CN113908840A - Fe-based multifunctional catalyst and preparation method and application thereof - Google Patents
Fe-based multifunctional catalyst and preparation method and application thereof Download PDFInfo
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- CN113908840A CN113908840A CN202111369229.9A CN202111369229A CN113908840A CN 113908840 A CN113908840 A CN 113908840A CN 202111369229 A CN202111369229 A CN 202111369229A CN 113908840 A CN113908840 A CN 113908840A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 215
- 238000002360 preparation method Methods 0.000 title claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 103
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000008878 coupling Effects 0.000 claims abstract description 20
- 238000010168 coupling process Methods 0.000 claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 claims abstract description 20
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 4
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 76
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 238000005470 impregnation Methods 0.000 claims description 21
- 238000007873 sieving Methods 0.000 claims description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 20
- 238000010000 carbonizing Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000013082 iron-based metal-organic framework Substances 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 52
- 230000003197 catalytic effect Effects 0.000 abstract description 34
- 238000006555 catalytic reaction Methods 0.000 abstract description 19
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 88
- 229910002092 carbon dioxide Inorganic materials 0.000 description 72
- 239000000047 product Substances 0.000 description 45
- 239000001569 carbon dioxide Substances 0.000 description 44
- 238000001035 drying Methods 0.000 description 31
- 230000008569 process Effects 0.000 description 29
- 238000001816 cooling Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- 229910052783 alkali metal Inorganic materials 0.000 description 15
- 150000001340 alkali metals Chemical class 0.000 description 15
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000543 intermediate Substances 0.000 description 11
- 239000006004 Quartz sand Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000000975 co-precipitation Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000012495 reaction gas Substances 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000002431 foraging effect Effects 0.000 description 8
- 238000010335 hydrothermal treatment Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000005431 greenhouse gas Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012494 Quartz wool Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- -1 lithium modified silica Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 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
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- 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
- B01J23/70—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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J37/031—Precipitation
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
Abstract
The invention provides a Fe-based multifunctional catalyst, which is formed by coupling a Na-ZnFe @ C catalyst and a K-CuZnAl catalyst; the Na-ZnFe @ C catalyst is a sodium ion-loaded iron carbide-based metal organic framework material (ZnFe-MOFs); the K-CuZnAl catalystThe catalyst is a CuZnAl catalyst loaded with potassium ions. The invention realizes CO by optimizing the coupling mode among different catalytic active components of the multifunctional catalyst and considering both the reverse water gas conversion and the Fischer-Tropsch synthesis carbon chain growth in the reaction process2One-step hydrogenation high-selectivity synthesis of ethanol and CO2The conversion rate is as high as 39.2%, the selectivity of ethanol is 35.0%, and the selectivity of olefin is 33.0%, so that the high-efficiency synergistic effect among different catalytic active components is realized. The invention opens up a new CO2The catalytic reaction path for preparing the ethanol by hydrogenation has higher economic value and social benefit.
Description
Technical Field
The invention relates to the technical field of chemical catalysis, in particular to a Fe-based multifunctional catalyst and a preparation method and application thereof.
Background
Since the industrial revolution, which is rapidly developed in various countries, energy consumption structures mainly based on coal, oil and natural gas result in carbon dioxide (CO) which is a greenhouse gas2) Of the emission of large amounts of, by far, atmospheric CO2The concentration has already exceeded the alarm value (400 ppm). This directly leads to global warming, sea level elevation, etcThe ecological environment is a problem, and the survival and development of human beings are seriously threatened. Thus, reduction of atmospheric CO2The concentration is particularly important. Especially, the proposal of carbon neutralization call in China is now realized to realize CO2The beneficial transformation of (A) is more urgent.
With CO2The preparation of high-end chemicals as raw materials can not only relieve CO2The environmental problem brought by excessive discharge and a feasible technical route for the synthesis of high value-added chemicals. CO commonly used at present2The catalytic conversion method includes electrocatalysis, photocatalysis, photoelectrocatalysis and the like, wherein the thermocatalysis method attracts a plurality of researchers with high reaction activity, excellent target product selectivity and larger industrial application potential. CO 22The catalytic hydrogenation reaction is the most efficient CO at present2Means for converting chemicals if H is present during the reaction2Hydrogen-rich tail gas from refineries or sustainable photo/electrocatalytic water splitting, CO2The hydrogenation catalytic conversion has more application prospect.
Despite the use of thermocatalytic hydrogenation means for CO2The conversion of carbon compounds such as carbon monoxide, methane, methanol and formic acid has been studied with great progress, but is limited by the CO2The chemical inertness of the catalyst and the higher C-C bond coupling energy barrier in the hydrogenation reaction process, and CO is separated2Conversion to C2+The compounds still present challenges.
Ethanol is an important chemical product, has high economic value and application value, and is widely applied to the fields of daily life, industrial production and medical treatment and health. The ethanol can be used as a reaction raw material for synthesizing basic chemicals such as low-carbon olefin, aromatic hydrocarbon and the like, and the obtained product can be further used as a synthetic intermediate of effective components such as medicines, coatings and the like; meanwhile, ethanol is an excellent solvent for numerous organic reactions, and can provide an ideal reaction environment for high-selectivity synthesis of important organic compounds. In addition, under the condition of increasingly serious environmental pollution at present, ethanol as a low-carbon liquid fuel has the advantages of high combustion release energy, easiness in storage, no sulfur, nitrogen and other environmental pollution components, is a clean energy with extremely high application value, and the properties make the ethanol attractive.
The current methods for preparing ethanol mainly comprise a grain fermentation method, an ethylene hydration method and a synthesis gas conversion method. However, the traditional grain fermentation method is contrary to the grain crisis to be solved in many regions in the world at present, and has long time consumption and low efficiency; the synthesis of low-carbon alcohol by using chemical raw materials such as ethylene or synthesis gas has the problem of over-dependence on fossil fuel, and simultaneously, a large amount of greenhouse gas CO is discharged in the synthesis process2And causes pollution to the environment. Against the background of the above, a method of using CO has been developed2The process for producing the ethanol by the hydrogenation reaction of the raw materials can change waste into valuable and change greenhouse gas CO into useful2The product is converted into a high value-added chemical product, and accords with the concept of green sustainable development at present; on the other hand, the synthesis process of the ethanol can be enriched, and the high points of the brand-new catalytic process and system intellectual property are occupied. In addition, the method aims at high emission CO of current refineries and coal-fired power plants2The unit faces the dilemma of energy conservation and emission reduction, and CO takes hydrogen-rich tail gas produced by refinery plants as hydrogen source2The technology for synthesizing the ethanol by hydrogenation is a feasible route in economic terms and has more important environmental and strategic meanings.
