CN113441129A - Composite metal oxide type alkane dehydrogenation catalyst and preparation method thereof - Google Patents
Composite metal oxide type alkane dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN113441129A CN113441129A CN202110901280.3A CN202110901280A CN113441129A CN 113441129 A CN113441129 A CN 113441129A CN 202110901280 A CN202110901280 A CN 202110901280A CN 113441129 A CN113441129 A CN 113441129A
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- active component
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- alkane dehydrogenation
- dehydrogenation catalyst
- alkane
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 40
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- 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 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001294 propane Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 6
- 239000001282 iso-butane Substances 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical group CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000005216 hydrothermal crystallization Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000009718 spray deposition Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910019923 CrOx Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
-
- 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
-
- 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
- C07C2523/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of gallium, indium or thallium
-
- 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
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
-
- 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
- C07C2523/18—Arsenic, antimony or bismuth
-
- 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
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
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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)
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- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of preparation of alkane dehydrogenation catalysts, and particularly relates to a preparation method of a composite metal oxide type alkane dehydrogenation catalyst. The catalyst prepared by the method comprises an active component AxB2-xO3, wherein A is one of La, Fe, Sc, In, Ga and Y, B is one of Al, Bi and B, a carrier is one or more of alumina, silica, zirconia and titania, Cr and noble metals are not contained, the catalyst is environment-friendly and cheap, and the catalyst can be applied to fixed bed, moving bed and fluidized bed devices through different forming processes.
Description
Technical Field
The invention belongs to the technical field of preparation of alkane dehydrogenation catalysts, and particularly relates to a composite metal oxide type alkane dehydrogenation catalyst and a preparation method of the catalyst.
Background
The alkane dehydrogenation technology has been industrialized, and the catalysts used at present mainly have two types: pt-based catalysts and CrOx-based catalysts. The Pt-based catalyst has high cost and is sensitive to sulfur, olefin and other poisons, so the requirements on raw materials are strict and the raw materials need to be pretreated. The CrOx-based catalyst is easy to coke and quickly deactivated and needs to be repeatedly regenerated; in addition, Cr6+ has strong toxicity, is a carcinogen published by the International center for anticancer research and the U.S. toxicological organization, hexavalent chromium is a first pollutant in the national industrial wastewater discharge standard, hexavalent chromium compounds are listed in the poisonous and harmful pollutant directory (first batch) at 7-24.7.2019, and serious environmental pollution can be caused in the preparation, use and subsequent recovery links of Cr-based catalysts. Therefore, there is a need to develop low cost, environmentally friendly alkane dehydrogenation catalysts.
Chinese patents CN111036260A and CN109939688A respectively disclose an iron-based propane dehydrogenation catalyst, but the catalyst conversion rate and selectivity are low, and industrialization is difficult to realize; CN109382090A discloses a molybdenum-vanadium bimetallic oxide catalyst, which has very good activity, but vanadium oxide has higher toxicity and stronger carcinogenicity; CN202011090154.6 discloses a Ga-based alkane dehydrogenation catalyst, but noble metals are added as auxiliary agents, and the evaluation method has larger difference with the industrial application condition; CN102451677, CN104610768 and CN105289622 provide a series of Al2O3、SiO2、ZrO2、TiO2And MgO as a carrier, and a plurality of metals as active components, the alkane dehydrogenation catalyst has the problems of incapability of coordinating conversion rate and selectivity and still has a space for optimizing and improving although a better propylene yield is obtained.
Disclosure of Invention
Aiming at the defects of the prior art, the invention develops a composite metal oxide type environment-friendly alkane dehydrogenation catalyst which has higher alkane conversion rate and alkene selectivity and can be used in fluidized bed, fixed bed and moving bed devices.
The application discloses a preparation method of the catalyst, which is simple in process, strong in operability and suitable for industrial application.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a composite metal oxide type alkane dehydrogenation catalyst, which comprises an active component AxB2-xO3 and a carrier; the active component AxB2-xO3 accounts for 5-35% of the total weight of the catalyst by the content of oxides, and the balance is a carrier, wherein the total mass percentage content is 100%.
In a preferred embodiment of the present application, a In the active component AxB2-xO3 is selected from any one of La, Fe, Sc, In, Ga, and Y.
In a preferred embodiment of the present invention, B in the active component AxB2-xO3 is selected from any one of Al, Bi and B.
In a preferred embodiment of the present application, x in the active component AxB2-xO3 is 0.05 to 1.95, preferably 0.4 to 1.6.
