WV Coal Member Meeting 2024 1240x200 1 1

USDOE CO2 + Hydrogen = Methanol and Ethanol

United States Patent: 7858667

Since we have lately been documenting the facts, as seen recently in:

West Virginia Coal Association | USDOE Efficient Hydrogen for Liquid Fuel Synthesis | Research & Development; concerning:

"United States Patent Application 20120149789 - Apparatus and Methods for the Electrolysis of Water; 2012; Inventor: Elias Greenbaum; Assignee: UT-Battelle, LLC; Oak Ridge, TN; ("UT-Battelle, LLC is a limited liability partnership between the University of Tennessee and Battelle Memorial Institute that manages the Oak Ridge National Laboratory for the United States Department of Energy.") Abstract: An apparatus for the electrolytic splitting of water into hydrogen and/or oxygen";
and, in:

West Virginia Coal Association | Efficient September, 2012, CO2 Air Capture | Research & Development; concerning:

"United States Patent 8,273,160 - Method and Apparatus for Extracting Carbon Dioxide from Air; 2012;
Inventors: Alan Wright, Klaus Lackner, and Ursula Ginster, AZ; Assignee: Kilimanjaro Energy, Inc., San Francisco, CA; Abstract: A method and apparatus for extracting CO2 from air comprising an anion exchange material formed in a matrix exposed to a flow of the air, and for delivering that extracted CO2 to controlled environments. The present invention contemplates the extraction of CO2 from air using conventional extraction methods or by using one of the extraction methods disclosed; e.g., humidity swing or electro dialysis. The present invention also provides delivery of the CO2";

that we can, using environmental energies to drive the processes, efficiently harvest and extract both Carbon Dioxide and Hydrogen from our environment, we wanted herein to affirm another fact:

Once we have Carbon Dioxide and Hydrogen in hand, no matter what the sources of them might be, we can, on a practical basis, react them catalytically together in the synthesis of fuel alcohols.

As seen in excerpts from the initial link in this dispatch to:

"United States Patent 7,858,667 - Alcohol Synthesis from CO or CO2

Alcohol synthesis from CO or CO2 - Battelle Memorial Institute

Date: December 28, 2010

Inventors: Jianli Hu, et. al., WA and TX

Assignee: Battelle Memorial Institute, WA

(John (Jianli) Hu | LinkedIn; "Research Project Manager; Pacific Northwest National Laboratory; 1999 – 2007; Managed and supervised chemical process and catalysis R&D projects funded by U.S federal agencies, DOE, DOD, USDA and NASA as well as industrial companies: Biomass conversion to bio-fuels and chemcals, Fischer-Tropsch catalyst and process".

Pacific Northwest National Laboratory; "United States Department of Energy; Pacific Northwest National Laboratory; Proudly operated by Battelle since 1965".

http://www.battelle.org/; "Committed to science and technology for the greater good, Battelle is a global research and development organization creating value through innovation for our clients, the nation and the world. Battelle Memorial Institute is the world’s largest nonprofit research and development organization, with over 20,000 employees at more than 100 locations globally. Based in Columbus, Ohio, Battelle is a 501(c)(3) charitable trust founded in 1929 on industrialist-turned-researcher Gordon Battelle’s vision that business and scientific interests can go hand-in-hand as forces for positive change".

Battelle Memorial Institute - Wikipedia, the free encyclopedia; "Battelle Memorial Institute is a private nonprofit applied science and technology development company headquartered in Columbus, Ohio. Battelle is a charitable trust organized as a nonprofit corporation under the laws of the State of Ohio and is exempt from taxation under Section 501(c)(3) of the Internal Revenue Code because it is organized for charitable, scientific and education purposes. The institute opened in 1929 but traces its origins to the 1923 will of Ohio industrialist Gordon Battelle which provided for its creation. Originally focusing on contract research and development work in the areas of metals and material science, Battelle is now an international science and technology enterprise that explores emerging areas of science, develops and commercializes technology, and manages laboratories for customers".)

Abstract: Methods for producing alcohols from CO or CO2 and H2 utilizing a palladium-zinc (Pd--Zn) on alumina catalyst are described. Methods of synthesizing alcohols over various catalysts in microchannels are also described. Ethanol, higher alcohols, and other C2+ oxygenates can be produced utilizing Rh--Mn (Rhodium and Manganese) or a Fisher-Tropsch catalyst.

A portion of this work was funded by the U.S. DOE ... under Contract DE-AC06-76RL01830.

Claims: A method of synthesizing alcohols from CO or CO2 comprising: flowing a reactant gas mixture comprising H2 and CO or CO2 into contact with a catalyst; wherein the catalyst comprises a Pd--Zn alloy dispersed on alumina; and forming an alcohol or alcohols.

The method ... wherein the alcohol or alcohols formed in the step of forming an alcohol or alcohols consists essentially of methanol.

