DIRECT HYDROGENATION OF METAL CARBONATE AND RELATED SALTS TO METHANOL, METHANE AND METAL HYDROXIDE
20250236575 ยท 2025-07-24
Assignee
Inventors
- Alain GOEPPERT (Los Angeles, CA, US)
- Christopher J. KOCH (Los Angeles, CA, US)
- G.K. Surya PRAKASH (Los Angeles, US, US)
- Raktim SEN (Los Angeles, CA, US)
Cpc classification
C07C29/132
CHEMISTRY; METALLURGY
C07C2531/12
CHEMISTRY; METALLURGY
International classification
Abstract
A liquid phase process for direct utilization of inorganic metal carbonate and related salts under hydrogenative conditions to produce value-added fuels and feedstocks such as methanol, methane, carbon monoxide, and higher hydrocarbons. Advantageously, the reaction can use heterogeneous catalysts. The hydrogenation proceeds with high selectivity and yield for the desired product at relatively low temperatures, along with co-production of metal hydroxide. The metal hydroxide can be used to capture CO.sub.2, forming metal carbonates and bicarbonates that can be reused to produce more methanol and methane, hydrocarbons and carbon monoxide, closing the loop. Such a hydrogenation process can thus also be used in a carbon capture and recycling manner to produce renewable methane, methanol, carbon monoxide, hydrocarbons, and other carbon feedstocks from CO.sub.2 sourced from any natural and anthropogenic emissions as well as from ambient air.
Claims
1. A method for conversion of a carbonate/formate component comprising: contacting the carbonate/formate component with hydrogen to produce methanol, methane, carbon monoxide or hydrocarbons or a mixture thereof over a catalyst in a solvent, the catalyst including a transition metal, a post-transition metal, a lanthanide, or combinations thereof.
2. The method of claim 1, wherein the catalyst is heterogeneous.
3. The method of claim 1, wherein the carbonate/formate component is a metal carbonate, metal bicarbonate, metal formate salt, or mixtures thereof.
4. The method of claim 1, wherein a metal hydroxide is produced as a co-product.
5. The method of claim 1, wherein the carbonate/formate component is a metal carbonate selected from the group consisting of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, and mixtures thereof.
6. The method of claim 1, wherein the carbonate/formate component is a metal bicarbonate selected from the group consisting of lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, and mixtures thereof.
7. The method of claim 1, wherein the carbonate/formate component is a metal formate salt selected from the group consisting of lithium formate, sodium formate, potassium formate, rubidium formate, cesium formate, and mixtures thereof.
8. The method of claim 1, wherein the solvent comprises water, an alcohol, a diol, a polyol or a mixture thereof.
9. The method of claim 1, wherein the solvent comprises methanol, ethanol, isopropanol, n-butanol, ethanol propanol, 2-methoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,4-butanediol or a mixture thereof.
10. The method of claim 1, wherein the carbonate/formate component is a metal carbonate and/or a metal bicarbonate each independently including a component selected from the group consisting of: naturally occurring minerals; seashells, oyster shells, eggshells; carbonates and bicarbonate salts made by direct CO.sub.2 capture from CO.sub.2 sources using alkali hydroxides and/or amines; synthetic carbonates and bicarbonates; and combinations thereof.
11. The method of claim 1, wherein the carbonate/formate component includes naturally occurring minerals are selected from the group consisting of calcite (CaCO.sub.3), magnesite (MgCO.sub.3), siderite (FeCO.sub.3), aragonite (CaCO.sub.3), witherite (BaCO.sub.3), natrite (Na.sub.2CO.sub.3), ankerite (CaFeCO.sub.3), dolomite (CaMg(CO.sub.3).sub.2), huntite (Mg.sub.3Ca(CO.sub.3).sub.4), minrecordite (CaZn(CO.sub.3).sub.2), barytocalcite (BaCa(CO.sub.3).sub.2), hydromagnesite (Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.Math.4H.sub.2O), ikaite (CaCO.sub.3.Math.6(H.sub.2O)), lansfordite (MgCO.sub.3.Math.5(H.sub.2O)), monohydrocalcite (CaCO.sub.3.Math.H.sub.2O), natron (Na.sub.2CO.sub.3.Math.10(H.sub.2O)), and combinations thereof.
12. The method of claim 1, wherein the hydrogen is produced from a fossil or renewable source.
13. The method of claim 1, wherein a heterogeneous catalyst system includes the catalyst.
14. The method of claim 13, wherein the heterogeneous catalyst system includes a component selected from the group consisting of copper-based catalysts, indium-based catalysts, nickel-based, indium and nickel/gallium-based catalysts modified with lanthanides and/or precious metals, and combinations thereof.
15. The method of claim 13, wherein the heterogeneous catalyst system further includes additional components selected from the group consisting of additives, supports, and combinations thereof.
16. The method of claim 15, wherein the additional components are selected from the group consisting of ZnO, ZrO.sub.2, MOFs, Ga, Al.sub.2O.sub.3, SiO.sub.2. TiO.sub.2, and combinations thereof.
17. The method of claim 13, wherein the heterogeneous catalyst system includes an indium-based species having the formula In.sub.2O.sub.3/ZrO.sub.2.
18. The method of claim 13, wherein the heterogeneous catalyst system includes a nickel-based species selected from the group consisting of NiGa/SiO.sub.2, Ni.sub.3Ga/SiO.sub.2, and Ni.sub.5Ga.sub.3/SiO.sub.2.
19. The method of claim 1, wherein the catalyst comprises a heterogeneous catalyst based on nickel, cobalt, ruthenium, platinum, palladium, iron, iridium or rhodium and combinations thereof either in their pure form or deposited on a support.
20. The method of claim 19, wherein the support is selected from the group consisting of silica, alumina, zirconia, titanium oxide, cerium oxide, silica-alumina, and mixtures thereof.
21. The method of claim 1, wherein the catalyst includes a heterogeneous catalyst selected from the group consisting of Fischer-Tropsch type catalysts based on iron, cobalt, and/or ruthenium and catalysts based on iron, copper, molybdenum, cobalt, metal carbides, zeolites or mixtures thereof.
22. The method of claim 1, wherein the conversion is conducted at temperatures between 50 C. and 600 C. and gauge pressures between 0 and 200 bar.
23. The method of claim 1, wherein the carbonate/formate component is a metal carbonate and/or a metal bicarbonate which is the product of a reaction of a metal hydroxide with CO.sub.2 contained in CO.sub.2 sources.
24. The method of claim 23, wherein the CO.sub.2 sources include a CO.sub.2 source selected from the group consisting of fossil fuel power plant flue gases, emissions from industrial and commercial sources, and CO.sub.2 contained in air.
25. The method of claim 23, wherein the metal hydroxide comprises lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide or mixtures thereof.
26. The method of claim 1 wherein the carbonate/formate component reacts to form a metal hydroxide or a metal hydroxide mixture.
27. The method of claim 26, wherein the metal hydroxide or the metal hydroxide mixture is used to capture CO.sub.2 from sources containing between 0.04% and 100% CO.sub.2, including ambient air, indoor air, industrial flue gases, fossil fuel burning power plants, natural gas purification facilities, cement plants, breweries, biogas, biomass burning facilities and biomass gasification facilities to obtain a metal carbonate, metal bicarbonate or a mixture thereof.