In a preferred embodiment of the present invention, the carrier is a composite carrier formed of one or more of alumina, silica, zirconia, and titania.
As a preferred embodiment herein, the above catalyst is used for alkane dehydrogenation, wherein the alkane comprises an alkane having 2 to 6 carbon atoms, more preferably, the alkane comprises ethane, propane, n-butane or isobutane, preferably propane or isobutane.
As a preferred embodiment herein, the preparation method of the alkane dehydrogenation catalyst comprises the following steps:
(1) dissolving a certain amount of A, B precursor in water, stirring uniformly, drying and roasting by adopting a sol-gel method, a coprecipitation method or a hydrothermal synthesis method to obtain an active component AxB2-xO 3;
(2) grinding the active component obtained in the step (1) into fine powder with the particle size of less than 20 microns, uniformly mixing the fine powder with a precursor of a carrier, and roasting the mixture at the temperature of 450-800 ℃ for 2-8 hours by adopting different forming processes to obtain the catalyst suitable for a fixed bed, a moving bed and a fluidized bed.
The raw material for preparing the dehydrogenation catalyst of the present invention has no special requirements in terms of the reactivity of the catalyst, and may be a salt, an alkali or an oxide. However, there are certain requirements in terms of catalyst physical properties, for example, when the catalyst is used in a fixed bed dehydrogenation reactor, the selected raw material must meet the requirement of catalyst extrusion molding; if the catalyst is used in a fluidized bed reactor, the raw materials must be selected to form a slurry with a certain fluidity to facilitate spray granulation.
The catalyst prepared by the extrusion method is used for a fixed bed reactor, the catalyst prepared by the oil ammonia column dropping ball method is used for a moving bed reactor, and the catalyst prepared by the spray granulation method is used for a fluidized bed reactor. The particle size distribution is mainly determined by adjusting some operation parameters in the spray granulation process, such as temperature, water amount or pump rotation speed. Of course, the catalyst formed by spray granulation may not necessarily have sufficient abrasion resistance, and some additives may be added.
The alkane dehydrogenation catalyst may further comprise optional additives such as extrusion agents, rheology control agents, binders, surfactants, and the like.
Compared with the prior art, the positive effects of the invention are as follows:
the catalyst does not contain noble metals such as Pt and the like, has relatively low price and is not sensitive to elements such as oxygen, sulfur and the like in the raw materials; the catalyst does not contain toxic components such as Cr and the like, and does not pollute the environment; the catalyst has high activity, and the selectivity of the alkane dehydrogenation to generate corresponding olefin is high; the catalyst has good stability and high mechanical strength.
And (II) the active component AxB2-xO3 is loaded on the carrier, so that the dispersion of the active component is promoted, the stability of the specific surface area is kept after high temperature, and the activity and the stability of the catalyst are improved.
And (III) lattice oxygen in the active component AxB2-xO3 can react with product hydrogen at high temperature to promote further dehydrogenation reaction, so that the activity of the catalyst is improved, and the amount and the activity of the lattice oxygen can be adjusted by adjusting A, B components and the content thereof.
Detailed Description
A composite metal oxide type alkane dehydrogenation catalyst, which comprises an active component AxB2-xO3 and a carrier; the active component AxB2-xO3 accounts for 5-35% of the total weight of the catalyst by the content of oxides, and the balance is a carrier, wherein the total mass percentage content is 100%.
Preferably, A In the active component AxB2-xO3 is selected from any one of La, Fe, Sc, In, Ga and Y.
Preferably, B in the active component AxB2-xO3 is selected from any one of Al, Bi and B.
Preferably, x in the active component AxB2-xO3 is 0.05-1.95, preferably 0.4-1.6.
Preferably, the carrier is a composite carrier formed by any one or more of alumina, silica, zirconia and titania.
Preferably, the catalyst is used for alkane dehydrogenation, the alkane comprises alkane with 2-6 carbon atoms, more preferably, the alkane comprises ethane, propane, n-butane or isobutane, and preferably propane and isobutane.
Preferably, the preparation method of the alkane dehydrogenation catalyst comprises the following steps:
(1) dissolving a certain amount of A, B precursor in water, stirring uniformly, drying and roasting by adopting a sol-gel method, a coprecipitation method or a hydrothermal synthesis method to obtain an active component AxB2-xO 3;
(2) grinding the active component obtained in the step (1) into fine powder with the particle size of less than 20 microns, uniformly mixing the fine powder with a precursor of a carrier, and roasting the mixture at the temperature of 450-800 ℃ for 2-8 hours by adopting different forming processes to obtain the catalyst suitable for a fixed bed, a moving bed and a fluidized bed.
