CN110560153B - Aluminum-shared metal-zeolite bifunctional catalyst, and preparation method and application thereof - Google Patents
Aluminum-shared metal-zeolite bifunctional catalyst, and preparation method and application thereof Download PDFInfo
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- CN110560153B CN110560153B CN201910906918.5A CN201910906918A CN110560153B CN 110560153 B CN110560153 B CN 110560153B CN 201910906918 A CN201910906918 A CN 201910906918A CN 110560153 B CN110560153 B CN 110560153B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000010457 zeolite Substances 0.000 title claims abstract description 56
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 54
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 26
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000005751 Copper oxide Substances 0.000 claims abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 239000003570 air Substances 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910017773 Cu-Zn-Al Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- 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
- C07C29/154—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 copper, silver, gold, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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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
- Y02P20/00—Technologies relating to chemical industry
- 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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Abstract
The invention relates to environmental protection and CO2The technical field of hydrogenation catalysis, in particular to an aluminum shared metal-zeolite bifunctional catalyst, which comprises: Cu-MOx‑Al2O3Nanoparticles and nano ZSM-5 zeolite; m is a metal element, and Cu exists in the form of copper metal or copper oxide; the nano ZSM-5 zeolite grows in situ in the Cu-MOx‑Al2O3The surface of the nano particles, and the nano ZSM-5 zeolite and Cu-MOx‑Al2O3The nanoparticles share Al atoms. The nanometer ZSM-5 zeolite and the CMAl nanometer particles in the bifunctional catalyst share Al atoms, and are tightly combined by taking Al as a medium, so that the distance between two catalyst components in the traditional bifunctional catalyst is greatly shortened, the synergistic effect of the two catalyst components is obviously enhanced, and the catalytic performance is optimized. The invention also relates to a preparation method and application of the aluminum-shared metal-zeolite bifunctional catalyst.
Description
Technical Field
The invention relates to environmental protection and CO2The technical field of hydrogenation catalysis, in particular to a catalyst for CO2An aluminum-shared metal-zeolite bifunctional catalyst for hydrogenation reaction, a preparation method and application thereof.
Background
There is evidence that human activities are the major cause of the present global climate crisis, especially excessive emission of CO into the atmosphere2The effect is greatest. Compared with the traditional emission reduction methods such as improving the energy efficiency and developing renewable energy sources, the method directly uses CO through catalytic hydrogenation reaction2The technological route for conversion to lower carbon chemicals (methanol, dimethyl ether, aromatics, etc.) is receiving increasing attention. It can effectively reduce CO2The emission amount can promote the development of industries such as clean energy and chemical engineering, and the like, thereby having wide application prospect.
CO2The conversion process to lower carbon chemicals mainly comprises two reaction steps, namely a reversible Methanol Synthesis (MS) reaction and an irreversible Methanol Dehydration (MD) reaction. Wherein, the MS reaction needs to be carried out at high temperature (200-300 ℃) and high pressure (3-10 MPa), and the common catalyst is Cu-ZnO-Al2O3A copper-based catalyst as represented; the MD reaction needs to be carried out at a high temperature (300-350 ℃), and the commonly used catalyst is a solid acid catalyst, such as a zeolite molecular sieve, active alumina and the like. The two-step method is to realize CO2In the traditional method for synthesizing low-carbon chemicals, raw gas firstly passes through a hydrogenation catalyst bed layer to generate methanol, and then passes through a dehydration catalyst bed layer to generate liquid fuel. However, since the reaction conditions of the two-step reaction are different, different reaction beds are often required to be designed and constructed, which leads to increased cost and is not favorable for improving economic benefits. In response to this problem, the skilled person further proposes a solution to the one-step process, where it is desirable to simultaneously perform both the MS and MD reactions in the same reaction bed. This will significantly improve the economics of the processHowever, higher demands are also made on the catalyst.