28. The method of claim 1, wherein the carbonate/formate component includes a metal carbonate, metal bicarbonate or mixtures thereof, the carbonate/formate component reacting to form a metal hydroxide or metal hydroxide mixture and wherein the metal hydroxide or the metal hydroxide mixture obtained therefrom is used to capture CO.sub.2 from sources containing between 0.04% and 100% CO.sub.2 to obtain the metal carbonate, metal bicarbonate or mixtures thereof and wherein the metal carbonates, metal bicarbonates or mixtures thereof are reusable.
29. The method of claim 28, wherein the sources are selected from the group consisting of ambient air, indoor air, industrial flue gases, fossil fuel burning power plants, natural gas purification facilities, cement plants, breweries, biogas, biomass burning facilities and biomass gasification facilities.
30. The method of claim 1 run either under batch conditions or continuous conditions.
31. A method for producing methanol, methane, carbon monoxide, hydrocarbons, or a mixture thereof from CO.sub.2 comprising the following steps: a) capturing CO.sub.2 with a metal hydroxide or metal hydroxide mixture from a CO.sub.2 source that includes between 0.04% and 100% CO.sub.2 to obtain metal carbonates, metal bicarbonates or mixtures thereof; b) converting the metal carbonates, metal bicarbonates and mixtures thereof with hydrogen to produce methanol, methane, carbon monoxide, hydrocarbons, or a mixture thereof over a catalyst in a solvent while regenerating the metal hydroxide or the metal hydroxide mixture; and c) reusing the metal hydroxide or the metal hydroxide mixture is to capture CO.sub.2 as described in step (a).
32. The method of claim 31, wherein the CO.sub.2 source is selected from the group consisting of ambient air, indoor air, industrial flue gases, fossil fuel burning power plants, natural gas purification facilities, cement plants, breweries, biogas, biomass burning facilities, and biomass gasification facilities
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] For a further understanding of the nature, objects, and advantages of the present disclosure, reference should be made to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
[0021]
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
DETAILED DESCRIPTION
[0028] Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the invention presently known to the inventors. The Figures are not necessarily to scale. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for any aspect of the invention and/or as a representative basis for teaching one skilled in the art to variously employ the present invention.
[0029] Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word about in describing the broadest scope of the invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: all R groups (e.g. R.sub.i where i is an integer) include hydrogen, alkyl, lower alkyl, C.sub.1-6 alkyl, C.sub.6-10 aryl, C.sub.6-10 heteroaryl, alkylaryl (e.g., C.sub.1-8 alkyl C.sub.6-10 aryl), NO.sub.2, NH.sub.2, N(RR), N(RRR).sup.+L.sup., Cl, F, Br, CF.sub.3, CCl.sub.3, CN, SO.sub.3H, PO.sub.3H.sub.2, COOH, CO.sub.2R, COR, CHO, OH, OR, OM+, SO.sub.3.sup.M.sup.+, PO.sub.3.sup.M.sup.+, COO.sup.M.sup.+, CF.sub.2H, CF.sub.2R, CFH.sub.2, and CFRR where R, R and R are C.sub.1-10 alkyl or C.sub.6-18 aryl groups, M.sup.+ is a metal ion, and L.sup. is a negatively charged counter ion; R groups on adjacent carbon atoms can be combined as OCH.sub.2O; single letters (e.g., n or o) are 1, 2, 3, 4, or 5; in the compounds disclosed herein a CH bond can be substituted with alkyl, lower alkyl, C.sub.1-6 alkyl, C.sub.6-10 aryl, C.sub.6-10 heteroaryl, NO.sub.2, NH.sub.2, N(RR), N(RRR).sup.+L.sup., Cl, F, Br, CF.sub.3, CCl.sub.3, CN, SO.sub.3H, PO.sub.3H.sub.2, COOH, CO.sub.2R, COR, CHO, OH, OR, OM+, SO.sub.3.sup.M.sup.+, PO.sub.3.sup.M.sup.+, COO.sup.M.sup.+, CF.sub.2H, CF.sub.2R, CFH.sub.2, and CFRR where R, R and R are C.sub.1-10 alkyl or C.sub.6-18 aryl groups, M.sup.+ is a metal ion, and L.sup. is a negatively charged counter ion; hydrogen atoms on adjacent carbon atoms can be substituted as OCH.sub.2O; when a given chemical structure includes a substituent on a chemical moiety (e.g., on an aryl, alkyl, etc.) that substituent is imputed to a more general chemical structure encompassing the given structure; percent, parts of, and ratio values are by weight; the term polymer includes oligomer, copolymer, terpolymer, and the like; molecular weights provided for any polymers refers to weight average molecular weight unless otherwise indicated; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.
[0030] It must also be noted that, as used in the specification and the appended claims, the singular form a, an, and the comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.
[0031] As used herein, the term about means that the amount or value in question may be the specific value designated or some other value in its neighborhood. Generally, the term about denoting a certain value is intended to denote a range within +/5% of the value. As one example, the phrase about 100 denotes a range of 100+/5, i.e. the range from 95 to 105. Generally, when the term about is used, it can be expected that similar results or effects according to the invention can be obtained within a range of +/5% of the indicated value.
[0032] As used herein, the term and/or means that either all or only one of the elements of said group may be present. For example, A and/or B shall mean only A, or only B, or both A and B. In the case of only A, the term also covers the possibility that B is absent, i.e. only A, but not B.
[0033] It is also to be understood that this invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way.
[0034] The term comprising is synonymous with including, having, containing, or characterized by. These terms are inclusive and open-ended and do not exclude additional, unrecited elements or method steps.
[0035] The phrase consisting of excludes any element, step, or ingredient not specified in the claim. When this phrase appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
[0036] The phrase consisting essentially of limits the scope of a claim to the specified materials or steps, plus those that do not materially affect the basic and novel characteristic(s) of the claimed subject matter.
[0037] The phrase composed of means including or consisting of. Typically, this phrase is used to denote that an object is formed from a material.
[0038] With respect to the terms comprising, consisting of, and consisting essentially of, where one of these three terms is used herein, the presently disclosed and claimed subject matter can include the use of either of the other two terms.
[0039] The term one or more means at least one and the term at least one means one or more. The terms one or more and at least one include plurality and multiple as a subset. In a refinement, one or more includes two or more.
[0040] The term substantially, generally, or about may be used herein to describe disclosed or claimed embodiments. The term substantially may modify a value or relative characteristic disclosed or claimed in the present disclosure. In such instances, substantially may signify that the value or relative characteristic it modifies is within +0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5% or 10% of the value or relative characteristic.
[0041] It should also be appreciated that integer ranges explicitly include all intervening integers. For example, the integer range 1-10 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Similarly, the range 1 to 100 includes 1, 2, 3, 4 . . . 97, 98, 99, 100. Similarly, when any range is called for, intervening numbers that are increments of the difference between the upper limit and the lower limit divided by 10 can be taken as alternative upper or lower limits. For example, if the range is 1.1 to 2.1 the following numbers 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 can be selected as lower or upper limits.
[0042] When referring to a numeral quantity, in a refinement, the term less than includes a lower non-included limit that is 5 percent of the number indicated after less than. For example, less than 20 includes a lower non-included limit of 1 in a refinement. Therefore, this refinement of less than 20 includes a range between 1 and 20. In another refinement, the term less than includes a lower non-included limit that is, in increasing order of preference, 20 percent, 10 percent, 5 percent, or 1 percent of the number indicated after less than.
[0043] In the examples set forth herein, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 50 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples. In a refinement, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 30 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples. In another refinement, concentrations, temperature, and reaction conditions (e.g., pressure, pH, flow rates, etc.) can be practiced with plus or minus 10 percent of the values indicated rounded to or truncated to two significant figures of the value provided in the examples.
