CN107486195A - Preparation method of low-carbon alkane dehydrogenation catalyst - Google Patents
Preparation method of low-carbon alkane dehydrogenation catalyst Download PDFInfo
- Publication number
- CN107486195A CN107486195A CN201610412871.3A CN201610412871A CN107486195A CN 107486195 A CN107486195 A CN 107486195A CN 201610412871 A CN201610412871 A CN 201610412871A CN 107486195 A CN107486195 A CN 107486195A
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- China
- Prior art keywords
- catalyst
- dehydrogenation
- low
- preparation
- carbon paraffin
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000011651 chromium Substances 0.000 claims abstract description 37
- 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 32
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 30
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- 239000012188 paraffin wax Substances 0.000 claims description 30
- 238000005470 impregnation Methods 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 235000001727 glucose Nutrition 0.000 claims description 13
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 30
- 239000003643 water by type Substances 0.000 description 16
- 229910052593 corundum Inorganic materials 0.000 description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical class O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 235000013844 butane Nutrition 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910000423 chromium oxide Inorganic materials 0.000 description 5
- 238000001802 infusion Methods 0.000 description 5
- 239000001282 iso-butane Substances 0.000 description 5
- 235000013847 iso-butane Nutrition 0.000 description 5
- 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
- 239000001273 butane Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910001680 bayerite Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- -1 alkanes alkene Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000012684 catalyst carrier precursor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- 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
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
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- 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
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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
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a low-carbon alkane dehydrogenation catalyst, which comprises the steps of dissolving a high-valence chromium precursor in a reducing agent solution, dipping the high-valence chromium precursor into an alumina-based carrier, reacting at the reaction temperature of 30-200 ℃ for 0.5-20 h, washing, filtering, drying, dipping an auxiliary agent, drying and roasting to obtain the low-carbon alkane dehydrogenation catalyst. The method has the advantages that the Cr clusters are controllable, the catalyst with moderate Cr dispersion degree is obtained by an in-situ reduction method, the acid content of B on the surface of the catalyst is reduced, the utilization efficiency of active atom Cr is improved, and the dehydrogenation activity, selectivity and anti-carbon deposition performance of the catalyst are improved.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, particularly a kind of preparing propylene by dehydrogenating propane and
The preparation method of the catalyst of butane dehydrogenation butylene.
Background technology
In recent years, it is also growing to the demand of low-carbon alkene with the fast development of Global Oil chemical industry.Low-carbon
Dehydrating alkanes technology is to increase production the effective way of C3~C4 alkene.
Low-carbon alkanes catalytic dehydrogenating reaction is limited by thermodynamical equilibrium, must high temperature, low pressure harsh conditions under carry out.
Too high temperature, decline alkane cracking reaction and deep dehydrogenation aggravation, selectivity；Accelerate catalyst surface carbon distribution simultaneously, make
Rapid catalyst deactivation.
At present, overseas enterprise has developed more set catalytic dehydrogenation of butanes butylene industrialization technologies, and supporting dehydrogenation is urged
Agent is Pt/Al respectively2O3Series catalysts and chromium oxide/aluminum oxide (Cr2O3/Al2O3) series catalysts.
Traditional chromium oxide/aluminum oxide catalyst is typically prepared using infusion process, and CN86104031A discloses one kind and prepared
Aluminum oxide with microballoon shape is carried out double roasting, will be calcined by the method for C3~C5 paraffin hydrocarbon dehydrogenation catalysts, this method
Product afterwards is impregnated and dried with the solution containing chromium and potassium compound, then soaks products obtained therefrom with siliceous compound solution
Stain, finally it is dried and is calcined.Dehydrogenation of isobutane conversion ratio is 53%, and selectivity is 88%, and dehydrogenating propane conversion ratio is
46%, selectivity is 82%.CN1213662A is prepared for a kind of microspherical catalyst of fluid bed, the catalyst system and catalyzing chromium content 6%
~30%, K2O content 0.4%~3%, silica content 0.08%~3%, Theil indices are 0.1%~3.5%, use aluminum oxide
Supply to 100%.