Aiming at the current CO2Due to the defects of the catalyst for preparing ethanol by hydrogenation, researchers have developed researches on active components, carriers, auxiliaries and the like of the catalyst. Kiyomi Okabe et al (Catal. today,1996,28,261) from the national institute of materials, Supported rhodium on alkali lithium modified silica (Li-Rh/SiO)2) As catalysts for CO2Preparation of ethanol by hydrogenation in CO2The selectivity to ethanol was 15.5% at a conversion of 7.0%. Further studies showed that ethanol is mainly formed by CO molecules with the CH3Radical coupling to form CH3CO intermediate, and is generated through a subsequent hydrogenation process. Titanium dioxide (TiO) rich in surface hydroxyl groups (-OH) was studied in the project group of the university of tianjin, sclerjinlong professor (chem.sci.,2019,10,3161) system2) Supported Rh-based catalyst on CO2Enhancement of selectivity in ethanol production by hydrogenation in CO2When the conversion rate is 15.0%, the selectivity of the ethanol can reach 32.0%. Research shows that TiO2The hydroxyl groups on the surface contributeAnd generating CHxCO species, and then generating ethanol by hydrogenating CHxCO intermediate generated by coupling CO molecules with the CHx.
In summary, CO can be achieved by selecting different catalysts through different catalytic networks2The ethanol is prepared by catalytic conversion, however, the yield of the ethanol is low, the research on the reaction mechanism is not deep enough, and the real catalytic network is not clear. Therefore, the reaction mechanism thereof has been studied in an intensive manner to solve the above problems, and a novel CO has been constructed2Catalytic network for preparing ethanol by hydrogenation and simultaneously considering ethanol selectivity and CO2The conversion rate, which results in excellent ethanol per pass yield, is that CO is currently achieved2The development trend of the industrial application of the ethanol preparation by the hydroconversion is also a bottleneck which needs to be broken through urgently.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an Fe-based multifunctional catalyst, a preparation method and an application thereof, wherein the Fe-based multifunctional catalyst can be used as CO2The catalyst in the reaction of hydrogenation to prepare ethanol has high CO content2Conversion and ethanol selectivity.
In order to achieve the aim, the invention provides a Fe-based multifunctional catalyst which is formed by coupling a Na-ZnFe @ C catalyst and a K-CuZnAl catalyst;
the Na-ZnFe @ C catalyst is a sodium ion-loaded iron carbide-based metal organic framework material (ZnFe-MOFs);
the K-CuZnAl catalyst is a CuZnAl catalyst loaded with potassium ions.
Preferably, the mass ratio of the Na-ZnFe @ C catalyst to the K-CuZnAl catalyst is 1: 0-1: 3; more preferably 1: 1.
Preferably, in the Na-ZnFe @ C catalyst, the load amount of sodium ions is 0.1-5 wt%, and more preferably 2 wt%.
Preferably, in the K-CuZnAl catalyst, the load amount of potassium ions is 0.1-10 wt%, and more preferably 5 wt%.
The coupling in the present invention means different combinations between the two components in the multifunctional catalyst. Specifically, the following four methods are included.
Preferably, the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst are coupled in any one of the methods 1) to 4):
method 1): mixing the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst, and then carrying out extrusion forming, crushing and sieving;
method 2) respectively carrying out extrusion forming, crushing and sieving on the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst, and then mixing the two;
method 3) respectively carrying out extrusion forming, crushing and sieving on a Na-ZnFe @ C catalyst and a K-CuZnAl catalyst, and then filling in a double-bed mode, wherein the Na-ZnFe @ C catalyst is arranged on the upper layer, and the K-CuZnAl catalyst is arranged on the lower layer;
method 4) respectively carrying out extrusion forming, crushing and sieving on the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst, and then filling in a double-bed mode, wherein the Na-ZnFe @ C catalyst is arranged at the lower layer, and the K-CuZnAl catalyst is arranged at the upper layer.
In the above methods 1) to 4), the mixing is preferably carried out by physical polishing.
The screening is preferably a 20-40 mesh screen.
The above method 2) can increase the distance between the two components.
Preferably, in the above method 3) or method 4), the two catalysts are separated by quartz wool to further increase the distance between the catalyst components.
The invention provides a preparation method of the Fe-based multifunctional catalyst, which comprises the following steps:
s1) carbonizing the Fe-based metal organic framework, and then dipping the Fe-based metal organic framework by a sodium ion solution to obtain a Na-ZnFe @ C catalyst;
s2) carrying out potassium ion solution impregnation on the CuZnAl catalyst to obtain a K-CuZnAl catalyst;
s3) coupling the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst to obtain the Fe-based multifunctional catalyst.
The source of the Fe-based metal organic framework is not particularly limited in the present invention, and can be generally commercially available or prepared according to methods well known to those skilled in the art, and the present invention is preferably prepared by a hydrothermal method, more preferably by the following method:
and mixing DMF (dimethyl formamide) solutions of a zinc source compound, an iron source compound and triethylene diamine and DMF (dimethyl formamide) solutions of terephthalic acid, and carrying out hydrothermal reaction to obtain the Fe-based metal organic framework (ZnFe-MOFs).
The zinc source compound is preferably Zn (NO)3)2·6H2O。
The iron source compound is preferably FeCl2·4H2O。
And then carbonizing.
The carbonization treatment temperature is preferably 500-800 ℃, and more preferably 550 ℃; the time is preferably 1 to 6 hours, and more preferably 3 hours. The carbonization treatment is preferably performed in a nitrogen atmosphere.
And then impregnated.
The sodium ion solution is preferably an aqueous solution of sodium carbonate.
The concentration of the sodium carbonate aqueous solution is preferably 0.2 mol/L.
Preferably, the sodium carbonate aqueous solution further contains ethanol.
The addition amount of the ethanol is preferably 0.1-1 g, and more preferably 0.4 g.
The invention can adjust the load of sodium ions by adjusting the dosage of sodium carbonate.
Preferably, the impregnation is an equal volume impregnation.
In the present invention, it is preferable to dry the impregnated product after impregnation.
The drying temperature is preferably 60-100 ℃, and more preferably 60 ℃; the time is preferably 6-24 h, and more preferably 24 h.
The source of the CuZnAl catalyst is not particularly limited in the present invention, and may be generally commercially available or prepared according to a method well known to those skilled in the art, and the present invention is preferably prepared by a coprecipitation method, and more preferably prepared by the following method:
mixing a copper source compound, a zinc source compound, an aluminum source compound and urea in deionized water, keeping the mixture for 1-5 hours (more preferably 2 hours) at 60-100 ℃ (more preferably 95 ℃) in a stirring state, and standing and aging for 12-24 hours (more preferably 24 hours) to obtain a CuZnAl catalyst precursor; and calcining the CuZnAl catalyst precursor for 1-3 h (preferably 1h) in the air at 300-600 ℃ (preferably 350 ℃) to obtain the CuZnAl catalyst.
