CN113522266A - Modified chromium propane dehydrogenation catalyst fixed bed carrier, preparation and application method - Google Patents
Modified chromium propane dehydrogenation catalyst fixed bed carrier, preparation and application method Download PDFInfo
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- CN113522266A CN113522266A CN202110956092.0A CN202110956092A CN113522266A CN 113522266 A CN113522266 A CN 113522266A CN 202110956092 A CN202110956092 A CN 202110956092A CN 113522266 A CN113522266 A CN 113522266A
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- dehydrogenation catalyst
- fixed bed
- carrier
- propane dehydrogenation
- auxiliary agent
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 40
- YQIQVBOOXSNZRO-UHFFFAOYSA-N CCC.[Cr] Chemical class CCC.[Cr] YQIQVBOOXSNZRO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 239000001294 propane Substances 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 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
- 239000000843 powder Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 28
- 239000011148 porous material Substances 0.000 claims description 20
- 238000004898 kneading Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- -1 organic acid salt Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052596 spinel Inorganic materials 0.000 claims description 4
- 239000011029 spinel Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011265 semifinished product Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 150000007524 organic acids Chemical class 0.000 claims 1
- 235000005985 organic acids Nutrition 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- 241000219782 Sesbania Species 0.000 description 25
- 238000005303 weighing Methods 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 22
- 238000005470 impregnation Methods 0.000 description 22
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000004575 stone Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000002872 contrast media Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FNIHDXPFFIOGKL-UHFFFAOYSA-N disodium;dioxido(oxo)germane Chemical compound [Na+].[Na+].[O-][Ge]([O-])=O FNIHDXPFFIOGKL-UHFFFAOYSA-N 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- XOUJQBZXQXPBNK-UHFFFAOYSA-K O.O.O.O.C(C)(=O)[O-].[Ce+3].C(C)(=O)[O-].C(C)(=O)[O-] Chemical compound O.O.O.O.C(C)(=O)[O-].[Ce+3].C(C)(=O)[O-].C(C)(=O)[O-] XOUJQBZXQXPBNK-UHFFFAOYSA-K 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QRRWWGNBSQSBAM-UHFFFAOYSA-N alumane;chromium Chemical compound [AlH3].[Cr] QRRWWGNBSQSBAM-UHFFFAOYSA-N 0.000 description 1
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- CRGGPIWCSGOBDN-UHFFFAOYSA-N magnesium;dioxido(dioxo)chromium Chemical compound [Mg+2].[O-][Cr]([O-])(=O)=O CRGGPIWCSGOBDN-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- YSUBIGXLOCNYKB-UHFFFAOYSA-N scandium(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[N+](=O)([O-])[O-].[Sc+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] YSUBIGXLOCNYKB-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/26—Chromium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a modified chromium propane dehydrogenation catalyst fixed bed carrier, and preparation and application methods thereof, wherein the fixed bed carrier comprises a porous carrier, a first auxiliary agent with the mass fraction of 1-40%, a second auxiliary agent with the mass fraction of 1-10% and a third auxiliary agent with the mass fraction of 1-10%, wherein the first auxiliary agent is one or more of IVA group elements, the second auxiliary agent is one or more of rare earth elements, and the third auxiliary agent is one or more of alkali metal elements or alkaline earth elements. The propane dehydrogenation catalyst is prepared by modifying the IVA group element, the rare earth element and the alkali metal or alkaline earth metal element into the low-carbon alkane dehydrogenation catalyst, has the characteristics of good activity, high selectivity, good stability, high strength, environmental friendliness and the like, and can realize industrialization.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a modified chromium propane dehydrogenation catalyst fixed bed carrier, and preparation and application methods thereof.
Background
Propylene has received wide attention from various large petrochemical refineries due to the characteristics of high added value, wide utilization rate and the like of downstream products in the petrochemical field. However, due to technical limitations, the capacity at the present stage cannot meet the use requirement. Currently, the main routes to propylene include the following: catalytic cracking technology, steam cracking technology, methanol to olefins technology (MTO) and propane direct dehydrogenation technology (PDH). At present, although more than half of the propylene capacity comes from the catalytic cracking technology and the steam cracking technology, the two methods have the problems of large energy consumption, low yield and the like. Furthermore, MTO technology is also less competitive in the market due to its high cost. Therefore, compared with the propylene obtaining technology, the PDH technology is strongly pursued by various large petrochemicals due to the characteristics of investment, high return, single product and the like, and is the most effective means for obtaining propylene.