[0044] For all compounds expressed as an empirical chemical formula with a plurality of letters and numeric subscripts (e.g., CH.sub.2O), values of the subscripts can be plus or minus 50 percent of the values indicated rounded to or truncated to two significant figures. For example, if CH.sub.2O is indicated, a compound of formula C.sub.(0.8-1.2)H.sub.(1.6-2.4)O.sub.(0.8-1.2). In a refinement, values of the subscripts can be plus or minus 30 percent of the values indicated rounded to or truncated to two significant figures. In still another refinement, values of the subscripts can be plus or minus 20 percent of the values indicated rounded to or truncated to two significant figures.
[0045] The term alkali metal means lithium, sodium, potassium, rubidium, cesium, and francium.
[0046] The alkaline earth metal means a chemical elements in group 2 of the periodic table. The alkaline earth metals include beryllium, magnesium, calcium, strontium, barium, and radium.
[0047] The term transition metal means an element whose atom has a partially filled d sub-shell, or which can give rise to cations with an incomplete d sub-shell. Examples of transition metals includes scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, and gold.
[0048] The term post-transition metal means gallium, indium, tin, thallium, lead, bismuth. zinc, cadmium, mercury, aluminum, germanium, or antimony.
[0049] The term lanthanide or lanthanoid series of chemical elements means an element with atomic numbers 57-71. The lanthanides metals includes lanthanum, cerium, praseodymium, samarium, europium, gadolinium neodymium, promethium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.
[0050] The term metal as used herein means an alkali metal, an alkaline earth metal, a transition metal, a lanthanide, an actinide, or a post-transition metal.
[0051] The term gauge pressure as used herein means the pressure measured relative to the ambient atmospheric pressure.
[0052] Throughout this application, where publications are referenced, the disclosures of these publications in their entireties are hereby incorporated by reference into this application to more fully describe the state of the art to which this invention pertains.
Abbreviations
[0053] CCU means carbon capture and utilization.
[0054] CCS means carbon capture and sequestration. CCR: carbon capture and recycling. Mmol: millimole.
[0055] In at least one aspect, a liquid phase system for catalytic direct hydrogenation of metal carbonate and bicarbonate salts at moderate to low temperatures in presence of molecular H.sub.2 is provided. Examples of these reactions of metal carbonates and bicarbonates to methanol and methane are provided in
[0056] In another aspect, a method for the conversion of a carbonate/formate component is provided. The method includes a step of contacting the carbonate/formate component with hydrogen to produce methanol, methane, carbon monoxide, hydrocarbons, or a mixture thereof over a catalyst in a solvent. Characteristically, the catalyst includes a transition metal, a post-transition metal, a lanthanide, or combinations thereof. In a refinement, the carbonate/formate component is a metal carbonate, a metal bicarbonate, and/or a metal formate. In another refinement, the carbonate/formate component is an ammonium or tetraalkyl ammonium carbonate, an ammonium or tetraalkyl ammonium bicarbonate, and/or an ammonium or tetraalkyl ammonium formate. In a refinement, the alkyl groups in the tetraalkyl ammonium can be C.sub.1-6 alkyl groups.
[0057] In another aspect, the reaction of the carbonate/formate component with hydrogen to produce methanol, methane, carbon monoxide, hydrocarbons, or a mixture thereof over a catalyst is performed under alkaline conditions. Therefore, the reaction is performed at a pH over 7. In some refinements, the reaction is performed at a pH greater than 7, 7.5, 8, 9, 10, 12 or 14. In a further refinement, the reaction is performed at a pH less than 14, 13, 12, or 10.
[0058] In another aspect, the reaction can be operated at ambient temperatures to high temperatures. The reaction efficiency and rates are higher at relatively moderate temperatures of 150 C. and above for methanol synthesis and the methanation reaction. For homogeneous catalysts, reaction temperature can be about 100 C. (e.g, 80 to 150 C.). The production of carbon monoxide, dimethyl ether, and mixtures of hydrocarbons is also possible. In a refinement, the reaction is performed at a temperature from about 20 C. to 250 C. In some variations, the reaction is performed at a temperature of at least 20 C., 30 C., 50 C., 70 C., 100 C., 120 C., 130 C., 140 C., or 120 C. In a refinement, the reaction is performed at a temperature of at most 700 C., 600 C., 500 C., 400 C., 350 C., 300 C., 350 C., 200 C., or 150 C.
[0059] In another aspect, the H.sub.2 pressure can be varied from 1 atm to higher pressures depending on the activity of the catalyst and other reaction parameters. In the case of the reaction producing methane, it should be noted that the gaseous product adds to the pressure of the system unless released to operate at constant pressure. In some refinements, the reaction is conducted at gauge pressures of at least 0 bar, 1 bar, 5 bar, 10 bar, 50 bar, 80 bar, 100 bar, or 150 bar. In further refinement, the reaction is conducted at gauge pressures of at most 400 bar, 350 bar, 300 bar, 250 bar, 200 bar, 150 bar, 100 bar, or 50 bar. In one example, the conversion of the metal carbonate, metal bicarbonate, metal formate salt, and mixtures thereof with hydrogen to produce methanol, methane, carbon monoxide, hydrocarbons, or mixtures thereof is conducted at temperatures between 50 C. and 600 C. and gauge pressures between 0 and 300 bar.
[0060] In another aspect, high selectivities of 90% and above can be achieved for the desired product, while the product yields can also be in the higher range (>80%). In a refinement, very high selectivities of 95% and above can be achieved for the desired product, while the product yields are also in the higher range (>90%).
[0061] In another aspect, the hydrogen used in the reaction is produced from any fossil or renewable source including natural gas, petroleum, coal, biomass, biogas, and water. In another refinement, the hydrogen used in the reaction is produced electrochemically from water. In another refinement, the hydrogen used in the reaction is produced by any other method able to split water, including photochemical, thermal, and photovoltaic. In still another refinement, the hydrogen used in the reaction is produced electrochemically from water obtained as a side product of the carbonate/bicarbonate hydrogenation reaction.
[0062] In another aspect, the process can be operated under batch and flow conditions. The product separation is straightforward in both cases. Under flow conditions, the products can be collected from the outlet stream. Under batch conditions, methanol (b.p. 64.7 C.) can for example be distilled off from the reaction mixture. Methane gas or methane/hydrogen gas mixtures can be released from the reactor to a storage container.
[0063] In another aspect, a suitable solvent can be chosen for effective hydrogenation of the substrate and; the conditions depend on the desired product. In a refinement, the solvent includes water, an alcohol, a diol, a polyol or a mixture thereof. For methanol synthesis, solvent systems including polar protic solvents like water, alcohol, or a mixture of these solvents with a co-solvent may be used. Examples of alcohol solvents are methanol, ethanol, isopropanol, n-butanol, 2-methoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols, propylene glycol, 1,4-butanediol, 2,3-butanediol and various amino-alcohols. For methane production, water is a preferred solvent. In a refinement, the solvent includes water, methanol, ethanol, isopropanol, n-butanol, ethanol propanol, 2-methoxyethanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,4-butanediol or a mixture thereof.
