CN110075855B - Dehydrogenation catalyst and preparation method and application thereof - Google Patents
Dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN110075855B CN110075855B CN201910408652.1A CN201910408652A CN110075855B CN 110075855 B CN110075855 B CN 110075855B CN 201910408652 A CN201910408652 A CN 201910408652A CN 110075855 B CN110075855 B CN 110075855B
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 169
- 239000003054 catalyst Substances 0.000 title claims abstract description 161
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 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 271
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 155
- 238000003756 stirring Methods 0.000 claims description 142
- 239000003513 alkali Substances 0.000 claims description 87
- 239000003607 modifier Substances 0.000 claims description 77
- 239000002253 acid Substances 0.000 claims description 69
- 239000012298 atmosphere Substances 0.000 claims description 63
- 238000007598 dipping method Methods 0.000 claims description 56
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 49
- 229910017604 nitric acid Inorganic materials 0.000 claims description 49
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 48
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 48
- 239000011148 porous material Substances 0.000 claims description 38
- 239000002243 precursor Substances 0.000 claims description 35
- 230000032683 aging Effects 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 31
- 238000002791 soaking Methods 0.000 claims description 31
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 25
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 24
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 24
- 229940044658 gallium nitrate Drugs 0.000 claims description 24
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- 239000001509 sodium citrate Substances 0.000 claims description 19
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 19
- 238000001704 evaporation Methods 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000012465 retentate Substances 0.000 claims description 16
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000001632 sodium acetate Substances 0.000 claims description 13
- 235000017281 sodium acetate Nutrition 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 238000005453 pelletization Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 4
- 229910018307 LaxSr1−x Inorganic materials 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 121
- 238000005470 impregnation Methods 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052733 gallium Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/83—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 rare earths or actinides
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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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/896—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
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- B01J35/615—
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- B01J35/638—
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- B01J35/651—
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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
- B01J37/0201—Impregnation
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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
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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
Abstract
The invention discloses a dehydrogenation catalyst, which takes modified alumina as a carrier, Pt as an active component and Ga-containing perovskite as an auxiliary agent; the weight percentage content of Pt in the dehydrogenation catalyst is 0.1-0.5%, and the weight percentage content of Ga is 0.4-3.1%. In addition, the invention also provides a method for preparing the dehydrogenation catalyst and application of the catalyst in preparing olefin by alkane dehydrogenation, the preparation method is simple, and the dehydrogenation catalyst prepared by the preparation method has high catalytic performance in alkane dehydrogenation; the dehydrogenation catalyst has the characteristics of high catalyst activity, carbon deposition resistance and good stability, and the preparation method is simple and easy to implement and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of dehydrogenation catalysts, and particularly relates to a dehydrogenation catalyst and a preparation method and application thereof.
Background
The dehydrogenation catalyst is mainly used for propane dehydrogenation to generate propylene, butane dehydrogenation to generate butadiene or ethylbenzene dehydrogenation to generate styrene, wherein the propylene is a raw material of polypropylene, the butadiene is a raw material of synthetic rubber or acrylic fiber, and the styrene is a raw material of synthetic resin. The dehydrogenation reaction is a reaction with reversible reaction process, heat absorption and increased molecular number, and the reaction is more favorably carried out under the conditions of high temperature and low pressure. At present, dehydrogenation reaction is usually carried out at the temperature of 300 ℃ to 900 ℃, side reaction is accompanied in the reaction process, and the currently commonly used dehydrogenation catalyst is easy to deposit carbon to reduce the service life. Suitable dehydrogenation catalysts can promote dehydrogenation reactions to a target direction, and reaction selectivity is an important index for investigating dehydrogenation catalysts.
The selection of a suitable dehydrogenation catalyst is critical to increasing the rate and selectivity of the dehydrogenation reaction, and a suitable dehydrogenation catalyst should have the following characteristics:
(1) the heat resistance is good, the regeneration capacity is strong, and the capability of not being sintered in a high-temperature environment is realized;
(2) the chemical stability is good, and the hydrogen reduction and water vapor corrosion resistance capability is realized in a high-temperature environment;
typical dehydrogenation catalysts are predominantly supported (e.g., platinum, copper, silver, nickel) and metal oxide (e.g., chromium oxide, iron oxide, zinc oxide, magnesium oxide) catalysts. The dehydrogenation catalyst has higher requirement on thermal stability, and the catalyst is easy to generate thermal deformation and structural sintering due to high reaction temperature and heat generated during coke regeneration, so that carbon deposition is generated to finally cause the catalyst to be deactivated, and the catalytic reaction performance is reduced. Therefore, it is important to research a dehydrogenation catalyst with strong structural thermal stability, high selectivity and strong reactivity.