Preferably, the alkane dehydrogenation catalyst may further comprise optional additives such as an extrusion agent, a rheology control agent, a binder, a surfactant, and the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
And (3) testing conditions are as follows: 100g of catalyst is prepared, performance evaluation is carried out on a fluidized bed device, pure propane is used as a raw material, the reaction temperature is 600 ℃, and the mass space velocity is 3h < -1 >.
Example 1:
dissolving 40.61g of ferric nitrate nonahydrate and 87.99g of aluminum nitrate nonahydrate in water, uniformly stirring, adding a proper amount of ammonia water, adjusting the pH to 6.5-7.5, standing for 4h, drying at 120 ℃ for 8h, and roasting at 620 ℃ for 4h to obtain an active component Fe0.6Al1.4O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing the fine powder with 54.29g of pseudo-boehmite and 166.7g of silica sol, adding a proper amount of nitric acid, adjusting the pH value to 3-4, carrying out spray forming, and roasting at 600 ℃ for 3 hours to obtain the catalyst 1.
The catalyst evaluation results show that: propane conversion was 34.65% with a selectivity of 85.76%.
Example 2:
dissolving 19.90g of scandium chloride and 73.94g of aluminum nitrate nonahydrate in water, uniformly stirring, adding a proper amount of sodium carbonate to precipitate the scandium chloride and the aluminum nitrate, filtering, washing with water for 4 times, drying at 100 ℃ for 6h, and roasting at 680 ℃ for 6h to obtain an active component Sc0.8Al1.2O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing with 80g of titanium oxide and 5.3g of sesbania powder, tabletting and molding, and roasting at 500 ℃ for 3 hours to obtain the catalyst 2.
The catalyst evaluation results show that: the propane conversion was 36.03% with a selectivity of 86.24%.
Example 3
Dissolving 11.27g of indium chloride and 4.73g of boric acid in water, uniformly stirring, adding a proper amount of ammonia water, adjusting the pH value to 5-6, carrying out hydrothermal crystallization at 80 ℃ for 24h, drying at 150 ℃ for 3h, and roasting at 500 ℃ for 3h to obtain an active component In0.8B1.2O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing with 92g of zirconia and 7.8g of polyvinylidene fluoride, tabletting and molding, and roasting at 500 ℃ for 3 hours to obtain the catalyst 3.
The catalyst evaluation results show that: propane conversion was 32.97% with selectivity 88.73%.
Example 4
Dissolving 38.37g of gallium nitrate nonahydrate and 28.96g of bismuth trichloride in water, uniformly stirring, adding a proper amount of ammonia water, adjusting the pH to 5-6, carrying out hydrothermal crystallization at 90 ℃ for 24 hours, drying at 125 ℃ for 3 hours, and roasting at 600 ℃ for 3 hours to obtain an active component GaBiO 3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing with 70g of zirconium oxide and 6.2g of polyvinyl alcohol, tabletting and molding, and roasting at 450 ℃ for 8 hours to obtain the catalyst 4.
The catalyst evaluation results show that: the propane conversion was 30.46% with a selectivity of 90.33%.
Example 5
Dissolving 20.78g of yttrium chloride and 26.58g of aluminum nitrate nonahydrate in water, uniformly stirring, adding a proper amount of sodium carbonate to precipitate scandium chloride and aluminum nitrate, filtering, washing with water for 4 times, drying at 130 ℃ for 4h, and roasting at 680 ℃ for 4h to obtain an active component Y1.2Al0.8O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing the fine powder with 122.86g of pseudo-boehmite, 5g of nitric acid and 5g of sesbania powder, extruding the mixture into strips, and roasting the strips at 800 ℃ for 3 hours to obtain the catalyst 5.
The catalyst evaluation results show that: propane conversion was 35.47% with selectivity 89.67%.
Example 6
Dissolving 31.50g of lanthanum nitrate and 1.50g of boric acid in water, uniformly stirring, adding a proper amount of ammonia water, adjusting the pH value to 5-6, carrying out hydrothermal crystallization at 100 ℃ for 12h, drying at 100 ℃ for 6h, and roasting at 600 ℃ for 4h to obtain an active component La1.5B0.5O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing with 43.5g of titanium oxide, 40g of zirconium oxide, 20g of water, 8g of glycerol and 5g of starch, extruding into strips, and roasting at 700 ℃ for 3 hours to obtain the catalyst 6.
The catalyst evaluation results show that: propane conversion was 33.70% with a selectivity of 86.44%.