[0064] In another aspect, a heterogeneous catalyst system includes the catalyst to produce methanol, methane, carbon monoxide hydrocarbons, or a mixture thereof set forth above. In a refinement, the heterogeneous catalyst system includes a component selected from the group consisting of copper-based catalysts, indium-based catalysts, nickel-based, indium and nickel/gallium-based catalysts modified with lanthanides and/or precious metals, and combinations thereof. In a refinement, the heterogeneous catalyst system includes an indium-based having formula In.sub.2O.sub.3/ZrO.sub.2. In another refinement, the heterogeneous catalyst system includes a nickel-based catalyst selected from the group consisting of NiGa/SiO.sub.2, Ni.sub.3Ga/SiO.sub.2, and Ni.sub.5Ga.sub.3/SiO.sub.2. In a further refinement, the heterogeneous catalyst system further includes additional components selected from the group consisting of additives, support, and combinations thereof. Examples for the additional components include but are not limited to ZnO, ZrO.sub.2, MOFs, Ga, Al.sub.2O.sub.3, SiO.sub.2. TiO.sub.2, or combinations thereof.
[0065] In another aspect, heterogeneous catalysts for carbonate, bicarbonate, and formate hydrogenation to methanol may include (but are not limited to) copper-based catalysts (with additives and supports such as ZnO, ZrO.sub.2, MOFs, Ga, Al.sub.2O.sub.3, SiO.sub.2. TiO.sub.2), indium based (In.sub.2O.sub.3/ZrO.sub.2), nickel based (NiGa/SiO.sub.2, Ni.sub.3Ga/SiO.sub.2, Ni.sub.5Ga.sub.3/SiO.sub.2), ruthenium, platinum, palladium based (Ru, Pt, Pd on various supports including silica, alumina, titania, zirconia, silica-alumina and carbon). Various promoters, such as precious metals (such as Pd, Pt, Rh, Ru) or lanthanides (such as La, Sm, Gd), can also be added to these heterogenous catalysts to improve selectivity and reactivity.
[0066] In another aspect, for methane and carbon monoxide synthesis, heterogeneous catalysts may include (but are not limited to) ruthenium, rhodium, nickel, cobalt, platinum, palladium, iron, iridium, etc. on a support (e.g., silica, alumina, titania, ceria, zirconia, silica-alumina etc.). Additives and promoters can be added to improve conversion and selectivities. In addition, homogeneous catalysts can also be used for this reaction. In a refinement, the catalyst to produce methane and carbon monoxide includes a heterogeneous catalyst based on nickel, cobalt, ruthenium, platinum, palladium, iron, iridium or rhodium and combinations thereof either in their pure form or deposited on a support including silica, alumina, zirconia, titanium oxide, cerium oxide and silica-alumina or mixtures thereof.
[0067] In another aspect, the heterogeneous catalyst are shaped into various forms that may include (but not limited to) granules, pellets, rings, tablets, spheres, cylinders and hollow cylinders.
[0068] In another aspect, the heterogeneous catalyst may be a powder.
[0069] In another aspect, the catalysts used herein have an average particle size less than or equal to 250 m. In some variations, the catalysts used herein have an average particle size greater than or equal to 50 nm, 100 nm, 500 nm, 1 m, 5 m, 10 m, 50 m, or 100 m. In some refinements, the catalysts used herein have an average particle size less than or equal to or 300 m, 250 m, 200 m, 150 m, 100 m, 50 m, 10 m, 1 m, or 500 nm.
[0070] In another aspect, the catalyst to produce methane and carbon monoxide by hydrogenation of metal carbonates, metal bicarbonates, and metal formate includes a homogenous catalyst based on a metal including (but not limited to) ruthenium, rhodium, nickel, cobalt, platinum, palladium, iron, iridium, and an organic ligand such as, but not limited to, pincer-type ligands. As used herein, when a catalyst is referred to as being based on a specified metal, it means that the catalyst includes the specified metal in an appropriate oxidation state to function as a catalyst for the reaction.
[0071] In another aspect, the catalyst to produce methanol by hydrogenation of metal carbonate, bicarbonate and formate includes a homogenous catalyst based on a metal including (but not limited to) ruthenium, rhodium, nickel, manganese, cobalt, platinum, palladium, iron, iridium, and an organic ligand, such as, but not limited to, pincer-type ligands.
[0072] In another aspect, for the production of mixtures of hydrocarbons, a Fischer-Tropsch type catalyst can be employed. These include typical Fischer-Tropsch type catalysts based on iron, cobalt, and ruthenium. In a refinement, the catalyst to produce a mixture of hydrocarbons comprises catalysts based on iron, copper, molybdenum, cobalt, ruthenium, metal carbides, zeolites or mixtures thereof.
[0073] In another aspect, for the production of other hydrocarbons such as dimethyl ethers, olefins, higher carbon alcohols, liquid hydrocarbons; and their mixtures, any metal catalyst based on prior art of transforming CO.sub.2 gas into such chemicals can be employed. These may include catalysts containing iron, copper, molybdenum, cobalt, metal carbides, zeolites, etc., and mixtures thereof.
[0074] In another aspect, apart from a single class of catalysts, various combinations of such catalysts can be used to obtain the desired hydrocarbon products.
[0075] In another aspect, the metal carbonate and metal bicarbonate are products of a reaction of a metal hydroxide with CO.sub.2 contained from various sources such as fossil fuel power plant flue gases, emissions from industrial and commercial sources and CO.sub.2 contained in air.
[0076] In another aspect, the metal carbonate and metal bicarbonate are products of a reaction of a metal phosphate with CO.sub.2 contained in various sources such as fossil fuel power plant flue gases, emissions from industrial and commercial sources and CO.sub.2 contained in air. Examples of metal phosphates include tripotassium phosphate (K.sub.3PO.sub.4), dipotassium phosphate (K.sub.2HPO.sub.4), trisodium phosphate (Na.sub.3PO.sub.4), disodium phosphate (Na.sub.2HPO.sub.4), trilithium phosphate (Li.sub.3PO.sub.4) and dilithium phosphate (Li.sub.2HPO.sub.4).
[0077] In another aspect, the metal carbonate, metal bicarbonate, metal formate salt, and mixtures thereof react to form a metal hydroxide or metal hydroxide mixture.
[0078] In another aspect, the substrates include carbonate, bicarbonate/hydrogen carbonate, alkyl carbonate and formate salts of any metal including alkali metal, alkali earth metal, transition metal as well as rare earth metal. Examples of metal carbonates include sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, cesium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, strontium carbonate, barium carbonate or mixtures thereof. Examples of metal bicarbonate include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate or mixtures thereof. Examples of metal formate salt include lithium formate, sodium formate, potassium formate, rubidium formate, cesium formate, or mixtures thereof.
[0079] In another aspect, the carbonate and bicarbonate salts may be obtained from any source. For example, commercially available metal carbonate and bicarbonate salts can be used. The carbonate/formate component is a metal carbonate and/or a metal bicarbonate each independently including a component selected from naturally occurring minerals; seashells, oyster shells, eggshells; carbonates and bicarbonate salts made by direct CO.sub.2 capture from CO.sub.2 sources (e.g, point source or air (DAC)) using alkali hydroxides and/or amines; synthetic (i.e., man-made) carbonates and bicarbonates; and combinations thereof. In a refinement, the carbonate/formate component includes naturally occurring minerals are selected from the group consisting of calcite (CaCO.sub.3), magnesite (MgCO.sub.3), siderite (FeCO.sub.3), aragonite (CaCO.sub.3), witherite (BaCO.sub.3), natrite (Na.sub.2CO.sub.3), ankerite (CaFeCO.sub.3), dolomite (CaMg(CO.sub.3).sub.2), huntite (Mg.sub.3Ca(CO.sub.3).sub.4), minrecordite (CaZn(CO.sub.3).sub.2), barytocalcite (BaCa(CO.sub.3).sub.2), hydromagnesite (Mg.sub.5(CO.sub.3).sub.4(OH).sub.2.Math.4H.sub.2O), ikaite (CaCO.sub.3.Math.6(H.sub.2O)), lansfordite (MgCO.sub.3.Math.5(H.sub.2O)), monohydrocalcite (CaCO.sub.3.Math.H.sub.2O), natron (Na.sub.2CO.sub.3.Math.10(H.sub.2O)), and combinations thereof. In some variations, carbon capture and recycling technologies can be deployed. For example, CO.sub.2 can be captured from any source including industrial and commercial flue gases, breweries, exhaust streams from various sources including transportation and indoor or ambient air on any metal hydroxide either in solid form or in a solvent to form the corresponding metal carbonate/bicarbonate salts. The capture can be performed at temperatures from 20 C. and up to the decomposition temperature of the corresponding carbonate salt, and an inlet gas stream pressure of about 1 atm or higher. The inlet stream for capture may be dry or humid. The obtained carbonate/bicarbonate salts can be processed further for hydrogenation.
