United States Patent Application: 0140239231

 
An advance note: The Carbon Dioxide utilization technology we report to you herein is comprehensive and, perhaps, overly-complex in it's presentation. That's not meant as a criticism, really; but, the scope of it all limits even further our already-limited ability to provide a concise and coherent exposition of it.

To be clear: Contained within the dissertation are summaries of the ways and means by which Carbon Dioxide, as we might recover from the stack gasses of our economically essential Coal-fired electric power generation plants, can be substituted as a raw material for everything, quite literally everything, all fuels and chemicals, we now allow our nation to be bled dry to continue making from imported OPEC petroleum.

The implications such could have for founding industries and creating jobs in US Coal Country should be seen, and appreciated, as astonishing.  

That said, we first remind you of our most recent report;

CO2 to Formic Acid | Research & Development | News; concerning: "US Patent 8,815,074 - Method for Reducing Carbon Dioxide; August 26, 2014; Assignee: Panasonic Corporation, (Japan); Abstract: A method for reducing carbon dioxide with use of a device for reducing carbon dioxide includes steps of (a) preparing the device (as described, and) (b) applying a voltage difference between the cathode electrode and the anode electrode so as to reduce the carbon dioxide (and thereby) generate ... formic acid. The present disclosure provides a novel method for reducing carbon dioxide. In particular, the disclosed methods are efficient in producing formic acid";

wherein it was seen that Japan's Panasonic Corporation has developed a low-energy process - - a process that can be powered by low-voltage, low-power solar photovoltaic electricity - - which converts Carbon Dioxide in a water solution, or, perhaps more properly, water suspension or dispersion, into the industrial chemical, Formic Acid, with elemental, molecular Oxygen as a valuable byproduct.  

We've discussed and documented the use of Carbon Dioxide as a raw material for the synthesis of Formic Acid multiple times previously; and, in some of those prior reports we've documented the uses to which Formic Acid is now applied.

And, as in:

England Improves Coal Liquid Hydrogenation with Formic Acid | Research & Development | News; concerning: "United States Patent 4,313,852 - Catalysts; 1982; Assignee: Coal Industry Limited, London; (United Kingdom); Abstract: A hydrotreating catalyst which is resistant to carbonaceous deposits and is particularly useful for hydrotreating coal-derived liquids, is molybdenum or tungsten disulphide ... . The catalyst can be made by absorbing molybdenum or tungsten trisulphide onto the active carbon support and reducing the trisulphide to the disulphide. Claims: A hydrotreatment catalyst comprising molybdenum or tungsten disulphide ... . (And, a) method of producing (the) catalyst comprising molybdenum or tungsten disulphide (by) absorbing molybdenum or tungsten trisulphide onto an active carbon support ...  and reducing the trisulphide to the disulphide. (And) wherein the reduction is effected using ... formic acid";.

we've also documented the intriguing potential uses in which Formic Acid could be utilized. However, as we intimated in our above-cited report concerning "US Patent 8,815,074 - Method for Reducing Carbon Dioxide", some new, perhaps even more intriguing, uses for Formic Acid, as made from Carbon Dioxide, have been recently developed.

By way of further introduction, we remind you, for only one example, of our report concerning:

USDOE Hires Illinois to Recycle CO2 into Fuels | Research & Development | News; concerning: "Amine Promotion Of Hydrogen Evolution Reaction Suppression And CO2 Conversion For Artificial Photosynthesis; Wei Zhu; Dissertation: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemical Engineering in the Graduate College of the University of Illinois at Urbana-Champaign, 2011; Doctoral Committee: Professor Richard I. Masel, Professor Paul Kenis, et. al.; Recycling CO2 back into fuels or other useful products is critically important (and, the) electrochemical method is regarded as a promising means to do this because it has the advantage that water can be used as the proton source. ... Artificial photosynthetic systems offer the possibility of producing fuels and chemicals from CO2 and sunlight in fewer steps and with higher efficiencies than is possible in natural photosynthesis. There are several ways to reduce carbon dioxide: (1) homogeneous photochemical reduction of CO2, (2) heterogeneous photochemical reduction of CO2, (3) photoelectrochemical CO2 fixation, and: (4) electrochemical reduction of CO2 using solar electric power. This work was supported by the US Department of Energy under grant DE-SC0004453. ... Artificial photosynthetic systems offer the possibility of producing fuels and chemicals from CO2 and sunlight in fewer steps and with higher efficiencies than is possible in natural photosynthesis. ... The long term goal of our research is to develop better electrochemical systems for CO2 reduction in room-temperature electrolyte that could lead to efficient processes for the large-scale conversion of CO2 into formic acid or other products";

