WO2018020347A1 - Process for high-pressure hydrogenation of carbon dioxide to oxo-syngas composition using a copper/zinc/zirconium mixed metal oxide catalyst - Google Patents
Process for high-pressure hydrogenation of carbon dioxide to oxo-syngas composition using a copper/zinc/zirconium mixed metal oxide catalyst Download PDFInfo
- Publication number
- WO2018020347A1 WO2018020347A1 PCT/IB2017/054175 IB2017054175W WO2018020347A1 WO 2018020347 A1 WO2018020347 A1 WO 2018020347A1 IB 2017054175 W IB2017054175 W IB 2017054175W WO 2018020347 A1 WO2018020347 A1 WO 2018020347A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mol
- mpa
- syngas
- containing composition
- carbon dioxide
- Prior art date
Links
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 75
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 230000008569 process Effects 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 36
- 229910003455 mixed metal oxide Inorganic materials 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 20
- 239000010949 copper Substances 0.000 title description 24
- 239000011701 zinc Substances 0.000 title description 18
- 229910052802 copper Inorganic materials 0.000 title description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 6
- 229910052725 zinc Inorganic materials 0.000 title description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title description 3
- 229910052726 zirconium Inorganic materials 0.000 title description 3
- 239000007789 gas Substances 0.000 claims abstract description 43
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 39
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 32
- 239000000376 reactant Substances 0.000 claims description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 238000007037 hydroformylation reaction Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 19
- 239000000047 product Substances 0.000 description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 229910001868 water Inorganic materials 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 230000000670 limiting effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000006315 carbonylation Effects 0.000 description 8
- 238000005810 carbonylation reaction Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- -1 oxyhalides Chemical class 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- 239000012702 metal oxide precursor Substances 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/061—Methanol production
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/72—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Definitions
- the invention generally concerns a process for hydrogenation of carbon dioxide (C0 2 ) to produce a synthesis gas (syngas) containing composition that includes hydrogen (H 2 ) and carbon monoxide (CO).
- the process includes contacting a CuZnZr mixed metal oxide catalyst under conditions suitable to produce a syngas composition suitable for use in oxo-product synthesis.
- Syngas (which includes carbon monoxide and hydrogen gases) is oftentimes used to produce chemicals such as methanol, tert-butyl methyl ether, ammonia, fertilizers, 2-ethyl hexanol, formaldehyde, acetic acid, and 1,4-butane diol.
- Syngas can be produced by common methods such as methane steam reforming technology as shown in reaction equation (1), partial oxidation of methane as shown in reaction (2), or dry reforming of methane as shown in reaction (3):
- Equation (3) illustrates the catalyst deactivation event due to carbonization.
- This process which is also known as a reverse water gas shift reaction, is mildly endothermic and generally takes place at temperatures of at least about 450 °C, with C0 2 conversion of 50% at temperatures between 560 °C to 580 °C. Furthermore, some methane can be formed as a by-product due to the methanation reaction as shown in equations (6) and (7).
- the discovery is premised on the use of a CuZnZr mixed metal oxide catalyst ⁇ i.e., CuO-ZnO-Zr0 2 ) at temperatures of at least 550 °C and a pressure greater than atmospheric pressure.
- Such a process has a C0 2 conversion of at least 20%) and can produce syngas compositions suitable as an intermediate or as feed material in a subsequent synthesis ⁇ e.g., methanol production, olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins) to form a chemical product or a plurality of chemical products.
- the syngas composition is applicable for oxo-product (e.g., C 2 + alcohols and ethers) synthesis.
- a process for hydrogenation of carbon dioxide (C0 2 ) to produce a syngas containing composition that includes hydrogen (H 2 ) and carbon monoxide (CO) is described.
- the process can include contacting a CuZnZr mixed metal oxide catalyst with a reactant feed that includes H 2 and C0 2 having a H 2 :C0 2 volume ratio of at least 0.5 : 1 at a reaction temperature of at least 550 °C or 550 °C to 650 °C, or 550 °C to 620 °C, or 550 °C to 600 °C, or about 580 °C and a pressure greater than atmospheric pressure (e.g., 0.5 MPa to 6 MPa, 1 MPa to 3 MPa, or 2.5 to 3.5 MPa, or 2.5 MPa to 3 MPa) to produce a product stream comprising the syngas containing composition that includes H 2 and CO having a H 2 :CO molar ratio of 0.7 to 1.4 (e.g., 0.5 MPa to 6 MPa
- the C0 2 is removed from the produced syngas composition (e.g., by amine adsorption).
- the syngas containing composition can include 15 mol.% to 20 mol.% CO, 50 mol.% to 65 mol.% C0 2 , 1 mol.% to 10 mol.% CH 4 and 15 mol.% to 25 mol.% H 2 .
- the syngas containing composition can include 16 mol.% to 17 mol.% CO, 60 mol.% to 65 mol.% C0 2 , 4 mol.% to 5 mol.% CH 4 and 15 mol.% to 16 mol.% H 2 .
- the CuZnZr mixed metal oxide catalyst can include 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO and 15 wt. % to 25 wt. % of Zr0 2 .
- the catalyst includes about 55.19 wt. % CuO, 24.9 wt. % ZnO, and 19.9 wt. % Zr0 2 .
- the CuZnAl mixed metal oxide catalyst can include 1% to 10 wt.% Cu, 1 wt.% to 30 wt.% of Zn, and 60% to 98% of Zr0 2 .
- the active copper is inhibited from leaching from the catalyst as the co-precipitation produces small particles of copper and zinc embedded in the high interface area of the zirconia particles with a common interface area.
- impregnation techniques produce large particles of pure copper and zinc and crystallized large particles of zirconia with little common interface area.
- the catalyst can have a surface area 103 m 2 /g.
- Phase composition of the catalyst includes mixed oxides in the form of crystal phases forming separate phases of Zr0 2 , ZnO and CuO/Cu. All phases are separate phases of oxides in the solid material forming solid solution of mixed oxides in the crystal lattice of the solid solution..
- wt.% refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component.
- 10 moles of component in 100 moles of the material is 10 mol.% of component.
- Embodiment 1 is a process for hydrogenating carbon dioxide (C0 2 ) to produce an oxo- synthesis syngas containing composition for a hydroformylation reaction.
- the process includes the step of contacting a CuZnZr mixed metal oxide catalyst with a reactant feed containing hydrogen (H 2 ) and C0 2 at a H 2 :C0 2 volume ratio of at least 0.5 : 1, wherein the reaction occurs at a temperature of at least 550 °C and a pressure of at least 0.5 MPa to produce a product stream containing H 2 and CO at a H 2 :CO molar ratio of 0.7 to 1.4.
- Embodiment 2 is the process of Embodiment 1, wherein temperature is from 550 °C to 650 °C, preferably 550 °C to 600 °C, or more preferably about 580 °C.
- Embodiment 3 is the process of any one of Embodiments 1 or 2, wherein the pressure is from 0.5 MPa to 6 MPa, preferably 2 MPa to 4 MPa, or more preferably 2.5 MPa to 3.5 MPa.
- Embodiment 4 is the process of any one of Embodiments 1 to 3, wherein the reaction conditions include a temperature of 550 °C to 600 °C and a pressure of 2.5 MPa to 3 MPa, wherein the syngas containing composition contains a H 2 :CO molar ratio of 0.9: 1 to 1.1 : 1.
- Embodiment 5 is the process of any one of Embodiments 1 to 4, wherein the syngas containing composition is used to produce oxo-products.
- Embodiment 6 is the process of any one of Embodiments 1 to 5, wherein the syngas containing composition contains 30 mol. % C0 2 or more.
- Embodiment 7 is the process of any one of Embodiments 1 to 6, wherein the CuZnZr mixed metal oxide catalyst comprises 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO, and 15 wt. % to 25 wt. % of Zr0 2 , preferably about 55.19 wt. % CuO, about 24.9 wt. % ZnO, and about 19.9 wt. % Zr0 2 .
- Embodiment 8 is the process of any one of Embodiments 1 to 7, wherein the methane content in the produced syngas containing composition is less than 10 mol.%.
- Embodiment 9 is the process of any one of Embodiments 1 to 8, further comprising a H 2 gas flow rate of 30 to 70 mL/min and the C0 2 gas flow rate of 30 to 70 mL/min.
- Embodiment 10 is the process of any one of Embodiments 1 to 9, wherein the syngas containing composition has a H 2 :CO molar ratio of 0.8: 1 to 1.2: 1, more preferably 0.9: 1 to l . : l .