CN1185994A discloses a kind of catalyst for producing isobutylene by catalytic dehydrogenation of isobutane, with coprecipitation and mixes
Catalyst expression prepared by slurry processes is AaBbCcDdOx, the expression of the loaded catalyst prepared with infusion process：AaBbCc/ carry
Body, elements A Cr, element B are Cu and La, and Elements C K, element D are Al, and the carrier of supported catalyst is γ-Al2O3.Different
Butane air speed 400h-1When, iso-butane conversion ratio is not more than 60%, selectivity 93% or so.
US2010/0312035 discloses a kind of dehydrogenation, catalyst composition is chromium oxide, lithia, sodium oxide molybdena,
Aluminum oxide and alkaline earth oxide.CN104010725A by be spray-dried bayerite powder, bayerite slurry in
Using acid come precipitated silica or using sodium silicate solution come the dioxy that impregnates bayerite or be coextruded and prepare therewith
The stable alumina powder of SiClx is found to be preferable catalyst carrier precursor, with these silica containing carrier materials of bag
The catalyst of preparation has higher hydrothermal stability.
CN103447065A is related to a kind of butane dehydrogenation catalyst and preparation method.Butane dehydrogenation catalyst is by following material
Form by weight percentage：Chrome green：12~20, potassium oxide：1~2, vanadic anhydride：1~2, silica：1~2,
Molecular sieve：Supply to 100.Processing step includes：(1) impregnate, molecular sieve is soaked with the solution containing chromium, potassium and vfanadium compound
Stain, product are dried；(2) lattice is fixed, and by step, (1) dried product carries out active component crystalline substance with silicon compound solution again
Lattice are fixed；(3) product is calcined, and by step, (2) dried product heats roasting with certain rate of warming, until reach 600 DEG C,
And it is incubated 1h；Beneficial effect is：The damage and loss of catalyst active phase in use are prevented, improves catalytic mechanical
Intensity and longtime running stability.
CN101940922 discloses a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, and the catalyst is with oxygen containing chromium
Change aluminium is carrier, and wherein the weight content of chromium oxide in the carrier is 2.0%~15%, and active metal component chromium introduces aluminum oxide
Method in carrier is that part uses kneading method, partly using infusion process, and is mixed into using three one-step baking methods and hydro-thermal method processing
The boehmite of chromium, it can so improve the pore structure and surface nature of carrier, a step of going forward side by side becomes active metal chromium in carrier
In content, the interaction between distribution and metal active and aluminum oxide, not only increase the activity and stability of catalyst, and
And the carbon accumulation resisting ability of catalyst is enhanced, extend the service life of catalyst.
CN103769078A discloses a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, and the catalyst is with Al2O3For
Carrier, using chromium as active component, using alkali metal as co-catalysis component, on the basis of the weight by final catalyst, chromium oxide contains
Measure as 10%~30%, alkali metal oxide content is 0.5%~3.0%, and surplus is aluminum oxide, and described active component chromium exists
Impregnate before alkali metal co-catalysis component and after dipping alkali metal co-catalysis component step impregnation on alumina support.Above-mentioned low-carbon
Dehydrating alkanes alkene catalyst is applied in preparing propylene by dehydrogenating propane, has high activity stability and Propylene Selectivity, and
And preparation method is simple, suitable for commercial Application.
CN103769079A discloses a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof, and the catalyst is aoxidized with La
Aluminium is carrier, using chromium as active component, in terms of the weight content of oxide, in final catalyst lanthanum oxide content be 0.1~
5.0, chromic oxide content is 5~20, and the La in alumina support containing La in aluminum oxide preparation process during plastic by introducing.Institute
The preparation method of catalyst for dehydrogenation of low-carbon paraffin is stated, is comprised the following steps：The preparation of the alumina support containing La and the oxidation containing La
Aluminium uses infusion process load active component chromium process.Described dehydrogenation is applied in preparing propylene by dehydrogenating propane, the catalysis
Agent does not contain basic anhydride, avoids the strong interaction between basic anhydride and active component, improves dehydrogenation
Activity, the selectivity of stability and propylene.
Above method for preparing catalyst often takes infusion process, and the dispersity of active component chromium is difficult regulation and control, too high point
Divergence can cause the stability of catalyst poor；Too low decentralization can cause the poor activity of catalyst.
The content of the invention
In view of the above-mentioned problems, the invention provides a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, by situ anti-
Dispersity of the Cr species on carrier should be adjusted, the activity, selectivity and stability of catalyst is accordingly improved.