The copper source compound is preferably Cu (NO)3)2·3H2O。
The zinc source compound is preferably Zn (NO)3)2·6H2O。
The aluminum source compound is preferably Al (NO)3)3·9H2O。
The molar ratio of the copper source compound, the zinc source compound, the aluminum source compound, and urea is preferably 1: 1: 1: 2.
the pH value of the mixing, standing and aging is preferably 7-8.
And then impregnated.
The potassium ion solution is preferably an aqueous solution of potassium carbonate.
The concentration of the potassium carbonate aqueous solution is preferably 0.1-1 mol/L, and more preferably 0.5 mol/L.
The invention can adjust the load of potassium ions by adjusting the dosage of potassium carbonate.
Preferably, the impregnation is an equal volume impregnation.
In the present invention, it is preferable to dry the impregnated product after impregnation.
The drying temperature is preferably 60-100 ℃, and more preferably 60 ℃; the time is preferably 6-24 h, and more preferably 24 h.
The invention provides the Fe-based multifunctional catalyst or the Fe-based multifunctional catalyst prepared by the preparation method as CO2The application of the catalyst for directly synthesizing ethanol by hydrogenation.
The Fe-based multifunctional catalyst is preferably treated with H before use2And (5) reduction treatment and activation.
Specifically, the Fe-based multifunctional catalyst is loaded in a fixed bed reactor and then subjected to activation treatment.
Said H2The temperature of the reduction treatment is preferably 200-400 ℃, and more preferably 400 ℃; the time is preferably 1-6 h, and more preferably 4 h; h2Has excellent flow ratePreferably 10 to 200mL/min, more preferably 60 mL/min.
The invention provides CO2The method for directly synthesizing the ethanol by hydrogenation takes the Fe-based multifunctional catalyst or the Fe-based multifunctional catalyst prepared by the preparation method as the catalyst.
Specifically, the invention provides a catalyst prepared from CO2The method for directly synthesizing the ethanol by hydrogenation comprises the following steps: filling Fe-based multifunctional catalyst into a fixed bed reactor, and introducing CO2And H2Mixing the gases with CO2And (5) adding hydrogen to prepare ethanol.
Preferred, according to the invention, CO2The temperature for preparing the ethanol by hydrogenation is 300-400 ℃, and more preferably 320 ℃; the reaction pressure is preferably 3-8 MPa, and more preferably 5 MPa.
The performance test can be carried out in the reaction process: and the gas-phase product is analyzed on line, and the liquid-phase product is collected by a cold trap and then is analyzed off line.
Preferably, the catalytic performance test of the Fe-based multifunctional catalyst is carried out in a fixed bed reactor, and the catalyst is preferably subjected to H at 400 ℃ before the test2Reducing for 4 hours; after the temperature is reduced to the reaction temperature (preferably 320 ℃), the gas is switched to the reaction gas (preferably H)2/CO23) and the reaction is started by increasing the pressure to the target pressure (preferably 5MPa) under back pressure.
Preferably, the reaction product is analyzed in a combination of online and offline. Collecting liquid phase (oil/water two-phase) products by flowing out of the reactor through a cold trap, and analyzing the composition of the liquid phase products by using off-line chromatography (FuliGC 9790II, FID detector, InerCap-5 chromatographic column); the tail gas after separating the liquid phase product is detected by on-line chromatography (Fuli GC9790II) connected with a TCD and FID dual detector, wherein a carbon molecular sieve column TDX-1 is connected with the TCD detector for analyzing Ar, CO and CH4And CO2The capillary column HP-PLOT-Q is connected with a FID detector for analyzing hydrocarbon; the post reactor line was insulated to 180 ℃ with a heating tape to prevent condensation of product in the line.
Experimental results show that the Fe-based multifunctional prepared by the inventionCatalyst in CO2In the performance test of ethanol preparation by hydrogenation, CO2The conversion was 39.2%, the ethanol selectivity was 35.0%, and the CO selectivity was 9.4%. Therefore, the catalyst can efficiently remove the greenhouse gas CO2The methanol is converted into high value-added chemical ethanol, and the selectivity of a main byproduct CO is low.
As a further improvement of the technical scheme, the yield of the ethanol reaches 12.4 percent by continuously optimizing reaction conditions (temperature, pressure, catalyst mass ratio, space velocity and the like).
Any range recited herein is inclusive of the endpoints.
Unless otherwise specified, the raw materials used in the present invention may be purchased commercially, and the apparatus used in the present invention is described in the prior art.
Compared with the prior art, the invention provides a Fe-based multifunctional catalyst which is formed by coupling a Na-ZnFe @ C catalyst and a K-CuZnAl catalyst; the Na-ZnFe @ C catalyst is a sodium ion-loaded Fe-based metal organic framework carbide material; the K-CuZnAl catalyst is a CuZnAl catalyst loaded with potassium ions.
The invention realizes CO by optimizing the coupling mode among different catalytic active components of the multifunctional catalyst and simultaneously considering reverse water gas conversion and Fischer-Tropsch synthesis carbon chain growth in the reaction process2One-step hydrogenation high-selectivity synthesis of ethanol and CO2The conversion rate is as high as 39.2%, the selectivity of ethanol is 35.0%, and the selectivity of olefin is 33.0%, so that the high-efficiency synergistic effect among different catalytic active components is realized. The invention opens up a new CO2A catalytic reaction path for preparing ethanol by hydrogenation. Compared with the traditional grain fermentation method, ethylene hydration method and synthesis method, the process uses greenhouse gas CO2As a carbon source, the carbon source can change waste into valuable, and has higher economic value and social benefit; the multifunctional catalyst system takes Fe as a main catalytic active component, the preparation process is simple, the cost is low, and the catalyst system is original and has great industrial application potential.
Detailed Description
In order to further illustrate the present invention, the following examples are provided to describe the Fe-based multifunctional catalyst and its preparation method and application in detail.
Example 1
S1, by carbonizing Fe-based metal organic frameworks (ZnFe-MOFs) and then reacting with Na2CO3And (3) carrying out alkali metal impregnation and drying to prepare the 2% Na-ZnFe @ C catalyst. The specific experimental process is as follows:
1mmol of Zn (NO)3)2.6H2O (0.297g) and 0.6g FeCl2.4H2Dissolving O (3mmol) in 50ml DMF, adding 0.22g triethylene diamine, and stirring for 30 minutes to prepare solution A; terephthalic acid (4.2mmol,0.70g) was dissolved in 10mL DMF to form solution B; adding the solution B into the solution A, stirring for 1h, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 h; after centrifugation, the product was washed 3 times with DMF and then dried overnight in a vacuum oven at 60 ℃ to give ZnFe-MOFs.
And carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. And naturally cooling to room temperature to obtain the ZnFe @ C catalyst.
0.046g of Na is taken2CO31g of ZnFe @ C was impregnated with an equal volume of Na as source in 2.5g of aqueous solution (containing 0.5g of ethanol) and dried overnight in a vacuum oven at 60 deg.C to give a 2% Na-ZnFe @ C catalyst.
S2, preparing CuZnAl catalytic CO by coprecipitation method2Hydrogenation reaction to generate catalytic active component of oxygen-containing intermediate such as formyl or formate, and using KNO3And (3) carrying out alkali metal impregnation and drying to obtain the 5% K-CuZnAl catalyst. The specific experimental process is as follows:
taking 24.2g of Cu (NO)3)2·3H2O,11.9g Zn(NO3)2·6H2O,5.0g Al(NO3)2·9H2O, 5g urea is dissolved in 200mL deionized water, stirred at 95 ℃ for 2h, and then left for aging for 24 h. And centrifuging the product, washing the product for 3 times by using deionized water, and then drying the product in a vacuum oven at 60 ℃ overnight to obtain the CuZnAl catalyst precursor.
And calcining the obtained precursor in a tubular furnace in an air atmosphere, wherein the calcining temperature is controlled to be 350 ℃ and the time is 1 h. And naturally cooling to room temperature to obtain the CuZnAl catalyst.
Taking 0.13g KNO3Dissolving the K source in 0.8g of deionized water, performing equal-volume impregnation on 1g of CuZnAl, and drying the CuZnAl in a vacuum oven at 60 ℃ overnight to obtain the 5% K-CuZnAl catalyst.
S3, coupling 2% of Na-ZnFe @ C with 5% of K-CuZnAl to obtain the Fe-based multifunctional catalyst. The specific experimental process is as follows:
tabletting 2% Na-ZnFe @ C catalyst under 10MPa, crushing, sieving and granulating to 20-40 meshes.
Tabletting 5% K-CuZnAl catalyst under 10MPa, crushing, sieving and granulating to 20-40 mesh.
0.1g of granulated 2% Na-ZnFe @ C and 0.1g of 5% K-CuZnAl catalyst were weighed respectively, mixed with 0.4g of quartz sand, and packed in a fixed bed reactor (inner diameter 6mm) at 400 ℃ in H2Reduction for 4H, H2The flow rate was 60 mL/min. After the temperature was reduced to the reaction temperature (320 ℃), the gas was switched to the reaction gas (3.04% Ar, 25.6% CO)2,71.36％H2) And the reaction was started by raising the pressure to the target pressure (5MPa) under the action of a back pressure valve. The catalytic reaction conditions and results are shown in table 1 below:
TABLE 1 catalytic reaction conditions and results in example 1a
aReaction conditions are as follows: 320 ℃ and 5MPa (25.6% CO)2,71.36％H2,and 3.04％Ar),15mL min-1. The mass of the catalyst is as follows: 0.1g of 2% Na-ZnFe @ C,0.1g of 5% K-CuZnAl.
Othersb: propanol, butanol, and the like.
Comparative example 1
S1, carbonizing an Fe-based metal organic framework (ZnFe-MOFs), then impregnating with alkali metal, and drying to prepare the 2% Na-ZnFe @ C catalyst. The specific experimental process is as follows:
1mmol of Zn (NO)3)2.6H2O (0.297g) and 0.6g FeCl2.4H2Dissolving O (3mmol) in 50ml DMF, adding 0.22g triethylene diamine, and stirring for 30 minutes to prepare solution A; terephthalic acid (4.2mmol,0.70g) was dissolved in 10mL DMF to form solution B; adding the solution B into the solution A, stirring for 1h, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 h; after centrifugation, the product was washed 3 times with DMF and then dried overnight in a vacuum oven at 60 ℃ to give ZnFe-MOFs.
And carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. And naturally cooling to room temperature to obtain the ZnFe @ C catalyst.
0.046g of Na is taken2CO31g of ZnFe @ C was impregnated with an equal volume of Na as source in 2.5g of aqueous solution (containing 0.5g of ethanol) and dried overnight in a vacuum oven at 60 deg.C to give a 2% Na-ZnFe @ C catalyst.
S2, preparing CuZnAl catalytic CO by coprecipitation method2And (3) carrying out hydrogenation reaction to generate catalytic active components of oxygen-containing intermediates such as formyl or formyl and the like, then carrying out alkali metal impregnation on the catalytic active components, and drying to obtain the 5% K-CuZnAl catalyst. The specific experimental process is as follows:
taking 24.2g of Cu (NO)3)2·3H2O,11.9g Zn(NO3)2·6H2O,5.0g Al(NO3)2·9H2O, 5g urea is dissolved in 200mL deionized water, stirred at 95 ℃ for 2h, and then left for aging for 24 h. And centrifuging the product, washing the product for 3 times by using deionized water, and then drying the product in a vacuum oven at 60 ℃ overnight to obtain the CuZnAl catalyst precursor.
And calcining the obtained precursor in a tubular furnace in an air atmosphere, wherein the calcining temperature is controlled to be 350 ℃ and the time is 1 h. And naturally cooling to room temperature to obtain the CuZnAl catalyst.
Taking 0.13g KNO3As a source of K, dissolved in 0.8g of deionized water1g of CuZnAl is dipped in the same volume and dried in a vacuum oven at 60 ℃ overnight to obtain the 5 percent K-CuZnAl catalyst.
S3, coupling 2% of Na-ZnFe @ C with 5% of K-CuZnAl to obtain the Fe-based multifunctional catalyst. The specific experimental process is as follows:
tabletting 2% Na-ZnFe @ C catalyst under 10MPa, crushing, sieving and granulating to 20-40 meshes.
Tabletting 5% K-CuZnAl catalyst under 10MPa, crushing, sieving and granulating to 20-40 mesh.
0.1g of granulated 2% Na-ZnFe @ C and 0.05g of 5% K-CuZnAl catalyst were weighed respectively, mixed with 0.4g of quartz sand, and packed in a fixed bed reactor (inner diameter 6mm) at 400 ℃ in H2Reduction for 4H, H2The flow rate was 60 mL/min. After the temperature was reduced to the reaction temperature (320 ℃), the gas was switched to the reaction gas (3.04% Ar, 25.6% CO)2,71.36％H2) And the reaction was started by raising the pressure to the target pressure (5MPa) under the action of a back pressure valve. The catalytic reaction conditions and results are shown in table 2 below:
TABLE 2 catalytic reaction conditions and results of comparative example 1a
aReaction conditions are as follows: 320 ℃ and 5MPa (25.6% CO)2,71.36％H2,and 3.04％Ar),15mL min-1. The mass of the catalyst is as follows: 0.1g of 2% Na-ZnFe @ C,0.05g of 5% K-CuZnAl.