[0080] Parallel to the carbon-based product (methane, methanol, carbon monoxide, or hydrocarbon mixtures or mixtures thereof), co-production of metal hydroxide or hydrated oxides can be achieved during the reaction.
[0081] Advantageously, such processes described herein based on carbonate/bicarbonate reduction can be developed as an energy and cost-effective process to produce metal hydroxides from their respective carbonate or bicarbonate feedstock in an alternate to the common thermal decomposition processes at very high temperatures utilizing a multi-step process..sup.1,4
[0082] The co-production of metal hydroxide in the described reaction offers a way to produce methanol, methane, carbon monoxide, hydrocarbons and derived products from any CO.sub.2 source available. The recycling of the metal hydroxide at the end of the reaction to capture CO.sub.2 and form more carbonate and bicarbonate allows for the metal hydroxide to be reused over many hydrogenation cycles with no or minimal need for the input of fresh metal hydroxide.
[0083] Furthermore, the convenient capture of CO.sub.2 from a sustainable and renewable source such as biomass, biogas, breweries, and ambient air and reaction of the formed metal carbonate and bicarbonate with renewable hydrogen allows for the production of renewable methanol, methane and hydrocarbons. These products and their derivatives have a low or neutral carbon footprint because the CO.sub.2 released by their utilization was captured from a renewable source. The capture, utilization and recycling of renewable CO.sub.2 with hydrogen generated using renewable electrical energy, essentially constitutes a sustainable anthropogenic version of nature's own carbon cycle.
[0084] In another aspect, a method to produce methanol, methane, carbon monoxide, hydrocarbons or a mixture thereof from CO.sub.2 is provided. The method includes the following steps: [0085] (a) capturing CO.sub.2 with a metal hydroxide or metal hydroxide mixture from a CO.sub.2 source containing between 0.04% and 100% CO.sub.2 to obtain metal carbonates, metal bicarbonates or mixtures thereof; [0086] (b) converting the metal carbonates, metal bicarbonates and mixtures thereof with hydrogen to produce methanol, methane, carbon monoxide, hydrocarbons or a mixture thereof over a catalyst in a solvent while regenerating the metal hydroxide or metal hydroxide mixture; and [0087] (c) reusing the metal hydroxide or metal hydroxide mixture to capture CO.sub.2 as described in step (a).
[0088] Examples of suitable CO.sub.2 sources include ambient air, indoor air, industrial flue gases, fossil fuel burning power plants, natural gas purification facilities, cement plants, biogas, breweries, biomass burning facilities and biomass gasification facilities
[0089] A particular embodiment of the invention disclosed herein is the capture of CO.sub.2 from air (direct air capture, DAC) using any available technology with a metal hydroxide to form metal carbonate, metal bicarbonate or mixtures thereof and further reacting these metal carbonate/bicarbonate with hydrogen in the presence of a catalyst in a liquid phase to make products including but not limited to methanol, methane, and hydrocarbons. At the same time, during the hydrogenation reaction, the metal hydroxide is regenerated and can be reused to capture more CO.sub.2 from the air. This allows the cycle to be closed on the metal hydroxide/carbonate/bicarbonate. Furthermore, once the hydrogenation products are used, all or part of the generated CO.sub.2 will be released back the atmosphere. This allows for the carbon cycle to be closed as well.
[0090] Illustrative examples of closed cycles for the production of methanol, methane, carbon monoxide and other hydrocarbons (C.sub.2) from captured CO.sub.2 and H.sub.2 using metal hydroxide/carbonate/bicarbonate are given in
[0091] In still another aspect, the metal hydroxide includes lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide or mixtures thereof.
[0092] In a further aspect, the metal hydroxide produced can be used for ocean alkalinity enhancement (also called ocean alkalinization) by forming metal carbonate and bicarbonates with dissolved CO.sub.2 when added to seawater.
[0093] In yet a further aspect, the products obtained by the hydrogenation of metal carbonates and bicarbonates (methane, methanol, carbon monoxide, hydrocarbons (C.sub.2) and others) can be combusted in a stream of oxygen or air and the resulting CO.sub.2 captured and sequestered or reused (CCS or CCU).
[0094] In still another aspect the hydrogen for the hydrogenation reaction is produced electrochemically from water obtained as a side product of the carbonate/bicarbonate hydrogenation reaction or from water obtained as a side product of CO.sub.2 capture from various sources including capture of CO.sub.2 from the air.
[0095] In still another aspect the hydrogen for the hydrogenation reaction is produced electrochemically from an aqueous solution of carbonate/bicarbonate used subsequently for the carbonate/bicarbonate hydrogenation reaction.
[0096] In still another aspect the hydrogen for the hydrogenation reaction is produced electrochemically from an aqueous solution of metal hydroxide obtained as a product reaction of the carbonate/bicarbonate hydrogenation reaction.
[0097] In yet another aspect, the hydrogen (H.sub.2) for the hydrogenation reaction is produced in-situ, inside the hydrogenation reactor by water electrolysis.
[0098] In an additional aspect hydrogen can be generated from other sources including dehydrogenation of a variety of alcohols or another process known to those skilled in the art for producing hydrogen.
[0099] In a further aspect a method for producing methanol, methane, carbon monoxide, hydrocarbons or a mixture thereof from CO.sub.2 is provided. The method includes the following steps: [0100] (a) capturing CO.sub.2 with a metal phosphate or metal phosphate mixture from a CO.sub.2 source containing between 0.04% and 100% CO.sub.2 to obtain metal carbonates, metal bicarbonates or mixtures thereof; [0101] (b) converting the metal carbonates, metal bicarbonates and mixtures thereof with hydrogen to produce methanol, methane, carbon monoxide, hydrocarbons, or a mixture thereof over a catalyst in a solvent while regenerating the metal phosphate or metal phosphate mixture; and [0102] (c) reusing the metal phosphate or metal phosphate mixture to capture CO.sub.2 as described in step (a).
[0103] The following examples illustrate various embodiments of the present invention. Those skilled in the art will recognize many variations that are within the spirit of the present invention and scope of the claims.