Up to now, the Camofin fixed bed process by Lummus and the Oleflex moving bed process by UOP in PDH technology have achieved large-scale industrialization. Wherein the Oleflex moving bed process of UOP adopts Pt-Sn/Al2O3The catalyst uses noble metal atoms as active sites, and simultaneously, in order to keep the carbon deposition resistance of the catalyst, the reaction is carried out in the presence of hydrogen. However, the high cost of the noble metal and the high strength of the support required for the moving bed catalyst reduce the economics of the process, and also present a certain safety hazard in carrying out the low propane dehydrogenation reaction due to the use of hydrogen.
The Camofin fixed bed process of Lummus adopts Cr/Al2O3The catalyst has the characteristics of low cost, good catalytic activity, high selectivity and the like. However, the catalyst mainly uses alumina as a carrier, so that the hydrothermal stability of the catalyst is poor. Therefore, the stability of the catalyst is greatly reduced in the steam purging link in the using process. Eventually, the catalyst forms an inactive chromium-aluminum dense phase, which greatly limits the service life of the catalyst.
Chinese patent CN106582613 reports a method of modifying a support with rare earth elements. However, due to the introduction of rare earth elements, the acidity and alkalinity of the surface of the catalyst are changed, so that the performance of the catalyst is reduced, and the carbon deposition resistance is weakened.
In summary, it is important to modify the support for the current chromium-based propane dehydrogenation to improve the stability of the support and to maintain the performance of the catalyst.
Disclosure of Invention
In order to solve the problem of poor stability of a fixed bed carrier of a chromium propane dehydrogenation catalyst, the invention provides a modified fixed bed carrier of the chromium propane dehydrogenation catalyst, and preparation and application methods thereof.
In order to achieve the technical effects, the invention provides the following technical scheme:
a modified chromium propane dehydrogenation catalyst fixed bed carrier comprises a porous carrier and 1-40% of a first auxiliary agent, 1-10% of a second auxiliary agent and 1-10% of a third auxiliary agent, wherein the first auxiliary agent is one or more of IVA group elements, the second auxiliary agent is one or more of rare earth elements, and the third auxiliary agent is one or more of alkali metal elements or alkaline earth elements.
The further technical scheme is that the fixed bed carrier is at least one of a spinel structure with multilevel pore channels, a perovskite structure, a molecular sieve structure and a porous carbon structure, the specific surface is 50-500 m2/g, and the pore size range is 5-40 nm.
The further technical scheme is that the specific surface area of the fixed bed carrier is 50-150 m2/g, and the pore diameter range is 10-30 nm.
The further technical proposal is that the porous carrier is one or more of aluminum oxide, silica or molecular sieve.
The further technical scheme is that the group IVA element is one or more selected from group IVA element simple substance powder, group IVA element oxide, group IVA element halide, group IVA element sulfide, group IVA element sulfate, group IVA element nitrate or group IVA element organic acid salt.
The further technical scheme is that the rare earth element is selected from one or more of rare earth metal simple substance, rare earth metal halide, rare earth metal oxide, rare earth metal sulfide, rare earth metal sulfate, rare earth metal nitrate or rare earth metal organic acid salt.
The further technical scheme is that the alkali metal element or the alkaline earth metal element is selected from one or more of corresponding simple substances, halides, oxides, sulfides, sulfates, nitrates or organic acid salts thereof.
The invention also provides a preparation method of the modified chromium propane dehydrogenation catalyst fixed bed carrier, which comprises the following steps: 1) mixing a porous carrier, concentrated nitric acid, sesbania powder, softened water, a first auxiliary agent, a second auxiliary agent and a third auxiliary agent in a ratio of 100: 6-13: 6-10: 60-80: 1-40: 1-10: 1-10, kneading, forming in a strip extruding machine, and drying at 80-150 ℃ for 8-12 hours to obtain a strip-shaped fixed bed carrier; 2) roasting the strip-shaped fixed bed carrier at 400-1000 ℃ for 1-10 hours to obtain the modified chromium propane dehydrogenation catalyst fixed bed carrier, wherein the specific surface area of the carrier is 50m 2/g-450 m2/g, and the pore diameter range is 3-40 nm.