As an important constituent in the dehydrogenation catalyst family, Al is predominant2O3、SiO2Platinum catalysts, which use platinum as a main active component, such as molecular sieves and the like, as carriers have attracted much attention. U.S. Pat. No. US7375049, published as 2008/5/20/discloses a platinum-based CATALYST for ethane dehydrogenation, which has a stable activity in the initial stage and causes carbon deposition and sintering in the later stage. Platinum-based gamma-Al is disclosed in U.S. Pat. No. 6,56515, published as 2004, 6/29, entitled Dehydrogenation Process Using Layered Catalyst Composition2O3Dehydrogenation catalyst, gamma-Al of said catalyst during the reaction2O3There are many side reactions at the acidic sites on the surface of the support, and at the same time, there are significant changes in crystallinity and specific surface area during the reaction due to the instability of the support structure under high temperature conditions and carbon deposition during dehydrogenation. The application number 871015137, published as 10/12/1988, and named as "platinum, tin, lithium and sulfur catalyst for dehydrogenating saturated hydrocarbons", discloses a dehydrogenation catalyst for saturated hydrocarbons, which is prepared by coprecipitation method to prepare alumina pellets, and carries platinum metal, and the carrier of the catalyst has the defects of low specific surface area, easy loss of the carried noble metal, etc. The research and development of the catalyst with macropore, high activity, high selectivity, carbon deposition resistance and stable sintering performance are very important.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a dehydrogenation catalyst, a preparation method and an application thereof, aiming at the defects of the prior art. The dehydrogenation catalyst has high-efficiency dehydrogenation catalytic performance; the preparation method is simple, and the dehydrogenation catalyst prepared by the preparation method has high catalytic performance in alkane dehydrogenation; the dehydrogenation catalyst, the preparation method and the application thereof have the characteristics of high catalyst activity, carbon deposition resistance and good stability, and the preparation method is simple and easy to implement and has wide application prospects.
In order to solve the technical problems, the invention adopts the technical scheme that: a dehydrogenation catalyst is characterized in that the dehydrogenation catalyst takes modified alumina as a carrier, Pt as an active component and Ga-containing perovskite as an auxiliary agent; the weight percentage content of Pt in the dehydrogenation catalyst is 0.1-0.5%, and the weight percentage content of Ga is 0.4-3.1%.
The dehydrogenation catalyst is characterized in that the molecular formula of the Ga-containing perovskite is LaxSr1-xCoyGa1- yO3，0.1≤x≤0.9，0.1≤y≤0.9。
The above dehydrogenation catalyst is characterized in that the preparation method of the Ga-containing perovskite comprises the following steps:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.0-10.5 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 10-20%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain Ga-containing perovskite; the drying temperature is 90-110 ℃, and the drying time is 10-15 h; the roasting atmosphere is air atmosphere, the roasting temperature is 800-1000 ℃, and the roasting time is 5-10 h; the grain diameter of the Ga-containing perovskite is 200-300 meshes.
The dehydrogenation catalyst is characterized in that the average pore diameter of the dehydrogenation catalyst is 95 nm-325 nm; the pore volume of the dehydrogenation catalyst is 1.2mL/g to 1.7 mL/g; the dehydrogenation catalyst has a specific surface area of 260m2/g～390m2/g。
The dehydrogenation catalyst is characterized in that the mass percentage of Ga in the dehydrogenation catalyst is 1.1-3.1%.
In addition, the present invention also provides a method for preparing the above dehydrogenation catalyst, which is characterized by comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature, and drying to obtain modified alumina;
step three, stirring and dipping the modified alumina obtained in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature, evaporating the solvent of the aged modified alumina impregnated with Pt at 70-80 ℃, and then drying, roasting and grinding to obtain modified alumina loaded with Pt;
step five, uniformly mixing the Ga-containing perovskite with the Pt-loaded modified alumina in the step four, and forming to obtain the dehydrogenation catalyst.
The method is characterized in that in the step one, the mass concentration of the dilute nitric acid is 4-8%, and the mass of the dilute nitric acid is 4-8 times of that of the alumina; the temperature of the pretreatment in the step one is 80-110 ℃, and the time of the pretreatment is 0.5-2 h; in the step one, the drying temperature is 80-150 ℃, and the drying time is 3-10 h; in the step one, the roasting temperature is 300-400 ℃, and the roasting time is 3-6 h;
in the second step, the mass concentration of the modifier in the modifier solution is 5-15%, and the modifier is one or more of sodium carbonate, potassium carbonate, sodium acetate and sodium citrate; the mass of the modifier solution in the second step is 3-6 times of that of the pretreated alumina; the stirring time in the step two is 30-90 min.
The method is characterized in that the stirring and dipping method in the step three comprises the following steps: adding modified alumina into a chloroplatinic acid solution with the mass concentration of 0.01-0.03 g/mL, dropwise adding alkali liquor to adjust the pH to 9-11, stirring and soaking at 40-70 ℃ for 5-8 h, and removing residual liquid to obtain the modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.01-0.03 g/mL, dropwise adding an alkali liquor to adjust the pH to 9-11, stirring and dipping at 40-70 ℃ for 5-8 h, and removing residual liquid to obtain modified alumina dipped with Pt; the alkali liquor is ammonia water with the mass concentration of 5-10%.