Example 1. Hydrogenation of Potassium Carbonate to Methanol Using Cu/ZnO/Al.SUB.2.O.SUB.3.Under Various Conditions
[0104] Commercial Cu/ZnO/Al.sub.2O.sub.3 catalyst was purchased from Alfa Aesar (63.5 wt % CuO, 24.7 wt % ZnO, 10.1 wt % Al.sub.2O.sub.3, 1.3 wt % MgO fume). The pellets were then crushed and sieved to a size of 250 m or less. For activating the Cu/ZnO/Al.sub.2O.sub.3 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h, then the temperature was ramped up to 270 C. (at 10 C./min) with an H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 5 h. The so-treated catalyst was then stored under Argon for use at a later time. In a nitrogen-filled chamber, potassium carbonate, pre-activated catalyst, and the solvent were introduced to a 125 mL Parr reactor. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes. Afterwards, the gases inside the vessel were partly collected in a gas sampling bag for GC analysis whereas the remaining gas was slowly released. The methanol formed was detected by .sup.1H NMR and isolated in vacuo. The results of the hydrogenation of potassium carbonate to methanol following the method described here are shown in Table 1.
TABLE-US-00001 TABLE 1 Hydrogenation of potassium carbonate to methanol with Cu/ZnO/Al.sub.2O.sub.3 under various conditions: Cu/ZnO/ Temper- Al.sub.2O.sub.3 Product ature Pressure Loading Time Methanol Methanol Trial ( C.) (bar) (mg) (hours) (mmol) Yield (%) 1 170 70 300 48 0.7 7 2 200 70 300 48 5.6 56 3 250 70 300 48 7.2 72 4 200 60 300 48 5.4 54 5 200 80 300 48 5.8 58 6 200 70 150 48 1.9 19 7 200 70 450 48 7.4 74 8 200 70 300 24 4.6 46 9 200 70 300 72 7.1 71 10 .sup.[a] 200 70 300 72 9.9 99 Reaction conditions: 10 mmol potassium carbonate, pressure of H.sub.2 at room temperature, 800 rpm magnetic stirring, 10 mL of ethylene glycol. .sup.[a] 5 mL of ethylene glycol, no magnetic stirring. CH.sub.3OH yields calculated relative to the carbonate as determined by .sup.1H NMR. Yield calculations 5%.
Example 2. Hydrogenation of Some Metal Carbonates to Methanol
[0105] Commercial Cu/ZnO/Al.sub.2O.sub.3 catalyst was purchased from Alfa Aesar (63.5 wt % CuO, 24.7 wt % ZnO, 10.1 wt % Al.sub.2O.sub.3, 1.3 wt % MgO fume). The pellets were then crushed and sieved to a size of 250 m or less. For activating the Cu/ZnO/Al.sub.2O.sub.3 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h, then the temperature was ramped up to 270 C. (at 10 C./min) with an H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 5 h. The so-treated catalyst was then stored under Argon for use at a later time. In a nitrogen-filled chamber, the substrate, pre-activated catalyst, and the solvent were introduced to a 125 mL Parr reactor. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes. Afterwards, the gases inside the vessel were partly collected in a gas sampling bag for GC analysis whereas the remaining gas was slowly released. The methanol formed was detected by .sup.1H NMR and isolated in vacuo. The results of the hydrogenation of some metal carbonates to methanol following the method described here are shown in Table 2.
TABLE-US-00002 TABLE 2 Hydrogenation of some metal carbonates to methanol Products Carbonate Formate Methanol Methanol used (mmol) (mmol) Yield (%) Li.sub.2CO.sub.3 0 1.1 11 Na.sub.2CO.sub.3 0 5.9 59 K.sub.2CO.sub.3 0.1 9.9 99 Rb.sub.2CO.sub.3 0.9 8.7 87 Cs.sub.2CO.sub.3 0.9 6.2 62 MgCO.sub.3 0 1.2 12 CaCO.sub.3 0 1.2 12 BaCO.sub.3 0 0.9 9 MgCO.sub.3.sup.[a] 0 4.8 48 CaCO.sub.3.sup.[a] 0 6.0 60 BaCO.sub.3.sup.[a] 0 4.6 46 Reaction conditions: 10 mmol carbonate salt, ethylene glycol (5 mL), 70 bar H.sub.2 at room temperature, 200 C., 72 hours, 300 mg Cu/ZnO/Al.sub.2O.sub.3. .sup.[a]85 bar H.sub.2 at room temperature, 250 C., 800 rpm magnetic stirring. CH.sub.3OH yields calculated relative to the carbonate as determined by .sup.1H NMR. Yield calculations 5%.
Example 3. Hydrogenation of Some Metal Bicarbonates and Formates to Methanol
[0106] Commercial Cu/ZnO/Al.sub.2O.sub.3 catalyst was purchased from Alfa Aesar (63.5 wt % CuO, 24.7 wt % ZnO, 10.1 wt % Al.sub.2O.sub.3, 1.3 wt % MgO fume). The pellets were then crushed and sieved to a size of 250 m or less. For activating the Cu/ZnO/Al.sub.2O.sub.3 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h, then ramped up to 270 C. (at 10 C./min) with a H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 5 h. The so treated catalyst was then stored afterwards under Argon for use at a later time. In a nitrogen-filled chamber, the substrate, pre-activated catalyst and the solvent were introduced to a 125 mL Parr reactor with a magnetic stirrer. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes. Afterwards, the gases inside the vessel were partly collected in a gas sampling bag for GC analysis whereas the remaining gas was slowly released. The methanol formed was detected by .sup.1H NMR and isolated in vacuo. The results of the hydrogenation of some metal carbonates and metal formates to methanol following the method described here are shown in Table 3.
TABLE-US-00003 TABLE 3 Hydrogenation of some metal bicarbonates and formates to methanol Products Formate Methanol Methanol Substrate (mmol) (mmol) yield (%) NaHCO.sub.3 0 6.2 62 NaHCO.sub.2 0 7.1 71 KHCO.sub.3 0 9.7 97 KHCO.sub.2 0 9.8 98 CsHCO.sub.3 1.3 8.7 87 CsHCO.sub.2 0 8.2 82 LiHCO.sub.2 0 1.3 13 Mg(HCO.sub.2).sub.2.sup.[a] 0 2.8 28 Ca(HCO.sub.2).sub.2.sup.[a] 0 0.8 8 Reaction conditions: 10 mmol salt(substrate), ethylene glycol (5 mL), 200 C., 70 bar H.sub.2, 72 hours, 300 mg Cu/ZnO/Al.sub.2O.sub.3 .sup.[a]Reaction conditions: 5 mmol salt, ethylene glycol (5 mL), 200 C., 70 bar H.sub.2, 72 hours, 300 mg Cu/ZnO/Al.sub.2O.sub.3. CH.sub.3OH yields calculated relative to the carbonate as determined by .sup.1H NMR. Yield calculations 5%.
Example 4. Hydrogenation of Carbonates in Biomass Samples
[0107] Commercial Cu/ZnO/Al.sub.2O.sub.3 catalyst was purchased from Alfa Aesar (63.5 wt % CuO, 24.7 wt % ZnO, 10.1 wt % Al.sub.2O.sub.3, 1.3 wt % MgO fume). The pellets were then crushed and sieved to a size of 250 m or less. For activating the Cu/ZnO/Al.sub.2O.sub.3 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h, then the temperature was ramped up to 270 C. (10 C./min) with a H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 5 h. The so treated catalyst was then stored under Argon for use at a later time. The biomaterial was crushed and sieved to a fine powder form. In a nitrogen-filled chamber, the biomaterial substrate, pre-activated catalyst and the solvent were introduced to a 125 mL Parr reactor with a magnetic stirrer. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes. Afterwards, the gases inside the vessel were partly collected in a gas sampling bag for GC analysis whereas the remaining gas was slowly released. The methanol formed can be detected by .sup.1H NMR and isolated in vacuo. The results of the hydrogenation of some bio-materials to methanol following the method described here are shown in Table 4.