- Embodiment 11 is the process of any one of Embodiments 1 to 10, wherein the syngas containing composition containing 15 mol.% to 20 mol.% CO, 50 mol.% to 65 mol.% C0 2 , 1 mol.% to 10 mol.% CH 4 , and 10 mol.% to 25 mol.% H 2 .
- Embodiment 12 is the process of any one of Embodiments 1 to 11, wherein the syngas containing composition containing 16 mol.% to 17 mol.% CO, 60 mol.% to 65 mol.% C0 2 , 4 mol.% to 5 mol.% CH 4 , and 15 mol.% to 16 mol.% H 2 .
- Embodiment 13 is the process of any one of Embodiments 1 to 12, wherein the C0 2 conversion is at least 20%.
- Embodiment 14 is the process of any one of Embodiments 1 to 13, wherein the H 2 :C0 2 volume ratio is 0.5: 1 to 2.0: 1, preferably 0.5: 1 to 1.2: 1, more preferably 0.5: 1 to 1 : 1.
- Embodiment 15 is the process of any one of Embodiments 1 to 14, further including the step of removing the C0 2 from the product stream.
- Embodiment 16 is the process of any one of Embodiments 1 to 15, further including using the produced syngas mixture as an intermediate or as feed material in a subsequent reaction to form an oxo- product.
- Embodiment 17 is the process of Embodiment 16, wherein the oxo-product comprises a C2+ alcohol, an alkyl ether, or a dimethyl ether.
- FIG. 1 is an illustration of a process of the present invention to produce syngas using a combined C0 2 and H 2 containing reactant feed gas and the CuZnZr mixed metal oxide catalyst of the present invention.
- FIG. 2 is an illustration of a process of the present invention to produce syngas using a H 2 reactant feed gas source, a C0 2 reactant feed gas source, and the CuZnZr mixed metal oxide catalyst of the present invention.
- the discovery is premised on the use of a CuZnZr mixed metal oxide catalyst in the hydrogenation of carbon dioxide reaction to produce syngas compositions suitable for the use in synthesis of oxo-products. Furthermore, these results can be achieved at processing conditions having a temperature of at least 550 °C and greater than atmospheric pressure.
- Conditions sufficient to produce syngas from the hydrogenation of C0 2 reaction include temperature, time, flow rate of feed gases, and pressure.
- the temperature range for the hydrogenation reaction can range from at least 550 °C to 650 °C, from about 570 °C to 650 °C, or 580 °C to 645 °C and all ranges and values there between (e.g., 550 °C, 555 °C, 560 °C, 565 °C, 570 °C, 575 °C, 580 °C, 585 °C, 590 °C, 595 °C, 600 °C, 605 °C, 610 °C, 615 °C, 620 °C, 625 °C, 630 °C, 635 °C, 640 °C, 645 °C, and 650 °C).
- the average pressure for the hydrogenation reaction can range from above atmospheric pressure or from 0.5 MPa to about 6 MPa, preferably, about 2 MPa to about 4 MPa and all pressures there between ⁇ e.g., 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, and 6 MPa).
- the upper limit on pressure can be determined by the reactor used.
- the conditions for the hydrogenation of C0 2 to syngas can be varied based on the type of the reactor used.
- the combined flow rate for the for the reactants ⁇ e.g., H 2 and C0 2 ) in hydrogenation reaction can range from at least 90 mL/min, 100 mL/min to 140 mL/min, from about 90 mL/min to about 105 mL/ min or all ranges and values there between (e.g., at least 90 mL/min, 91 mL/min, 92 mL/min, 93 mL/min, 94 mL/min, 95 mL/min, 96 mL/min, 97 mL/min 98 mL/min, 99 mL/min, 100 mL/min, 101 mL/min, 102 mL/min, 103 mL/min, 104 mL/min, 105 mL/min, 106 mL/min, 107 mL/min 108 mL/min, 109 mL/min, 1 10 mL/min, 1 1
- the H 2 flow rate can range from 30 mL/min to 70 mL/min, 35 to 65 mL/min, 40 to 60 mL/min, or all ranges and values there between (e.g., 30 mL/min, 31 mL/min, 32 mL/min, 33 mL/min, 34 mL/min, 35 mL/min, 36 mL/min, 37 mL/min, 38 mL/min, 39 mL/min, 40 mL/min, 41 mL/min, 42 mL/min, 43 mL/min, 44 mL/min, 45 mL/min, 46 mL/min, 47 mL/min, 48 mL/min, 49 mL/min, 50 mL/min, 51 mL/min, 52 mL/min, 53 mL/min, 54 mL/min, 55 mL/min, 56 mL/min, 57 mL/min,
- the C0 2 gas flow rate can range from 30 mL/min to 70 mL/min, 35 to 65 mL/min, 40 to 60 mL/min, or all ranges and values there between (e.g., 30 mL/min, 31 mL/min, 32 mL/min, 33 mL/min, 34 mL/min, 35 mL/min, 36 mL/min, 37 mL/min, 38 mL/min, 39 mL/min, 40 mL/min, 41 mL/min, 42 mL/min, 43 mL/min, 44 mL/min, 45 mL/min, 46 mL/min, 47 mL/min, 48 mL/min, 49 mL/min, 50 mL/min, 51 mL/min, 52 mL/min, 53 mL/min, 54 mL/min, 55 mL/min, 56 mL/min, 57 mL/min,
- the H 2 gas flow rate is 30 to 50 mL/min and the C0 2 gas flow rate is 50 to 70 mL/min at 2 MPa to 4 MPa.
- the reaction can be carried out over the CuZnZr mixed metal oxide catalyst of the current invention having particular syngas selectivity and conversion results. Therefore, in one aspect, the reaction can be performed with a C0 2 conversion of at least 20 mol.%, at least 30 mol.%, at least 50 mol.%, at least 80 mol.%, or at least 99 mol.%.
- the method can further include collecting or storing the produced syngas along with using the produced syngas as a feed source, solvent, or a commercial product.
- the catalyst Prior to use, the catalyst can be subjected to reducing conditions to convert the copper oxide and the other metals in the catalyst to a lower valance state (e.g., Cu +2 to Cu +1 and Cu° species, Zn +2 to Zn°, etc.).
- reducing conditions includes flowing a gaseous stream that includes a hydrogen gas or a hydrogen gas containing mixture (e.g., a H 2 and argon gas mixture) at a temperature of 250 °C to 280 °C for a sufficient period of time (e.g., 1, 2, or 3 hours).
- the system 100 can be used to convert a reactant gas stream of carbon dioxide (C0 2 ) and hydrogen (H 2 ) into syngas using the CuZnZr mixed metal oxide catalyst of the present invention.
- the system 100 can include a combined reactant gas source 102, a reactor 104, and a collection device 106.
- the combined reactant gas source 102 can be configured to be in fluid communication with the reactor 104 via an inlet 108 on the reactor.
- the combined reactant gas source 102 can be configured such that it regulates the amount of reactant feed (e.g., C0 2 and H 2 ) entering the reactor 104.
- the combined reactant gas source 102 is one unit feeding into one inlet 108.
- FIG. 2 depicts a system 200 for the process of the present invention having two feed inlets.
- a hydrogen gas reactant feed source 202 and a carbon dioxide reactant gas feed source 204 are in fluid communication with reactor 104 via hydrogen gas inlet 206 and carbon dioxide gas inlet 208, respectively.
- the reactor 104 can include a reaction zone 1 10 having the CuZnZr mixed metal oxide catalyst 1 12 of the present invention.
- the reactor can include various automated and/or manual controllers, valves, heat exchangers, gauges, etc., for the operation of the reactor.
- the reactor can have insulation and/or heat exchangers to heat or cool the reactor as desired.
- the amounts of the reactant feed and the mixed metal oxide catalyst 1 12 used can be modified as desired to achieve a given amount of product produced by the systems 100 or 200.
- a continuous flow reactor can be used.
- Non-limiting examples of continuous flow reactors include fixed-bed reactors, fluidized reactors, bubbling bed reactors, slurry reactors, rotating kiln reactors, moving bed reactors or any combinations thereof when two or more reactors are used.
- the reactant gas is preheated prior to being fed to the reactor.
- reaction zone 1 10 is a multi-zone reactor with different stages of heating in each zone.
- the reactor 104 can include an outlet 1 14 configured to be in fluid communication with the reaction zone 1 10 and configured to remove a first product stream comprising syngas from the reaction zone.
- Reaction zone 1 10 can further include the reactant feed and the first product stream.
- the products produced can include hydrogen (H 2 ) and carbon monoxide.
- the product stream can also include unreacted carbon dioxide, water, and less than 10 mol.% of alkanes (e.g., methane).