The invention also provides an application method of the modified chromium propane dehydrogenation catalyst fixed bed carrier, the chromium propane dehydrogenation catalyst is prepared by adopting the carrier, and the preparation method specifically comprises the following steps: 1) preparing a mixed solution containing required active component elements, dipping the modified chromium propane dehydrogenation catalyst fixed bed carrier prepared in the claim 8 and the mixed solution under a vacuum condition, stirring, and aging for 0.5-8 hours to obtain a semi-finished product dehydrogenation catalyst; 2) and drying the semi-finished dehydrogenation catalyst for 0.5-8 hours, and then roasting at 600-1000 ℃ for 0.5-12 hours to obtain the modified chromium propane dehydrogenation catalyst prepared by the fixed bed carrier.
Compared with the prior art, the invention has the following beneficial effects: firstly, three auxiliary agents are added in the preparation process of the carrier, the modified carrier can be obtained in one step, and then the modified carrier can reach the use standard of the catalyst only by one-step impregnation; secondly, compared with an unmodified carrier, the modified carrier disclosed by the invention contains various stable structures, including but not limited to a mei-alumina spinel, a ca-alumina spinel and a la-al-perovskite structure, and the structures can make up the coordination defect of pure alumina and enhance the stability of the alumina coordination structure. The porous carbon and silicon-aluminum molecular sieve structure can change the surface electrical property of an alumina structure, so that the acidity and alkalinity are changed, and the acidity and alkalinity requirements of the surface of the chromium propane dehydrogenation catalyst carrier are met; thirdly, due to the adjustability of the carrier structure and the surface acidity and alkalinity, the conversion rate, the selectivity, the stability and the carbon deposition resistance of the catalyst in the propane dehydrogenation process are enhanced in the application of the catalyst; in addition, the raw materials used in the invention are simple and easily available, can be adjusted according to the use requirements, are easy for industrial production, and have good application prospects.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the embodiments of the present invention are described in detail and completely, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
Adding 120g of aluminum stone powder, 9g of sodium chloride, 12.2g of sodium germanate, 2g of yttrium nitrate hexahydrate and 5g of sesbania powder into a kneader and uniformly mixing; weighing 4g of concentrated nitric acid, adding the concentrated nitric acid into 50g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier A; the water absorption capacity was found to be 42%, and the specific surface area was found to be 150m2(ii) in terms of/g. Weighing 24.5g of chromic anhydride, and dissolving in 42g of water to obtain an impregnation liquid; adding 100g of the carrier A into a filter flask, and vacuumizing for 2 hours at a vacuum degree of-100 kPa; 39g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 deg.C oven for 8 hr to obtain dried powderA dried catalyst; and roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining the fixed bed catalyst 1 when the catalyst is naturally cooled to below 200 ℃.
Example 2
Adding 50g of aluminum stone powder, 30g of silica powder, 10g of magnesium acetate tetrahydrate, 7g of stannous chloride, 5.35g of lanthanum nitrate hexahydrate and 3g of sesbania powder into a kneader and uniformly mixing; weighing 10g of concentrated nitric acid, adding the concentrated nitric acid into 45g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier B; it was found to have a water absorption of 40% and a specific surface area of 123m2(ii) in terms of/g. Weighing 32.9g of chromic anhydride, and dissolving in 40g of water to obtain an impregnation liquid; adding 100g of the carrier B into a filter flask, and vacuumizing for 2 hours at the vacuum degree of-100 kPa; 11.7g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining the fixed bed catalyst 2 when the temperature of the catalyst is naturally reduced to below 200 ℃.
Example 3
Adding 80g of ZSM-5 molecular sieve, 8g of sodium silicate, 3g of potassium chloride, 3g of cerous nitrate hexahydrate and 2g of sesbania powder into a kneader, and uniformly mixing; weighing 1.5g of concentrated nitric acid, adding the concentrated nitric acid into 30g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier C; it was found to have a water absorption of 41% and a specific surface area of 140m2(ii) in terms of/g. Weighing 20g of potassium dichromate, and dissolving in 42g of water to obtain a steeping fluid; 100g of the above-mentioned carrier C was added to a filtration flaskVacuumizing for 2 hours, wherein the vacuum degree is-100 kPa; 11.7g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining the fixed bed catalyst 3 when the catalyst is naturally cooled to below 200 ℃.