wherein the Carbon Dioxide utilization interests of Dr. Richard Masel, and his colleagues, at the University of Illinois were documented. 

As we've also separately reported, Dr. Masel and some of his colleagues have founded a company, "Dioxide Materials, Inc.", to further develop and to commercialize the CO2 recycling technologies developed by them initially in their University of Illinois laboratories. 

More about "Dioxide Materials" can be learned via:  

Dioxide Materials- Technology to lower the carbon footprint of homes and businesses; "Dioxide Materials Inc. is a three year old startup based in Champaign IL to develop ... CO2 utilization based on a patent pending catalyst that allows CO2 conversion to occur at record selectivity and energy efficiency (>97% selectivity and >80% energy efficiency). Dioxide Materials is currently developing ... methods to convert CO2 into high value chemicals. Dioxide Materials' long-term vision is to create a new chemical value chain using carbon dioxide feedstock and renewable energy (instead of oil and gas) to obtain high value fuels and chemicals. Our technology lowers the cost of converting carbon dioxide (and, creates a) cost-competitive route to large-volume renewable fuels and chemicals. The goal is to develop a new industry where waste carbon dioxide from power plants is used as a feedstock to produce gasoline, diesel fuel, jet fuel and industrial chemicals".

And, herein we learn that Richard Masel and colleagues at Dioxide Materials have developed the needed technology to use Formic Acid, as made from Carbon Dioxide, as the basic raw material for the further synthesis of a broad range, a "wealth" as they put it, of such hydrocarbon products.

The use of Formic Acid as an intermediate product in the recycling of Carbon Dioxide has important implications for deriving other, more valuable products from CO2 - - as opposed to other, related Carbon Dioxide utilization technologies, wherein the immensely valuable fuel alcohol, and hydrocarbon raw material, Methanol, is made from Carbon Dioxide both as an end and an intermediate product.

As we attempt to explain in comments following and inserted within excerpts from the initial link in this dispatch to:

"United States Patent Application 20140239231 - Carbon Dioxide Conversion to Fuels and Chemicals

Carbon Dioxide Conversion To Fuels And Chemicals - DIOXIDE MATERIALS, INC.

August 28, 2014

Inventors: Richard Masel, et. al., IL

Assignee: Dioxide Materials, Inc.; Champaign, IL

Abstract: An environmentally beneficial process for the production of fuels and chemicals employs carbon dioxide from a natural source or from an artificial chemical source that would otherwise be discharged into the environment. The carbon dioxide is converted to formic acid and the formic acid is then non-biologically converted to fuels and/or chemicals without the intermediate process of hydrogenating the formic acid to methanol or reacting the formic acid with ammonia to form formamide. In the present process, formic acid is converted to one of seven primary feedstocks: formaldehyde, acrylic acid, methane, ethylene, propylene, syngas, and C5-C7 carbohydrates. The formaldehyde, acrylic acid, methane, ethylene, propylene, syngas and/or short chain carbohydrates can either be used directly, or can be converted into a wealth of other products.

Claims:A process for the production of fuels and chemicals comprising the steps of: forming an amount of formic acid; and non-biologically converting said amount of formic acid to a product comprising an organic intermediate, wherein less than 10% of said amount of formic acid is hydrogenated to methanol or reacted with ammonia to form formamide.

The process ... further comprising initially converting an amount of carbon dioxide obtained from a natural source or from an artificial chemical source to produce said amount of formic acid, thereby reducing said amount of carbon dioxide present in nature or diverting said amount of carbon dioxide from being discharged into the environment by said artificial chemical source.