Othersb: propanol, butanol, and the like.
Comparative example 2
S1, carbonizing an Fe-based metal organic framework (ZnFe-MOFs), then impregnating with alkali metal, and drying to prepare the 2% Na-ZnFe @ C catalyst. The specific experimental process is as follows:
1mmol of Zn (NO)3)2.6H2O (0.297g) and 0.6g FeCl2.4H2Dissolving O (3mmol) in 50ml DMF, adding 0.22g triethylene diamine, and stirring for 30 minutes to prepare solution A; mixing terephthalic acid(4.2mmol,0.70g) in 10mL DMF to form solution B; adding the solution B into the solution A, stirring for 1h, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 h; after centrifugation, the product was washed 3 times with DMF and then dried overnight in a vacuum oven at 60 ℃ to give ZnFe-MOFs.
And carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. And naturally cooling to room temperature to obtain the ZnFe @ C catalyst.
0.046g of Na is taken2CO31g of ZnFe @ C was impregnated with an equal volume of Na as source in 2.5g of aqueous solution (containing 0.5g of ethanol) and dried overnight in a vacuum oven at 60 deg.C to give a 2% Na-ZnFe @ C catalyst.
S2, preparing CuZnAl catalytic CO by coprecipitation method2And (3) carrying out hydrogenation reaction to generate catalytic active components of oxygen-containing intermediates such as formyl or formyl and the like, then carrying out alkali metal impregnation on the catalytic active components, and drying to obtain the 5% K-CuZnAl catalyst. The specific experimental process is as follows:
taking 24.2g of Cu (NO)3)2·3H2O,11.9g Zn(NO3)2·6H2O,5.0g Al(NO3)2·9H2O, 5g urea is dissolved in 200mL deionized water, stirred at 95 ℃ for 2h, and then left for aging for 24 h. And centrifuging the product, washing the product for 3 times by using deionized water, and then drying the product in a vacuum oven at 60 ℃ overnight to obtain the CuZnAl catalyst precursor.
And calcining the obtained precursor in a tubular furnace in an air atmosphere, wherein the calcining temperature is controlled to be 350 ℃ and the time is 1 h. And naturally cooling to room temperature to obtain the CuZnAl catalyst.
Taking 0.13g KNO3Dissolving the K source in 0.8g of deionized water, performing equal-volume impregnation on 1g of CuZnAl, and drying the CuZnAl in a vacuum oven at 60 ℃ overnight to obtain the 5% K-CuZnAl catalyst.
S3, coupling 2% of Na-ZnFe @ C with 5% of K-CuZnAl to obtain the Fe-based multifunctional catalyst. The specific experimental process is as follows:
tabletting 2% Na-ZnFe @ C catalyst under 10MPa, crushing, sieving and granulating to 20-40 meshes.
Tabletting 5% K-CuZnAl catalyst under 10MPa, crushing, sieving and granulating to 20-40 mesh.
0.1g of granulated 2% Na-ZnFe @ C and 0.2g of 5% K-CuZnAl catalyst were weighed respectively, mixed with 0.4g of quartz sand, and packed in a fixed bed reactor (inner diameter 6mm) at 400 ℃ in H2Reduction for 4H, H2The flow rate was 60 mL/min. After the temperature was reduced to the reaction temperature (320 ℃), the gas was switched to the reaction gas (3.04% Ar, 25.6% CO)2,71.36％H2) And the reaction was started by raising the pressure to the target pressure (5MPa) under the action of a back pressure valve. The catalytic reaction conditions and results are shown in table 3 below:
TABLE 3 catalytic reaction conditions and results of comparative example 2a
aReaction conditions are as follows: 320 ℃ and 5MPa (25.6% CO)2,71.36％H2,and 3.04％Ar),15mL min-1. The mass of the catalyst is as follows: 0.1g of 2% Na-ZnFe @ C,0.2g of 5% K-CuZnAl.
Othersb: propanol, butanol, and the like.
Comparative example 3
S1, carbonizing an Fe-based metal organic framework (ZnFe-MOFs), then impregnating with alkali metal, and drying to prepare the 2% Na-ZnFe @ C catalyst. The specific experimental process is as follows:
1mmol of Zn (NO)3)2.6H2O (0.297g) and 0.6g FeCl2.4H2Dissolving O (3mmol) in 50ml DMF, adding 0.22g triethylene diamine, and stirring for 30 minutes to prepare solution A; terephthalic acid (4.2mmol,0.70g) was dissolved in 10mL DMF to form solution B; adding the solution B into the solution A, stirring for 1h, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 h; after centrifugation, the product was washed 3 times with DMF and then dried overnight in a vacuum oven at 60 ℃ to give ZnFe-MOFs.
And carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. And naturally cooling to room temperature to obtain the ZnFe @ C catalyst.
0.046g of Na is taken2CO31g of ZnFe @ C was impregnated with an equal volume of Na as source in 2.5g of aqueous solution (containing 0.5g of ethanol) and dried overnight in a vacuum oven at 60 deg.C to give a 2% Na-ZnFe @ C catalyst.
S2, preparing CuZnAl catalytic CO by coprecipitation method2Hydrogenation reaction to generate catalytic active components of oxygen-containing intermediates such as formyl or formyl and the like. The specific experimental process is as follows:
taking 24.2g of Cu (NO)3)2·3H2O,11.9g Zn(NO3)2·6H2O,5.0g Al(NO3)2·9H2O, 5g urea is dissolved in 200mL deionized water, stirred at 95 ℃ for 2h, and then left for aging for 24 h. And centrifuging the product, washing the product for 3 times by using deionized water, and then drying the product in a vacuum oven at 60 ℃ overnight to obtain the CuZnAl catalyst precursor.
And calcining the obtained precursor in a tubular furnace in an air atmosphere, wherein the calcining temperature is controlled to be 350 ℃ and the time is 1 h. And naturally cooling to room temperature to obtain the CuZnAl catalyst.
S3, coupling 2% of Na-ZnFe @ C with a CuZnAl catalyst to obtain the Fe-based multifunctional catalyst. The specific experimental process is as follows:
tabletting 2% Na-ZnFe @ C catalyst under 10MPa, crushing, sieving and granulating to 20-40 meshes.
The CuZnAl catalyst is tabletted under 10MPa, and then crushed, sieved and granulated into 20-40 meshes.
