable for higher CO2 conversion and higher CH4 selectivity";

is one in which Carbon Dioxide and elemental, molecular Hydrogen can be made to react together, when properly catalyzed, to form Methane, CH4, and co-product H2O, with such "ease", as Sabatier said, that the reaction is "exothermic", and generates so much heat energy that heat must be extracted from the reactor to maintain "higher CO2 conversion and higher CH4 (Methane) selectivity".

If anyone is motivated enough to research the literature, you will find some smug dismissals of the Sabatier process, for producing Methane from Carbon Dioxide, offered by partisans of the natural gas industry, on the basis that producing the needed Hydrogen is too expensive. How producing Hydrogen could be more expensive than drilling and fracking a mile deep for shale gas, or be more expensive than thinly-veiled revenue grabs like Cap and Trade carbon taxation, is beyond us. And, it is patently untrue.

As NASA themselves explained, as in our report of:

NASA Hydrogen from Water and Sunlight | Research & Development | News; 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";

we can generate the needed Hydrogen by using freely-available sunlight to extract it from the abundant Water, H2O, molecule.

Also, you will find, even in some popular and generally accepted web references, the Sabatier reaction summed, or illustrated, incorrectly. It is occasionally expressed as if heat energy needs to be applied to the Carbon Dioxide and the Hydrogen to drive the reaction to form Methane. That is untrue. An initial temperature of the catalyst bed must be achieved to start the reaction. Then, the exothermic heat generated by the reaction itself is enough to keep it going. In fact, the exothermic heat of the Sabatier reaction is produced in such abundance that the reaction chamber or vessel must be cooled in order to maintain the CO2-to-Methane conversion at it's highest efficiency.  

As NASA put it in their above report "Compact and Lightweight Sabatier Reactor for Carbon Dioxide Reduction", it is possible to maintain the reaction conditions so that "high CO2 conversion and near 100% CH4 selectivity" can be achieved.

And, that was the focus of a NASA-sponsored development about which we earlier reported, via:

NASA Improves CO2 to Methane Conversion | Research & Development | News; concerning: "United States Patent Application 20120029095 - Sabatier Process and Apparatus for Controlling Exothermic Reaction; 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 InterestsThis 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";

in which NASA contractors designed a Sabatier reactor that would control the temperature of, and remove exothermic heat from, the Carbon Dioxide + Hydrogen = Methane reaction. 

And, herein we learn that, less than one month ago, technical experts in the employ of our United States Government's Patent and Trademark Office validated that Methane synthesis innovation as real and practicable technology, via their allowance of, as excerpted from the initial link in this dispatch:

"United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction

Patent US8710106 - Sabatier process and apparatus for controlling exothermic reaction - Google Patents

Sabatier process and apparatus for controlling exothermic reaction - Precision Combustion, Inc.

Date: April 29, 2014

Inventors: Christian Junaedi, et. al., CT

Assignee: Precision Combustion, Inc., CT

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 Support: 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: The tax money collected from each and every one of us paid to have this CO2-to-Methane process developed; and, thus, through our "U.S. Government", We the People, all of us, own "rights in this invention". We, here, wonder if those rights extend to even being told, openly and publicly, that such valuable Carbon Dioxide utilization technology even exists.)

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.

(With regards to the above "carbon dioxide ... obtained from ... Earth's atmosphere", see, for just one example, our report of:

Efficient Capture of Atmospheric CO2 | Research & Development | News; concerning: "United States Patent 7,993,432 - Air Collector ... for Capturing Ambient CO2; 2011; Assignee: Kilimanjaro Energy, Inc., WI; Abstract: An apparatus for capture of CO2 from the atmosphere".)

The process ... wherein the hydrogen is obtained from ... 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 (and) 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 "Group VIII metals", after revisions to the original and older versions of the Periodic Chart of Elements would include, now, realistically for these purposes, only Iron and Ruthenium. Nickel, once a Group "VIIIB" metal, was the original catalyst used by Paul Sabatier to convert CO2 into Methane. Cobalt might work, as well, but: As explained in the full Disclosure and by literature referenced by the Disclosure, Iron and Ruthenium are the preferred catalytic metals since the CO2-to-Methane conversion proceeds a little more slowly over them, and, less exothermic reaction heat is generated. Use of those catalysts helps to maintain the temperature in the reaction zone in the optimal range for Methane production. Temperatures that are too high or too low can result in the generation of other, unwanted, products, such as Carbon Monoxide and elemental Carbon. Note, however, that, a full exposition of the complete Sabatier reaction demonstrates that it is a combination of Carbon Dioxide reduction by Hydrogen, to first form Carbon Monoxide, as in the reverse water gas shift reaction explained in our report of:

France Efficient CO2 to Carbon Monoxide Conversion | Research & Development | News; concerning: "United States Patent Application 20030113244 - Method for Producing Carbon Monoxide by Reverse Conversion with an Adapted Catalyst; 2003; Assignee: Air Liquide; Abstract: The invention concerns a method for producing carbon monoxide by reverse conversion, in gas phase, of carbonic acid gas and gaseous hydrogen while minimising the production of methane";

followed by the hydrogenation of the Carbon Monoxide by Hydrogen to form Methane. Thus, either Carbon Monoxide or Methane, which are both valuable products, can be made from Carbon Dioxide via reaction with elemental, molecular Hydrogen. In the case of our NASA-sponsored technology herein, the temperature and other conditions are being controlled to maximize the production of Methane and minimize the production of Carbon Monoxide, while in the case of Air Liquide's above-cited process of "Application 20030113244" the reverse is desired.)