- the catalyst can be included in the product stream.
- the collection device 106 can be in fluid communication with the reactor 104 via the product outlet 1 14. Reactant gas inlets 108, 206, and 208, and the outlet 1 14 can be opened and closed as desired.
- the collection device 106 can be configured to store, further process, or transfer desired reaction products (e.g., syngas) for other uses.
- collection device 106 can be a separation unit or a series of separation units that are capable of separating the gaseous components from each other (e.g., separate carbon dioxide or water from the stream). Water and carbon dioxide can be removed from the product stream with any suitable method known in the art (e.g., condensation, liquid/gas separation, membrane separation, etc.).
- Any unreacted reactant gas can be recycled and included in the reactant feed to maximize the overall conversion of C0 2 to syngas, which increases the efficiency and commercial value of the C0 2 to syngas conversion process of the present invention.
- the resulting syngas can be sold, stored or used in other processing units as a feed source.
- the systems 100 or 200 can also include a heating/cooling source (not shown).
- the heating/cooling source can be configured to heat or cool the reaction zone 1 10 to a temperature sufficient (e.g., at least 550 °C or 550 °C to 630 °C, preferably 570 °C to 620 °C, or more preferably 580 °C) to convert C0 2 in the reactant feed to syngas via hydrogenation.
- a heating/cooling source can be a temperature controlled furnace or an external, electrical heating block, heating coils, or a heat exchanger.
- the CuZnZr mixed metal oxide catalyst of the present invention can include 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO and 10 wt. % to 25 wt. % of Zr0 2 or any value or range there between.
- the catalyst can include 50 wt. %, 51 wt. %, 52 wt. %, 53 wt. %, 54 wt. %, 55 wt. %, 56 wt. %, 57 wt. %, 58 wt. %, 59 wt. %, 60 wt.
- the catalyst can include 20 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, 25 wt. %, 26 wt. %, 27 wt. %, 28 wt. %, 29 wt. %, or 30 wt. % ZnO.
- the catalyst can include 10 wt. %, 1 1 wt. %, 12 wt. %, 13 wt. %, 14 wt. %, 15 wt. %, 16 wt. %, 17 wt. %, 18 wt.
- the catalyst includes about 55.19% CuO, 24.9% ZnO, and 19.9% Zr0 2 .
- the weight ratio of Cu:Zn:Zr can range from 2.5 : 1.1 : 1 to 3.0: 1.5 : 1 or 2.8: 1.25 : 1.
- Suitable sources for the metals for use in the preparation of the catalysts of this invention include, without limitation, nitrates, halides, organic acid, inorganic acid, hydroxides, carbonates, oxyhalides, sulfates, and other groups which may exchange with oxygen under high temperatures so that the metal compounds become metal oxides.
- the catalyst can be made using a co- precipitation method.
- a first metal salt e.g., copper metal salt
- a second metal salt e.g., zinc metal salt
- a third metal salt e.g., zirconium metal salt
- the first metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of copper.
- the second metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of zinc.
- Examples of the third metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, halides of zirconium.
- Cu(N0 3 ) 3 , Zn(N0 3 ) 2 , and Zr(N0 3 ) 3 can be solubilized in deionized water.
- three solutions are prepared and mixed together.
- the ratio of Cu:Zn:Zr in the salts can be 2.5 : 1.1 : 1 to 3.0: 1.5 : 1 or 2.8: 1.25 : 1.
- the metal salts can be obtained from commercial vendors, for example, Sigma-Aldrich ® (U.S.A.).
- Aqueous base e.g., ammonium hydroxide or sodium hydroxide
- the pH of the solution can be 7 to 9, 7.5 to 8.5, or 8 after addition of the base.
- the Cu/Zn/Zr metal hydroxide precursor can be heated from 55 °C to 75 °C, 60 °C to 70 °C and all values there between including 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 64 °C, 65 °C, 66 °C, 67 °C , 68 °C , 69 °C, 70 °C, 71 °C, 72 °C, 73 °C, 74 °C, or 75 °C, with agitation to further the formation of the Cu/Zn/Zr metal hydroxide precursor.
- the Cu/Zn/Zr precursor precipitate can be separated from the solution using known separation techniques (e.g., centrifugation, filtration, etc.).
- the separated Cu/Zn/Zr precursor precipitate can be washed with water (e.g., deionized water) to remove any excess base. Washing and filtering the Cu/Zn/Zr precursor precipitate can be repeated as necessary to remove all, or substantially all, of the base from the Cu/Zn/Zr precursor precipitate.
- Residual water can be removed from the Cu/Zn/Zr precursor by heating the solution (e.g., drying the solution) at a temperature from 90 °C to 1 10 °C, or 95 °C to 105 °C, or any value there between including 90 °C, 91 °C, 92 °C, 93 °C, 94 °C, 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C, 106 °C, 107 °C, 108 °C, 109 °C, or 1 10 °C for a time period sufficient (e.g., 3 to 24 hours, 8 to 20 hours, or 12 hours) to remove all or a majority of the water to produce a dried powdered material.
- a time period sufficient (e.g., 3 to 24 hours, 8 to 20
- drying is performed at 105 °C for 12 hours.
- the dried CuZnZr material can be then be calcined within 8 hours of drying by heating the dried material to an average temperature between 350 °C and 600 °C, 400 °C to 550 °C, with 400 °C being preferred, for 3 to 12 hours or 4 to 8 hours in the presence of a flow of an oxygen source (e.g., air at 250 cc/per minute) to form the CuZnZr mixed metal oxide catalyst.
- an oxygen source e.g., air at 250 cc/per minute
- the catalyst particles can be reduced in size (e.g., crushed) to a particle size of 20-50 mesh.
- Carbon dioxide gas and hydrogen gas can be obtained from various sources.
- the carbon dioxide can be obtained from a waste or recycle gas stream (e.g., from a plant on the same site such as from ammonia synthesis) or after recovering the carbon dioxide from a gas stream.
- a benefit of recycling such carbon dioxide as a starting material in the process of the invention is that it can reduce the amount of carbon dioxide emitted to the atmosphere (e.g., from a chemical production site).
- the hydrogen may be from various sources, including streams coming from other chemical processes, like water splitting (e.g., photocatalysis, electrolysis, or the like), additional syngas production, ethane cracking, methanol synthesis, or conversion of methane to aromatics.
- the molar H 2 :C0 2 reactant gas ratio for the hydrogenation reaction can range from 0.5 : 1 to 2.0: 1, 0.6: 1 to 1.2: 1, or 0.6: 1 to 1.0: 1.
- the reactant gas stream includes 30 to 70 vol.% H 2 and 30 to 70 vol.% C0 2 .
- the reactant gas stream includes 40 to 60 vol.% H 2 and 40 to 60 vol.% C0 2 .
- the reactant gas stream includes about 50 vol.%) H 2 and about 50 vol.%> C0 2 .
- the reactant gas stream includes about 60 vol.%> H 2 and 40 vol.%> C0 2 .
- the streams are not combined.
- the hydrogen gas and carbon dioxide can be delivered at the same H 2 :C0 2 molar ratio.
- the remainder of the reactant gas stream can include another gas or gases provided the gas or gases are inert, such as argon (Ar) or nitrogen (N 2 ), and/or do not negatively affect the reaction. All possible percentages of C0 2 plus H 2 plus inert gas in the current embodiments can have the described H 2 :C0 2 ratios herein.
- the reactant mixture is highly pure and substantially devoid of water or steam.
- the carbon dioxide can be dried prior to use (e.g., pass through a drying media) to contain minimal amounts of water or no water.
- the reactant feed contains only C0 2 and H 2 or a minimal amount of alkanes (e.g., less than 5 mol.% methane and/or CO).
- the process of the present invention can produce a product stream that includes a mixture of H 2 and CO having a molar H 2 :CO ratio suitable for the synthesis of various chemical products.
- Non-limiting examples of synthesis include methanol production, olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins.
- Non-limiting examples of products that can be produced include aliphatic oxygenates, methanol, olefin synthesis, aromatics production, carbonylation of methanol, carbonylation of olefins, or reduction of iron oxide in steel production.
- the molar H 2 :CO ratio can be 0.7: 1 to 1.4: 1, 0.8: 1 to 1.2: 1 or about 0.9: 1 to about 0.95 : 1, or 1 : 1 which is suitable for oxo-products (e.g., C 2 + alcohols, dimethyl ether, etc.).
- the amount of alkane (e.g., methane) produced in the process of the present reaction can be less than 10 mol.%, less than 5 mol.%, 3 mol.%, 2 mol.%, 1 mol.%, or 0 mol.% based on the total moles of components in the product stream.