0.1g of granulated 2% Na-ZnFe @ C and 0.1g of CuZnAl catalyst are respectively weighed, fully mixed with 0.4g of quartz sand, and filled in a fixed bed reactor (the inner diameter is 6mm) and the temperature is 400 ℃ under H2Reduction for 4H, H2The flow rate was 60 mL/min. After the temperature was reduced to the reaction temperature (320 ℃), the gas was switched to the reaction gas (3.04% Ar, 25.6% CO)2,71.36％H2) And the reaction was started by raising the pressure to the target pressure (5MPa) under the action of a back pressure valve. The catalytic reaction conditions and results are shown in table 4 below:
TABLE 4 catalytic reaction conditions and results of comparative example 3a
aReaction conditions are as follows: 320 ℃ and 5MPa (25.6% CO)2,71.36％H2,and 3.04％Ar),15mL min-1. The mass of the catalyst is as follows: 0.1g of 2% Na-ZnFe @ C,0.1g of CuZnAl.
Othersb: propanol, butanol, and the like.
Comparative example 4
S1, carbonizing an Fe-based metal organic framework (ZnFe-MOFs), then impregnating with alkali metal, and drying to prepare the 2% Na-ZnFe @ C catalyst. The specific experimental process is as follows:
1mmol of Zn (NO)3)2.6H2O (0.297g) and 0.6g FeCl2.4H2Dissolving O (3mmol) in 50ml DMF, adding 0.22g triethylene diamine, and stirring for 30 minutes to prepare solution A; terephthalic acid (4.2mmol,0.70g) was dissolved in 10mL DMF to form solution B; adding the solution B into the solution A, stirring for 1h, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 h; after centrifugation, the product was washed 3 times with DMF and then dried overnight in a vacuum oven at 60 ℃ to give ZnFe-MOFs.
And carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. And naturally cooling to room temperature to obtain the ZnFe @ C catalyst.
0.046g of Na is taken2CO31g of ZnFe @ C was impregnated with an equal volume of Na as source in 2.5g of aqueous solution (containing 0.5g of ethanol) and dried overnight in a vacuum oven at 60 deg.C to give a 2% Na-ZnFe @ C catalyst.
S2, preparing CuZnAl catalytic CO by coprecipitation method2And (3) carrying out hydrogenation reaction to generate catalytic active components of oxygen-containing intermediates such as formyl or formyl and the like, then carrying out alkali metal impregnation on the catalytic active components, and drying to obtain the 1% K-CuZnAl catalyst. The specific experimental process is as follows:
taking 24.2g of Cu (NO)3)2·3H2O,11.9g Zn(NO3)2·6H2O,5.0g Al(NO3)2·9H2O, 5g urea is dissolved in 200mL deionized water, stirred at 95 ℃ for 2h, and then left for aging for 24 h. And centrifuging the product, washing the product for 3 times by using deionized water, and then drying the product in a vacuum oven at 60 ℃ overnight to obtain the CuZnAl catalyst precursor.
And calcining the obtained precursor in a tubular furnace in an air atmosphere, wherein the calcining temperature is controlled to be 350 ℃ and the time is 1 h. And naturally cooling to room temperature to obtain the CuZnAl catalyst.
Taking 0.026g KNO3Dissolving the K source in 0.8g of deionized water, performing equal-volume impregnation on 1g of CuZnAl, and drying the CuZnAl in a vacuum oven at 60 ℃ overnight to obtain the 1% K-CuZnAl catalyst.
S3, coupling 2% of Na-ZnFe @ C with 1% of K-CuZnAl to obtain the Fe-based multifunctional catalyst. The specific experimental process is as follows:
tabletting 2% Na-ZnFe @ C catalyst under 10MPa, crushing, sieving and granulating to 20-40 meshes.
Tabletting 1% of K-CuZnAl catalyst under 10MPa, crushing, sieving and granulating to 20-40 meshes.
0.1g of granulated 2% Na-ZnFe @ C and 0.1g of granulated 1% K-CuZnAl catalyst were weighed respectively, mixed with 0.4g of quartz sand, and packed in a fixed bed reactor (inner diameter 6mm) at 400 ℃ in H2Reduction for 4H, H2The flow rate was 60 mL/min. After the temperature was reduced to the reaction temperature (320 ℃), the gas was switched to the reaction gas (3.04% Ar, 25.6% CO)2,71.36％H2) And the reaction was started by raising the pressure to the target pressure (5MPa) under the action of a back pressure valve. The catalytic reaction conditions and results are shown in table 5 below:
TABLE 5 catalytic reaction conditions and results in comparative example 4a
aReaction conditions are as follows: 320 ℃ and 5MPa (25.6% CO)2,71.36％H2,and 3.04％Ar),15mL min-1. The mass of the catalyst is as follows: 0.1g of 2% Na-ZnFe @ C,0.1g of 1% K-CuZnAl.
Othersb: propanol, butanol, and the like.
Comparative example 5
S1, carbonizing an Fe-based metal organic framework (ZnFe-MOFs), then impregnating with alkali metal, and drying to prepare the 2% Na-ZnFe @ C catalyst. The specific experimental process is as follows:
1mmol of Zn (NO)3)2.6H2O (0.297g) and 0.6g FeCl2.4H2Dissolving O (3mmol) in 50ml DMF, adding 0.22g triethylene diamine, and stirring for 30 minutes to prepare solution A; terephthalic acid (4.2mmol,0.70g) was dissolved in 10mL DMF to form solution B; adding the solution B into the solution A, stirring for 1h, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 h; after centrifugation, the product was washed 3 times with DMF and then dried overnight in a vacuum oven at 60 ℃ to give ZnFe-MOFs.
And carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. And naturally cooling to room temperature to obtain the ZnFe @ C catalyst.
0.046g of Na is taken2CO31g of ZnFe @ C was impregnated with an equal volume of Na as source in 2.5g of aqueous solution (containing 0.5g of ethanol) and dried overnight in a vacuum oven at 60 deg.C to give a 2% Na-ZnFe @ C catalyst.
S2, preparing CuZnAl catalytic CO by coprecipitation method2And (3) carrying out hydrogenation reaction to generate catalytic active components of oxygen-containing intermediates such as formyl or formyl and the like, then carrying out alkali metal impregnation on the catalytic active components, and drying to obtain the 5% K-CuZnAl catalyst. The specific experimental process is as follows:
taking 24.2g of Cu (NO)3)2·3H2O,11.9g Zn(NO3)2·6H2O,5.0g Al(NO3)2·9H2O, 5g urea is dissolved in 200mL deionized water, stirred at 95 ℃ for 2h, and then left for aging for 24 h. And centrifuging the product, washing the product for 3 times by using deionized water, and then drying the product in a vacuum oven at 60 ℃ overnight to obtain the CuZnAl catalyst precursor.
And calcining the obtained precursor in a tubular furnace in an air atmosphere, wherein the calcining temperature is controlled to be 350 ℃ and the time is 1 h. And naturally cooling to room temperature to obtain the CuZnAl catalyst.
Taking 0.13g KNO3Dissolving the K source in 0.8g of deionized water, performing equal-volume impregnation on 1g of CuZnAl, and drying the CuZnAl in a vacuum oven at 60 ℃ overnight to obtain the 5% K-CuZnAl catalyst.
