United States Patent: 7879749

Every once in a while in the course of our research - - concerning the now-plain and incontrovertible facts, that, we can efficiently convert, by various means and methods, both our abundant domestic United States Coal and our, some say too-abundant, Carbon Dioxide natural resources into anything and everything we now squander our grandchildren's future prosperity, and our current US national security, to continue buying from our close friends, and enthusiastic boosters of democracy and the American way, in OPEC - - we trip over something that makes us go "Aha! It is the Grail!". (http://www.heroofcamelot.com/legend/holy-grail).

 

It could be, in other words, The Truth and The Answer.

And, maybe we do have that here, i.e.:

An ultimate expression of technology that answers all the questions about how we can make the United States of America completely self-sufficient in her supply of hydrocarbon fuels, and, if we want, reduce the rate of accumulation of Carbon Dioxide in the atmosphere while we do so.

First, since it is key, we note, that, as seen in our report of:

USDOE Renewable Energy Extracts Hydrogen from Water | Research & Development | News; concerning: "US Patent 8,444,846 - Method and System for Producing Hydrogen Using Sodium Ion Separation Membranes; 2013; Assignee: Battelle Energy Alliance, LLC, Idaho Falls (USDOE Idaho National Laboratory); Abstract: A method of producing hydrogen from sodium hydroxide and water is disclosed (and, 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. A method of producing hydrogen, comprising: providing an electrochemical cell (as described, and) 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 US citizens now own some rather revolutionary technology that enables us to, using various forms of environmental energy to drive the process, extract Hydrogen efficiently, and on a large scale, from plain old Water, H2O.

We know that there are concerns about our supply of clean drinking water, and the quality of the water in our streams and rivers. But, to extract Hydrogen from water, just about any water source, including that in the constantly-renewing oceans, can be utilized.

In any case, we remind you of another of our earlier reports:

Conoco Converts Coal to Methanol and Dimethyl Ether | Research & Development | News; concerning: "United States Patent 6,638,892 - Syngas Conversion and Catalyst Employed Therefor; 2003; Assignee: ConocoPhillips Company, Houston, (Texas); Abstract: A process for the conversion of syngas by contact of syngas under conversion conditions with catalyst having as components zinc oxide, copper oxide, aluminum oxide, ... zeolite and clay in ... a one step process for conversion of syngas to dimethyl ether (and) a two step process for conversion of syngas to light olefins ... . ...Synthesis gas (syngas) is a gaseous mixture of hydrogen and at least one carbon oxide, particularly carbon monoxide. Syngas is obtained using well known processes by the partial combustion or gasification of any organic material such as coal";

wherein a blend of Carbon Oxides, both CO and CO2, and Hydrogen, as perhaps derived by the "gasification of ... coal", can be converted in "a two step" process into "light olefins", that is, into gaseous and liquid hydrocarbons, via an initial condensation of the "syngas" into "dimethyl ether" and/or the closely-related Methanol, with subsequent, in the second "step", conversion of that intermediate product into hydrocarbon fuels, the "light olefins".

In passing, we'll note, that, as too often happens, the link we included in that report, to the official United States Patent and Trademark Office electronic record of  "United States Patent 6,638,892 - Syngas Conversion and Catalyst Employed Therefor", no longer functions properly. Here's a backup to an independent site's record of it:

Syngas conversion and catalyst system employed therefor - ConocoPhillips Company.

In any case, the ConocoPhillips "two-step" process of "United States Patent 6,638,892 - Syngas Conversion" is cited as direct, precedent art by the United States Department of Energy scientists, at the USDOE's Idaho National Laboratory, who have developed and demonstrated a process whereby the multiple steps of "United States Patent 6,638,892" are combined in a single, consolidated process for the conversion of Carbon Dioxide, and/or Carbon Monoxide, as obtained from whatever source, into fuel-grade hydrocarbons, including Gasoline.