The present invention provides a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, wherein, high valence chrome predecessor is dissolved in also
In former agent solution, it is impregnated into alumina-based supports, is 30~200 DEG C in reaction temperature, the reaction time is 0.5~20h bar
Reacted under part, be washed out, filter, after drying, impregnation aids, then obtain catalyst for dehydrogenation of low-carbon paraffin after drying, roasting.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the high valence chrome predecessor is preferably
CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4In one or more.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the reductant solution is preferably second
Glycol, glycerine, glucose, the aqueous solution of oxalic acid or vitamin c component.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the reductant solution be glucose,
During the aqueous solution of oxalic acid or vitamin c component, the mass concentration of glucose, oxalic acid or vitamin c component is preferably 1wt.%
~60wt.%, more preferably 3wt.%~30wt.%.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the alumina-based supports are preferably
Alumina support or the alumina support containing refractory inorganic oxides；The refractory inorganic oxides are preferably silica, oxygen
Change the one or more in zirconium and titanium oxide；Content of the refractory inorganic oxides in alumina-based supports be preferably
Below 5wt.%.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the reducing agent and high valence chrome forerunner
The mol ratio of thing is preferably 0.1~10：1, more preferably 0.5~5:1.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the auxiliary agent be preferably Na, K, Ca,
One or more of nitrate or acetate in Sr, La, Sn, Cu, Ni, Co, Fe and Zn.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the drying, roasting are in air gas
Carried out under atmosphere, 1~8h is preferably dried in the drying at 60~150 DEG C；The roasting preferably roasts at 600~750 DEG C
Burn 1~20h.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, wherein, the reaction temperature is preferably 60~
140 DEG C, the reaction time is preferably 0.5~3h.
It is an advantage of the invention that Cr clusters are controllable, the catalyst of moderate Cr decentralization is obtained by the method for in-situ reducing,
Catalyst surface B acid acid amounts are reduced, improve active atomic Cr utilization ratio, it is the dehydrogenation activity of catalyst, selective, anti-
Carbon distribution performance improves.
Embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out lower premised on technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
The experimental method of unreceipted actual conditions in example, generally according to normal condition.
The present invention is achieved by the following technical solutions：The predecessor of high valence chrome is dissolved in reductant solution, impregnated
Into alumina-based supports, under the conditions of temperature is 30~200 DEG C, preferably 60~140 DEG C, 0.5~20h is reacted, is preferably
0.5~3h, it is washed out, filters, after drying, impregnates function additive, then catalyst is obtained after drying, roasting.In catalyst
Cr2O3Content be 3wt.%~20wt.%, auxiliary agent content is 0.5wt.%~6wt.%.
The predecessor of described high valence chrome is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、
Na2CrO4、K2CrO4One or more.
Described reductant solution is that high valence chrome can be made to be reduced to the reagent of positive trivalent chromium, selected from ethylene glycol, glycerine,
Or containing glucose, oxalic acid, vitamin c component the aqueous solution.Described reductant solution is preferably ethylene glycol and glucose
The aqueous solution.In the present invention to it is described containing glucose, oxalic acid, vitamin c component the aqueous solution mass concentration do not make it is special
Limit, as long as its concentration can dissolve the predecessor of high valence chrome, its mass concentration is generally 1wt.%~60wt.%,
Preferably 3wt.%~30wt.%.
Described alumina-based supports refer to that alumina support or the aluminum oxide containing other a small amount of refractory inorganic oxides are
Carrier, other refractory inorganic oxides are generally the one or more of silica, zirconium oxide, titanium oxide, in alumina-based supports
In content in below 5wt.%.
The mol ratio 0.1~10 of the reducing agent and high valence chrome：1, preferably 0.5~5:1.
Described auxiliary agent is Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe, Zn one or more nitrate, acetic acid
The nitrate or acetate of salt, preferably K and Cu.
Described catalyst is dry, roasting is to carry out in air atmosphere, and described drying is dried at 60~150 DEG C
1~8h；Described roasting is 1~20h of roasting at 600~750 DEG C.
It is as follows using the catalyst property obtained by the inventive method：80~200m of specific surface area2·g-1, pore volume 0.2~
0.6cm3·g-1, 4~15nm of average pore diameter.