The method is characterized in that the aging time in the fourth step is 5-10 h; the drying temperature in the fourth step is 110-130 ℃, and the drying time is 10-15 h; in the fourth step, the roasting atmosphere is air atmosphere, the roasting temperature is 400-600 ℃, and the roasting time is 4-6 h; in the fourth step, the grain diameter of the modified alumina loaded with Pt is 200 meshes-300 meshes; and the molding in the fifth step comprises granulation molding, pelletizing molding or integral molding.
Furthermore, the invention also provides an application of the dehydrogenation catalyst in preparing olefin by alkane dehydrogenation.
Compared with the prior art, the invention has the following advantages:
1. the dehydrogenation catalyst takes modified alumina as a carrier to load an active component Pt, takes perovskite containing Ga as an auxiliary agent, and has the mass percentage content of Pt of 0.1-0.5% and the mass percentage content of Ga of 0.4-3.1%; pt is highly dispersed on the surface of modified alumina as an active component, has high reaction activity, rich oxygen vacancies of Ga-containing perovskite can further promote the dispersion of the surface active component and synergistically promote the dehydrogenation of the catalyst, the dehydrogenation catalyst has high alkane conversion rate and olefin selectivity, high carbon deposition resistance and sintering capacity, high halogen poisoning inhibition capacity and long service life in the dehydrogenation reaction process, and the dehydrogenation catalyst still has high reaction activity after being activated.
2. The dehydrogenation catalyst takes the modified alumina as a carrier, and the surface of the carrier alumina is modified by dilute nitric acid, so that the surface of the carrier has rich oxygen-containing functional groups, the average specific surface area, the pore volume and the pore diameter of the carrier alumina are increased, metal can be effectively anchored, and hydrogen can be adsorbed; the modified alumina is beneficial to the uniform dispersion of metal and the interaction between the metal and the modified alumina when the metal is impregnated, is beneficial to the adsorption of reactant molecules and the desorption of product molecules when the catalytic dehydrogenation reaction is carried out, and can effectively reduce the generation of carbon deposition.
3. In the invention, one or more of sodium carbonate, potassium carbonate, sodium acetate and sodium citrate are preferably used as modifiers, so that the average specific surface area, pore volume and pore diameter of the alumina carrier can be effectively enhanced, oxygen-containing functional groups and alkaline sites on the surface of the carrier are enriched, and the conversion rate of alkane dehydrogenation reaction is improved.
4. The invention adopts stirring impregnation to obtain modified aluminum chloride loaded with Pt, and carries out twice impregnation processes of active components on a modified aluminum chloride carrier so as to ensure that the active components are completely impregnated on the carrier and realize good dispersion of the active components.
5. The invention takes the gallium-containing perovskite as an auxiliary agent, can promote the introduction of gallium into the dehydrogenation catalyst, takes the gallium-containing perovskite as an oxygen exchange material with good performance, and has rich oxygen vacancies to synergistically promote the dehydrogenation of the catalyst; the gallium-containing perovskite is prepared by adopting a coprecipitation method, and the preparation method is simple and easy to operate.
6. The dehydrogenation catalyst has simple preparation process, easy mass production and low production cost.
The technical solution of the present invention is further described in detail below with reference to the embodiments and the accompanying drawings.
Drawings
FIG. 1 is an XRD pattern of a Ga-containing perovskite produced in example 1 of the present invention.
Detailed Description
Example 1
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 10%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, preparing the Ga-containing perovskite in the step oneThe driver is dried, roasted and ground in sequence to obtain the molecular formula La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 90 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 800 ℃, and the roasting time is 5 hours; the particle size of the Ga-containing perovskite is 200 meshes.
The XRD pattern of the Ga-containing perovskite prepared in this example is shown in FIG. 1, and the diffraction peaks are 23.2 °, 32.9 °, 40.6 °, 47.4 °, 58.8 °, 68.9 ° and 78.6 °, which are similar to those of LaCoO3PDF48-0123 matching of a standard card; due to the doping of Sr and Ga, the peak position of the diffraction peak of the Ga-containing perovskite is shifted to a low-angle direction relative to the standard card, and Sr, Ga, La and Co are shown to exist in the crystal structure of the perovskite.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 4%, and the mass of the dilute nitric acid is 4 times of that of the alumina; the pretreatment temperature is 80 ℃, and the pretreatment time is 0.5 h; the drying temperature is 80 ℃, and the drying time is 10 hours; the roasting temperature is 300 ℃, and the roasting time is 3 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 5%, the modifier is sodium carbonate, or more than two of sodium carbonate, potassium carbonate, sodium acetate and sodium citrate, or potassium carbonate, sodium acetate or sodium citrate; the stirring time is 30 min; the mass of the modifier solution is 6 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.1%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.01g/mL, dropwise adding alkali liquor to adjust the pH to 9, stirring and soaking at 40 ℃ for 5 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.01g/mL, dropwise adding alkali liquor to adjust the pH to 9, stirring and dipping for 5 hours at the temperature of 40 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 5%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 70 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 200 meshes; the aging time is 5 h; the drying temperature is 110 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 500 ℃, and the roasting time is 4 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:7, and granulating and molding to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 95nm and the specific surface area of 263m2Pore volume was 1.22 mL/g.