In the prior art, the direct mechanical mixing of the hydrogenation catalyst and the dehydration catalyst (i.e. bifunctional catalysis) is the most common technical solution. The invention patent CN104368378A discloses a method for directly preparing a dimethyl ether catalyst by carbon dioxide hydrogenation, which adopts a mechanical grinding and mixing mode to uniformly mix a copper-based catalyst and HZSM-5 zeolite for preparing dimethyl ether by catalytic hydrogenation. In order to improve the performance of the catalyst, the invention patent CN1356163A discloses a method for directly preparing dimethyl ether by synthesis gas, and a coprecipitation deposition method is adopted to load metal oxide on gamma-alumina, so that the distance between a hydrogenation active component and a dehydration active component is shortened; the invention patent CN102600852A discloses a catalyst for preparing dimethyl ether, a preparation method and application thereof, wherein a precursor of an active component and a precursor of a zirconia-alumina mixed oxide are respectively prepared, then the precursor and the precursor are added into the same solution to be uniformly stirred, and a composite catalyst is obtained after drying, which is beneficial to uniform dispersion of the precursor and the precursor. Further, in patent CN102228834A, one or more of silica, activated carbon, γ -alumina and ZSM-5 are used as a carrier, and a volume fractional impregnation method is used to load active components on the catalyst carrier, and in patent CN104148083B and CN107970943A, an equivalent volume impregnation method is also used to load active metals on the activated carbon, so as to obtain the bifunctional catalyst for hydrogenation of unsaturated hydrocarbons. The method increases the specific surface area of the catalyst to a certain extent and optimizes the mass transfer process. In addition, researchers in the field have also developed a series of core-shell catalysts. The invention patent CN103212418A uses methanol to synthesize catalyst CuO-ZnO-Al2O3Dispersing the core in solution containing silicon source and additional aluminum source, and coating a layer of independent SiO on the surface of the original catalyst2-Al2O3And (4) shell layer. The invention patents CN101934232A and CN105170179A adopt a chemical uniform precipitation method to prepare the nuclear shell Cu-ZnO/HZSM-5 by taking copper nitrate, zinc nitrate and an HZSM-5 molecular sieve as raw materials, and the nuclear shell Cu-ZnO/HZSM-5 is used for directly synthesizing dimethyl ether by synthesis gas. Although the core-shell type catalyst shows good structural performance, the completely wrapped form is not beneficial to the discharge of products and is easy to be usedResulting in overheating of the core.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of poor synergistic effect, low target product selectivity and the like of the existing bifunctional catalyst, the invention provides an aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst, and a preparation method and application thereof.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in one aspect, the present invention provides an aluminum-shared metal-zeolite bifunctional catalyst comprising:
Cu-MOx-Al2O3nanoparticles and nano ZSM-5 zeolite;
m is a metal element, and Cu exists in the form of copper metal or copper oxide;
the nano ZSM-5 zeolite grows in situ in the Cu-MOx-Al2O3The surface of the nano particles, and the nano ZSM-5 zeolite and Cu-MOx-Al2O3The nanoparticles share Al atoms.
ZSM-5 molecular sieve has wide application in China, and can increase the content of olefin in gas molecules when used as a catalyst.
In one embodiment of the present invention, the expression of the bifunctional catalyst is: (Cu)xMyAlzO0.5*m*y+1.5*z)·[Hn(AlnSi96-nO192)](ii) a Wherein x, y, z and n are natural numbers, and n is less than 27; wherein, M is Zn, Zr, Mn, Ce or Co, and M is the valence state of the metal ion M.
In one embodiment of the present invention, the Cu-MOx-Al2O3The nanoparticles have an average particle size of not more than 100nm, the ZSM-5 zeolite has an average particle size of not more than 200nm, and the ZSM-5 zeolite is bound to the Cu-MOx-Al2O3The surface of the nanoparticles.