Example 4
Adding 120g of aluminum stone powder into a kneader, weighing 11g of magnesium chromate, 5g of scandium nitrate hexahydrate, 3g of barium chloride dihydrate, 9g of 2-hydroxyethyl-1-tin sulfonate and 2g of cerium acetate tetrahydrate, dissolving in 41g of water, and uniformly mixing 6g of sesbania powder; weighing 8g of concentrated nitric acid, adding the concentrated nitric acid into 50g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier D; the water absorption capacity was found to be 39%, the specific surface area was 102m2(ii) in terms of/g. Weighing 30g of chromium nitrate, and dissolving in 40g of water to obtain an impregnation solution; adding 100g of the carrier D into a filter flask, and vacuumizing for 2 hours at the vacuum degree of-100 kPa; 12.7g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 750 ℃ for 4 hours at a heating rate of 5 ℃ per minute, and obtaining a fixed bed catalyst 4 when the temperature of the catalyst is naturally reduced to below 200 ℃.
Comparative example 1
Adding 100g of aluminum stone powder and 5g of potassium chloride into a kneader, adding 3g of sesbania powder, and uniformly mixing; weighing 2.8g of concentrated nitric acid, adding the concentrated nitric acid into 45g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip carrier at 120 deg.C for 2 hr, granulating, and cooling to 3 deg.CHeating to 900 ℃ at the speed of every minute, and roasting for 4-8 hours at the temperature to obtain a comparative example carrier A; it was found to have a water absorption of 40% and a specific surface area of 178m2(ii) in terms of/g. Weighing 20g of potassium dichromate, and dissolving in 42g of water to obtain a steeping fluid; 100g of the comparative example carrier A is added into a filter flask, and the vacuum degree is-100 kPa for 2 hours; 11.7g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining the fixed bed contrast agent 1 when the catalyst is naturally cooled to below 200 ℃.
Comparative example 2
Adding 100g of aluminum stone powder and 6g of calcium carbonate into a kneader, and uniformly mixing 3g of yttrium carbonate and 3g of sesbania powder; weighing 2.8g of concentrated nitric acid, adding the concentrated nitric acid into 45g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, cutting into granules, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a comparative example carrier B; it was found to have a water absorption of 40% and a specific surface area of 158m2(ii) in terms of/g. Weighing 34g of chromic anhydride, and dissolving in 40g of water to obtain a steeping fluid; 100g of the comparative example carrier B is added into a filter flask, and the vacuum degree is-100 kPa for 2 hours; 40g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 550 ℃ for 8 hours at the heating rate of 5 ℃ per minute, and obtaining the fixed bed contrast agent 2 when the catalyst is naturally cooled to below 200 ℃.
Comparative example 3
Adding 120g of aluminum stone powder, 12.2g of sodium germanate and 5g of sesbania powder into a kneader and uniformly mixing; 4g of concentrated nitric acid are weighed into 50g of water to prepare a nitric acid solution, and the nitric acid solution is addedKneading the mixture of pseudo-boehmite and sesbania powder for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier A; the water absorption capacity was found to be 42%, and the specific surface area was found to be 150m2(ii) in terms of/g. Weighing 24.5g of chromic anhydride, and dissolving in 42g of water to obtain an impregnation liquid; adding 100g of the carrier A into a filter flask, and vacuumizing for 2 hours at a vacuum degree of-100 kPa; 39g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining the fixed bed contrast agent 3 when the catalyst is naturally cooled to below 200 ℃.
Comparative example 4
Adding 120g of aluminum stone powder, 9g of sodium chloride and 5g of sesbania powder into a kneader and uniformly mixing; weighing 4g of concentrated nitric acid, adding the concentrated nitric acid into 50g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier A; the water absorption capacity was found to be 42%, and the specific surface area was found to be 150m2(ii) in terms of/g. Weighing 24.5g of chromic anhydride, and dissolving in 42g of water to obtain an impregnation liquid; adding 100g of the carrier A into a filter flask, and vacuumizing for 2 hours at a vacuum degree of-100 kPa; 39g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining a fixed bed contrast agent 4 when the catalyst is naturally cooled to below 200 ℃.
Comparative example 5
120g of alumina powder was added to the kneader,2g of yttrium nitrate hexahydrate and 5g of sesbania powder are uniformly mixed; weighing 4g of concentrated nitric acid, adding the concentrated nitric acid into 50g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier A; the water absorption capacity was found to be 42%, and the specific surface area was found to be 150m2(ii) in terms of/g. Weighing 24.5g of chromic anhydride, and dissolving in 42g of water to obtain an impregnation liquid; adding 100g of the carrier A into a filter flask, and vacuumizing for 2 hours at a vacuum degree of-100 kPa; 39g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining a fixed bed contrast agent 5 when the catalyst is naturally cooled to below 200 ℃.