The catalyst is used for the catalytic dehydrogenation of C3~C6 alkane components.
High valence chrome and reducing agent reaction generation Cr2O3, pass through the confinement effect in duct and the regulation and control of reaction condition, Cr2O3Directly
Deliver a child into the cluster of sub- nanometer and then be attached on hole wall, cluster size is homogeneous in the process and can regulate and control.Relative to leaching
The methods of stain method, precipitation method, the method for this reaction in-situ can obtain the Cr of different decentralization2O3Base catalyst.High degree of dispersion
Cr surfaces contain more Cr-OH, corresponding more B acid sites, in dehydrogenating low-carbon alkane reaction, easily cause depth to be split
Solution reaction lures the quick carbon distribution of catalyst into and inactivated that the selectivity of catalyst is poor, and deactivation rate is very fast；In low polydispersity situation
Under, Cr atoms are gathered into the Cr of bulky grain2O3, because dehydrogenating low-carbon alkane reaction is surface-catalyzed reactions, the Cr inside particle is former
Son, which is completely wrapped, causes atom utilization ratio step-down, meanwhile, the Cr of bulky grain2O3The side reactions such as easy inducing lysis occur, phase
It is corresponding that there is relatively low catalytic activity and selectivity.The present invention by effectively regulating and controlling dispersity of the Cr species on carrier,
Activity, selectivity and the stability of catalyst are accordingly improved.
Embodiment 1
2.23g(NH4)2Cr2O7It is dissolved in 8ml ethylene glycol, incipient impregnation to 10g porous gammas-Al2O3In powder.The powder
End is placed into 120 DEG C of baking ovens and handles 4h, is washed with deionized, filters, 2h is dried at 80 DEG C.0.37gKNO38ml is dissolved in go
In ionized water, incipient impregnation is dried 4h, 680 DEG C of roasting 5h, sieved through overmolding into above-mentioned treated powder at 80 DEG C
Obtain catalyst and be denoted as catalyst A.
Comparative example 1
7.08gCr(NO3)3·9H2O、0.37gKNO3It is dissolved in 4ml deionized waters, incipient impregnation to 10g porous gammas-
Al2O3In powder, 4h, 680 DEG C of roasting 5h are dried at 80 DEG C, sieves to obtain catalyst through overmolding and is denoted as catalyst B.
Embodiment 2
1.77gCrO3、2.48g(NH4)2C2O4It is dissolved in 8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3
In powder.Powder is placed into 60 DEG C of baking ovens and handles 6h, is washed with deionized, filters, 2h is dried at 100 DEG C.0.78gCu
(NO3)2·3H2O、1.12gFe(NO3)3·9H2O is dissolved in 7ml deionized waters, incipient impregnation to above-mentioned treated powder
In, 3h, 700 DEG C of roasting 6h are dried at 120 DEG C, sieves to obtain catalyst through overmolding and is denoted as catalyst C.
Comparative example 2
7.08gCr(NO3)3·9H2O、0.78gCu(NO3)2·3H2O、1.12gFe(NO3)3·9H2O be dissolved in 3.5ml go from
In sub- water, incipient impregnation to 10g porous gammas-Al2O3In powder, 4h is dried at 80 DEG C, 700 DEG C of roasting 6h, is sieved through overmolding
Obtain catalyst and be denoted as catalyst D.
Embodiment 3
1.30gK2Cr2O7It is dissolved in 8ml glycerine, incipient impregnation to 10g porous gammas-Al2O3In powder.Powder is placed
1h is handled into 140 DEG C of baking ovens, is washed with deionized, filters, 4h is dried at 80 DEG C.0.33gNaNO3、0.82gNi
(NO3)2·6H2O is dissolved in 8ml deionized waters, and incipient impregnation is into above-mentioned treated powder, dry 6h at 60 DEG C, and 720
DEG C roasting 4h, sieves to obtain catalyst and is denoted as catalyst E through overmolding.
Comparative example 3
3.54gCr(NO3)3·9H2O、0.33gNaNO3、0.82gNi(NO3)2·6H2O is dissolved in 6.0ml deionized waters,
Incipient impregnation is to 10g porous gammas-Al2O3In powder, 4h is dried at 80 DEG C, 720 DEG C of roasting 4h, sieves and is urged through overmolding
Agent is denoted as catalyst F.