For emphasis, we present a passage from the full USDOE patent Disclosure, which will be repeated in our more extended excerpts, i.e.: 

- - "Carbon dioxide gas (CO2) may be converted into liquid fuels such as, for example, hydrocarbon molecules of between about 5 and about 12 carbon atoms per molecule (e.g., gasoline) through multi-step reactions. For example, carbon dioxide (CO2) gas and hydrogen (H2) may be converted to carbon monoxide (CO) gas and water (H2O) through the Reverse Water-Gas Shift Reaction ... CO2 + H2 = CO + H2O.
Synthesis gas, which is a mixture of carbon monoxide gas (CO) and hydrogen gas (H2) then may be produced from the reaction products of the Reverse Water-Gas Shift Reaction by adding additional hydrogen gas (H2) to the reaction products. This synthesis gas may be further reacted through either Fischer-Tropsch (FT) processes, or through methanol synthesis (MS) plus methanol-to-gasoline (MTG) processes, to provide liquid fuels". - -

We'll reinforce and document some of the above via comments inserted within, and appended to, as excerpted from the initial link in this dispatch:

"United States Patent 7,879,749 - Methods of Using Structures Including Catalytic Materials Disposed Within Porous Zeolite Materials to Synthesize Hydrocarbons

Patent US7879749 - Methods of using structures including catalytic materials disposed within ... - Google Patents

Methods of using structures including catalytic materials disposed within porous zeolite materials to synthesize hydrocarbons

Date: February 1, 2011

Inventors: Harry Rollins, et. al., Idaho

Assignee: Battelle Energy Alliance, LLC, Twin Falls, Idaho

(http://www.battelle.org/our-work/laboratory-management/idaho-national-laboratory; "Idaho National Laboratory: Areas of Research: ... national security research and testing; development of sustainable energy and environmental solutions. Owned by: U.S. Department of Energy; Managed By:Battelle Energy Alliance, LLC (Battelle is the LLC member company, with Babcock & Wilcox, URS Corporation, Electric Power Research Institute and the Massachusetts Institute of Technology as integrated subcontractors)".)

Abstract: Catalytic structures include a catalytic material disposed within a zeolite material. The catalytic material may be capable of catalyzing a formation of methanol from carbon monoxide and/or carbon dioxide, and the zeolite material may be capable of catalyzing a formation of hydrocarbon molecules from methanol. The catalytic material may include copper and zinc oxide. The zeolite material may include a first plurality of pores substantially defined by a crystal structure of the zeolite material and a second plurality of pores dispersed throughout the zeolite material. Systems for synthesizing hydrocarbon molecules also include catalytic structures. Methods for synthesizing hydrocarbon molecules include contacting hydrogen and at least one of carbon monoxide and carbon dioxide with such catalytic structures. Catalytic structures are fabricated by forming a zeolite material at least partially around a template structure, removing the template structure, and introducing a catalytic material into the zeolite material.

Government Interests: This invention was made with government support under Contract No. DE-AC07-05ID14517 awarded by the United States Department of Energy. The government has certain rights in the invention.

Claims: A method of synthesizing hydrocarbon molecules having two or more carbon atoms, the method comprising: contacting hydrogen and at least one of carbon monoxide and carbon dioxide with a catalytic structure at a temperature greater than about 200 C and a pressure (as specified), the catalytic structure comprising: a zeolite material comprising: a (structure as described) ; and at least one catalytic material differing from the zeolite material disposed within pores of (the zeolite); catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen within (the) pores using the at least one catalytic material; and catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol within (the) pores using the zeolite material.

(We've discussed the use of "zeolite"s in hydrocarbon synthesis and conversion reactions in previous reports. More will follow in additional comment further on.) 

The method ... wherein contacting at least one of carbon monoxide and carbon dioxide with a catalytic structure comprises supplying a mixture of hydrogen and at least one of carbon monoxide and carbon dioxide to a reactor containing the catalytic structure. 

The method ... further comprising: removing reaction products and unreacted reactants from the reactor; cooling the reaction products and unreacted reactants; and separating unreacted reactants from the reaction products, the reaction products comprising hydrocarbon molecules having two or more carbon atoms (and) further comprising recombining the separated unreacted reactants with the mixture supplied to the reactor. 