Example 2
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 10.5 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 20%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 110 ℃, and the drying time is 15 h; the roasting atmosphere is air atmosphere, the roasting temperature is 1000 ℃, and the roasting time is 10 hours; the particle size of the Ga-containing perovskite is 300 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 8%, and the mass of the dilute nitric acid is 8 times of that of the alumina; the pretreatment temperature is 110 ℃, and the pretreatment time is 2 h; the drying temperature is 90 ℃; the drying time is 8 h; the roasting temperature is 400 ℃, and the roasting time is 6 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of the modifier in the modifier solution is 15%, the modifier is sodium carbonate and potassium carbonate with the mass ratio of 1:1, or one, three or four of sodium carbonate, potassium carbonate, sodium acetate and sodium citrate, or sodium carbonate and sodium acetate, or sodium carbonate and sodium citrate, or potassium carbonate and sodium acetate, or potassium carbonate and sodium citrate, or sodium acetate and sodium citrate; the stirring time is 90 min; the mass of the modifier solution is 3 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.1%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding an alkali liquor to adjust the pH to 11, stirring and soaking at 70 ℃ for 8 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding alkali liquor to adjust the pH to 11, stirring and dipping for 8 hours at the temperature of 70 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 8%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 300 meshes; the aging time is 10 h; the drying temperature is 130 ℃, and the drying time is 15 h; the roasting atmosphere is air atmosphere, the roasting temperature is 600 ℃, and the roasting time is 6 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:18, and granulating and molding to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 120nm and the specific surface area of 329m2Pore volume was 1.52 mL/g.
Example 3
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.5 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 15%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h; the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 8 hours; the grain size of the Ga-containing perovskite is 250 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 6%, and the mass of the dilute nitric acid is 5 times of that of the alumina; the pretreatment temperature is 100 ℃, and the pretreatment time is 1 h; the drying temperature is 100 ℃; the drying time is 6 h; the roasting temperature is 350 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of the modifier in the modifier solution is 10%, the modifier is sodium carbonate, potassium carbonate, sodium acetate and sodium citrate with the mass ratio of 1:1:2:1, and the modifier can also be one, two or three of the sodium carbonate, the potassium carbonate, the sodium acetate and the sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 5 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.1%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 60 ℃ for 6 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 8 hours at 70 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 10%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 250 meshes; the aging time is 8 h; the drying temperature is 120 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 550 ℃, and the roasting time is 5 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:14, and granulating and molding to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 200nm and the specific surface area of 358m2Pore volume was 1.37 mL/g.
Example 4
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 10.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 15%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h; the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 8 hours; the particle size of the Ga-containing perovskite is 300 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 6%, and the mass of the dilute nitric acid is 5 times of that of the alumina; the pretreatment temperature is 100 ℃, and the pretreatment time is 1 h; the drying temperature is 110 ℃; the drying time is 5 h; the roasting temperature is 350 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 5 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.5%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 60 ℃ for 6 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 6 hours at the temperature of 60 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 5%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 300 meshes; the aging time is 8 h; the drying temperature is 120 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 550 ℃, and the roasting time is 5 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:14, and granulating and molding to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 230nm and the specific surface area of 374m2Pore volume was 1.67 mL/g.
Example 5
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 10%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h; the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 8 hours; the particle size of the Ga-containing perovskite is 300 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 6%, and the mass of the dilute nitric acid is 5 times of that of the alumina; the pretreatment temperature is 100 ℃, and the pretreatment time is 1 h; the drying temperature is 120 ℃; the drying time is 5 h; the roasting temperature is 350 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 5 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 60 ℃ for 6 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 6 hours at the temperature of 60 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 8%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 300 meshes; the aging time is 8 h; the drying temperature is 120 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 550 ℃, and the roasting time is 5 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:14, and granulating and molding to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 300nm and the specific surface area of 389m2Pore volume was 1.71 mL/g.
Example 6
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 10%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h;the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 8 hours; the particle size of the Ga-containing perovskite is 200 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 5%, and the mass of the dilute nitric acid is 6 times of that of the alumina; the pretreatment temperature is 90 ℃, and the pretreatment time is 1 h; the drying temperature is 130 ℃; the drying time is 4 h; the roasting temperature is 400 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 4 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.03g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 60 ℃ for 8 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.03g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 8 hours at the temperature of 60 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 5%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt; the aging time is 8 h; the drying temperature is 120 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 500 ℃, and the roasting time is 5 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:14, and pelletizing and forming to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 325nm and the specific surface area of 365m2Pore volume was 1.57 mL/g.