In another aspect, the present invention also provides a method for preparing an aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst, comprising the steps of:
s1 preparation of Cu-containing composition2+、Mm+And Al3+Mixed metal salt solution of (4);
s2, dripping the metal salt solution obtained in the step S1 into the precipitator solution which is continuously stirred until the pH value of the solution is stabilized between 7 and 8 to obtain a mixed solution;
s3, standing and aging the mixed solution in the S2, and calcining a filter cake obtained after filtering, washing and drying at high temperature to obtain the hydrogenation catalyst Cu-MOx-Al2O3Powder (abbreviated CMAl);
s4 preparation of Cu-MO from S3x-Al2O3Uniformly dispersing the powder in deionized water, sequentially adding a template agent and sodium chloride, and continuously stirring at room temperature;
s5 is carried out by Cu-MO according to the requirement of the preset silicon-aluminum ratio in ZSM-5 zeolitex-Al2O3Aluminum in the powder is the only aluminum source, a proper amount of silicon source is dropwise added into the solution obtained in S4, the solution is stirred for 0.5 to 5 hours at room temperature and then stirred under heating, and after full stirring, the solution is kept stand and aged at room temperature;
s6, transferring the aged mixed solution in the S5 into a high-pressure reaction kettle, carrying out hydrothermal reaction for 2-4 days under a heating condition, cooling, filtering, washing and drying to obtain a catalyst precursor;
and S7, calcining the catalyst precursor obtained in the step S6 at high temperature to remove the template agent, then placing the catalyst precursor in an ammonium salt solution for ion exchange for 3-5 times, washing, filtering, drying and then calcining again to obtain the aluminum-shared metal-zeolite bifunctional catalyst (ASMZ).
Preferably, in step S1, the mixed metal salt solution is subjected to ultrasonic treatment for 10-30 min.
Preferably, in step S2, the precipitant solution is kept at a constant temperature of 45-70 ℃.
Preferably, in step S2, the dropping rate of the metal salt solution is 1-5 mL/min.
Preferably, in the step S3, the aging temperature is 45-70 ℃; the calcination temperature of the filter cake is 350-500 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
Preferably, in step S4, the template agent is one or more selected from the group consisting of, but not limited to, tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia water, and pyridine.
Preferably, in step S4, stirring is continued at room temperature for 0.5-10 h.
Preferably, in step S5, the stirring under heating means that the temperature is 75-90 ℃ and the stirring time is 1-10 h.
Preferably, in step S5, Cu-MO is usedx-Al2O3The aluminum in the powder is the only aluminum source, and a silicon source is added to ensure that the silicon-aluminum ratio is not lower than 5.
Preferably, in step S5, the silicon source includes, but is not limited to, tetraethoxysilane, monodisperse SiO2One or more of silica sol and white carbon black.
Preferably, in step S6, the temperature of the hydrothermal reaction is 120-180 ℃. The lower the hydrothermal reaction temperature is, the longer the reaction time is required; the hydrothermal reaction is preferably carried out with stirring.
Preferably, in step S7, the calcination temperature for removing the template agent is 450-600 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
Preferably, in step S7, the ammonium salt used for ammonium ion exchange includes, but is not limited to, one or more of ammonium chloride, ammonium nitrate and aqueous ammonia.
Preferably, in step S7, the re-calcination temperature is 250-500 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
In addition, the invention also relates to the application of the aluminum shared metal-zeolite (ASMZ) bifunctional catalyst to CO2And (3) carrying out catalytic hydrogenation to prepare methanol and/or dimethyl ether.
(III) advantageous effects
The invention has the beneficial effects that:
the invention provides an aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst, which is prepared by mixing nano ZSM-5 zeolite and Cu-MO in the bifunctional catalyst based on the prior artx-Al2O3Al atoms are shared among the nano particles (abbreviated as CMAl), and the nano particles and the CMAl are tightly combined by taking the Al as a medium, so that the distance between two catalyst components in the traditional bifunctional catalyst is greatly shortened, the synergistic effect of the catalyst is obviously enhanced, and the catalytic performance is optimized. At present, no report related to the aluminum shared metal-zeolite bifunctional catalyst is found.
In addition, the invention also provides a method for preparing the aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst, which can effectively control the sizes of the CMAl catalyst and the ZSM-5 zeolite and realize the controllable growth of the latter on the basis of the former.
Drawings
FIG. 1 is a schematic representation of the microstructure of an aluminum-shared metal-zeolite (ASMZ) dual-function catalyst of the present invention.
Figure 2 is an XRD spectrum of the ASMZ bifunctional catalyst of example 1 of the present invention.
FIG. 3 is an SEM photograph of an ASMZ bifunctional catalyst of example 1 of the present invention.