The method ... wherein contacting hydrogen and ... carbon dioxide with a catalytic structure comprises contacting hydrogen and ... carbon dioxide with a plurality of pellets each comprising the zeolite material and the at least one catalytic material (and) further comprising selecting the plurality of particles of the catalytic material to comprise a plurality of metallic particles (and, which) metallic particles ... comprise at least one of copper, magnesium, zinc, cobalt, iron, nickel, ruthenium, platinum, palladium, and cesium. 

(If "copper, magnesium, zinc, cobalt, iron, nickel" will work, then we don't really need anything too rare, or too expensive.)

The method ... further comprising selecting the plurality of particles of the catalytic material to comprise a plurality of metal oxide particles (which) comprise at least one of zinc oxide, magnesium oxide, zirconium oxide, iron oxide, and tungsten oxide (and) further comprising selecting the at least one catalytic material to comprise copper and zinc oxide. 

The method ... further comprising forming the second plurality of pores to comprise a plurality of elongated channels (of shape and size described and specified; and) further comprising selecting the zeolite material to comprise a framework type selected from (specified groups, and) further comprising selecting the zeolite material to comprise an aluminosilicate-based material, an aluminophosphate-based material, or a silicoaluminophosphate-based material.

(The USDOE inventors include general specifications for the applicable zeolite minerals, which can be naturally-occurring or man-made. Although the mineralogical shorthand used to identify them in the full Disclosure will be gibberish to most of us, those specifications will be quite clear to those schooled in such matters. For some background, if interested, see:

http://www.asdn.net/asdn/chemistry/zeolites.shtml; "Zeolites are crystalline solids structures made of silicon, aluminum and oxygen that form a framework with cavities and channels inside where cations, water and/or small molecules may reside. They are often also referred to as molecular sieves. Many of them occur naturally as minerals, and are extensively mined in many parts of the world finding applications in industry and medicine. However, most of zeolites have been made synthetically some of them made for commercial use while others created by scientists to study their chemistry. At present, there are 191 unique zeolite frameworks identified, and over 40 naturally occurring zeolite frameworks are known".)

The method ... further comprising selecting the zeolite material to comprise ZSM-5.

(As seen, for one example, in our report of:

Mobil Oil 1978 Coal Conversion with Zeolite Catalyst | Research & Development | News; concerning: "United States Patent 4,086,262 - Conversion of Synthesis Gas to Hydrocarbon Mixtures; 1978; Assignee: Mobil Oil Corporation; Abstract: Contacting a mixture of carbon monoxide and hydrogen with an intimate mixture of a carbon monoxide reduction catalyst, such as a Fischer-Tropsch catalyst or a methanol synthesis catalyst, and an acidic crystalline aluminosilicate having a pore dimension greater than about 5 Angstroms to produce hydrocarbon mixtures useful in the manufacture of heating fuels, high octane gasoline .... and chemicals intermediates. ... The method ... wherein said acidic crystalline aluminosilicate is a H-ZSM-5 crystalline zeolite (and) wherein said carbon monoxide reducing catalyst is a Fischer-Tropsch catalyst (and) wherein said catalyst is formulated from a metal or compound of zinc, iron, cobalt, nickel (etc).
Processes for the conversion of coal ... to a gaseous mixture consisting essentially of hydrogen and carbon monoxide, or of hydrogen and carbon dioxide, or of hydrogen and carbon monoxide and carbon dioxide, are well known. Although various processes may be employed for the gasification, those of major importance depend either on the partial combustion of the fuel with an oxygen-containing gas or on the high temperature reaction of the fuel with steam, or on a combination of these two reactions";

the use of "ZSM-5" zeolite frameworks as the bases for the catalytic transformation of Carbon Oxides, whether or not derived from "the conversion of coal ... to a gaseous mixture ... of hydrogen and carbon monoxide and carbon dioxide", is well-known and is long-established art.)