The method ... wherein the catalyst further comprises a Fisher-Tropsch catalyst and wherein the alcohol or alcohols formed (is) a mixture of alcohols in which ethanol is the principle alcohol.

The method ... wherein the catalyst comprises the Pd--Zn alloy dispersed on alumina catalyst and a Fisher-Tropsch catalyst that are mixed together (and, wherein) the contact time is less than 1 second.

(Note, above, that this is a fast process, with implications for high productivity.)

The method ...wherein the catalyst comprises crystalline ZnO (Zinc Oxide).

The method ... wherein the reactant gas mixture comprises CO, and CO reacts with H2 to form methanol.

A method of synthesizing ethanol or higher alcohols from CO2 comprising: flowing a reactant gas mixture comprising CO2 and H2 into contact with a catalyst; wherein the catalyst comprises: (a) Pd--Zn alloy dispersed on alumina and (b) a Fischer-Tropsch catalyst; and forming ethanol or higher alcohols.

The method ... wherein the alcohol synthesis catalyst and Fischer-Tropsch catalyst are mixed together (or) are sequentially arranged ... .

A method of synthesizing alcohols from CO or CO2 comprising: flowing a reactant gas mixture comprising H2 and CO or CO2 into contact with a catalyst; wherein the catalyst comprises Pd and Zn dispersed on alumina; wherein the catalyst has been activated by reducing in the presence of hydrogen at a temperature of at least 350 C.; and forming an alcohol or alcohols.

(Note, that, as the full Disclosure makes clear, either Carbon Monoxide or Carbon Dioxide alone, or a mixture of the two gases, can be used and consumed; with the result being variations in the mix of product alcohols; with Methanol, as we read it, being preferentially synthesized from Carbon Monoxide; while Ethanol is formed from Carbon Dioxide. That, again, is just as we read it. Other products, too, can be formed, by varying the ways in which the alcohol synthesis and Fischer-Tropsch synthesis catalysts are disposed in relation to each other. Should the product mix obtainable via use of Carbon Monoxide be for some reason preferable, we remind you, that, as seen for just one example in our report of: 

West Virginia Coal Association | Germany 98% Pure Carbon Monoxide from Coal, CO2 and O2 | Research & Development; concerning: "Carbon Monoxide from Coke, Carbon Dioxide and Oxygen; Hydrocarbon Process(US); 1986; Research Organization: Lurgi GmbH";

we can make any desired Carbon Monoxide from Carbon Dioxide - and, a little Coal.)

Background and Field: The invention relates to methods of alcohol synthesis, catalysts for alcohol synthesis, and systems for synthesizing alcohols. Methods of reacting alcohols are also included in some aspects of the invention.

The synthesis of ethanol and higher alcohols from CO2 is possible via the use of composite catalysts that include a Fisher-Tropsch catalyst ... .

(Since the employment of "a Fisher-Tropsch", i.e., Fischer-Tropsch, "catalyst" is specified, without a lot of further explanation, we remind you that Fischer-Tropsch technology is now nearly ancient, and was developed originally to help effect the indirect conversion of Coal into liquid hydrocarbon fuels. The range of catalysts that will work for the Fischer-Tropsch synthesis of hydrocarbons from "synthesis gas" is fairly broad, and doesn't necessarily include materials that are too expensive or exotic; with Iron and Iron Group metals being the original materials of choice.

A discussion of the basics and options can be accessed via:

http://en.wikipedia.org/wiki/Fischer%E2%80%93Tropsch_process#Process_conditions;

and, we'll have more to offer on the subject in future reports. One problem for us has been that the basic Fischer-Tropsch Coal conversion technology seems to be treated almost as common knowledge, with few scientists or scholars making the effort to fully explain the elementary basics for what might be a more general, less technically-sophisticated audience - at least in a concise and readily-accessible form.)

In a further aspect, the invention provides a new method of synthesizing alcohols from CO2 comprising: flowing a reactant gas mixture comprising CO2 and H2 into contact with a catalyst; wherein the catalyst comprises Pd and Zn dispersed on alumina; and forming an alcohol or alcohols.

In (one) aspect, the invention provides a method of synthesizing ethanol and higher alcohols from CO2 comprising: flowing a reactant gas mixture comprising CO2 and H2 into contact with a catalyst; wherein the catalyst comprises: (a) Pd--Zn alloy dispersed on alumina and (b) a Fisher-Tropsch catalyst; and forming ethanol and higher alcohols."

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The full Disclosure is actually much more complicated and extensive, and includes details about the further reaction of synthesized alcohols to create higher alcohols.

But, the thing to keep in mind is, at it's basis, our subject herein, "United States Patent 7,858,667", is the disclosure of a technology for "Alcohol Synthesis from CO or" Carbon Dioxide.