Example 7
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 20%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h; the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 6 hours; the particle size of the Ga-containing perovskite is 300 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 5%, and the mass of the dilute nitric acid is 6 times of that of the alumina; the pretreatment temperature is 100 ℃, and the pretreatment time is 1 h; the drying temperature is 140 ℃; the drying time is 4 h; the roasting temperature is 350 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium acetate; the stirring time is 60 min; the mass of the modifier solution is 4 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.01g/mL, dropwise adding an alkali liquor to adjust the pH to 9, stirring and soaking at 50 ℃ for 8 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.01g/mL, dropwise adding alkali liquor to adjust the pH to 9, stirring and dipping for 8 hours at the temperature of 50 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 8%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 300 meshes; the aging time is 8 h; the drying temperature is 110 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 400 ℃, and the roasting time is 4 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:14, and pelletizing and forming to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 280nm and the specific surface area of 344m2Pore volume was 1.48 mL/g.
Example 8
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 10%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h; the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 6 hours; the grain size of the Ga-containing perovskite is 250 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 5%, and the mass of the dilute nitric acid is 6 times of that of the alumina; the pretreatment temperature is 90 ℃, and the pretreatment time is 1 h; the drying temperature is 150 ℃; the drying time is 3 h; the roasting temperature is 400 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium acetate; the stirring time is 60 min; the mass of the modifier solution is 4 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.01g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 50 ℃ for 8 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.01g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 8 hours at the temperature of 50 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 10%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 250 meshes; the aging time is 8 h; the drying temperature is 110 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 400 ℃, and the roasting time is 4 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:14, and pelletizing and forming to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 270nm and the specific surface area of 286m2Pore volume was 1.63 mL/g.
Example 9
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 15%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 5:5:3: 7;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.5Sr0.5Co0.3Ga0.7O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h; the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 8 hours; the particle size of the Ga-containing perovskite is 300 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 6%, and the mass of the dilute nitric acid is 5 times of that of the alumina; the pretreatment temperature is 100 ℃, and the pretreatment time is 2 hours; the drying temperature is 130 ℃; the drying time is 4 h; the roasting temperature is 350 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 5 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 60 ℃ for 6 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 6 hours at the temperature of 60 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 8%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 300 meshes; the aging time is 8 h; the drying temperature is 120 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 550 ℃, and the roasting time is 5 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:14, and integrally forming to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 230nm and the specific surface area of 294m2Pore volume was 1.58 mL/g.
Example 10
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 10.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 10%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 9:1:1: 9;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.9Sr0.1Co0.1Ga0.9O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h; the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 8 hours; the particle size of the Ga-containing perovskite is 300 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 6%, and the mass of the dilute nitric acid is 5 times of that of the alumina; the pretreatment temperature is 100 ℃, and the pretreatment time is 1 h; the drying temperature is 120 ℃; the drying time is 5 h; the roasting temperature is 350 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 5 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 60 ℃ for 6 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 6 hours at the temperature of 60 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 8%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 300 meshes; the aging time is 8 h; the drying temperature is 120 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 550 ℃, and the roasting time is 5 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:7, and granulating and molding to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is an averageMacroporous dehydrogenation catalyst with 318nm pore diameter and specific surface area of 370m2Pore volume was 1.60 mL/g.
Example 11
The preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 10.0 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 10%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate, and the mass ratio of the lanthanum nitrate to the strontium nitrate to the cobalt nitrate to the gallium nitrate is 1:9:9: 1;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain the precursor with the molecular formula of La0.1Sr0.9Co0.9Ga0.1O3Ga-containing perovskites of (1); the drying temperature is 100 ℃, and the drying time is 12 h; the roasting atmosphere is air atmosphere, the roasting temperature is 900 ℃, and the roasting time is 8 hours; the particle size of the Ga-containing perovskite is 300 meshes.
A method of preparing a dehydrogenation catalyst comprising the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 6%, and the mass of the dilute nitric acid is 5 times of that of the alumina; the pretreatment temperature is 100 ℃, and the pretreatment time is 1 h; the drying temperature is 120 ℃; the drying time is 5 h; the roasting temperature is 350 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 5 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 60 ℃ for 6 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.02g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 6 hours at the temperature of 60 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 8%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying, roasting, and grinding to obtain modified alumina loaded with Pt, wherein the grain size of the modified alumina is 300 meshes; the aging time is 8 h; the drying temperature is 120 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 550 ℃, and the roasting time is 5 hours;
step five, uniformly mixing the Ga-containing perovskite and the Pt-loaded modified alumina in the step four according to the mass ratio of 1:7, and granulating and molding to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 293nm and the specific surface area of 1.54m2Pore volume was 335 mL/g.