Background and Field: The present invention relates to catalytic materials, structures, systems, and methods. More particularly, the present invention relates to catalytic structures including zeolite materials, and to systems and methods for synthesizing hydrocarbon molecules from hydrogen and at least one of carbon monoxide and carbon dioxide using such catalytic structures. The present invention also relates to methods of fabricating catalytic structures that include zeolite materials. 

Carbon dioxide gas (CO2) may be converted into liquid fuels such as, for example, hydrocarbon molecules of between about 5 and about 12 carbon atoms per molecule (e.g., gasoline) through multi-step reactions.

For example, carbon dioxide (CO2) gas and hydrogen (H2) may be converted to carbon monoxide (CO) gas and water (H2O) through the Reverse Water-Gas Shift Reaction ...: CO2 + H2 = CO +H2O ... .

(Concerning the above, and for more info on the long-known "Reverse Water-Gas Shift Reaction", see, for example, 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 (France); 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. ... Said method is preferably carried out continuously and comprises preferably the following steps which consist in: a) preparing a gas mixture rich in carbon dioxide and in hydrogen ... between 300 and 520 C (and) b) reacting said gas mixture, forming carbon monoxide and water vapour, by passing said mixture through a catalytic bed based on zinc oxide and chromium oxide maintained under pressure between 10 and 40 bars".)

Synthesis gas, which is a mixture of carbon monoxide gas (CO) and hydrogen gas (H2) then may be produced from the reaction products of the Reverse Water-Gas Shift Reaction by adding additional hydrogen gas (H2) to the reaction products.

(Again, "additional hydrogen gas (H2)" needs to be supplied to this process and system, whether to convert a feed of Carbon Dioxide, as recovered from whatever source, into, ultimately hydrocarbon "Synthesis gas", or, to upgrade - and reduce the CO2 content of - synthesis gas derived from Coal, as in our above-cited report concerning "United States Patent 4,086,262 - Conversion of Synthesis Gas to Hydrocarbon Mixtures; 1978; Mobil Oil Corporation".

And, as seen for yet another example in our report of:

NASA Hydrogen from Water and Sunlight | Research & Development | News; concerning: "US Patent 4,045,315 - Solar Photolysis of Water; 1977; NASA; Hydrogen is produced by the solar photolysis of water";

we are becoming proficient at extracting H2 from H2O in processes driven by environmental energy. )

This synthesis gas may be further reacted through either Fischer-Tropsch (FT) processes, or through methanol synthesis (MS) plus methanol-to-gasoline (MTG) processes, to provide liquid fuels.

Summary: In one example embodiment, the present invention includes a catalytic structure that includes a substantially crystalline zeolite material (as described) that is capable of catalyzing the formation of hydrocarbon molecules having two or more carbon atoms from methanol, and at least one catalytic material that is capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen disposed within the zeolite material.

In an additional example embodiment, the present invention includes methods of fabricating catalytic structures. A zeolite material capable of catalyzing the formation of hydrocarbon molecules from methanol may be formed at least partially around at least one template structure (and) at least one catalytic material capable of catalyzing the formation of methanol from at least one of carbon monoxide and carbon dioxide in the presence of hydrogen". 

-----------------------------

In sum, using the method, system and catalysts herein specified by the United States Department of Energy, we can convert Coal, into, first, Methanol, and, then, into Gasoline and other hydrocarbons, with little or no release of Carbon Dioxide, through an initial process of gasification, perhaps like that disclosed in our report of:

Exxon Co-Gasifies Coal and Carbon-Recycling Biomass | Research & Development | News; concerning: "US Patent Application 20100083575 - Co-gasification Process for Hydrocarbon Solids and Biomass; 2010; Assignee: ExxonMobil Research and Engineering Company; Abstract: A process for the co-gasification of carbonaceous solids (coal) and biomass ... .wherein the solid carbonaceous particles comprise coal (and) wherein the biomass comprises biological matter selected from wood, plant matter, municipal waste, green waste, byproducts of farming or food processing waste, sewage sludge, black liquor from wood pulp, and algae. One established route to the production of hydrocarbon liquids is the gasification of carbonaceous materials followed by the conversion of the produced synthesis gas to form liquids by processes such as Fischer-Tropsch and its variants. In this way, solid fuels such as coal ...may be converted to liquids";

wherein, again, Coal can be gasified along with any number of Carbon-recycling and continuously renewable organic wastes and products.