- the product stream can include unreacted C0 2 .
- the product stream can include 30 mol%, 35 mol.% 40 mol.%, 45 mol.% 55 mol%, 60 mol%, 65 mol%, of C0 2 based on the total moles of components in the product stream.
- the product stream can include 15 mol.% to 20 mol.% CO, 50 mol.% to 65 mol.% C0 2 , 1 mol.% to 10 mol.% CH 4 , and 10 mol.%) to 25 mol.%) H 2 .
- the syngas containing composition can include 16 mol.% to 17 mol.% CO, 60 mol.% to 65 mol.% C0 2 , 4 mol.% to 5 mol.% CH 4 , and 15 mol.% to 16 mol.% H 2 .
- Copper nitrate (35.7 g, Cu(N0 3 ) 3 *3H 2 0), zinc nitrate (20.9 g, ⁇ ( ⁇ 0 3 ) 3 ⁇ 6 ⁇ 2 0), and zirconium nitrate (1 1.6 g, Zr(N0 3 ) 3 *6H 2 0) were dissolved in water (500 mL).
- Sodium hydroxide (NaOH, 30%) was added gradually to the solution to co-precipitate the CuZnZr metal oxide precursor material.
- the pH of the solution was maintained at 8 and heated to a temperature of 65 °C.
- the CuZnZr metal oxide precursor material was isolated by filtration and washed with water (3 X 500 mL) to remove excess base.
- the washed CuZnZr metal oxide precursor material was dried at 105 °C for 12 hours.
- the dried CuZnZr metal oxide precursor material was calcined at 400 °C in air flow of 250 cc/min for 8 hours to form the CuZnZr mixed metal oxide catalyst of the present invention.
- Prior to use the CuZnZr mixed metal oxide catalyst was crushed to a particle size of 20-50 mesh.
- the CuZnZr mixed metal oxide catalyst had a surface area of 103 m 2 /g.
- equation (8) presents the sum of all carbon, products divided by the total number of carbons.
- Example 2 The general procedure of Example 2 was followed with the following conditions: a pressure of 2.8 MPa, a temperature of 620 °C, a H 2 flow rate of 50 cc/min and a C0 2 flow rate of 50 cc/min.
- Time on stream (TOS) Time on stream
- molar percentage of components in the product stream and % carbon dioxide conversion and results are listed in Table 1.
- Example 2 The general procedure of Example 2 was followed using the following conditions: a pressure of 2.8 MPa, a temperature of 580 °C, a H 2 flow rate of 40 cc/min, and a C0 2 flow rate of 60 cc/min. Results are listed in Table 2.
- Example 2 The general procedure of Example 2 was followed using the following conditions: a pressure of 1.0 MPa, a temperature of 580 °C, a H 2 flow rate of 40 cc/min and a C0 2 flow rate of 60 cc/min. Results are listed in Table 3.
- Example 4 From the comparison of the Examples 3-5, it was determined that the reaction conditions of 2.8 MPa and 580 °C (Example 4) produced a syngas composition having a H 2 :CO ratio closest to 1 (0.94: 1 and 0.96: 1), which is suitable for use as an intermediate or as feed material in a oxo-product synthesis (e.g., hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins) to form a chemical product or a plurality of chemical products (e.g., C 2 + alcohols, ethers, dimethyl ether and the like).
- a oxo-product synthesis e.g., hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins
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Abstract
Processes and catalysts for the hydrogenation of carbon dioxide (CO2) to produce a synthesis gas containing composition are disclosed. The process can include contacting a CuZnZr mixed metal oxide catalyst with hydrogen (H2) and CO2 at a temperature of at least 550 °C and a pressure greater than atmospheric pressure to produce the syngas containing composition suitable for use in oxo-products synthesis.
Description
PROCESS FOR HIGH-PRESSURE HYDROGENATION OF CARBON DIOXIDE TO
OXO-SYNGAS COMPOSITION USING A
COPPER/ZINC/ZIRCONIUM MIXED METAL OXIDE CATALYST
CROSS REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of priority of U.S. Provisional Patent Application No. 62/366,234, filed July 25, 2016, which is hereby incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
A. Field of the Invention [0002] The invention generally concerns a process for hydrogenation of carbon dioxide (C02) to produce a synthesis gas (syngas) containing composition that includes hydrogen (H2) and carbon monoxide (CO). In particular, the process includes contacting a CuZnZr mixed metal oxide catalyst under conditions suitable to produce a syngas composition suitable for use in oxo-product synthesis. B. Description of Related Art
[0003] Syngas (which includes carbon monoxide and hydrogen gases) is oftentimes used to produce chemicals such as methanol, tert-butyl methyl ether, ammonia, fertilizers, 2-ethyl hexanol, formaldehyde, acetic acid, and 1,4-butane diol. Syngas can be produced by common methods such as methane steam reforming technology as shown in reaction equation (1), partial oxidation of methane as shown in reaction (2), or dry reforming of methane as shown in reaction (3):
CH4 + H20 ^CO + 3 H2 ΔΗ298Κ = 206 kJ (1)
CH + 0 ^ CO + 2H
"2 ΔΗ298Κ = - 8 kcal/mol (2)
CH4 + C02 2CO + 2H2 ΔΗ298Κ = 247 kJ (3)
While the reactions in equations (1) and (2) do not utilize carbon dioxide, equation (3) does. Commercialization attempts of the dry reforming of methane to produce syngas have suffered due to high-energy consumption, catalyst deactivation, and applicability of the syngas
composition produced. Equation (4) illustrates the catalyst deactivation event due to carbonization.
CH4 + 2C02 C + 2CO + 2H20 (4)
[0004] Other attempts to convert carbon dioxide into carbon monoxide include the catalytic reduction of carbon dioxide using hydrogen as shown in equation (5).
C02+ H2 ¾ CO + H20 ΔΗ= 10 kcal/mol (5)
This process, which is also known as a reverse water gas shift reaction, is mildly endothermic and generally takes place at temperatures of at least about 450 °C, with C02 conversion of 50% at temperatures between 560 °C to 580 °C. Furthermore, some methane can be formed as a by-product due to the methanation reaction as shown in equations (6) and (7).
CO + 3 H2 ¾ CH4 + H20 (6)
C02 + 4 H2 ¾ CH4 + 2 H20 (7)
[0005] Various catalysts have been used for the catalysis of the hydrogenation of carbon dioxide reaction. By way of example, U.S. Patent No. 7,435,759 to Jung et al. describes a ZnO supported on or co-precipitated with A1203 or Zr02, which after calcination is then impregnated with copper. This results in a copper impregnated catalyst for catalyzing the reverse water gas shift reaction at atmospheric pressure. This catalyst suffers from catalyst deactivation at high reactant flow rates in the presence of high amounts of C02 (H2:C02 ratio of 1 :3). [0006] Despite the foregoing, hydrogenation of carbon dioxide processes still suffer from production of the by-product methane, processing inefficiencies, and catalyst deactivation.
SUMMARY OF THE INVENTION
[0007] A discovery has been made that provides an alternate process for the production of syngas from hydrogen and carbon dioxide. The discovery is premised on the use of a CuZnZr mixed metal oxide catalyst {i.e., CuO-ZnO-Zr02) at temperatures of at least 550 °C and a pressure greater than atmospheric pressure. Such a process has a C02 conversion of at least 20%) and can produce syngas compositions suitable as an intermediate or as feed material in a subsequent synthesis {e.g., methanol production, olefin synthesis, aromatics
production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins) to form a chemical product or a plurality of chemical products. In preferred instances, the syngas composition is applicable for oxo-product (e.g., C2+ alcohols and ethers) synthesis. [0008] In a particular aspect of the invention, a process for hydrogenation of carbon dioxide (C02) to produce a syngas containing composition that includes hydrogen (H2) and carbon monoxide (CO) is described. The process can include contacting a CuZnZr mixed metal oxide catalyst with a reactant feed that includes H2 and C02 having a H2:C02 volume ratio of at least 0.5 : 1 at a reaction temperature of at least 550 °C or 550 °C to 650 °C, or 550 °C to 620 °C, or 550 °C to 600 °C, or about 580 °C and a pressure greater than atmospheric pressure (e.g., 0.5 MPa to 6 MPa, 1 MPa to 3 MPa, or 2.5 to 3.5 MPa, or 2.5 MPa to 3 MPa) to produce a product stream comprising the syngas containing composition that includes H2 and CO having a H2:CO molar ratio of 0.7 to 1.4 (e.g., 0.7: 1 to 1.2: 1, 0.8: 1 to 1.2: 1, or 0.9: 1 to 1.1 : 1). In some embodiments, the C02 is removed from the produced syngas composition (e.g., by amine adsorption). In some aspects, the syngas containing composition can include 15 mol.% to 20 mol.% CO, 50 mol.% to 65 mol.% C02, 1 mol.% to 10 mol.% CH4 and 15 mol.% to 25 mol.% H2. In yet another aspect, the syngas containing composition can include 16 mol.% to 17 mol.% CO, 60 mol.% to 65 mol.% C02, 4 mol.% to 5 mol.% CH4 and 15 mol.% to 16 mol.% H2.