Comparative example 1
The process for preparing a dehydrogenation catalyst of this comparative example includes the steps of:
drying and roasting alumina to obtain pretreated alumina; the drying temperature is 130 ℃; the drying time is 4 h; the roasting temperature is 400 ℃, and the roasting time is 5 hours;
secondly, adding the pretreated alumina in the first step into a chloroplatinic acid solution with the mass concentration of 0.03g/mL according to the mass percent of Pt in the dehydrogenation catalyst of 0.3%, dropwise adding alkali liquor to adjust the pH value to 10, stirring and soaking at 50 ℃ for 8 hours, and removing residual liquid to obtain Pt-impregnated aluminum chloride; the alkali liquor is ammonia water with the mass concentration of 5%;
step three, aging the Pt-impregnated aluminum chloride in the step two at room temperature, evaporating the solvent of the aged Pt-impregnated aluminum chloride at 80 ℃, drying, and roasting to obtain Pt-loaded alumina; the aging time is 8 h; the drying temperature is 110 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 400 ℃, and the roasting time is 4 hours;
step four, pelletizing and forming the Pt-loaded alumina in the step three to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 84nm and the specific surface area of 150m2Pore volume was 0.98 mL/g.
Comparative example 2
The process for preparing a dehydrogenation catalyst of this comparative example includes the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 5%, and the mass of the dilute nitric acid is 6 times of that of the alumina; the pretreatment temperature is 90 ℃, and the pretreatment time is 1 h; the drying temperature is 130 ℃; the drying time is 4 h; the roasting temperature is 400 ℃, and the roasting time is 5 hours;
secondly, adding the pretreated alumina in the first step into a chloroplatinic acid solution with the mass concentration of 0.03g/mL according to the mass percent of Pt in the dehydrogenation catalyst of 0.3%, dropwise adding alkali liquor to adjust the pH value to 10, stirring and soaking at 50 ℃ for 8 hours, and removing residual liquid to obtain Pt-impregnated aluminum chloride; the alkali liquor is ammonia water with the mass concentration of 5%;
step three, aging the Pt-impregnated aluminum chloride in the step two at room temperature of 25 ℃, evaporating the solvent of the aged Pt-impregnated aluminum chloride at 80 ℃, drying, and roasting to obtain Pt-loaded alumina; the aging time is 8 h; the drying temperature is 110 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 400 ℃, and the roasting time is 4 hours;
step four, pelletizing and forming the Pt-loaded alumina in the step three to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 143nm and the specific surface area of 230m2Pore volume was 0.89 mL/g.
Comparative example 3
The process for preparing a dehydrogenation catalyst of this comparative example includes the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 5%, and the mass of the dilute nitric acid is 6 times of that of the alumina; the pretreatment temperature is 90 ℃, and the pretreatment time is 1 h; the drying temperature is 130 ℃, and the drying time is 4 h; the roasting temperature is 400 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 4 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.03g/mL, dropwise adding alkali liquor to adjust the pH value to 10, stirring and soaking for 8 hours at the temperature of 50 ℃, and removing residual liquid to obtain modified alumina impregnated with Pt; the alkali liquor is ammonia water with the mass concentration of 5%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying and roasting to obtain modified alumina loaded with Pt; the aging time is 8 h; the drying temperature is 110 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 400 ℃, and the roasting time is 4 hours;
step five, pelletizing and molding the modified alumina loaded with Pt in the step four to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 204nm and the specific surface area of 290m2Pore volume was 1.24 mL/g.
Comparative example 4
The process for preparing a dehydrogenation catalyst of this comparative example includes the steps of:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina; the mass concentration of the dilute nitric acid is 5%, and the mass of the dilute nitric acid is 6 times of that of the alumina; the pretreatment temperature is 90 ℃, and the pretreatment time is 1 h; the drying temperature is 130 ℃, and the drying time is 4 h; the roasting temperature is 400 ℃, and the roasting time is 5 hours;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature of 25 ℃, and fully drying to obtain modified alumina; the mass concentration of a modifier in the modifier solution is 10%, and the modifier is sodium citrate; the stirring time is 60 min; the mass of the modifier solution is 4 times of the mass of the pretreated alumina;
step three, according to the mass percentage content of Pt in the dehydrogenation catalyst of 0.3%, stirring and dipping the modified alumina in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
the stirring and dipping method comprises the following steps: adding the modified alumina obtained in the step two into a chloroplatinic acid solution with the mass concentration of 0.03g/mL, dropwise adding an alkali liquor to adjust the pH value to 10, stirring and soaking at 50 ℃ for 8 hours, and removing residual liquid to obtain modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.03g/mL, dropwise adding alkali liquor to adjust the pH to 10, stirring and dipping for 8 hours at the temperature of 50 ℃, and removing residual liquid to obtain modified alumina dipped with Pt; the volume ratio of the chloroplatinic acid solution used for the first stirring impregnation to the chloroplatinic acid solution used for the second stirring impregnation is 1: 1; the alkali liquor is ammonia water with the mass concentration of 5%;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature of 25 ℃, evaporating the solvent of the aged modified alumina impregnated with Pt at 80 ℃, drying and roasting to obtain modified alumina loaded with Pt; the aging time is 8 h; the drying temperature is 110 ℃, and the drying time is 10 hours; the roasting atmosphere is air atmosphere, the roasting temperature is 400 ℃, and the roasting time is 4 hours;
step five, pelletizing and molding the modified alumina loaded with Pt in the step four to obtain a dehydrogenation catalyst; the dehydrogenation catalyst is a macroporous dehydrogenation catalyst with the average pore diameter of 187nm and the specific surface area of 283m2Pore volume was 1.45 mL/g.