FIG. 4 is an EDX spectrum of an ASMZ bifunctional catalyst of example 1 of the present invention.
FIG. 5 is a graph of the catalytic performance of the ASMZ dual-function catalyst of example 1 of the present invention as a function of time.
[ description of reference ]
10. A zeolite; 20. CMAl nanoparticles; 21. an Al atom; 22. cu atoms.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The present invention for the first time proposes an aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst whose microstructure can be seen in FIG. 1. The dual-function catalyst comprises two parts, wherein one part is a copper 22, metal oxide and alumina heterogeneous composite catalyst, namely Cu-MOx-Al2O3Nanoparticles 20, another part of zeolite 10, and in-situ growth of zeolite 10 in Cu-MOx-Al2O3On the nanoparticles 20 (i.e., CMAl), the aluminum atoms 21 that form the zeolite 10 also form Cu-MOx-Al2O3The aluminum atoms of the nanoparticles 20, i.e., the zeolite 10 and the shared aluminum atoms 21 of the CMAl nanoparticles 20. The two parts of the bifunctional catalyst are tightly combined by the combination point of the aluminum atom 21, so that the distance between the two catalyst components in the traditional bifunctional catalyst is greatly shortened, the synergistic effect of the bifunctional catalyst is obviously enhanced, and the catalytic performance is optimized. In the catalyst, Cu is present as copper metal or copper oxide, possibly 0, 1 and 2.
To prepare the aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst, the present invention provides the following preparation:
s1 preparation of Cu-containing alloy2+、Mm+And Al3+Mixing metal salt solution and carrying out ultrasonic pretreatment for 10-30 min.
S2, keeping the temperature of the precipitant solution at 45-70 ℃, and slowly dripping the solution obtained in the step S1 into the precipitant solution under continuous stirring at the dripping speed of 1-5mL/min until the pH value of the solution is stabilized between 7 and 8.
S3, after the dropwise addition is finished, standing and aging the mixed solution in the S2 at the aging temperature of 45-70 ℃, and calcining the filter cake obtained after filtering, washing and drying at the high temperature of 350-500 ℃, wherein the calcining atmosphere is air, nitrogen or argon, and the calcining time is 4-6h, so that the hydrogenation catalyst CMAl is obtained.
S4, uniformly dispersing the CMAl powder obtained in the S3 in deionized water, sequentially adding a template and sodium chloride, and continuously stirring for 1h at room temperature; the template agent includes, but is not limited to, one or more of tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia water, and pyridine.
And S5, according to the requirement on the silicon-aluminum ratio of the ZSM-5 zeolite, taking aluminum in CMAl as a unique aluminum source, dropwise adding a proper amount of silicon source into the solution obtained in the S4, stirring for 0.5h at room temperature, then stirring for 1h at the temperature of 75-90 ℃, cooling to room temperature, and standing for aging. The silicon-aluminum ratio of the ZSM-5 zeolite is not less than 5; silicon sources include, but are not limited to, ethyl orthosilicate, monodisperse SiO2Silicon, siliconOne or more of sol and white carbon black.
And S6, transferring the aged mixed solution in the S5 to a high-pressure reaction kettle, carrying out hydrothermal reaction for 2-4 days at 120-180 ℃, filtering, washing and drying to obtain a catalyst precursor.
Generally, the hydrothermal reaction temperature is, and the lower the hydrothermal reaction temperature is, the longer the reaction time is required; stirring may be accompanied with hydrothermal reaction.
S7, calcining the catalyst precursor obtained in the step S6 at the temperature of 450-600 ℃ for 4-6 hours to remove the template agent, wherein the calcining atmosphere is air, nitrogen or argon; and then carrying out ion exchange on the calcined product in an ammonium salt solution for 3-5 times, washing, filtering, drying, calcining again at the temperature of 250-500 ℃, calcining for 4-6h in air, nitrogen or argon atmosphere, and calcining to obtain the product of the aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst. The ammonium salt used for ammonium ion exchange includes, but is not limited to, one or a mixture of ammonium chloride, ammonium nitrate and ammonia water.