[0009] In the processes of the present invention, the CuZnZr mixed metal oxide catalyst can include 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO and 15 wt. % to 25 wt. % of Zr02. In a preferred aspect of the invention, the catalyst includes about 55.19 wt. % CuO, 24.9 wt. % ZnO, and 19.9 wt. % Zr02. In the processes of the present invention, the CuZnAl mixed metal oxide catalyst can include 1% to 10 wt.% Cu, 1 wt.% to 30 wt.% of Zn, and 60% to 98% of Zr02. Without wising to be bound by theory, it is believe that since the CuO phase is co-precipitated with the ZnO and Zr02 phases, the active copper is inhibited from leaching from the catalyst as the co-precipitation produces small particles of copper and zinc embedded in the high interface area of the zirconia particles with a common interface area. In contrast, impregnation techniques produce large particles of pure copper and zinc and crystallized large particles of zirconia with little common interface area. The catalyst can have a surface area 103 m2/g. Phase composition of the catalyst includes mixed oxides in the form of crystal phases forming separate phases of Zr02, ZnO and CuO/Cu. All phases are
separate phases of oxides in the solid material forming solid solution of mixed oxides in the crystal lattice of the solid solution..
[0010] The following includes definitions of various terms and phrases used throughout this specification. [0011] The terms "about" or "approximately" are defined as being close to as understood by one of ordinary skill in the art, and in one non-limiting embodiment the terms are defined to be within 10%, preferably, within 5%, more preferably, within 1%, and most preferably, within 0.5%.
[0012] The terms "wt.%", "vol.%" or "mol%" refers to a weight, volume, or molar percentage of a component, respectively, based on the total weight, the total volume, or the total moles of material that includes the component. In a non-limiting example, 10 moles of component in 100 moles of the material is 10 mol.% of component.
[0013] The term "substantially" and its variations are defined to include ranges within 10%, within 5%, within 1%, or within 0.5%. [0014] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any variation of these terms, when used in the claims and/or the specification includes any measurable decrease or complete inhibition to achieve a desired result.
[0015] The term "effective," as that term is used in the specification and/or claims, means adequate to accomplish a desired, expected, or intended result. [0016] The use of the words "a" or "an" when used in conjunction with the term "comprising" in the claims or the specification may mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."
[0017] The words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include") or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
[0018] The process of the present invention can "comprise," "consist essentially of," or "consist of particular ingredients, components, compositions, etc. disclosed throughout the specification. With respect to the transitional phase "consisting essentially of," in one non- limiting aspect, a basic and novel characteristic of the process of the present invention is the ability to hydrogenate carbon dioxide to produce syngas suitable for use in synthesis of oxo- products.
[0019] In the context of the present invention 17 Embodiments are now described. Embodiment 1 is a process for hydrogenating carbon dioxide (C02) to produce an oxo- synthesis syngas containing composition for a hydroformylation reaction. The process includes the step of contacting a CuZnZr mixed metal oxide catalyst with a reactant feed containing hydrogen (H2) and C02 at a H2:C02 volume ratio of at least 0.5 : 1, wherein the reaction occurs at a temperature of at least 550 °C and a pressure of at least 0.5 MPa to produce a product stream containing H2 and CO at a H2:CO molar ratio of 0.7 to 1.4. Embodiment 2 is the process of Embodiment 1, wherein temperature is from 550 °C to 650 °C, preferably 550 °C to 600 °C, or more preferably about 580 °C. Embodiment 3 is the process of any one of Embodiments 1 or 2, wherein the pressure is from 0.5 MPa to 6 MPa, preferably 2 MPa to 4 MPa, or more preferably 2.5 MPa to 3.5 MPa. Embodiment 4 is the process of any one of Embodiments 1 to 3, wherein the reaction conditions include a temperature of 550 °C to 600 °C and a pressure of 2.5 MPa to 3 MPa, wherein the syngas containing composition contains a H2:CO molar ratio of 0.9: 1 to 1.1 : 1. Embodiment 5 is the process of any one of Embodiments 1 to 4, wherein the syngas containing composition is used to produce oxo-products. Embodiment 6 is the process of any one of Embodiments 1 to 5, wherein the syngas containing composition contains 30 mol. % C02 or more. Embodiment 7 is the process of any one of Embodiments 1 to 6, wherein the CuZnZr mixed metal oxide catalyst comprises 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO, and 15 wt. % to 25 wt. % of Zr02, preferably about 55.19 wt. % CuO, about 24.9 wt. % ZnO, and about 19.9 wt. % Zr02. Embodiment 8 is the process of any one of Embodiments 1 to 7, wherein the methane content in the produced syngas containing composition is less than 10 mol.%. Embodiment 9 is the process of any one of Embodiments 1 to 8, further comprising a H2 gas flow rate of 30 to 70 mL/min and the C02 gas flow rate of 30 to 70 mL/min. Embodiment 10 is the process of any one of Embodiments 1 to 9, wherein the syngas containing composition has a H2:CO molar ratio of 0.8: 1 to 1.2: 1, more preferably 0.9: 1 to l . : l . Embodiment 11 is the process of any one of Embodiments 1 to 10, wherein the syngas containing composition
containing 15 mol.% to 20 mol.% CO, 50 mol.% to 65 mol.% C02, 1 mol.% to 10 mol.% CH4, and 10 mol.% to 25 mol.% H2. Embodiment 12 is the process of any one of Embodiments 1 to 11, wherein the syngas containing composition containing 16 mol.% to 17 mol.% CO, 60 mol.% to 65 mol.% C02, 4 mol.% to 5 mol.% CH4, and 15 mol.% to 16 mol.% H2. Embodiment 13 is the process of any one of Embodiments 1 to 12, wherein the C02 conversion is at least 20%. Embodiment 14 is the process of any one of Embodiments 1 to 13, wherein the H2:C02 volume ratio is 0.5: 1 to 2.0: 1, preferably 0.5: 1 to 1.2: 1, more preferably 0.5: 1 to 1 : 1. Embodiment 15 is the process of any one of Embodiments 1 to 14, further including the step of removing the C02 from the product stream. Embodiment 16 is the process of any one of Embodiments 1 to 15, further including using the produced syngas mixture as an intermediate or as feed material in a subsequent reaction to form an oxo- product. Embodiment 17 is the process of Embodiment 16, wherein the oxo-product comprises a C2+ alcohol, an alkyl ether, or a dimethyl ether.
[0020] Other objects, features and advantages of the present invention will become apparent from the following figures, detailed description, and examples. It should be understood, however, that the figures, detailed description, and examples, while indicating specific embodiments of the invention, are given by way of illustration only and are not meant to be limiting. Additionally, it is contemplated that changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. In further embodiments, features from specific embodiments may be combined with features from other embodiments. For example, features from one embodiment may be combined with features from any of the other embodiments. In further embodiments, additional features may be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Advantages of the present invention may become apparent to those skilled in the art with the benefit of the following detailed description and upon reference to the accompanying drawings.
[0022] FIG. 1 is an illustration of a process of the present invention to produce syngas using a combined C02 and H2 containing reactant feed gas and the CuZnZr mixed metal oxide catalyst of the present invention.
[0023] FIG. 2 is an illustration of a process of the present invention to produce syngas using a H2 reactant feed gas source, a C02 reactant feed gas source, and the CuZnZr mixed metal oxide catalyst of the present invention.
[0024] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings. The drawings may not be to scale.
DETAILED DESCRIPTION OF THE INVENTION
[0025] A discovery has been made that addresses the aforementioned problems and inefficiencies associated with the production of syngas from hydrogenation of carbon dioxide. The discovery is premised on the use of a CuZnZr mixed metal oxide catalyst in the hydrogenation of carbon dioxide reaction to produce syngas compositions suitable for the use in synthesis of oxo-products. Furthermore, these results can be achieved at processing conditions having a temperature of at least 550 °C and greater than atmospheric pressure.
[0026] These and other non-limiting aspects of the present invention are discussed in further detail in the following sections with reference to the Figures.