Comparative example 6
Adding 120g of aluminum stone powder, 12.2g of sodium germanate, 2g of yttrium nitrate hexahydrate and 5g of sesbania powder into a kneader and uniformly mixing; weighing 4g of concentrated nitric acid, adding the concentrated nitric acid into 50g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier A; the water absorption capacity was found to be 42%, and the specific surface area was found to be 150m2(ii) in terms of/g. Weighing 24.5g of chromic anhydride, and dissolving in 42g of water to obtain an impregnation liquid; adding 100g of the carrier A into a filter flask, and vacuumizing for 2 hours at a vacuum degree of-100 kPa; 39g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at a temperature of 5 ℃ per minute until the catalyst is naturally cooled to below 200 DEG CThen, a fixed bed control 6 was obtained.
Comparative example 7
Adding 120g of aluminum stone powder, 9g of sodium chloride, 12.2g of sodium germanate and 5g of sesbania powder into a kneader and uniformly mixing; weighing 4g of concentrated nitric acid, adding the concentrated nitric acid into 50g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier A; the water absorption capacity was found to be 42%, and the specific surface area was found to be 150m2(ii) in terms of/g. Weighing 24.5g of chromic anhydride, and dissolving in 42g of water to obtain an impregnation liquid; adding 100g of the carrier A into a filter flask, and vacuumizing for 2 hours at a vacuum degree of-100 kPa; 39g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; and roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining a fixed bed contrast agent 7 when the catalyst is naturally cooled to below 200 ℃.
Comparative example 8
Adding 120g of aluminum stone powder, 9g of sodium chloride, 2g of yttrium nitrate hexahydrate and 5g of sesbania powder into a kneader and uniformly mixing; weighing 4g of concentrated nitric acid, adding the concentrated nitric acid into 50g of water to prepare a nitric acid solution, adding the nitric acid solution into a mixture of pseudo-boehmite and sesbania powder, kneading for 1 hour, and extruding strips on a 4.5mm pore plate; drying the extruded strip-shaped carrier at 120 ℃ for 2 hours, granulating, heating to 900 ℃ at the speed of 3 ℃ per minute, and roasting at the temperature for 4-8 hours to obtain a fixed bed carrier A; the water absorption capacity was found to be 42%, and the specific surface area was found to be 150m2(ii) in terms of/g. Weighing 24.5g of chromic anhydride, and dissolving in 42g of water to obtain an impregnation liquid; adding 100g of the carrier A into a filter flask, and vacuumizing for 2 hours at a vacuum degree of-100 kPa; 39g of the impregnation solution were slowly added to the filter flask and the wet catalyst was stirred every 10 minutes until the catalyst surface was air-dried. Drying in a 120 ℃ oven for 8 hours to obtain a dried catalyst; will dryAnd roasting the dried catalyst in a muffle furnace at 650 ℃ for 4 hours at the heating rate of 5 ℃ per minute, and obtaining a fixed bed contrast agent 8 when the catalyst is naturally cooled to below 200 ℃.
Test examples
Propane dehydrogenation test
The fixed bed catalysts 1 to 4 obtained in examples 1, 2, 3, 4 and the fixed bed contrast agents 1 and 2 in comparative examples 1 to 8 were subjected to propane dehydrogenation tests, respectively;
the adopted process flow is the existing fixed bed process flow, the reactor is a constant temperature reactor, and the specific control parameters are as follows: the space velocity of propane is 1h-1The propane partial pressure was 50kPa, the bed temperature was 600 ℃ and the results are shown in Table 1:
table 1 examples propane dehydrogenation evaluation data
Claims (9)
1. A modified chromium propane dehydrogenation catalyst fixed bed carrier is characterized by comprising a porous carrier, 1-40% of a first auxiliary agent by mass, 1-10% of a second auxiliary agent by mass and 1-10% of a third auxiliary agent by mass, wherein the first auxiliary agent is one or more of elements in a group IVA, the second auxiliary agent is one or more of rare earth elements, and the third auxiliary agent is one or more of alkali metal elements or alkaline earth elements.
2. The modified chromium-based propane dehydrogenation catalyst fixed-bed support according to claim 1, wherein the fixed-bed support is selected from the group consisting of a spinel structure having multi-stage pore channels, a perovskite structure, a molecular sieve structure, and a porous carbon structureOne less, the specific surface area is 50-500 m2The pore diameter is 3-40 nm.
3. The modified chromium-based propane dehydrogenation catalyst fixed-bed support according to claim 1, wherein the fixed-bed support has a specific surface area of 50 to 150m2The pore diameter is 10-30 nm.