Embodiment 4
2.30gNa2CrO4, 0.39g glucose be dissolved in 8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3
In powder.Powder is placed into 85 DEG C of baking ovens and handles 4h, is washed with deionized, filters, 3h is dried at 95 DEG C.0.37gKNO3、
0.32gLa(NO3)3·6H2O、1.14gFe(NO3)2·9H2O is dissolved in 7ml deionized waters, and incipient impregnation treats to above-mentioned
Powder in, 5h, 690 DEG C of roasting 6h are dried at 70 DEG C, sieves to obtain catalyst through overmolding and is denoted as catalyst G.
Comparative example 4
5.66gCr(NO3)3·9H2O、0.37gKNO3、0.32gLa(NO3)3·6H2O、1.14gFe(NO3)2·9H2O is molten
In 4.8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3In powder, 4h, 690 DEG C of roasting 6h are dried at 80 DEG C,
Sieve to obtain catalyst through overmolding and be denoted as catalyst H.
Embodiment 5
3.77gK2CrO4, 2.82g ascorbic acid be dissolved in 8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3
In powder.Powder is placed into 60 DEG C of baking ovens and handles 1h, is washed with deionized, filters, 4h is dried at 80 DEG C.0.28gKNO3、
0.65gCu(NO3)2·3H2O is dissolved in 8ml deionized waters, and incipient impregnation is dried into above-mentioned treated powder at 60 DEG C
6h, 720 DEG C of roasting 4h, sieve to obtain catalyst and are denoted as catalyst I through overmolding.
Comparative example 5
7.79gCr(NO3)3·9H2O、0.28gKNO3、0.65gCu(NO3)2·3H2O is dissolved in 3.0ml deionized waters, etc.
Volume impregnation is to 10g porous gammas-Al2O3In powder, 4h is dried at 80 DEG C, 720 DEG C of roasting 4h, sieves and is catalyzed through overmolding
Agent is denoted as catalyst J.
Embodiment 6
3.23g(NH4)2CrO4It is dissolved in 8ml ethylene glycol, incipient impregnation to 10g porous gammas-Al2O3In powder.The powder
It is placed into 150 DEG C of baking ovens and handles 0.5h, is washed with deionized, filters, 2h is dried at 80 DEG C.0.28gKNO3、0.65gCu
(NO3)2·3H2O is dissolved in 8ml deionized waters, and incipient impregnation is into above-mentioned treated powder, dry 4h at 80 DEG C, and 680
DEG C roasting 8h, sieves to obtain catalyst and is denoted as catalyst K through overmolding.
Comparative example 6
3.23g(NH4)2CrO4、0.28gKNO3、0.65gCu(NO3)2·3H2O is dissolved in 7.6ml deionized waters, in equal volume
It is impregnated into above-mentioned treated powder, 4h, 680 DEG C of roasting 8h is dried at 80 DEG C, sieves to obtain catalyst through overmolding and be denoted as
Catalyst L.
The catalyst prepared by various embodiments above is taken to be evaluated on micro-reactor, propane catalytic dehydrogenation appreciation condition is：
Volume space velocity 1200h-1, 610 DEG C of reaction temperature, reaction pressure is normal pressure；Catalytic dehydrogenation of isobutane appreciation condition is：Volume space velocity
600h-1, 590 DEG C of reaction temperature, reaction pressure is normal pressure.
Embodiment 7
1.66g(NH4)2Cr2O7、1.63gNa2CrO4, 0.92g glucose be dissolved in 8ml deionized waters, incipient impregnation arrives
10g porous gammas-Al2O3In powder.The powder is placed into 95 DEG C of baking ovens and handles 2h, is washed with deionized, filters, at 60 DEG C
Dry 10h.0.16gCa(NO3)2·4H2O、0.11gSr(NO3)2、2.33gCo(NO3)2·6H2O is dissolved in 7ml deionized waters,
Incipient impregnation dries 4h, 750 DEG C of roasting 10h, sieves and be catalyzed through overmolding into above-mentioned treated powder at 80 DEG C
Agent is denoted as catalyst M.