Example 7
Dissolving 20.74g of ferric nitrate nonahydrate and 85.59g of aluminum nitrate nonahydrate in water, uniformly stirring, adding a proper amount of ammonia water, adjusting the pH to be about 6.5-7.5, standing for 6h, drying at 120 ℃ for 8h, and roasting at 700 ℃ for 4h to obtain an active component Fe0.75Al1.25O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing with 260g of silica sol, spray-forming, and roasting at 700 ℃ for 4 hours to obtain the catalyst 7. The catalyst evaluation results show that: propane conversion was 37.12% with selectivity 85.64%.
Example 8
Dissolving 9.79g of indium chloride and 17.06g of bismuth trichloride in water, stirring uniformly, adding a proper amount of ammonia water, adjusting the pH value to 5-6, carrying out hydrothermal crystallization at 85 ℃ for 12h, drying at 120 ℃ for 3h, and roasting at 650 ℃ for 4h to obtain an active component In0.9Bi1.1O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing with 275g of silica sol, spray-forming, and roasting at 600 ℃ for 7 hours to obtain the catalyst 8.
The catalyst evaluation results show that: the propane conversion was 32.25% with a selectivity of 86.49%.
Example 9
Dissolving 5.57g of scandium chloride and 7.73g of bismuth chloride in water, stirring uniformly, adding a proper amount of sodium carbonate to precipitate the scandium chloride and the bismuth chloride, filtering, washing with water for 4 times, drying at 100 ℃ for 6h, and roasting at 540 ℃ for 4h to obtain an active component Sc1.2Bi0.8O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing with 91.5g of titanium oxide, 18g of water, 5g of sesbania powder and 5.4g of polyvinyl alcohol, extruding into strips, and roasting at 500 ℃ for 3 hours to obtain the catalyst 9.
The catalyst evaluation results show that: the propane conversion was 34.71% with a selectivity of 88.38%.
Example 10
57.04g of lanthanum nitrate and 32.95g of aluminum nitrate nonahydrate are dissolved in water, evenly stirred, added with a proper amount of ammonia water, adjusted to pH of 6.5-7.5, kept stand for 4h, dried at 120 ℃ for 8h, and roasted at 580 ℃ for 4h to obtain an active component La1.2Al0.8O3;
grinding the obtained active component into fine powder with the particle size of less than 20 mu m, uniformly mixing with 223.3g of silica sol, spray-forming, and roasting at 600 ℃ for 3h to obtain the catalyst 10.
The catalyst evaluation results show that: the propane conversion was 31.59% with a selectivity of 92.24%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A composite metal oxide type alkane dehydrogenation catalyst is characterized by comprising an active component AxB2-xO3 and a carrier; in terms of the content of oxides, the active component AxB2-xO3 accounts for 5-35% of the total weight of the catalyst, the balance is a carrier, and the sum of the total mass percentage is 100%.
2. The alkane dehydrogenation catalyst of claim 1, wherein: a In the active component AxB2-xO3 is any one of La, Fe, Sc, In, Ga and Y.
3. An alkane dehydrogenation catalyst according to claim 1 or 2, wherein: and B in the active component AxB2-xO3 is any one of Al, Bi and B.
4. An alkane dehydrogenation catalyst according to claim 1 or 2, wherein: the value of x in the active component AxB2-xO3 is 0.05-1.95.
5. The alkane dehydrogenation catalyst of claim 1, wherein: the carrier is a composite carrier formed by any one or more of alumina, silica, zirconia and titania.
6. Use of an alkane dehydrogenation catalyst according to any of claims 1-5, wherein: the catalyst is used for alkane dehydrogenation, and the alkane comprises alkane with 2-6 carbon atoms.
7. Use of an alkane dehydrogenation catalyst according to claim 6, wherein: the alkane is ethane, propane, n-butane or isobutane.
8. A process for the preparation of an alkane dehydrogenation catalyst according to any of claims 1 to 5, comprising the steps of:
(1) dissolving a certain amount of A, B precursor in water, stirring uniformly, drying and roasting by adopting a sol-gel method, a coprecipitation method or a hydrothermal synthesis method to obtain an active component AxB2-xO 3;
(2) grinding the active component obtained in the step (1) into fine powder with the particle size of less than 20 microns, uniformly mixing the fine powder with a precursor of a carrier, forming by adopting a forming process, and roasting at 450-800 ℃ for 2-8 hours to obtain the alkane dehydrogenation catalyst suitable for a fixed bed, a moving bed and a fluidized bed.
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