A. Process to Produce Syngas
[0027] Conditions sufficient to produce syngas from the hydrogenation of C02 reaction include temperature, time, flow rate of feed gases, and pressure. The temperature range for the hydrogenation reaction can range from at least 550 °C to 650 °C, from about 570 °C to 650 °C, or 580 °C to 645 °C and all ranges and values there between (e.g., 550 °C, 555 °C, 560 °C, 565 °C, 570 °C, 575 °C, 580 °C, 585 °C, 590 °C, 595 °C, 600 °C, 605 °C, 610 °C, 615 °C, 620 °C, 625 °C, 630 °C, 635 °C, 640 °C, 645 °C, and 650 °C). The average pressure for the hydrogenation reaction can range from above atmospheric pressure or from 0.5 MPa to about 6 MPa, preferably, about 2 MPa to about 4 MPa and all pressures there between {e.g., 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, and 6 MPa). The upper limit on pressure can be determined by the reactor used. The conditions for the hydrogenation of C02 to syngas can be varied based on the type of the reactor used.
[0028] The combined flow rate for the for the reactants {e.g., H2 and C02) in hydrogenation reaction can range from at least 90 mL/min, 100 mL/min to 140 mL/min, from about 90 mL/min to about 105 mL/ min or all ranges and values there between (e.g., at least
90 mL/min, 91 mL/min, 92 mL/min, 93 mL/min, 94 mL/min, 95 mL/min, 96 mL/min, 97 mL/min 98 mL/min, 99 mL/min, 100 mL/min, 101 mL/min, 102 mL/min, 103 mL/min, 104 mL/min, 105 mL/min, 106 mL/min, 107 mL/min 108 mL/min, 109 mL/min, 1 10 mL/min, 1 1 1 mL/min, 1 12 mL/min, 1 13 mL/min, 1 14 mL/min, 1 15 mL/min, 1 16 mL/min, 1 17 mL/min, 1 18 mL/min, 1 19 mL/min, 120 mL/min, 121 mL/min, 122 mL/min, 123 mL/min, 124 mL/min, 125 mL/min, 126 mL/min, 127 mL/min, 128 mL/min, 129 mL/min, 130 mL/min, 131 mL/min, 132 mL/min, 133 mL/min, 134 mL/min, 135 mL/min, 136 mL/min, 137 mL/min, 138 mL/min, 139 mL/min, or 140 mL/min). In some instances, the H2 flow rate can range from 30 mL/min to 70 mL/min, 35 to 65 mL/min, 40 to 60 mL/min, or all ranges and values there between (e.g., 30 mL/min, 31 mL/min, 32 mL/min, 33 mL/min, 34 mL/min, 35 mL/min, 36 mL/min, 37 mL/min, 38 mL/min, 39 mL/min, 40 mL/min, 41 mL/min, 42 mL/min, 43 mL/min, 44 mL/min, 45 mL/min, 46 mL/min, 47 mL/min, 48 mL/min, 49 mL/min, 50 mL/min, 51 mL/min, 52 mL/min, 53 mL/min, 54 mL/min, 55 mL/min, 56 mL/min, 57 mL/min, 58 mL/min, 59 mL/min, 60 mL/min, 61 mL/min, 62 mL/min, 63 mL/min, 64 mL/min, 65 mL/min, 66 mL/min, 67 mL/min, 68 mL/min, 69 mL/min, or 70 mL/min). The C02 gas flow rate can range from 30 mL/min to 70 mL/min, 35 to 65 mL/min, 40 to 60 mL/min, or all ranges and values there between (e.g., 30 mL/min, 31 mL/min, 32 mL/min, 33 mL/min, 34 mL/min, 35 mL/min, 36 mL/min, 37 mL/min, 38 mL/min, 39 mL/min, 40 mL/min, 41 mL/min, 42 mL/min, 43 mL/min, 44 mL/min, 45 mL/min, 46 mL/min, 47 mL/min, 48 mL/min, 49 mL/min, 50 mL/min, 51 mL/min, 52 mL/min, 53 mL/min, 54 mL/min, 55 mL/min, 56 mL/min, 57 mL/min, 58 mL/min, 59 mL/min, 60 mL/min, 61 mL/min, 62 mL/min, 63 mL/min, 64 mL/min, 65 mL/min, 66 mL/min, 67 mL/min, 68 mL/min, 69 mL/min, or 70 mL/min). In a particular instance, the H2 gas flow rate is 30 to 50 mL/min and the C02 gas flow rate is 50 to 70 mL/min at 2 MPa to 4 MPa. [0029] In another aspect, the reaction can be carried out over the CuZnZr mixed metal oxide catalyst of the current invention having particular syngas selectivity and conversion results. Therefore, in one aspect, the reaction can be performed with a C02 conversion of at least 20 mol.%, at least 30 mol.%, at least 50 mol.%, at least 80 mol.%, or at least 99 mol.%. The method can further include collecting or storing the produced syngas along with using the produced syngas as a feed source, solvent, or a commercial product. Prior to use, the catalyst can be subjected to reducing conditions to convert the copper oxide and the other metals in the catalyst to a lower valance state (e.g., Cu+2 to Cu+1 and Cu° species, Zn+2 to Zn°, etc.). A non-limiting example of reducing conditions includes flowing a gaseous stream that
includes a hydrogen gas or a hydrogen gas containing mixture (e.g., a H2 and argon gas mixture) at a temperature of 250 °C to 280 °C for a sufficient period of time (e.g., 1, 2, or 3 hours).
[0030] Referring to FIG. 1, a system 100 is illustrated. The system 100 can be used to convert a reactant gas stream of carbon dioxide (C02) and hydrogen (H2) into syngas using the CuZnZr mixed metal oxide catalyst of the present invention. The system 100 can include a combined reactant gas source 102, a reactor 104, and a collection device 106. The combined reactant gas source 102 can be configured to be in fluid communication with the reactor 104 via an inlet 108 on the reactor. The combined reactant gas source 102 can be configured such that it regulates the amount of reactant feed (e.g., C02 and H2) entering the reactor 104. As shown, the combined reactant gas source 102 is one unit feeding into one inlet 108. By comparison, FIG. 2 depicts a system 200 for the process of the present invention having two feed inlets. As shown in FIG. 2, a hydrogen gas reactant feed source 202 and a carbon dioxide reactant gas feed source 204 are in fluid communication with reactor 104 via hydrogen gas inlet 206 and carbon dioxide gas inlet 208, respectively. It should be understood that the number of inlets and/or separate feed sources can be adjusted to reactor sizes and/or configurations. The reactor 104 can include a reaction zone 1 10 having the CuZnZr mixed metal oxide catalyst 1 12 of the present invention. The reactor can include various automated and/or manual controllers, valves, heat exchangers, gauges, etc., for the operation of the reactor. The reactor can have insulation and/or heat exchangers to heat or cool the reactor as desired. The amounts of the reactant feed and the mixed metal oxide catalyst 1 12 used can be modified as desired to achieve a given amount of product produced by the systems 100 or 200. In a preferred aspects, a continuous flow reactor can be used. Non-limiting examples of continuous flow reactors include fixed-bed reactors, fluidized reactors, bubbling bed reactors, slurry reactors, rotating kiln reactors, moving bed reactors or any combinations thereof when two or more reactors are used. In some embodiments, the reactant gas is preheated prior to being fed to the reactor. In some embodiments, reaction zone 1 10 is a multi-zone reactor with different stages of heating in each zone. The reactor 104 can include an outlet 1 14 configured to be in fluid communication with the reaction zone 1 10 and configured to remove a first product stream comprising syngas from the reaction zone. Reaction zone 1 10 can further include the reactant feed and the first product stream. The products produced can include hydrogen (H2) and carbon monoxide. The product stream can also include unreacted carbon dioxide, water, and less than 10 mol.% of alkanes (e.g.,
methane). In some aspects, the catalyst can be included in the product stream. The collection device 106 can be in fluid communication with the reactor 104 via the product outlet 1 14. Reactant gas inlets 108, 206, and 208, and the outlet 1 14 can be opened and closed as desired. The collection device 106 can be configured to store, further process, or transfer desired reaction products (e.g., syngas) for other uses. In a non-limiting example, collection device 106 can be a separation unit or a series of separation units that are capable of separating the gaseous components from each other (e.g., separate carbon dioxide or water from the stream). Water and carbon dioxide can be removed from the product stream with any suitable method known in the art (e.g., condensation, liquid/gas separation, membrane separation, etc.). [0031] Any unreacted reactant gas can be recycled and included in the reactant feed to maximize the overall conversion of C02 to syngas, which increases the efficiency and commercial value of the C02 to syngas conversion process of the present invention. The resulting syngas can be sold, stored or used in other processing units as a feed source. Still further, the systems 100 or 200 can also include a heating/cooling source (not shown). The heating/cooling source can be configured to heat or cool the reaction zone 1 10 to a temperature sufficient (e.g., at least 550 °C or 550 °C to 630 °C, preferably 570 °C to 620 °C, or more preferably 580 °C) to convert C02 in the reactant feed to syngas via hydrogenation. Non-limiting examples of a heating/cooling source can be a temperature controlled furnace or an external, electrical heating block, heating coils, or a heat exchanger. B. Catalyst and Preparation Thereof
[0032] The CuZnZr mixed metal oxide catalyst of the present invention can include 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO and 10 wt. % to 25 wt. % of Zr02 or any value or range there between. For example, and with respect to CuO, the catalyst can include 50 wt. %, 51 wt. %, 52 wt. %, 53 wt. %, 54 wt. %, 55 wt. %, 56 wt. %, 57 wt. %, 58 wt. %, 59 wt. %, 60 wt. % CuO. With respect to ZnO, the catalyst can include 20 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, 25 wt. %, 26 wt. %, 27 wt. %, 28 wt. %, 29 wt. %, or 30 wt. % ZnO. With respect to Zr02, the catalyst can include 10 wt. %, 1 1 wt. %, 12 wt. %, 13 wt. %, 14 wt. %, 15 wt. %, 16 wt. %, 17 wt. %, 18 wt. %, 19 wt. %, 20 wt. %, 21 wt. %, 22 wt. %, 23 wt. %, 24 wt. %, or 25 wt. % of Zr02. In a particular embodiment, the catalyst includes about 55.19% CuO, 24.9% ZnO, and 19.9% Zr02. The weight ratio of Cu:Zn:Zr can range from 2.5 : 1.1 : 1 to 3.0: 1.5 : 1 or 2.8: 1.25 : 1.