The alcohols which can be synthesized via the process of the invention are specified to include Methanol and Ethanol; and, to beat it to death, once we have Methanol and/or Ethanol, as efficiently synthesized via the process of our subject herein, "United States Patent 7,858,667 - Alcohol Synthesis from CO or CO2", we can, as seen for one example in:

West Virginia Coal Association | Mobil Oil 1977 Coal-Derived Alcohols to Gasoline | Research & Development; concerning:

"United States Patent 4,025,575 - Process for Manufacturing Olefins; 1977; Mobil Oil Corporation;   Abstract: A lower alcohol and/or ether feed is selectively converted to a mixture of light olefins, including ethylene and propylene, by catalytic contact of the feed, for example methanol or dimethyl ether, ... with certain crystalline aluminosilicate zeolite catalysts exemplified by HZSM-5. (A) method for converting a feed to light olefins ... wherein said feed comprises methanol or ... ethanol. Generally, the mixture of olefins produced by this invention, even with a single alcohol feed, contains mostly ethylene, propylene, and the butylenes with a small pentenes component. The alcohols may be manufactured from synthesis gas, i.e. a mixture of CO and H2 made from coal";

convert those alcohols into a range of hydrocarbons, including gasoline blending stock and the basic building blocks for polymers, i.e. "ethylene" and "propylene", from which can be made valuable plastics, wherein the Carbon Dioxide consumed, via the process of our subject, "United States Patent 7,858,667 - Alcohol Synthesis from CO or CO2", would be permanently and productively "sequestered".

And, even though that would seem a good place to end our dissertation, the above has even more, rather direct and interesting, implications for both the fuller, more profitable employment, and the conservation, of our precious Coal resources.

As we've previously reported, for one instance in:

West Virginia Coal Association | GE Converts China Coal to Methanol | Research & Development; concerning:

"'One of the World’s Largest Coal-to-Olefins Gasification Units Starts Up in China'; Beijing, August 12, 2010; The gasification unit at one of the world’s largest coal-to-olefins projects successfully started up at the China Shenhua Coal to Liquid and Chemical Co. Ltd.’s project in Baotou, Inner Mongolia (Shenhua Baotou Coal to Olefins project). The gasification unit uses advanced coal gasification technology provided by GE (NYSE:GE). The gasification technology converts coal into a synthesis gas (or syngas). Syngas can then be used to produce methanol, which will be transformed into olefins, a building block for producing polyethylene and polypropylene. At full production—scheduled for fourth quarter of 2010—the Shenhua Baotou Coal to Olefins project will produce nearly 1.8 million tons of methanol for approximately 600,000 tons of polyethylene and polypropylene per year";

Coal, too, can be converted into Methanol, and, subsequently, into "ethylene" and "propylene", and, thence, into "polyethylene and polypropylene".

And, interestingly, as can be learned separately via:

Coal-to-chemical projects are risky, Deloitte warns -- Shanghai Daily | ???? -- English Window to China New; "Coal-to-Chemical Projects Are Risky; Shanghai Daily; November 30, 2012";

the "Dow Chemical Company and top Chinese (actually, top world) coal producer Shenhua Group" are second-guessing another planned facility for the conversion of Coal into "ethylene and propylene" which are to be used "in the production of ... polymers", such as, we submit, "polyethylene and polypropylene", because, in part, of "uncertainty" over a "carbon tax", which might "offset the cost advantages of (such Coal conversion) projects".

The article explains that, although China currently has export capacity of "polyethylene and polypropylene" based in part on their manufacture from petroleum, making those polymers from domestic Coal is much cheaper.

Those "cost advantages" might be lost, however, if a "carbon tax" were to be applied to any co-product CO2 arising from the Coal conversion facility; and, China, like the US, is considering, in the face of international pressure, just such a counterproductive, and we think suspicion-arousing, move.

What if, instead, they were to utilize the process of our subject herein, "US Patent 7,858,667 - Alcohol Synthesis from CO or CO2", to make, through Methanol and Ethanol, and "ethylene and propylene", even more "polyethylene and polypropylene" from any Carbon Dioxide emitted by the Coal-to-"polyethylene and polypropylene" facility?

How productive, and how competitive, would such a Coal conversion plant then be, with a Carbon Dioxide emission control system that actually made even more of the core products being synthesized, primarily, from Coal?

CO2 emissions, and taxes on them, would be avoided; production of the key products would be maximized; and, Coal would be conserved through much more complete utilization of it's basic Carbon content.

All the tools, without argument, are in place and available for us to use to create a win-win situation for ourselves - and for our families, for our friends - if we have any, and, our for fellow US citizens in US Coal Country.

And, we, here, have to ask the question: Do we, all of us in US Coal Country, want to win?

If so, then, Coal Country press, silence is no longer an option.

Only the losers walk off the field and disappear, slink into the tunnel, quietly.