The dehydrogenation catalysts of the above examples and comparative examples were loaded into a fixed bed reactor to perform propane dehydrogenation under the following reaction conditions: the reaction temperature is 590-600 ℃, the reaction pressure is 0.1MPa, and the space velocity of the propane is 3.2h-1The reaction time was 48h, and the results of the performance tests are shown in Table 1. Wherein propane conversion, propylene selectivity and propylene yield are all averages.
TABLE 1 dehydrogenation catalyst results of the reaction for producing propylene from propane
As can be seen from table 1, in the same evaluation system, the dehydrogenation catalysts of examples 1 to 11 have a propane conversion of 36.1% to 41.4%, corresponding propylene selectivity of 92.9% to 98.1%, and a propylene yield of 34.1% to 40.5%, which are significantly better than the comparative example, indicating that the dehydrogenation catalysts of the present invention have excellent reaction performance in propane dehydrogenation, higher conversion activity for propane, higher propylene selectivity, and yield of the target product.
Table 2 shows the results of the performance test of the dehydrogenation catalyst of example 6 of the present invention after 5 regenerations, wherein the regeneration method of the dehydrogenation catalyst is reduction in a hydrogen atmosphere, and the specific operations of the regeneration and the performance test after the regeneration are as follows: placing the reacted dehydrogenation catalyst in a pure hydrogen atmosphere, heating the dehydrogenation catalyst to 550-610 ℃ from room temperature at a heating rate of 10 ℃/min, and reducing the reacted dehydrogenation catalyst for 2-3 h; and introducing raw material gas propane into the reduced dehydrogenation catalyst for reaction, and switching hydrogen atmosphere for regeneration after the raw material reaction is finished. The dehydrogenation catalyst still has higher reaction performance after regeneration, which shows that the dehydrogenation catalyst has high carbon deposition resistance, sintering resistance and halogen poisoning inhibition capability, and has long service life.
Table 2 results of performance tests after 5 regenerations of the dehydrogenation catalyst of example 6 of this invention
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. A dehydrogenation catalyst is characterized in that the dehydrogenation catalyst takes modified alumina as a carrier, Pt as an active component and Ga-containing perovskite as an auxiliary agent; the weight percentage content of Pt in the dehydrogenation catalyst is 0.1-0.5%, and the weight percentage content of Ga is 0.4-3.1%; the molecular formula of the Ga-containing perovskite is LaxSr1-xCoyGa1-yO3，0.1≤x≤0.9，0.1≤y≤0.9；
The dehydrogenation catalyst is prepared by the following method, and the method comprises the following steps:
firstly, putting alumina into dilute nitric acid for pretreatment, filtering, drying and roasting retentate obtained by filtering to obtain pretreated alumina;
step two, placing the pretreated alumina in the step one into a modifier solution, stirring at room temperature, and drying to obtain modified alumina;
step three, stirring and dipping the modified alumina obtained in the step two by using chloroplatinic acid solution to obtain modified alumina dipped with Pt;
step four, aging the modified alumina impregnated with Pt in the step three at room temperature, evaporating the solvent of the aged modified alumina impregnated with Pt at 70-80 ℃, and then drying, roasting and grinding to obtain modified alumina loaded with Pt;
step five, uniformly mixing the Ga-containing perovskite with the Pt-loaded modified alumina in the step four, and forming to obtain a dehydrogenation catalyst;
in the first step, the mass concentration of the dilute nitric acid is 4-8%, and the mass of the dilute nitric acid is 4-8 times that of the alumina; the temperature of the pretreatment in the step one is 80-110 ℃, and the time of the pretreatment is 0.5-2 h; in the step one, the drying temperature is 80-150 ℃, and the drying time is 3-10 h; in the step one, the roasting temperature is 300-400 ℃, and the roasting time is 3-6 h;
in the second step, the mass concentration of the modifier in the modifier solution is 5-15%, and the modifier is one or more of sodium carbonate, potassium carbonate, sodium acetate and sodium citrate; the mass of the modifier solution in the second step is 3-6 times of that of the pretreated alumina; the stirring time in the step two is 30-90 min;
the stirring and dipping method in the third step comprises the following steps: adding modified alumina into a chloroplatinic acid solution with the mass concentration of 0.01-0.03 g/mL, dropwise adding alkali liquor to adjust the pH to 9-11, stirring and soaking at 40-70 ℃ for 5-8 h, and removing residual liquid to obtain the modified alumina after the first stirring and soaking; adding the modified alumina after the first stirring and dipping into a chloroplatinic acid solution with the mass concentration of 0.01-0.03 g/mL, dropwise adding an alkali liquor to adjust the pH to 9-11, stirring and dipping at 40-70 ℃ for 5-8 h, and removing residual liquid to obtain modified alumina dipped with Pt; the alkali liquor is ammonia water with the mass concentration of 5-10%;
the aging time in the fourth step is 5-10 h; the drying temperature in the fourth step is 110-130 ℃, and the drying time is 10-15 h; in the fourth step, the roasting atmosphere is air atmosphere, the roasting temperature is 400-600 ℃, and the roasting time is 4-6 h; in the fourth step, the grain diameter of the modified alumina loaded with Pt is 200 meshes-300 meshes; and the molding in the fifth step comprises granulation molding, pelletizing molding or integral molding.