TABLE-US-00004 TABLE 4 Hydrogenation of carbonates in biomass samples Starting material Products Bio- Amount % Formate Methanol Methanol material (g) CaCO.sub.3 (mmol) (mmol) Yield (%) Seashell 1.0 99.6% traces 5.8 58 Eggshell 1.0 57.3% traces 3.2 56 Reaction conditions: 1 gram bio-material, ethylene glycol (10 mL), 85 bar H.sub.2 at room temperature, 250 C., 72 hours, 800 rpm, and 300 mg Cu/ZnO/Al.sub.2O.sub.3. CH.sub.3OH yields calculated relative to the carbonate as determined by .sup.1H NMR. Yield calculations 5%.
Example 5. CO.SUB.2 .Capture and Hydrogenation to Methanol
[0108] CO.sub.2 capture from pure CO.sub.2 stream: A known amount of alkali hydroxide (KOH) was dissolved in ethylene glycol (10 mL) in a vial with a magnetic stir bar. The gases inside the vial were then removed under vacuum. CO.sub.2 was subsequently added while stirring the solution at 800 rpm for 3 h and maintaining the CO.sub.2 pressure inside the reactor at about 1 psi above atmospheric pressure. The amounts of CO.sub.2 captured were calculated through gravimetric analysis of the solutions before and after the capture.
[0109] CO.sub.2 capture from air: In a 30 mL vial, a specific amount of KOH was dissolved in 10 mL ethylene glycol. Atmospheric air containing 420 ppm CO.sub.2 was then bubbled through the solution at a flowrate of 200 mL/min for 72 h using a pump. The resulting solution was then sparged with N.sub.2 for 2 h. Afterwards, imidazole (Im) was added as an internal standard to 0.5 mL aliquot of the homogeneous solution that was analyzed by .sup.1H and .sup.13C NMR with DMSO-d.sub.6 as the deuterated solvent. The amount of CO.sub.2 captured was calculated through .sup.13C NMR analysis. The remaining solution was used for hydrogenation.
[0110] Hydrogenation of captured carbonate species: For activating the Cu/ZnO/Al.sub.2O.sub.3 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h. Then the temperature was ramped up to 270 C. (at 10 C./min) with a H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 5 h. The so treated catalyst was then stored under Argon for use at a later time. In a nitrogen-filled chamber, the CO.sub.2 loaded ethylene glycol solution and the pre-activated catalyst were introduced to a 125 mL Parr reactor with a magnetic stirrer. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes. Afterwards, the gases inside the vessel were partly collected in a gas sampling bag for GC analysis whereas the remaining gas was slowly released. The methanol formed can be detected by .sup.1H NMR and isolated in vacuo. The results of the hydrogenation of the CO.sub.2 capture with KOH to methanol following the method described here are shown in Table 5.
TABLE-US-00005 TABLE 5 CO.sub.2 capture and hydrogenation to methanol CO.sub.2 Methanol Methanol Base Time CO.sub.2 captured produced yield Entry (mmol) (h) source (mmol) (mmol) (%) 1 KOH 3 pure CO.sub.2 10.0 10.0 >99 2 (10) 72 indoor air 6.6 6.4 97 Capture conditions: solvent = 10 mL, rt, stirring at 800 rpm. Hydrogenation conditions: H.sub.2 = 70 bar at rt, catalyst loading = 300 mg, T = 200 C., t = 72 h, CH.sub.3OH yields calculated relative to CO.sub.2 captured. Yield calculations error 5%.
Example 6. Hydrogenation of .SUP.13.C Labelled Potassium Carbonate to .SUP.13.C Labelled Methanol in Naturally Abundant Methanol and Water Solvent
[0111] Commercial Cu/ZnO/Al.sub.2O.sub.3 catalyst was purchased from Alfa Aesar (63.5 wt % CuO, 24.7 wt % ZnO, 10.1 wt % Al.sub.2O.sub.3, 1.3 wt % MgO fume). The pellets were then crushed and sieved to a size of 250 m or less. For activating the Cu/ZnO/Al.sub.2O.sub.3 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h, then ramped up to 270 C. (at 10 C./min) with a H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 5 h. The so treated catalyst was then stored under Argon for use at a later time. In a nitrogen-filled chamber, the .sup.13C labelled potassium carbonate, pre-activated catalyst and the solvents were introduced to a 125 mL Parr reactor with a magnetic stirrer. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes. Afterwards, the gases inside the vessel were partly collected in a gas sampling bag for GC analysis whereas the remaining gas was slowly released. The .sup.13C methanol formed was detected by 1H NMR and isolated in vacuo. The results of the hydrogenation of potassium carbonate to methanol following the method described here are shown in Table 6.
TABLE-US-00006 TABLE 6 Hydrogenation of .sup.13C labelled potassium carbonate to .sup.13C labelled methanol in naturally abundant methanol and water solvent .sup.13C CH.sub.3OH CH.sub.3OH substrate time Produced yield Entry (mmol) solvent (mL) (h) (mmol) (%) 1 K.sub.2CO.sub.3 (5) methanol (5 mL) 72 3.1 62 2 K.sub.2CO.sub.3 (5) methanol (5 mL) + 72 3.9 78 water (0.5 mL) Hydrogenation conditions: H.sub.2 = 80 bar at rt, Cu/ZnO/Al.sub.2O.sub.3 loading = 600 mg, T = 200 C., t = 72 h. Yield calculations error 5%.
Example 7. Hydrogenation of Metal Carbonates and Bicarbonates to Methane with Ni/CaAl.SUB.2.O.SUB.4 .in Water
[0112] Commercial HIFUEL R110 Ni/CaAl.sub.2O.sub.4 catalyst was purchased from Alfa Aesar. For activating the Ni/CaAl.sub.2O.sub.4 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h, then ramped up to 700 C. (at 10 C./min) with a H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 6 h. The so treated catalyst was then stored under Argon for use at a later time. In a nitrogen-filled chamber, potassium bicarbonate or carbonate salts, pre-activated catalyst and water were introduced to a 125 mL Parr reactor. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes. The methane formed was analyzed by GC. The results of the hydrogenation of potassium carbonate and potassium bicarbonate to methane following the method described here are shown in Table 7.
TABLE-US-00007 TABLE 7 Hydrogenation of metal carbonates and bicarbonates to methane with Ni/CaAl.sub.2O.sub.4 in water substrate Methane amount H.sub.2 Temperature Time produced Methane Entry substrate (mmol) (bar) ( C.) (hours) (mmol) yield (%) 1 KHCO.sub.3 10 50 170 48 0.6 6 2 KHCO.sub.3 10 50 200 48 0.7 7 3 KHCO.sub.3 10 50 225 48 9.7 97 4 KHCO.sub.3 10 40 225 48 5.4 54 5 KHCO.sub.3 10 50 225 48 9.7 97 6 KHCO.sub.3 10 60 225 48 8.2 82 7 KHCO.sub.3 10 70 225 48 6.3 63 8 KHCO.sub.3 10 50 225 24 2.2 22 9 KHCO.sub.3 10 50 225 72 9.8 98 10 K.sub.2CO.sub.3 10 50 225 48 5.3 53 Reaction conditions: water (10 mL), H.sub.2 pressure at room temperature, 300 mg Ni/CaAl.sub.2O.sub.4. Methane yields were calculated relative to the carbonate as determined by gas chromatography. Yield calculations 5%.