To further demonstrate the advantages and technical effects of the aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst of the present invention, reference is made to the following examples.
Preparation example
Example 1
This example provides a specific aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst prepared as follows:
(1) adding Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O、Al(NO3)3·9H2Dissolving O in deionized water according to the molar ratio of Cu to Zn to Al of 6 to 3 to 1, preparing 100mL of 1mol/L metal salt solution, and carrying out ultrasonic treatment for 30 min;
(2) mixing Na2CO3Dissolving in deionized water to prepare 250mL of 1mol/L solution; mixing Na2CO3The solution is heated to 55 ℃ in a water bath, and the metal salt solution is dripped dropwise under magnetic stirring until the pH value is stabilized at 7-8.
(3) After complete precipitation, aging at 55 ℃ overnight, filtering, washing, and drying a filter cake sample at 120 ℃ for 12h to obtain a CZAl precursor; the filter cake sample was calcined at 400 ℃ for 4h to give sample CZAl.
(4) Dissolving the CZAl in deionized water, dropwise adding tetrapropylammonium hydroxide, uniformly stirring, adding NaCl, and placing the mixed solution in a room-temperature environment to stir for 1 h.
(5) And (3) dropwise adding ethyl orthosilicate into the mixed solution according to the molar ratio of Si to Al being 20, uniformly mixing, stirring for 0.5h at room temperature, then placing the mixture into an oil bath at the temperature of 80 ℃, stirring for 1h, fully stirring, and standing and aging for 20h at room temperature.
(6) Transferring the obtained solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 48h at 180 ℃; and cooling, suction filtering, washing and drying to obtain the bifunctional catalyst precursor.
(7) Calcining the precursor of the bifunctional catalyst for 5 hours at 550 ℃ in an air atmosphere to remove the template agent; and (3) carrying out ion exchange on the calcined product in 0.2mmol/L ammonium chloride solution for 3 times (the solid-to-liquid ratio is less than 1:100) at 50 ℃, carrying out suction filtration, washing and drying, and calcining for 5 hours at 500 ℃ in air atmosphere to remove ammonium ions, thus obtaining the ASMZ bifunctional catalyst product.
Example 2
This example provides a specific aluminum-sharing metal-zeolite (ASMZ) bifunctional catalyst prepared as follows:
(1) adding Cu (NO)3)2·3H2O、Zn(NO3)2·6H2O、Al(NO3)3·9H2Dissolving O in deionized water according to the molar ratio of Cu to Zn to Al of 6 to 3 to 1, preparing 100mL of 1mol/L metal salt solution, and carrying out ultrasonic treatment for 30 min.
(2) Mixing Na2CO3Dissolving in deionized water to prepare 250mL of 1mol/L solution; mixing Na2CO3The solution is heated to 55 ℃ in a water bath, and the metal salt solution is dripped dropwise under magnetic stirring until the pH value is stabilized at 7-8.
(3) After complete precipitation, aging at 55 ℃ overnight, filtering, washing, and drying a filter cake sample at 120 ℃ for 12h to obtain a CZAl precursor; the filter cake sample was calcined at 400 ℃ for 4h to give sample CZAl.
(4) Dissolving the CZAl in deionized water, dropwise adding tetrapropylammonium hydroxide, uniformly stirring, adding NaCl, and placing the mixed solution in a room-temperature environment to stir for 1 h.
(5) And (2) dropwise adding ethyl orthosilicate into the mixed solution according to the molar ratio of Si to Al of 10, uniformly mixing, stirring for 0.5h at room temperature, then placing the mixture into an oil bath at the temperature of 80 ℃, stirring for 1h, fully stirring, and standing and aging for 20h at room temperature.
(6) Transferring the obtained solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 48h at 180 ℃; and cooling, suction filtering, washing and drying to obtain the bifunctional catalyst precursor.
(7) Calcining the precursor of the bifunctional catalyst for 5 hours at 550 ℃ in an air atmosphere to remove the template agent; and (3) performing ion exchange on the calcined product in 0.2mmol/L ammonium chloride solution for 3 times (the solid-to-liquid ratio is less than 1:100) at 50 ℃, performing suction filtration, washing and drying, and calcining for 5 hours at 500 ℃ in air atmosphere to remove ammonium ions to obtain the ASMZ bifunctional catalyst product, wherein the molar ratio of Si to Al in the product is about 10.0, and the product has a good microstructure.