S3, coupling 2% of Na-ZnFe @ C with 5% of K-CuZnAl to obtain the Fe-based multifunctional catalyst. The specific experimental process is as follows:
mixing 2% Na-ZnFe @ C and 5% K-CuZnAl catalyst (mass ratio is 1: 1), grinding for 10 minutes, and naming as 2% Na-ZnFe @ C and 5% K-CuZnAl. The catalyst is tabletted under 10MPa, and then crushed, sieved and granulated into 20-40 meshes.
0.2g of granulated 2% Na-ZnFe @ C was weighed&5% of K-CuZnAl catalyst, 0.4g of quartz sand, and filling the mixture in a fixed bed reactor (the inner diameter is 6mm) at 400 ℃ under H2Reduction for 4H, H2The flow rate was 60 mL/min. After the temperature was reduced to the reaction temperature (320 ℃), the gas was switched to the reaction gas (3.04% Ar, 25.6% CO)2,71.36％H2) And the reaction was started by raising the pressure to the target pressure (5MPa) under the action of a back pressure valve. The catalytic reaction conditions and results are shown in table 6 below:
TABLE 6 catalytic reaction conditions and results of comparative example 5a
Comparative example 6
S1, carbonizing an Fe-based metal organic framework (ZnFe-MOFs), then impregnating with alkali metal, and drying to obtain the 2% Na-ZnFe @ C catalyst. The specific experimental process is as follows:
1mmol of Zn (NO)3)2.6H2O (0.297g) and 0.6g FeCl2.4H2Dissolving O (3mmol) in 50ml DMF, adding 0.22g triethylene diamine, and stirring for 30 minutes to prepare solution A; terephthalic acid (4.2mmol,0.70g) was dissolved in 10mL DMF to form solution B; adding the solution B into the solution A, stirring for 1h, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 h; the product was centrifuged, washed 3 times with DMF and then dried in a vacuum oven at 60 deg.CAnd drying overnight to obtain ZnFe-MOFs.
And carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. And naturally cooling to room temperature to obtain the ZnFe @ C catalyst.
0.046g of Na is taken2CO31g of ZnFe @ C was impregnated with an equal volume of Na as source in 2.5g of aqueous solution (containing 0.5g of ethanol) and dried overnight in a vacuum oven at 60 deg.C to give a 2% Na-ZnFe @ C catalyst.
S2, preparing CuZnAl catalytic CO by coprecipitation method2And (3) carrying out hydrogenation reaction to generate catalytic active components of oxygen-containing intermediates such as formyl or formyl and the like, then carrying out alkali metal impregnation on the catalytic active components, and drying to obtain the 5% K-CuZnAl catalyst. The specific experimental process is as follows:
taking 24.2g of Cu (NO)3)2·3H2O,11.9g Zn(NO3)2·6H2O,5.0g Al(NO3)2·9H2O, 5g urea is dissolved in 200mL deionized water, stirred at 95 ℃ for 2h, and then left for aging for 24 h. And centrifuging the product, washing the product for 3 times by using deionized water, and then drying the product in a vacuum oven at 60 ℃ overnight to obtain the CuZnAl catalyst precursor.
And calcining the obtained precursor in a tubular furnace in an air atmosphere, wherein the calcining temperature is controlled to be 350 ℃ and the time is 1 h. And naturally cooling to room temperature to obtain the CuZnAl catalyst.
Taking 0.13g KNO3As a source of K, dissolved in 0.8g of deionized water. 1g of CuZnAl is dipped in the same volume and dried in a vacuum oven at 60 ℃ overnight to obtain the 5 percent K-CuZnAl catalyst.
S3, coupling 2% of Na-ZnFe @ C with 5% of K-CuZnAl to obtain the Fe-based multifunctional catalyst. The specific experimental process is as follows:
tabletting 2% Na-ZnFe @ C catalyst under 10MPa, crushing, sieving and granulating to 20-40 meshes.
Tabletting 5% K-CuZnAl catalyst under 10MPa, crushing, sieving and granulating to 20-40 mesh.
The two catalyst components which are respectively granulated are carried out by adopting a double-bed modeAnd (6) filling. 0.1g of 2% Na-ZnFe @ C catalyst is weighed, fully mixed with 0.2g of quartz sand, filled in the upper layer (the inner diameter is 6mm) of a fixed bed reactor, and the middle part is separated by quartz wool to further increase the distance between catalyst components. 0.1g of 5% K-CuZnAl catalyst was weighed, mixed well with 0.2g of quartz sand, and packed in the lower layer (inner diameter 6mm) of the fixed bed reactor. The multifunctional catalyst in the filling mode is named as 2% Na-ZnFe @ C | | | 5% K-CuZnAl. H at 400 DEG C2Reduction for 4H, H2The flow rate was 60 mL/min. After the temperature was reduced to the reaction temperature (320 ℃), the gas was switched to the reaction gas (3.04% Ar, 25.6% CO)2,71.36％H2) And the reaction was started by raising the pressure to the target pressure (5MPa) under the action of a back pressure valve. The catalytic reaction conditions and results are shown in table 7 below:
TABLE 7 catalytic reaction conditions and results in comparative example 6a
aReaction conditions are as follows: 320 ℃ and 5MPa (25.6% CO)2,71.36％H2,and 3.04％Ar),15mL min-1. The mass of the catalyst is as follows: 0.2g of 2% Na-ZnFe @ C | | | 5% K-CuZnAl.
Othersb: propanol, butanol, and the like.
Comparative example 7
S1, carbonizing an Fe-based metal organic framework (ZnFe-MOFs), then impregnating with alkali metal, and drying to prepare the 2% Na-ZnFe @ C catalyst. The specific experimental process is as follows:
1mmol of Zn (NO)3)2.6H2O (0.297g) and 0.6g FeCl2.4H2Dissolving O (3mmol) in 50ml DMF, adding 0.22g triethylene diamine, and stirring for 30 minutes to prepare solution A; terephthalic acid (4.2mmol,0.70g) was dissolved in 10mL DMF to form solution B; adding the solution B into the solution A, stirring for 1h, transferring into a hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 24 h; after centrifugation, the product was washed 3 times with DMF and then dried overnight in a vacuum oven at 60 ℃ to give ZnFe-MOFs.
And carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. And naturally cooling to room temperature to obtain the ZnFe @ C catalyst.
0.046g of Na is taken2CO31g of ZnFe @ C was impregnated with an equal volume of Na as source in 2.5g of aqueous solution (containing 0.5g of ethanol) and dried overnight in a vacuum oven at 60 deg.C to give a 2% Na-ZnFe @ C catalyst.