Example 8. Hydrogenation of Metal Carbonates and Bicarbonates to Methane with Ni/Al.SUB.2.O.SUB.3 .in Water
[0113] The catalyst used in the experiments in this example was composed of 33 wt % Ni on Al.sub.2O.sub.3. For activating the Ni/Al.sub.2O.sub.3 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h, then ramped up to 700 C. (at 10 C./min) with a H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 6 h. In a nitrogen-filled chamber, potassium bicarbonate or carbonate salts, pre-activated catalyst and water were introduced to a 125 mL Parr reactor. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes. The methane formed was analyzed by GC. The results of the hydrogenation of some metal carbonates and bicarbonates to methane following the method described here are shown in Table 8.
TABLE-US-00008 TABLE 8 Hydrogenation of metal carbonates and bicarbonates to methane with Ni/Al.sub.2O.sub.3 in water substrate Methane amount H.sub.2 Temperature Time produced Methane Entry substrate (mmol) (bar) ( C.) (hours) (mmol) yield (%) 1 KHCO.sub.3 10 50 225 48 10 100 2 K.sub.2CO.sub.3 10 50 225 48 10 100 3 K.sub.2CO.sub.3 20 50 225 48 11 55 4 Na.sub.2CO.sub.3 10 50 225 48 10 100 5 CaCO.sub.3 10 50 225 48 1 10 Reaction conditions: water (10 mL), 50 bar H.sub.2 pressure at room temperature, 48 h, 300 mg Ni/Al.sub.2O.sub.3. Methane yields calculated relative to the carbonate as determined by gas chromatography. Yield calculations 5%.
Example 9. Hydrogenation of Potassium Carbonate to Methane with Ni/Al.SUB.2.O.SUB.3 .in Water, Over Several CO.SUB.2 .Absorption/Metal Carbonate Reduction Cycles
[0114] The catalyst used in the experiments in this example was composed of 33 wt % Ni on Al.sub.2O.sub.3. For activating the Ni/Al.sub.2O.sub.3 catalyst, the catalyst was subjected to a flow of N.sub.2 (100 mL/min) at 120 C. for 1 h, then ramped up to 700 C. (at 10 C./min) with a H.sub.2 flow (35 mL/min) in N.sub.2 (100 mL/min) at 1 atm and kept at that temperature for 6 h. The so treated catalyst was then stored under Argon for use at a later time. Separately, a solution of KOH (4 mmol) in water (10 mL) was prepared in a flask. The flask was then purged to remove any atmosphere and placed under a pure CO.sub.2 atmosphere while the solution was stirred at 800 rpm. The amount of CO.sub.2 captured was measured by both the volume of CO.sub.2 added and gravimetrically. In a nitrogen-filled chamber, the solution resulting from the reaction of KOH with CO.sub.2, and the pre-activated catalyst were introduced to a 125 mL Parr reactor. The sealed vessel was then filled to the desired pressure with H.sub.2. The reactor was placed in a preheated aluminum block and heated to the desired temperature. After heating for a given reaction period, the reactor was cooled to room temperature. The vessel was then cooled in an ice bath for 30 minutes and then pressure was released. Part of the gas released was collected into a collection bag for gas chromatography analysis to determine the amount of methane formed. The liquid was decanted from the catalyst and placed in a 100 mL round bottom flask. The flask was then purged to remove any atmosphere and placed under a pure CO.sub.2 atmosphere while the solution was stirred at 800 rpm. The amount of CO.sub.2 captured was measured by both the volume of CO.sub.2 added and gravimetrically. The obtained solution was then used again in the hydrogenation reaction to methane as described earlier in this paragraph. This operation was repeated four more times after that to check the recyclability of both the catalyst and the base/carbonate species. The results of these consecutive CO.sub.2 capture/hydrogenation reactions to methane following the method described here are shown in Table 9.
TABLE-US-00009 TABLE 9 Hydrogenation of potassium bicarbonate to methane with Ni/Al.sub.2O.sub.3 in water, over several CO.sub.2 absorption/metal carbonate reduction cycles. Amount of CO.sub.2 Methane Methane Temperature Pressure captured produced Yield Cycle ( C.) H.sub.2 (bar) (mmol) (mmol) (%) 1 225 50 4 4 100 2 225 50 4 4 100 3 225 50 4 4 100 4 225 50 4 3.95 100 5 225 50 3.95 3.95 100 Capture conditions: KOH (4 mmol), water (10 mL), t = 48 h, stirring at 800 rpm, rt, Methanation conditions: water (10 mL), 50 bar H.sub.2 pressure at room temperature, 225 C., 300 mg Ni/Al.sub.2O.sub.3. Methane yields calculated relative to the carbonate as determined by Gas chromatography. Yield calculations 5%.
Example 10. Hydrogenation of Potassium Carbonate to Methane Over Various Catalysts in Water
TABLE-US-00010 TABLE 10 Hydrogenation of potassium carbonate to methane with various catalysts in water. Methane Methane produced yield Entry Catalyst (mmol) (%) 1 33% Ni/Al.sub.2O.sub.3 6.4 64 2 5% Ru/Al.sub.2O.sub.3 10 100 3 5% Rh/Al.sub.2O.sub.3 1.4.sup.[a] .sup.14.sup.[a] 4 12% Ni/Al.sub.2O.sub.3 1.2 12 5 12% Ni/3% Y/Al.sub.2O.sub.3 6.9 69 6 12% Ni/3% La/Al.sub.2O.sub.3 6.2 62 7 12% Ni/3% Ce/Al.sub.2O.sub.3 4.8 48 8 12% Ni/3% Pr/Al.sub.2O.sub.3 6.3 63 9 12% Ni/3% Nd/Al.sub.2O.sub.3 6.3 63 10 12% Ni/3% Sm/Al.sub.2O.sub.3 6.4 64 11 12% Ni/3% Gd/Al.sub.2O.sub.3 6.9 69 12 12% Ni/3% Dy/Al.sub.2O.sub.3 6.9 69 13 12% Ni/3% Yb/Al.sub.2O.sub.3 6.9 69 Reaction conditions: water (10 mL), 10 mmol K.sub.2CO.sub.3, 50 bar H.sub.2 pressure at room temperature, reaction temperature 225 C., 24 h, 300 mg catalyst. Methane yields calculated relative to the carbonate as determined by gas chromatography. Yield calculations 5%. .sup.[a]Also produced 2.4 mmol of CO.sub.2.
Example 11. Hydrogenation of Metal Carbonates to Methanol Using Ni.SUB.5.Ga.SUB.3./Gd/SiO.SUB.2
TABLE-US-00011 TABLE 11 Hydrogenation of metal carbonates to methanol using Ni.sub.5Ga.sub.3/Gd/SiO.sub.2. Products Metal Formate Methanol Methanol Trial Catalyst carbonate (mmol) (mmol) Yield (%) 1 Ni.sub.5Ga.sub.3/Gd/SiO.sub.2 K.sub.2CO.sub.3 1.49 6.03 60 2 Ni.sub.5Ga.sub.3/Gd/SiO.sub.2 Na.sub.2CO.sub.3 Traces 6.75 68 3 Ni.sub.5Ga.sub.3/Gd/SiO.sub.2 Rb.sub.2CO.sub.3 4.49 1.82 18 4 Ni.sub.5Ga.sub.3/Gd/SiO.sub.2 Li.sub.2CO.sub.3 traces 7.79 78 Reaction conditions: ethylene glycol (5 mL), 10 mmol metal carbonate, 60 bar H.sub.2 pressure at room temperature, reaction temperature 225 C., 48 h, 300 mg catalyst. CH.sub.3OH yields calculated relative to the carbonate as determined by .sup.1H NMR. Yield calculations 5%.
[0115] While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention.
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