[0033] Suitable sources for the metals for use in the preparation of the catalysts of this invention include, without limitation, nitrates, halides, organic acid, inorganic acid, hydroxides, carbonates, oxyhalides, sulfates, and other groups which may exchange with oxygen under high temperatures so that the metal compounds become metal oxides. [0034] As further illustrated in the Examples, the catalyst can be made using a co- precipitation method. In a non-limiting example, a first metal salt (e.g., copper metal salt), a second metal salt (e.g., zinc metal salt), and a third metal salt (e.g., zirconium metal salt) can be completely solubilized, or substantially solubilized, in a solvent (e.g., aqueous solution). Examples of the first metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of copper. Examples of the second metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, or halides of zinc. Examples of the third metal salt include nitrates, ammonium nitrates, carbonates, oxides, hydroxides, halides of zirconium. In a particular embodiment, Cu(N03)3, Zn(N03)2, and Zr(N03)3 can be solubilized in deionized water. In some embodiments, three solutions are prepared and mixed together. The ratio of Cu:Zn:Zr in the salts can be 2.5 : 1.1 : 1 to 3.0: 1.5 : 1 or 2.8: 1.25 : 1. The metal salts can be obtained from commercial vendors, for example, Sigma-Aldrich ® (U.S.A.). Aqueous base (e.g., ammonium hydroxide or sodium hydroxide) can be added to the solution in an amount effective to precipitate a Cu/Zn/Zr metal hydroxide precursor from the solution. The pH of the solution can be 7 to 9, 7.5 to 8.5, or 8 after addition of the base. The Cu/Zn/Zr metal hydroxide precursor can be heated from 55 °C to 75 °C, 60 °C to 70 °C and all values there between including 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 64 °C, 65 °C, 66 °C, 67 °C , 68 °C , 69 °C, 70 °C, 71 °C, 72 °C, 73 °C, 74 °C, or 75 °C, with agitation to further the formation of the Cu/Zn/Zr metal hydroxide precursor. In some embodiments, the Cu/Zn/Zr precursor precipitate can be separated from the solution using known separation techniques (e.g., centrifugation, filtration, etc.). The separated Cu/Zn/Zr precursor precipitate can be washed with water (e.g., deionized water) to remove any excess base. Washing and filtering the Cu/Zn/Zr precursor precipitate can be repeated as necessary to remove all, or substantially all, of the base from the Cu/Zn/Zr precursor precipitate. Residual water can be removed from the Cu/Zn/Zr precursor by heating the solution (e.g., drying the solution) at a temperature from 90 °C to 1 10 °C, or 95 °C to 105 °C, or any value there between including 90 °C, 91 °C, 92 °C, 93 °C, 94 °C, 95 °C, 96 °C, 97 °C, 98 °C, 99 °C, 100 °C, 101 °C, 102 °C, 103 °C, 104 °C, 105 °C, 106 °C, 107 °C, 108 °C, 109 °C, or 1 10 °C for a time period sufficient (e.g., 3 to 24 hours, 8 to 20
hours, or 12 hours) to remove all or a majority of the water to produce a dried powdered material. In some instances, drying is performed at 105 °C for 12 hours. The dried CuZnZr material can be then be calcined within 8 hours of drying by heating the dried material to an average temperature between 350 °C and 600 °C, 400 °C to 550 °C, with 400 °C being preferred, for 3 to 12 hours or 4 to 8 hours in the presence of a flow of an oxygen source (e.g., air at 250 cc/per minute) to form the CuZnZr mixed metal oxide catalyst. Prior to use in the process of the invention, the catalyst particles can be reduced in size (e.g., crushed) to a particle size of 20-50 mesh.
C. Reactants and Products [0035] Carbon dioxide gas and hydrogen gas can be obtained from various sources. In one non-limiting instance, the carbon dioxide can be obtained from a waste or recycle gas stream (e.g., from a plant on the same site such as from ammonia synthesis) or after recovering the carbon dioxide from a gas stream. A benefit of recycling such carbon dioxide as a starting material in the process of the invention is that it can reduce the amount of carbon dioxide emitted to the atmosphere (e.g., from a chemical production site). The hydrogen may be from various sources, including streams coming from other chemical processes, like water splitting (e.g., photocatalysis, electrolysis, or the like), additional syngas production, ethane cracking, methanol synthesis, or conversion of methane to aromatics. The molar H2:C02 reactant gas ratio for the hydrogenation reaction can range from 0.5 : 1 to 2.0: 1, 0.6: 1 to 1.2: 1, or 0.6: 1 to 1.0: 1. In one instance, the reactant gas stream includes 30 to 70 vol.% H2 and 30 to 70 vol.% C02. In another embodiments, the reactant gas stream includes 40 to 60 vol.% H2 and 40 to 60 vol.% C02. In a preferred embodiment, the reactant gas stream includes about 50 vol.%) H2 and about 50 vol.%> C02. In yet another instance the reactant gas stream includes about 60 vol.%> H2 and 40 vol.%> C02. In some embodiments, the streams are not combined. In these instances, the hydrogen gas and carbon dioxide can be delivered at the same H2:C02 molar ratio. In some examples, the remainder of the reactant gas stream can include another gas or gases provided the gas or gases are inert, such as argon (Ar) or nitrogen (N2), and/or do not negatively affect the reaction. All possible percentages of C02 plus H2 plus inert gas in the current embodiments can have the described H2:C02 ratios herein. Preferably, the reactant mixture is highly pure and substantially devoid of water or steam. In some embodiments, the carbon dioxide can be dried prior to use (e.g., pass through a drying media) to contain minimal amounts of water or no water. In some embodiments, the
reactant feed contains only C02 and H2 or a minimal amount of alkanes (e.g., less than 5 mol.% methane and/or CO).
[0036] The process of the present invention can produce a product stream that includes a mixture of H2 and CO having a molar H2:CO ratio suitable for the synthesis of various chemical products. Non-limiting examples of synthesis include methanol production, olefin synthesis, aromatics production, hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins. Non-limiting examples of products that can be produced include aliphatic oxygenates, methanol, olefin synthesis, aromatics production, carbonylation of methanol, carbonylation of olefins, or reduction of iron oxide in steel production. The molar H2:CO ratio can be 0.7: 1 to 1.4: 1, 0.8: 1 to 1.2: 1 or about 0.9: 1 to about 0.95 : 1, or 1 : 1 which is suitable for oxo-products (e.g., C2+ alcohols, dimethyl ether, etc.). The amount of alkane (e.g., methane) produced in the process of the present reaction can be less than 10 mol.%, less than 5 mol.%, 3 mol.%, 2 mol.%, 1 mol.%, or 0 mol.% based on the total moles of components in the product stream. The product stream can include unreacted C02. In some particular instances, By way of example, the product stream can include 30 mol%, 35 mol.% 40 mol.%, 45 mol.% 55 mol%, 60 mol%, 65 mol%, of C02 based on the total moles of components in the product stream. In a particular instance, the product stream can include 15 mol.% to 20 mol.% CO, 50 mol.% to 65 mol.% C02, 1 mol.% to 10 mol.% CH4, and 10 mol.%) to 25 mol.%) H2. In yet another aspect, the syngas containing composition can include 16 mol.% to 17 mol.% CO, 60 mol.% to 65 mol.% C02, 4 mol.% to 5 mol.% CH4, and 15 mol.% to 16 mol.% H2.