The process ... wherein said amount of formic acid is converted to a product comprising at least one of formaldehyde, acrylic acid, ethane, propane, ethylene, propylene, butene, and a carbohydrate comprising at least five carbon atoms.

The process ... wherein said amount of formic acid is hydrogenated to form a product comprising formaldehyde.
The process ... wherein said catalyst is a metal oxide comprising at least one of cerium (IV) oxide and tellurium (IV) oxide (and) wherein reaction temperature is between 8 C and 300 C (and) further comprising a formose step wherein said formaldehyde is converted to formose sugars (and) wherein said formose step comprises reacting said formaldehyde in the presence of Ca(OH)2 to produce C5 and C6 sugars.

The process ... further comprising a hydrocarbon step wherein said formose sugars are converted to a product comprising at least one of ... parafins and olefins ethane, propane, ethylene, propylene and butene.

(and) wherein said hydrocarbon step employs a catalyst comprising a silico-alumino-phosphate zeolite.

The process ... wherein said formose sugars are converted to a product comprising propylene (and) wherein said formose sugars are converted by a catalyst comprising an aluminosilicate zeolite.

The process ... further comprising an acid-converting step wherein said amount of formic acid is converted to ... at least one of acrylic acid and methylacrylic acid.

The process ... further comprising converting said amount of formic acid to a product comprising ...  both of carbon monoxide and hydrogen produced by reacting said amount of formic acid in at least two parallel reactors having temperatures independently controllable, one of said reactors containing a metallic catalyst capable of yielding hydrogen and the other of said reactors containing a catalyst comprising at least one of an oxide, an acid and a base to yield carbon monoxide, and mixing said hydrogen and said carbon monoxide to yield syngas.

A process for the production of formaldehyde comprising hydrogenating an amount of formic acid to form a product comprising formaldehyde, wherein said formaldehyde is formed without hydrogenating more than 10% of said amount of formic acid to methanol.

The process ... further comprising initially converting an amount of carbon dioxide obtained from a natural source or from an artificial chemical source to produce said amount of formic acid, thereby reducing said amount of carbon dioxide present in nature or diverting said amount of carbon dioxide from being discharged into the environment by said artificial chemical source (and) further comprising reacting said amount of formic acid with hydrogen in the presence of a catalyst comprising ... at least one of cerium (IV) oxide and tellurium (IV) oxide (and) wherein said reaction temperature is between 60 C and 100 C.

A process of the production of an organic acid having at least three carbon atoms comprising the steps of: forming an amount of formic acid; and reacting said amount of formic acid with an amount of an unsaturated hydrocarbon (and) wherein said unsaturated hydrocarbon is one of acetylene and methylacetylene (and)wherein said organic acid is one of acrylic acid and methyl acrylic acid.

A process for the production of at least one of a C5 sugar and a C6 sugar comprising the steps of: forming an amount of formic acid; and non-biologically converting said amount of formic acid to a product comprising an organic intermediate, wherein less than 10% of said amount of formic acid is hydrogenated to form a product comprising formaldehyde. reacting said product comprising formaldehyde over a base catalyst to yield a solution comprising at least one of a C5 sugar and a C6 sugar (and) wherein reaction temperature is between 50 C and 70 C (and) wherein said base catalyst comprises Ca(OH)2. (and) further comprising removing calcium from said sugar solution by bubbling a gas comprising carbon dioxide through said sugar solution to produce a sugar solution substantially free of calcium (and) wherein said sugar solution substantially free of calcium has a pH value between 4 and 7.

(The "Ca(OH)2" is just Calcium Hydroxide, which is what you get when you react Calcium Oxide, a primary component of Portland-type cement, with water. They are describing what is known, we're instructed, as a "base-catalyzed hydrolysis" of the sugars that have been made from Carbon Dioxide, a chemical process that has actually been discussed in these reports previously as a method of converting Coal, along with Carbon-recycling botanical products, into liquid hydrocarbons. See, for example:

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; 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. Claims: The process of converting a biomaterial to a fuel product comprising the steps of: providing a biomaterial selected from the group consisting of coal, cellulosic products, (etc.); hydrolyzing said biomaterial using a base or alkalized catalyst comprising hydrides of groups IA, IIA or IIIA metals, oxides or hydrides of groups IA or IIA metals, or groups of organometallic compounds containing groups IA, IIA, or IIIA and at a temperature of about 319 C to yield a reaction product, wherein a hydrocarbon fuel product in the reaction product has a hydrogen to carbon ratio of 1.6; acidifying said reaction product to form CO2 and a liquid hydrocarbon fuel product. The process ... wherein said step of acidifying said reaction product further comprises adding HCl to the reaction product and thereby forming a KCl reaction product (and) wherein following said acidifying step, an electrolysis of the KCl reaction product solution is performed within a fuel cell to form a caustic, the fuel cell providing a source of heat. ... The process ... wherein acidifying step to form CO2 removes carbon and oxygen from available reactants, thereby preventing undesired side reactions that would lower a yield of desired reaction products. The process ... wherein said CO2 from the acidifying step may be recovered at an at least about 95% purity level. The process ... wherein said liquid hydrocarbon fuel product is a distillable product that can be processed by a petroleum refinery".

Other, related examples include:

Utah Converts Coal and Wood into Gasoline | Research & Development | News; concerning: "United States Patent 4,728,418 - Process for the Low-temperature Depolymerization of Coal and its Conversion to a Hydrocarbon Oil; 1988; Inventors: Joseph Shabtai, UT, and Ikuo Saito, Japan; Assignee: The University of Utah, Salt Lake City; Abstract: A novel process for the low-temperature depolymerization and liquefaction of coal wherein the coal is subjected to sequential processing steps for the cleavage of different types of intercluster linkages during each processing step. A metal chloride catalyst is intercalated in finely crushed coal and the coal is partially depolymerized under mild hydrotreating conditions during the first processing step. In the second processing step the product from the first step is subjected to base-catalyzed depolymerization with an alcoholic solution of an alkali hydroxide, yielding an almost fully depolymerized coal, which is then hydroprocessed with a sulfided cobalt molybdenum catalyst in a third processing step to obtain a hydrocarbon oil as the final product";

which report includes examples of related technology wherein carbon-recycling renewable materials, like wood, can be processed with the Coal, and:

Amoco Liquefies Coal with Methanol and Lye | Research & Development | News; concerning: "United States Patent 5,266,189 - Integrated Low Severity Alcohol-Base Coal Liquefaction Process; 1993; Assignee: Amoco Corporation (Illinois); Abstract: An improved, low severity coal liquefaction process is disclosed. In accordance with the process, coal is first decarboxylated and demineralized with hot sulfurous acid. The decarboxylated coal is then liquefied in the presence of an alcohol and an alkali metal hydroxide. In several embodiments, alkali metal-containing materials are reclaimed to produce alkali metal hydroxide for the liquefaction step. In other embodiments, the liquefaction is conducted in the presence of a relatively high-boiling diluent such as a coal-derived liquid. Claims: A low severity liquefaction process comprising the steps of: reacting a solid carbonaceous material and sulfurous acid ... to decarboxylate the solid material and dissolve minerals present in the solid material; and, liquefying the decarboxylated solid ... in the presence of at least one alkali metal hydroxide and at least one alcohol having one to four carbon atoms to produce a hydrocarbon-containing liquid. (And) wherein the alcohol is methanol and the alkali metal hydroxide is sodium hydroxide".)

A process for the production of olefins comprising the steps of: forming an amount of formic acid; and non-biologically converting said amount of formic acid to a product comprising an organic intermediate, wherein less than 10% of said amount of formic acid is hydrogenated to form a product comprising formaldehyde; reacting said product comprising formaldehyde over a base catalyst comprising Ca(OH)2 to yield a solution comprising at least one of a C5 sugar and a C6 sugar; removing calcium from said sugar solution by bubbling a gas comprising carbon dioxide through said sugar solution to produce a sugar solution substantially free of calcium; reacting said sugars in the presence of an acid catalyst to form a product comprising at least one olefin (and) wherein said acid catalyst comprises a zeolite (and) wherein said zeolite comprising a silico-alumino-phosphate zeolite.