S2, preparing CuZnAl catalytic CO by coprecipitation method2And (3) carrying out hydrogenation reaction to generate catalytic active components of oxygen-containing intermediates such as formyl or formyl and the like, then carrying out alkali metal impregnation on the catalytic active components, and drying to obtain the 5% K-CuZnAl catalyst. The specific experimental process is as follows:
taking 24.2g of Cu (NO)3)2·3H2O,11.9g Zn(NO3)2·6H2O,5.0g Al(NO3)2·9H2O, 5g urea is dissolved in 200mL deionized water, stirred at 95 ℃ for 2h, and then left for aging for 24 h. And centrifuging the product, washing the product for 3 times by using deionized water, and then drying the product in a vacuum oven at 60 ℃ overnight to obtain the CuZnAl catalyst precursor.
And calcining the obtained precursor in a tubular furnace in an air atmosphere, wherein the calcining temperature is controlled to be 350 ℃ and the time is 1 h. And naturally cooling to room temperature to obtain the CuZnAl catalyst.
Taking 0.13g KNO3Dissolving the K source in 0.8g of deionized water, performing equal-volume impregnation on 1g of CuZnAl, and drying the CuZnAl in a vacuum oven at 60 ℃ overnight to obtain the 5% K-CuZnAl catalyst.
S3, coupling 2% of Na-ZnFe @ C with 5% of K-CuZnAl to obtain the Fe-based multifunctional catalyst. The specific experimental process is as follows:
tabletting 2% Na-ZnFe @ C catalyst under 10MPa, crushing, sieving and granulating to 20-40 meshes.
Tabletting 5% K-CuZnAl catalyst under 10MPa, crushing, sieving and granulating to 20-40 mesh.
The two catalyst components which are respectively granulated are filled in a double-bed mode. 0.1g of 5 percent K-CuZnAl catalyst is weighed, fully mixed with 0.2g of quartz sand and filled in a fixed bed reactorUpper layer (inner diameter 6 mm). The separation of the middle by quartz wool further increases the distance between the catalyst components. 0.1g of 2 percent Na-ZnFe @ C catalyst is weighed, fully mixed with 0.2g of quartz sand, filled in the lower layer (the inner diameter is 6mm) of the fixed bed reactor, and the multifunctional catalyst in the filling mode is named as 5 percent K-CuZnAl | |2 percent Na-ZnFe @ C. H at 400 DEG C2Reduction for 4H, H2The flow rate was 60 mL/min. After the temperature was reduced to the reaction temperature (320 ℃), the gas was switched to the reaction gas (3.04% Ar, 25.6% CO)2,71.36％H2) And the reaction was started by raising the pressure to the target pressure (5MPa) under the action of a back pressure valve. The catalytic reaction conditions and results are shown in table 8 below:
TABLE 8 catalytic reaction conditions and results in comparative example 7a
aReaction conditions are as follows: 320 ℃ and 5MPa (25.6% CO)2,71.36％H2,and 3.04％Ar),15mL min-1. The mass of the catalyst is as follows: 0.2g of 5% K-CuZnAl 2% Na-ZnFe @ C.
Othersb: propanol, butanol, and the like.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A Fe-based multifunctional catalyst is formed by coupling a Na-ZnFe @ C catalyst and a K-CuZnAl catalyst;
the Na-ZnFe @ C catalyst is a sodium ion-loaded iron carbide-based metal organic framework material ZnFe-MOFs;
the K-CuZnAl catalyst is a CuZnAl catalyst loaded with potassium ions.
2. The Fe-based multifunctional catalyst according to claim 1, characterized in that the mass ratio of the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst is 1: 0-1: 3.
3. the Fe-based multifunctional catalyst of claim 1, wherein the Na-ZnFe @ C catalyst has a sodium ion loading of 0.1 to 5 wt%;
in the K-CuZnAl catalyst, the load of potassium ions is 0.1-10 wt%.
4. The Fe-based multifunctional catalyst according to claim 1, wherein the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst are coupled in any one of the methods 1) to 4):
method 1): mixing the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst, and then carrying out extrusion forming, crushing and sieving;
method 2) respectively carrying out extrusion forming, crushing and sieving on the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst, and then mixing the two;
method 3) respectively carrying out extrusion forming, crushing and sieving on a Na-ZnFe @ C catalyst and a K-CuZnAl catalyst, and then filling in a double-bed mode, wherein the Na-ZnFe @ C catalyst is arranged on the upper layer, and the K-CuZnAl catalyst is arranged on the lower layer;
method 4) respectively carrying out extrusion forming, crushing and sieving on the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst, and then filling in a double-bed mode, wherein the Na-ZnFe @ C catalyst is arranged at the lower layer, and the K-CuZnAl catalyst is arranged at the upper layer.
5. A method of preparing an Fe-based multifunctional catalyst as claimed in any one of claims 1 to 4, comprising the steps of:
s1) carbonizing the Fe-based metal organic framework, and then dipping the Fe-based metal organic framework by a sodium ion solution to obtain a Na-ZnFe @ C catalyst;
s2) carrying out potassium ion solution impregnation on the CuZnAl catalyst to obtain a K-CuZnAl catalyst;
s3) coupling the Na-ZnFe @ C catalyst and the K-CuZnAl catalyst to obtain the Fe-based multifunctional catalyst.
6. The preparation method according to claim 5, wherein the temperature of the carbonization treatment in S1) is 500-800 ℃; the time is 1-6 h.
7. The production method according to claim 5, wherein the sodium ion solution is an aqueous solution of sodium carbonate;
the potassium ion solution is potassium carbonate aqueous solution.
8. The method of claim 5, wherein the Fe-based metal-organic framework is prepared by: mixing DMF solutions of a zinc source compound, an iron source compound and triethylene diamine and DMF solution of terephthalic acid, and carrying out hydrothermal reaction to obtain a Fe-based metal organic framework;
the CuZnAl catalyst is prepared according to the following method: mixing a copper source compound, a zinc source compound, an aluminum source compound and urea in deionized water, keeping the mixture at the temperature of 60-100 ℃ for 1-5 h under a stirring state, and standing and aging the mixture for 12-24 h to obtain a CuZnAl catalyst precursor; and calcining the CuZnAl catalyst precursor in the air at the temperature of 300-600 ℃ for 1-3 h to obtain the CuZnAl catalyst.
9. The Fe-based multifunctional catalyst of any one of claims 1 to 4 or the Fe-based multifunctional catalyst prepared by the preparation method of any one of claims 5 to 8 as CO2The application of the catalyst for directly synthesizing ethanol by hydrogenation.
10. CO (carbon monoxide)2A method for directly synthesizing ethanol by hydrogenation, which takes the Fe-based multifunctional catalyst as claimed in any one of claims 1 to 4 or the Fe-based multifunctional catalyst prepared by the preparation method as claimed in any one of claims 5 to 8 as a catalyst.
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