4. The modified chromium-based propane dehydrogenation catalyst fixed-bed support according to any one of claims 1 to 3, wherein the porous support is one or more of an aluminum oxide, silica or a molecular sieve.
5. The modified fixed bed carrier of a chromium-based propane dehydrogenation catalyst of claim 1 wherein the group IVA element is selected from one or more of group IVA elemental powder, group IVA element oxide, group IVA element halide, group IVA element sulfide, group IVA element sulfate, group IVA element nitrate or group IVA element organic acid salt.
6. The modified fixed bed support of a chromium-based propane dehydrogenation catalyst of claim 1, wherein the rare earth element is selected from one or more of elemental rare earth metals, halides of rare earth metals, oxides of rare earth metals, sulfides of rare earth metals, sulfates of rare earth metals, nitrates of rare earth metals, or salts of organic acids of rare earth metals.
7. The modified fixed bed carrier for a chromium-based propane dehydrogenation catalyst according to claim 1, wherein the alkali metal element or alkaline earth metal element is selected from one or more of its corresponding simple substance, halide, oxide, sulfide, sulfate, nitrate or organic acid salt.
8. A method for preparing the modified chromium propane dehydrogenation catalyst fixed bed carrier according to any one of claims 1 to 7, characterized in thatThe method comprises the following steps: 1) mixing a porous carrier, concentrated nitric acid, sesbania powder, softened water, a first auxiliary agent, a second auxiliary agent and a third auxiliary agent in a ratio of 100: 6-13: 6-10: 60-80: 1-40: 1-10: 1-10, kneading, forming in a strip extruding machine, and drying at 80-150 ℃ for 8-12 hours to obtain a strip-shaped fixed bed carrier; 2) roasting the strip-shaped fixed bed carrier at 400-1000 ℃ for 1-10 hours to obtain the modified chromium propane dehydrogenation catalyst fixed bed carrier with the specific surface area of 50m2/g～450m2The pore diameter is 3-40 nm.
9. An application method of a modified chromium propane dehydrogenation catalyst fixed bed carrier is characterized in that the carrier is adopted to prepare the chromium propane dehydrogenation catalyst, and the preparation method specifically comprises the following steps: 1) preparing a mixed solution containing required active component elements, dipping the modified chromium propane dehydrogenation catalyst fixed bed carrier prepared in the claim 8 and the mixed solution under a vacuum condition, stirring, and aging for 0.5-8 hours to obtain a semi-finished product dehydrogenation catalyst; 2) and drying the semi-finished dehydrogenation catalyst for 0.5-8 hours, and then roasting at 600-1000 ℃ for 0.5-12 hours to obtain the modified chromium propane dehydrogenation catalyst prepared by the fixed bed carrier.
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| CN111468101A (en) * | 2019-01-24 | 2020-07-31 | 中国石油天然气股份有限公司 | Chromium-based catalyst and preparation method and application thereof |
| CN112246236A (en) * | 2020-11-18 | 2021-01-22 | 润和催化材料(浙江)有限公司 | Low-carbon alkane chromium-based dehydrogenation catalyst containing spinel structure and preparation method thereof |
| CN113244907A (en) * | 2021-04-19 | 2021-08-13 | 润和催化材料(浙江)有限公司 | Rare earth metal modification-based low-carbon alkane dehydrogenation catalyst and preparation method thereof |
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| CN111468101A (en) * | 2019-01-24 | 2020-07-31 | 中国石油天然气股份有限公司 | Chromium-based catalyst and preparation method and application thereof |
| CN112246236A (en) * | 2020-11-18 | 2021-01-22 | 润和催化材料(浙江)有限公司 | Low-carbon alkane chromium-based dehydrogenation catalyst containing spinel structure and preparation method thereof |
| CN113244907A (en) * | 2021-04-19 | 2021-08-13 | 润和催化材料(浙江)有限公司 | Rare earth metal modification-based low-carbon alkane dehydrogenation catalyst and preparation method thereof |
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| CN115055178A (en) * | 2022-07-08 | 2022-09-16 | 润和科华催化剂(上海)有限公司 | Low-carbon alkane chromium dehydrogenation catalyst and preparation method and application thereof |
| WO2024008168A1 (en) * | 2022-07-08 | 2024-01-11 | 润和科华催化剂(上海)有限公司 | Low-carbon alkane chromium dehydrogenation catalyst, preparation method therefor and application thereof |
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