EXAMPLES
[0037] The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters, which can be changed or modified to yield essentially the same results.
Example 1
(Synthesis of CuZnZr Mixed Metal Oxide Catalyst)
[0038] Copper nitrate (35.7 g, Cu(N03)3*3H20), zinc nitrate (20.9 g, Ζη(Ν03)3·6Η20), and zirconium nitrate (1 1.6 g, Zr(N03)3*6H20) were dissolved in water (500 mL). Sodium hydroxide (NaOH, 30%) was added gradually to the solution to co-precipitate the CuZnZr
metal oxide precursor material. The pH of the solution was maintained at 8 and heated to a temperature of 65 °C. The CuZnZr metal oxide precursor material was isolated by filtration and washed with water (3 X 500 mL) to remove excess base. The washed CuZnZr metal oxide precursor material was dried at 105 °C for 12 hours. The dried CuZnZr metal oxide precursor material was calcined at 400 °C in air flow of 250 cc/min for 8 hours to form the CuZnZr mixed metal oxide catalyst of the present invention. Prior to use, the CuZnZr mixed metal oxide catalyst was crushed to a particle size of 20-50 mesh. The CuZnZr mixed metal oxide catalyst had a surface area of 103 m2/g.
Example 2
(General Process for Hydrogenation of Carbon Dioxide)
[0039] General Procedure. Catalyst testing was performed in a high throughput metal reactor system. The reactors are fixed bed type reactor with a 2.5 cm inner diameter and 40 cm in length. Gas flow rates were regulated using two mass flow controllers. Reactor pressure was maintained by using a back pressure regulator. The reactor temperature was maintained by an external, electrical heating block. The effluent of the reactors was connected to a gas chromatograph for online gas analysis using a molecular sieve and Hayesep D column and thermal conductivity detector (TCD). The catalyst (3 mL) was placed on top of inert material inside the reactor. Prior to the reaction test, the catalyst was reduced at 600 °C under 25 vol.% H2 in Ar for 2 h. In all examples, C02 conversion was calculated by the following formula.
CC-2 conversion, % mol = (%CO + %CH4) / (%CO + %C¾ + %C02) (8) which presents the reactions of equations (5) and (7) discussed above:
C02+ H2 ¾ CO + H20 (5)
C02 + 4 H2 ¾ CH4 + 2 H20 (7) Therefore, equation (8) presents the sum of all carbon, products divided by the total number of carbons.
Example 3
(Process for Hydrogenation of Carbon Dioxide)
[0040] The general procedure of Example 2 was followed with the following conditions: a pressure of 2.8 MPa, a temperature of 620 °C, a H2 flow rate of 50 cc/min and a C02 flow
rate of 50 cc/min. Time on stream (TOS), molar percentage of components in the product stream, and % carbon dioxide conversion and results are listed in Table 1.
Table 1
*Time on Stream
Example 4
(Process for Hydrogenation of Carbon Dioxide)
[0041] The general procedure of Example 2 was followed using the following conditions: a pressure of 2.8 MPa, a temperature of 580 °C, a H2 flow rate of 40 cc/min, and a C02 flow rate of 60 cc/min. Results are listed in Table 2.
Table 2
Example 5
(Process for Hydrogenation of Carbon Dioxide)
[0042] The general procedure of Example 2 was followed using the following conditions: a pressure of 1.0 MPa, a temperature of 580 °C, a H2 flow rate of 40 cc/min and a C02 flow rate of 60 cc/min. Results are listed in Table 3.
Table 3
[0043] From the comparison of the Examples 3-5, it was determined that the reaction conditions of 2.8 MPa and 580 °C (Example 4) produced a syngas composition having a
H2:CO ratio closest to 1 (0.94: 1 and 0.96: 1), which is suitable for use as an intermediate or as feed material in a oxo-product synthesis (e.g., hydroformylation of olefins, carbonylation of methanol, and carbonylation of olefins) to form a chemical product or a plurality of chemical products (e.g., C2+ alcohols, ethers, dimethyl ether and the like).
Claims
1. A process for hydrogenating carbon dioxide (C02) to produce an oxo-synthesis syngas containing composition for a hydroformylation reaction, the process comprising contacting a CuZnZr mixed metal oxide catalyst with a reactant feed comprising hydrogen (H2) and C02 at a H2:C02 volume ratio of at least 0.5: 1, wherein the reaction occurs at a temperature of at least 550 °C and a pressure of at least 0.5 MPa to produce a product stream comprising H2 and CO at a H2:CO molar ratio of 0.7 to 1.4.
2. The process of claim 1, wherein temperature is from 550 °C to 650 °C, preferably 550 °C to 600 °C, or more preferably about 580 °C.
3. The process of any one of claims 1 to 2, wherein the pressure is from 0.5 MPa to 6 MPa, preferably 2 MPa to 4 MPa, or more preferably 2.5 MPa to 3.5 MPa.
4. The process of claim 1, wherein the reaction conditions include a temperature of 550 °C to 600 °C and a pressure of 2.5 MPa to 3 MPa, wherein the syngas containing composition comprises a H2:CO molar ratio of 0.9: 1 to 1.1 : 1.
5. The process of any one of claims 1 to 4, wherein the syngas containing composition is used to produce oxo-products.
6. The process of any one of claims 1 to 5, wherein the syngas containing composition comprises 30 mol. % C02 or more.
7. The process of any one of claims 1 to 6, wherein the CuZnZr mixed metal oxide catalyst comprises 50 wt. % to 60 wt. % CuO, 20 wt. % to 30 wt. % of ZnO, and 15 wt. % to 25 wt. % of Zr02, preferably about 55.19 wt. % CuO, about 24.9 wt. % ZnO, and about 19.9 wt. % Zr02.
8. The process of any one of claims 1 to 7, wherein the methane content in the produced syngas containing composition is less than 10 mol.%.
9. The process of any one of claims 1 to 8, further comprising a H2 gas flow rate of 30 to 70 mL/min and the C02 gas flow rate of 30 to 70 mL/min.
10. The process of any one of claims 1 to 9, wherein the syngas containing composition has a H2:CO molar ratio of 0.8: 1 to 1.2: 1, more preferably 0.9: 1 to l . : l .
11. The process of any one of claims 1 to 10, wherein the syngas containing composition comprises 15 mol.% to 20 mol.% CO, 50 mol.% to 65 mol.% C02, 1 mol.% to 10 mol.% CH4, and 10 mol.% to 25 mol.% H2.
12. The process of any one of claims 1 to 11, wherein the syngas containing composition comprises 16 mol.% to 17 mol.% CO, 60 mol.% to 65 mol.% C02, 4 mol.% to 5 mol.% CH4, and 15 mol.% to 16 mol.% H2.
13. The process of any one of claims 1 to 12, wherein the C02 conversion is at least 20%.
14. The process of any one of claims 1 to 13, wherein the H2:C02 volume ratio is 0.5: 1 to 2.0: 1, preferably 0.5: 1 to 1.2: 1, more preferably 0.5: 1 to 1 : 1.
15. The process of any one of claims 1 to 14, further comprising removing the C02 from the product stream.
16. The process of any one of claims 1 to 15, further comprising using the produced syngas mixture as an intermediate or as feed material in a subsequent reaction to form an oxo-product.
17. The process of claim 16, wherein the oxo-product comprises a C2+ alcohol, an alkyl ether, or a dimethyl ether.
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US7435759B2 (en) * | 2003-09-17 | 2008-10-14 | Korea Institute Of Science And Technology | Method for the production of dimethyl ether |
CN101786001A (en) * | 2010-03-12 | 2010-07-28 | 厦门大学 | Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof |
CN102500381A (en) * | 2011-11-01 | 2012-06-20 | 昆明理工大学 | Preparation method of catalyst of carbon dioxide hydrogenation methanol synthesis |
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CN101786001A (en) * | 2010-03-12 | 2010-07-28 | 厦门大学 | Catalyst for hydrogenation of carbon dioxide to generate methanol and preparation method thereof |
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