A process for the production of propylene comprising the steps of: forming an amount of formic acid; non-biologically converting said amount of formic acid to a product comprising an organic intermediate, wherein less than 10% of said amount of formic acid is hydrogenated to form a product comprising formaldehyde; reacting said product comprising formaldehyde over a base catalyst comprising Ca(OH).sub.2 to yield a solution comprising at least one of a C5 sugar and a C6 sugar; removing calcium from said sugar solution by bubbling a gas comprising carbon dioxide through said sugar solution to produce a sugar solution substantially free of calcium; reacting said sugars in the presence of an aluminosilicate zeolite catalyst to form a product comprising propylene.

Background and Field: The present invention relates to catalytic chemistry and in particular to processes for catalytically converting carbon dioxide to useful fuels or chemicals, including formaldehyde, acrylic acid, ethane, propane, ethylene, propylene, butene, and carbohydrates comprising at least 5 carbon atoms.

(Keep in mind that the "formaldehyde .... ethylene, propylene", definitely, and, we think, the "acrylic acid", can all serve as the basic raw materials, as replacements for petroleum-based raw materials, for the further synthesis of a wide range of polymers and plastics, wherein the Carbon Dioxide consumed would remain forever chemically, and productively, "sequestered".)

Recycling generated carbon dioxide back to fuels and chemicals would make a tremendous difference to the U.S. economy. Presently, fuels and organic chemicals are usually made from petroleum ... .

However, if such fuels and chemicals could be made from CO2, then the U.S. dependence on imported oil would be lessened (and) CO2 produced in power plants would change from a waste product to a useful, economically viable feedstock.

Solar and wind energy could also be stored in the form of hydrocarbon fuels.

Presently, however, most large volume organic chemicals are made from fossil fuels. For example, most acrylic acid produced in the U.S. is currently made from propylene. The propylene is made from petroleum. ... Ethylene is made by cracking of light olefins from petroleum, or from methanol.

U.S. Pat. No. 8,212,088 describes an environmentally beneficial process for preparing a fuel or chemical, in which carbon dioxide from a natural source, or carbon dioxide from an artificial chemical source that would otherwise be discharged into the environment by the artificial chemical source, is converted to useful fuels and chemicals. In the process described in the '088 patent, CO2 is first converted to a mixture of formic acid and other compounds. The formic acid is then sent to a second process where it undergoes a 4-electron hydrogenation to form methanol. The methanol is then converted to fuels and chemicals using conventional chemical processes.

(With regards to the above-cited "U.S. Pat. No. 8,212,088",see our report of:

California July 2012 Efficient CO2 to Methanol | Research & Development | News; concerning: "United States Patent 8,212,088 - Efficient and Selective Chemical Recycling of Carbon Dioxide to Methanol, Dimethyl Ether and Derived Products; Date: July 3, 2012; Inventors: George Olah and G.K. Surya Prakash; Assignee: University of Southern California, Los Angeles; Abstract: An efficient and environmentally beneficial method of recycling and producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by chemical or electrochemical reduction secondary treatment to produce essentially methanol, dimethyl ether and derived products. Claims: An environmentally beneficial method of preparing a renewable fuel, which method comprises: obtaining carbon dioxide from a natural or chemical source that would otherwise be present in or discharged into the atmosphere; and producing an energy storage and transportation material or a fuel sufficient to generate energy by hydrogenatively converting the carbon dioxide thus obtained under conditions sufficient to produce methanol as the material or fuel (and) wherein the methanol is produced by reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, followed ...  by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol".

In "United States Patent 8,212,088", some of the intermediate Formic Acid is regenerated when the Formaldehyde product, itself a valuable industrial raw material, is converted to Methanol. The process of our subject, "United States Patent Application 20140239231 - Carbon Dioxide Conversion to Fuels and Chemicals", presents as being more efficient, since it can forgo the multi-step route to Methanol, and can produce hydrocarbon products withut forming Methanol as an intermediate.)..