2. A dehydrogenation catalyst according to claim 1, wherein the process for the preparation of the Ga-containing perovskite comprises the steps of:
dissolving the raw materials in alkali liquor, and continuously adding the alkali liquor until the pH value is 9.0-10.5 to obtain a Ga-containing perovskite precursor; the alkali liquor is ammonia water with the mass concentration of 10-20%; the raw materials are lanthanum nitrate, strontium nitrate, cobalt nitrate and gallium nitrate;
step two, drying, roasting and grinding the Ga-containing perovskite precursor in the step one in sequence to obtain Ga-containing perovskite; the drying temperature is 90-110 ℃, and the drying time is 10-15 h; the roasting atmosphere is air atmosphere, the roasting temperature is 800-1000 ℃, and the roasting time is 5-10 h; the grain diameter of the Ga-containing perovskite is 200-300 meshes.
3. The dehydrogenation catalyst of claim 1, wherein the dehydrogenation catalyst has an average pore size of from 95nm to 325 nm; the pore volume of the dehydrogenation catalyst is 1.2mL/g to 1.7 mL/g; the dehydrogenation catalyst has a specific surface area of 260m2/g～390m2/g。
4. A dehydrogenation catalyst according to claim 1 or 2 wherein the amount of Ga in the dehydrogenation catalyst is in the range of from 1.1 to 3.1% by weight.
5. Use of the dehydrogenation catalyst of claim 1 in the dehydrogenation of an alkane to produce an alkene.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4737355A (en) * | 1986-12-15 | 1988-04-12 | The Standard Oil Company | Preparation of vanadium III oxidic compounds, and dehydrogenation of paraffins |
| CN1473654A (en) * | 2002-08-06 | 2004-02-11 | 中国科学院大连化学物理研究所 | Composite oxide catalyst and its preparing method and use |
| CN104084198A (en) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | Platinum aluminium oxide series catalyst for preparing propylene by propane dehydrogenation and preparation method of catalyst |
| CN104525196A (en) * | 2014-12-11 | 2015-04-22 | 天津大学 | Platinum-gallium catalyst loaded on double-oxide composite carrier as well as preparation method and application of platinum-gallium catalyst |
| CN104588032A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Alkane dehydrogenation catalyst and preparation method thereof |
| CN105582977A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst |
-
2019
- 2019-05-16 CN CN201910408652.1A patent/CN110075855B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4737355A (en) * | 1986-12-15 | 1988-04-12 | The Standard Oil Company | Preparation of vanadium III oxidic compounds, and dehydrogenation of paraffins |
| CN1473654A (en) * | 2002-08-06 | 2004-02-11 | 中国科学院大连化学物理研究所 | Composite oxide catalyst and its preparing method and use |
| CN104588032A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Alkane dehydrogenation catalyst and preparation method thereof |
| CN104084198A (en) * | 2014-07-15 | 2014-10-08 | 华陆工程科技有限责任公司 | Platinum aluminium oxide series catalyst for preparing propylene by propane dehydrogenation and preparation method of catalyst |
| CN105582977A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of dehydrogenation catalyst |
| CN104525196A (en) * | 2014-12-11 | 2015-04-22 | 天津大学 | Platinum-gallium catalyst loaded on double-oxide composite carrier as well as preparation method and application of platinum-gallium catalyst |
Non-Patent Citations (1)
| Title |
|---|
| "Platinum-Promoted Ga/Al2O3 as Highly Active, Selective, and Stable Catalyst for the Dehydrogenation of Propane";Jesper J. H. B. Sattler et al.;《Angew. Chem. Int. Ed.》;20140702;第53卷;第9251-9256页 * |
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