Comparative example 7
9.3gCr(NO3)3·9H2O、0.16gCa(NO3)2·4H2O、0.11gSr(NO3)2、2.33gCo(NO3)2·6H2O
It is dissolved in 3.8ml deionized waters, incipient impregnation to 10g porous gammas-Al2O3In powder, 4h, 750 DEG C of roastings are dried at 80 DEG C
10h, sieves to obtain catalyst and is denoted as catalyst n through overmolding.
The activity rating of the catalyst of table 1
The catalyst (A, C, E, G, I, K, M) synthesized using in-situ reducing is can be seen that from the evaluating catalyst result of table 1 to turn
Better than the catalyst (B, D, F, H, J, L, N) of corresponding direct impregnation in rate, selectivity and stability.Prepared by change
Reaction condition, optimization auxiliary agent in journey, catalyst performance have further raising.Dehydrogenating propane starting yield ＞ 46%, iso-butane
Dehydrogenation starting yield ＞ 62.2%.
Claims (11)
1. a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, it is characterised in that it is molten that high valence chrome predecessor is dissolved in reducing agent
In liquid, it is impregnated into alumina-based supports, is 30~200 DEG C in reaction temperature, the reaction time is anti-under conditions of 0.5~20h
Should, it is washed out, filters, after drying, impregnation aids, then obtain catalyst for dehydrogenation of low-carbon paraffin after drying, roasting.
2. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, it is characterised in that the high valence chrome forerunner
Thing is CrO3、(NH4)2Cr2O7、Na2Cr2O7、K2Cr2O7、(NH4)2CrO4、Na2CrO4And K2CrO4In one or more.
3. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, it is characterised in that the reductant solution
For the aqueous solution of ethylene glycol, glycerine, glucose, oxalic acid or vitamin c component.
4. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 3, it is characterised in that the reductant solution
For glucose, oxalic acid or vitamin c component the aqueous solution when, the mass concentration of glucose, oxalic acid or vitamin c component is
1wt.%~60wt.%.
5. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 4, it is characterised in that the reductant solution
For glucose, oxalic acid or vitamin c component the aqueous solution when, the mass concentration of glucose, oxalic acid or vitamin c component is
3wt.%~30wt.%.
6. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 1, it is characterised in that the aluminum oxide base load
Body is alumina support or the alumina support containing refractory inorganic oxides；The refractory inorganic oxides are silica, oxygen
Change the one or more in zirconium and titanium oxide；Content of the refractory inorganic oxides in alumina-based supports be 5wt.% with
Under.
7. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin as described in any one of claim 1~6, it is characterised in that described
The mol ratio of reducing agent and high valence chrome predecessor is 0.1~10：1.
8. the preparation method of catalyst for dehydrogenation of low-carbon paraffin as claimed in claim 7, it is characterised in that the reducing agent and height
The mol ratio of valency chromium predecessor is 0.5~5:1.
9. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin as described in any one of claim 1~6, it is characterised in that described
Auxiliary agent is one or more of nitrate or acetate in Na, K, Ca, Sr, La, Sn, Cu, Ni, Co, Fe and Zn.
10. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin as described in any one of claim 1~6, it is characterised in that described
It is to carry out in air atmosphere to dry, be calcined, and the drying is that 1~8h is dried at 60~150 DEG C；The roasting is 600
1~20h is calcined at~750 DEG C.
11. the preparation method of the catalyst for dehydrogenation of low-carbon paraffin as described in any one of claim 1~6, it is characterised in that described
Reaction temperature is 60~140 DEG C, and the reaction time is 0.5~3h.
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| CN113329814A (en) * | 2018-11-13 | 2021-08-31 | 科莱恩国际有限公司 | Alumina chromium dehydrogenation catalyst and preparation and use methods thereof |
| CN114054021A (en) * | 2020-07-31 | 2022-02-18 | 中国科学院大连化学物理研究所 | Application of Cu catalyst in alkane dehydrogenation reaction |
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| CN112221491A (en) * | 2019-06-30 | 2021-01-15 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with modified spherical mesoporous material as carrier and preparation method and application thereof |
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| CN114054021A (en) * | 2020-07-31 | 2022-02-18 | 中国科学院大连化学物理研究所 | Application of Cu catalyst in alkane dehydrogenation reaction |
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| CN112495422A (en) * | 2020-12-03 | 2021-03-16 | 昆明理工大学 | Method for preparing silicon-based chromium catalyst by in-situ roasting, product and application thereof |
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