The advantage of converting CO2 to methanol is that infrastructure already exists to convert methanol into other products (but, the) limitation in the process described in the '088 patent is that the hydrogenation to methanol is an extra step in the conversion process that wastes energy, and that may not be needed at all. For example, almost half of the methanol produced worldwide is further reacted to yield formaldehyde via an oxidative dehydrogenation process. Energy is wasted when formic acid is first hydrogenated to methanol and then dehydrogenated to formaldehyde ... .

As described in more detail below, the present environmentally beneficial process for the production of fuels and chemicals preferably employs carbon dioxide from a natural source or carbon dioxide from an artificial chemical source that would otherwise be discharged into the environment by the artificial chemical source. The carbon dioxide is converted to formic acid and other products. The formic acid is then converted to fuels and/or chemicals without the intermediate process of hydrogenating the formic acid to methanol or reacting the formic acid with ammonia to form formamide. By contrast, the '088 patent describes a method in which (a) carbon dioxide is converted to formic acid and other products, (b) the formic acid is hydrogenated to form methanol, and then (c) the methanol is converted to fuels and chemicals.

In the process disclosed herein, only a small fraction (namely, less than 10%) of the formic acid is hydrogenated to methanol. In the present process, formic acid can be made by any method, and the formic acid is then converted to fuels and chemicals without the intermediate process of hydrogenating the formic acid to methanol or reacting it with ammonia to form formamide. The present process produces fuels and chemicals in which formic acid is converted to one of seven primary feedstocks: formaldehyde, acrylic acid, methane, ethylene, propylene, syngas, and C5-C7 carbohydrates, without the intermediate process of hydrogenating the formic acid to methanol or reacting it with ammonia to form formamide. The formaldehyde, acrylic acid, methane, ethylene, propylene, syngas and/or short chain carbohydrates can either be used directly, or can be converted into a wealth of other products.

Recycling generated carbon dioxide back to fuels and chemicals would make a tremendous difference to the U.S. economy.

Presently, fuels and organic chemicals are usually made from petroleum ... . However, if such fuels and chemicals could be made from CO2, then the U.S. dependence on imported oil would be lessened (and)  CO2 produced in power plants would change from a waste product to a useful, economically viable feedstock.

Presently, however, most large volume organic chemicals are made from fossil fuels. For example, most acrylic acid produced in the U.S. is currently made from propylene. The propylene is made from petroleum.

Ethylene is made by cracking of light olefins from petroleum ... .

The present process also produces olefins such as ethylene and propylene and products synthesized from olefins, in which formic acid is converted to the olefins ethylene and/or propylene without a separate intermediate process of hydrogenating the formic acid to methanol. In the present process, formic acid is first converted to formaldehyde as described above and the formaldehyde is then further converted to olefins such as ethylene, propylene or butylene. The process can employ a base catalyst to condense the formaldehyde into a multi-carbon species, followed by an acid catalyst to convert the multi-carbon species into olefins. The acid catalyst can be in the form of a zeolite such as ZSM-5 ...

(Concerning the above "zeolite ... ZSM-5" catalyst, it is, as well, key to the Coal-to-Methanol-to-Gasoline process developed by ExxonMobil both before and after the Exxon and Mobil merger; as seen, for just one example, in our report of:

Mobil Oil 1978 Coal Conversion with Zeolite Catalyst | Research & Development | News; concerning: "US 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, aromatic hydrocarbons, and chemicals intermediates. ... The method ... wherein said acidic crystalline aluminosilicate is a H-ZSM-5 crystalline zeolite.  This invention is concerned with an improved process for converting synthesis gas, i.e., mixtures of gaseous carbon oxides with hydrogen ... to hydrocarbon mixtures. In one aspect, this invention is particularly concerned with a process for converting synthesis gas to hydrocarbon mixtures rich in aromatic hydrocarbons. In another aspect, this invention is concerned with a process for converting synthesis gas to hydrocarbon mixtures particularly rich in liquefiable petroleum gases such as propane. In still another aspect, this invention is concerned with providing novel catalysts for the conversion of synthesis gas to hydrocarbon mixtures. 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".)