Or, since we can start with a gas mixture containing just "at least one of carbon monoxide and carbondioxide in the presence of hydrogen" - - note that "carbon monoxide" isn't needed, just extra Hydrogen if we start only with Carbon Dioxide - - we could extract the necessary CO2 for the initial Methanol production from, as explained by a Nobel laureate chemist in our report of:

California Captures CO2 for Conversion to Hydrocarbons | Research & Development | News; concerning: "US Patent 7,795,175 - Absorbents for the Separation of CO2 from Gas Mixtures Including the Air; 2010; Inventors: George Olah, et. al., CA; Assignee: University of Southern California, Los Angeles; Abstract: The invention relates to regenerative, supported amine sorbents that includes an amine or an amine/polyol composition deposited on a nano-structured support such as nanosilica. The sorbent provides structural integrity, as well as high selectivity and increased capacity for efficiently capturing carbon dioxide from gas mixtures, including the air. ... A method for continuously capturing and separating carbon dioxide from a gas mixture with a sorbent, which comprises exposing the sorbent (as described and specified herein) to the gas mixture to effect absorption of carbon dioxide by the sorbent and treating the sorbent that contains absorbed or entrapped carbon dioxide to release a substantial amount or all the absorbed carbon dioxide. The method ... which further comprises reacting the released carbon dioxide to form useful products. The method ... wherein carbon dioxide is used to produce methanol";

the very air around us. Or, perhaps as intriguingly, as seen in our 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; 2014; Assignee: Savannah River Nuclear Solutions, LLC, South Carolina (USDOE); 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";

we could get "high purity CO2" delivered to the process of our subject,  "United States Patent 7,879,749 - Methods of Using Structures Including Catalytic Materials Disposed Within Porous Zeolite Materials to Synthesize Hydrocarbons", for subsequent conversion into fuel alcohol Methanol and/or, through Methanol and already-established "methanol-to-gasoline (MTG) processes", into other badly-needed "liquid fuels", from a process that is converting some of our abundant Coal, along with Carbon-recycling and renewable biological wastes, into, as well, "liquid fuel"s.

In sum, folks, and as will be even further confirmed in another report or two to follow, our United States Government's Department of Energy knows how to - - and owns the rights to do it - - convert Carbon Dioxide, as recovered from whatever handy source, directly, in one contiguous and integrated, though "multi-step", process, into fuel alcohol Methanol, and, through Methanol, into hydrocarbon fuels like Gasoline.

Using Carbon Dioxide - - rather than Coal syngas - - along with externally-supplied Hydrogen, would do a number of things for us, of course.

It would enable us to conserve our precious Coal for it's essential use in the generation of abundant and affordable electric power, and for, perhaps, use in processes that enable the consumption and use of Carbon-recycling organic wastes in the production of synthetic petroleum "liquid fuel", as in our above-cited report concerning "United States Patent 8,674,152 - Coal Liquefaction by Base-Catalyzed Hydrolysis with CO2 Capture".

And, it would also enable us to develop a regenerative and sustainable economy that, while still dependent on liquid hydrocarbon fuels, would help us to stabilize the amounts, or to slow the accumulation, of Carbon Dioxide in Earth's atmosphere.

Again, as specified herein by our US Government, We the People now own rights to a process whereby

"Carbon dioxide gas (CO2) may be converted into liquid fuels such as ... gasoline".

When, we must ask, are we to be informed that we own such technology?

And, when are we to be enabled to put it, and more of our fellow US citizens, to work - while we put an end to our economically crippling reliance on OPEC petroleum and secure a prosperous, sustainable future for our grandchildren?

This could, indeed, be the Grail, the key to our deliverance from OPEC economic and energy enslavement.

We need to lay hold of it, now, while it is right before us, while it is within our grasp.


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