Activation, characterization and catalytic Performance testing of catalysts
Activation of the catalyst
Activation of the ASMZ dual-function catalyst is achieved in a reducing gas atmosphere. First, the bifunctional catalyst powder prepared in example 1-2 was tableted at 60MPa (without adding a binder) to prepare catalyst pellets having a diameter of about 0.5 mm; keeping the temperature of the catalyst pellets at 200-350 ℃ for 2-6 h in a hydrogen atmosphere, and reducing CuO in the catalyst into Cu0(ii) a And naturally cooling the catalyst to room temperature in a reducing gas atmosphere or an inert gas atmosphere to obtain the activated ASMZ bifunctional catalyst. Experiments show that the activated catalyst can be stored for a long time under the anaerobic condition, and can be stored for more than 10 days even in dry air.
Compositional characterization of the catalyst
Inductively coupled plasma atomic emission spectroscopy (ICP) analysis showed that the overall Si element mass content of the ASMZ bifunctional catalyst prepared in example 1 was about 36.2%; x-ray photoelectron spectroscopy (XPS) analysis showed that the ASMZ bifunctional catalyst of example 1 showed about 34.3% of the mass content of the Si element. Both methods have similar values and both show that zeolite content has been present in the ASMZ dual-function catalyst prepared in example 1.
The result of low-temperature nitrogen adsorption and desorption tests shows that the BET specific surface area of the ASMZ dual-function catalyst of example 1 is as high as 260.3m2The/g, about 6.5 times that of the traditional Cu-Zn-Al catalyst, shows that the pore structure of the ASMZ dual-function catalyst is improved significantly.
Referring to fig. 2, the X-ray diffraction (XRD) results show that a distinct ZSM-5 characteristic diffraction peak is present in the ASMZ bifunctional catalyst of example 1, along with a CuO characteristic diffraction peak, indicating that the CZAl catalyst and ZSM-5 zeolite crystal structures are present in the ASMZ bifunctional catalyst, consistent with the expected results.
Referring to fig. 3, a Scanning Electron Microscope (SEM) photograph shows that both CZAl nanoparticles and cubic ZSM-5 zeolite are observed in the ASMZ bifunctional catalyst of example 1, confirming that the two are tightly bound together.
Referring to fig. 4, energy dispersive X-ray spectroscopy (EDX) results show that both copper and silicon are uniformly dispersed in the ASMZ bifunctional catalyst of example 1, but they tend to be dispersed in different regions, indicating that the CZAl catalyst and ZSM-5 zeolite are not fully composited, but instead grow on top of each other, conforming to the target structure illustrated in fig. 1.
In conclusion, the aluminum-shared metal-zeolite (ASMZ) bifunctional catalyst prepared by the invention has good structural performance and meets the expected design requirements.
Testing of catalytic Performance of the catalyst
The catalytic performance test of the ASMZ dual-function catalyst in example 1 was conducted in a fixed bed reactor. Single bed CO with 0.55g catalyst at 274 ℃ and 3.0MPa2The conversion rate is about 21.25%, and the total selectivity of methanol (MeOH) and dimethyl ether (DME) can reach about 85.3%, which is superior to the existing catalyst. After continuously reacting for 10 hours at 250 ℃ and 3.0MPa, all performance indexes of the product are allNo significant drop (see fig. 5) occurred, indicating good stability of the prepared ASMZ bifunctional catalyst.