The process ... wherein the first reaction zone is maintained at a first designated temperature greater than 300 C and less than 600 C, and the second reaction zone is maintained at a second designated temperature equal to or less than 350 C but greater than 100 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 (and) 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. 

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

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We're going to close our excerpts right there, even though the full Disclosure goes on at great length, explaining how a Carbon Dioxide conversion of roughly ninety percent, with a high Methane product selectivity, can be maintained, and demonstrating that a truly commendable and admirable amount of study and development has been devoted to this CO2-to-Methane technology. A full read is recommended.

Further, and importantly, the full Disclosure explains that, although this invention was originally conceived for application and use aboard spacecraft, or on, for instance, as per other NASA publications, the planet Mars, the disclosed technology can be adapted and sized for "industrial" applications.

Again, elemental, molecular Hydrogen is required herein to effect the transformation of Carbon Dioxide into substitute natural gas Methane, and, we remind you that, as seen for another example in our report of:

USDOE Renewable Energy Extracts Hydrogen from Water | Research & Development | News; concerning: "United States Patent 8,444,846 - Method and System for Producing Hydrogen Using Sodium Ion Separation Membranes; 2013; Abstract: A method of producing hydrogen from sodium hydroxide and water is disclosed. ... A system of producing hydrogen is also disclosed. Government Interests/Government Rights: This invention was made under a Cooperative Research and Development Agreement between Alberta Limited and Battelle Energy Alliance, LLC under Contract No. DE- AC07-051D14517, awarded by the U.S. Department of Energy. The U.S. Government has certain rights in the invention. Claims: A method of producing hydrogen ... wherein applying an electric potential to the electrochemical cell comprises supplying an electric potential to the electrochemical cell from at least one of solar power, geothermal power, hydroelectric power, wind power";

we're getting pretty good at harnessing environmental energy to help us extract Hydrogen from Water.

But, we're closing our excerpts from our subject, "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction", with the claim that "the methane" synthesized from CO2 "is converted to methanol" in order to remind you that, as seen for two examples in our reports of:

California 2013 CO2 + Methane = Methanol | Research & Development | News; concerning: "United States Patent 8,440,729 - Conversion of CO2 to Methanol Using Bi-Reforming of Methane; Date: May 14, 2013; Inventors: George Olah and G.K. Surya Prakash, CA; Assignee: University of Southern California, Los Angeles; Abstract: The invention provides for 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"; and:

US Gov Confirms Coal Can Be A CO2-Neutral Source Of Power | Research & Development | News; concerning: "United States Patent 8,461,215 - Rendering Coal As An Environmentally Carbon Dioxide Neutral Fuel And A Regenerative Carbon Source; June 11, 2013; Inventors: George Olah and G.K. Surya Prakash, CA; Assignee: The University of Southern California, Los Angeles; Abstract: The invention provides a method for rendering coal as an environmentally essentially carbon dioxide-neutral fuel. Carbon dioxide produced from coal combustion is captured, purified, combined with ... methane ... and reacted under reaction conditions sufficient to form methanol";

as taught by another Nobel Prize-winning chemist, one way to convert the Methane, made, via the process of our subject herein, "United States Patent 8,710,106 - Sabatier Process and Apparatus for Controlling Exothermic Reaction", from Carbon Dioxide, into, as per our final excerpted claim, "methanol", is to react that Carbon Dioxide-derived substitute natural gas Methane with even more Carbon Dioxide.

Now, as far as where we might get some of that, as herein, almost miraculously valuable raw material, Carbon Dioxide, we've documented a number of times, and will document further in reports to follow, how we can efficiently extract CO2 either from various industrial exhaust gases or even the atmosphere itself.

However, as seen in our recent report of:

USDOE 2014 Coal to Liquid Hydrocarbons + Pure CO2 | Research & Development | News; concerning: "United States Patent 8,674,152 - Coal Liquefaction by Base-Catalyzed Hydrolysis with CO2 Capture; March 18, 2014; Inventor: Xin Xiao, Georgia; Assignee: Savannah River Nuclear Solutions, LLC, South Carolina; Abstract: The one-step hydrolysis of diverse biomaterials including coal, cellulose materials such as lumber and forestry waste, non-food crop waste, lignin, vegetable oils, animal fats and other source materials used for biofuels under mild processing conditions which results in the formation of a liquid fuel product along with the recovery of a high purity CO2 product is provided. Government Interests: This invention was made with Government support under Contract No. DE-AC09-08SR22470 awarded by the United States Department of Energy. The Government has certain rights in the invention. ... The process ... wherein said CO2 ... may be recovered at an at least about 95% purity level.(and) wherein said liquid hydrocarbon fuel product is a distillable product that can be processed by a petroleum refinery";

there are other sources of "high purity CO2" available to us which might be even more profitable and productive, if, like the CO2-to-Methane synthesis  technology disclosed herein by "United States Patent 8,710,106", we were ever to be openly and fully informed of all the potentials available to us; and, then enabled to put them, and many more of our United States Coal Country fellow US citizens, to work.


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