The present process also produces carbohydrates or molecules produced from carbohydrates, in which formic acid is converted to a carbohydrate without a separate intermediate process of hydrogenating the formic acid to methanol. In the present process, the formic acid is converted to formaldehyde as described above, and the formaldehyde is then reacted in the presence of a base catalyst to yield a carbohydrate. Calcium hydroxide is a preferred catalyst in the present process, and the present process specifically encompasses the use of carbon dioxide for the removal of calcium from solution.

The present process also produces syngas or molecules produced from syngas, in which formic acid is converted to syngas without a separate intermediate process of hydrogenating the formic acid to methanol. The present process preferably employs two parallel reactors to convert the formic acid into syngas, wherein the temperatures of the two independent reactors can be independently controlled. It is preferred that one of the reactors contains an acid catalyst while the other reactor preferably contains a metallic catalyst.

Summary:  Shortcomings and limitations of existing processes for converting CO2 to useful fuels or chemicals are overcome by a process for the production of fuels and chemicals comprising the steps of forming an amount of formic acid and non-biologically converting the amount of formic acid to a product comprising an organic intermediate.

In a preferred embodiment, the process further comprises an acid-converting step in which the amount of formic acid is converted to an organic acid comprising at least 3 carbon atoms. The organic acid is preferably at least one of acrylic acid and methylacrylic acid.

In a preferred embodiment, the process further comprises converting the formic acid to a product comprising at least one of carbon monoxide and hydrogen. The product comprising both of carbon monoxide and hydrogen is preferably produced by reacting the formic acid in at least two parallel reactors having temperatures independently controllable. One of the reactors preferably contains a metallic catalyst capable of yielding hydrogen. The other reactor preferably contains a catalyst comprising at least one of an oxide, an acid and a base to yield carbon monoxide. The hydrogen and carbon monoxide are mixed to yield syngas.

A process for the production of propylene comprises the steps of forming an amount of formic acid; and non-biologically converting the amount of formic acid to a product comprising an organic intermediate, wherein less than 10% of the amount of formic acid is hydrogenated to form a product comprising formaldehyde, reacting the product comprising formaldehyde over a base catalyst comprising Ca(OH)2 to yield a solution comprising at least one of a C5 sugar and a C6 sugar, removing calcium from the sugar solution by bubbling a gas comprising carbon dioxide through the sugar solution to produce a sugar solution substantially free of calcium, and reacting the sugars in the presence of an aluminosilicate zeolite catalyst to form a product comprising propylene."

------------------------------ 

There is a lot more to "United States Patent Application 20140239231 - Carbon Dioxide Conversion to Fuels and Chemicals" than even our over-long excerpts from it might suggest. And, much of it begs more comment and explanation that we have, due to our concerns for length and to our own limitations, provided.

Keep in mind, for emphasis, that some of the key intermediate CO2 products mentioned, specifically the "formaldehyde" and the complex "sugars" or "carbohydrates", are themselves immensely valuable industrial raw materials which can be, and are currently being, processed into various plastics and polymers, wherein the Carbon Dioxide consumed in the basic formic acid synthesis would be forever, and productively "sequestered".

Further, note the potential for converting Carbon Dioxide, through Formic Acid, into a "syngas" blend of Carbon Monoxide and Hydrogen, as we can also make via the gasification of Coal, and which syngas can be used in the synthesis of a full range of hydrocarbon fuels and chemicals, as intimated by our above-cited report concerning ""US Patent 4,086,262 - Conversion of Synthesis Gas to Hydrocarbon Mixtures".

We'll have at least a little more to offer on some of the CO2-recycling specifics embodied in "United States Patent Application 20140239231 - Carbon Dioxide Conversion to Fuels and Chemicals" in some reports yet to follow - - all of which will confirm the statement published by Dioxide Materials, i.e.: 

"carbon dioxide from power plants (can be) used as a feedstock to produce gasoline, diesel fuel, jet fuel and industrial chemicals".

That is, Carbon Dioxide, as we might recover from our Coal-fired "power plants", can be "converted into a wealth of ... products", and thus create - - if the technologies embodied in Dioxide Materials' "United States Patent Application 20140239231 - Carbon Dioxide Conversion to Fuels and Chemicals" were to be reduced to industrial practice - -  "a wealth" of new industries and new jobs in United States Coal Country.


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