Claims (9)
1. A method of making an aluminum shared metal-zeolite (ASMZ) dual-function catalyst comprising the steps of:
s1 preparation of Cu-containing composition2+、Mm+And Al3+Mixed metal salt solution of (4); wherein, M is Zn, Zr, Mn, Ce or Co, and M is the valence state of the metal ion M;
s2, dripping the metal salt solution obtained in the step S1 into the precipitator solution which is continuously stirred until the pH value of the solution is stabilized between 7 and 8 to obtain a mixed solution;
s3, standing and aging the mixed solution in the S2, and calcining a filter cake obtained after filtering, washing and drying at high temperature to obtain the hydrogenation catalyst Cu-MOx-Al2O3Powder;
s4 preparation of Cu-MO from S3x-Al2O3Uniformly dispersing the powder in deionized water, sequentially adding a template agent and sodium chloride, and continuously stirring at room temperature;
s5 is carried out by Cu-MO according to the requirement of the preset silicon-aluminum ratio in ZSM-5 zeolitex-Al2O3Aluminum in the powder is the only aluminum source, a proper amount of silicon source is dropwise added into the solution obtained in S4, the solution is stirred for 0.5 to 5 hours at room temperature and then stirred under heating, and after full stirring, the solution is kept stand and aged at room temperature;
s6, transferring the aged mixed solution in the S5 into a high-pressure reaction kettle, carrying out hydrothermal reaction for 2-4 days under a heating condition, cooling, filtering, washing and drying to obtain a catalyst precursor;
and S7, calcining the catalyst precursor obtained in the step S6 at high temperature to remove the template agent, then placing the catalyst precursor in an ammonium salt solution for ion exchange for 3-5 times, washing, filtering, drying and then calcining again to obtain the aluminum-shared metal-zeolite bifunctional catalyst.
2. The method of claim 1, wherein the aluminum-shared metal-zeolite bifunctional catalyst obtained in step S7 comprises:
Cu-MOx-Al2O3nanoparticles and nano ZSM-5 zeolite;
m is a metal element, and Cu exists in the form of copper metal or copper oxide;
the nano ZSM-5 zeolite grows in situ in the Cu-MOx-Al2O3The surface of the nano particles, and the nano ZSM-5 zeolite and Cu-MOx-Al2O3The nanoparticles share Al atoms.
3. The method of claim 2, wherein the Cu-MO is present in the compositionx-Al2O3The nanoparticles have an average particle size of not more than 100nm, the ZSM-5 zeolite has an average particle size of not more than 200nm, and the ZSM-5 zeolite is bound to the Cu-MOx-Al2O3The surface of the nanoparticles.
4. The method according to claim 1, wherein the precipitant solution is maintained at a constant temperature of 45-70 ℃ in step S2.
5. The method according to claim 1, wherein in step S3, the aging temperature is 45-70 ℃; the calcination temperature of the filter cake is 350-500 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
6. The method according to claim 1, wherein in step S4, the template is one or more selected from the group consisting of but not limited to tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, ethylenediamine, ammonia water, and pyridine.
7. The method of claim 1, wherein in step S5, Cu-MO is usedx-Al2O3Aluminum in the powder is the only aluminum source, and a silicon source is added to ensure that the silicon-aluminum ratio is not lower than 5;
the silicon source includes but is not limited to tetraethoxysilane and monodisperse SiO2One or more of silica sol and white carbon black.
8. The method of claim 1, wherein in step S7,
the calcination temperature for removing the template agent is 450-600 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon;
ammonium salts for ammonium ion exchange include, but are not limited to, one or more of ammonium chloride, ammonium nitrate and aqueous ammonia;
the secondary calcination temperature is 250-500 ℃, the calcination time is 4-6h, and the calcination atmosphere is air, nitrogen or argon.
9. Use of the aluminum-shared metal-zeolite bifunctional catalyst prepared by the preparation method of any one of claims 1 to 8 for CO2And (3) carrying out catalytic hydrogenation to prepare methanol and/or dimethyl ether.
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CN101934233A (en) * | 2010-09-13 | 2011-01-05 | 浙江大学 | Preparation method of catalyst Cu-ZnO/HZSM-5 for directly synthesizing dimethyl ether by using synthesis gas |
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CN108295892A (en) * | 2018-01-30 | 2018-07-20 | 贵州大学 | A kind of preparation method of γ-Al2O3@CuO-ZnO@ZSM-5 double-core shell catalysts |
CN108339565A (en) * | 2018-01-30 | 2018-07-31 | 贵州大学 | A kind of preparation method of ZnO-Al2O3@ZSM-5 catalyst with core-casing structure |
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