CN113694923A - Low-carbon alkane dehydrogenation catalyst and preparation method and application thereof - Google Patents
Low-carbon alkane dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN113694923A CN113694923A CN202111149463.0A CN202111149463A CN113694923A CN 113694923 A CN113694923 A CN 113694923A CN 202111149463 A CN202111149463 A CN 202111149463A CN 113694923 A CN113694923 A CN 113694923A
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- Prior art keywords
- acid
- catalyst
- alkane dehydrogenation
- carrier
- dehydrogenation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002131 composite material Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 32
- 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 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 21
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 16
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 12
- 238000005470 impregnation Methods 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 52
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 26
- 229910052718 tin Inorganic materials 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052700 potassium Inorganic materials 0.000 claims description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003463 adsorbent Substances 0.000 claims description 14
- 230000002860 competitive effect Effects 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 13
- 238000004898 kneading Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- -1 hydroxycarbonates Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
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- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 claims description 3
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 2
- 229940061720 alpha hydroxy acid Drugs 0.000 claims description 2
- 150000001280 alpha hydroxy acids Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- DLVZBSZXZDGKQY-UHFFFAOYSA-N 2,2-dihydroxybutanoic acid Chemical compound CCC(O)(O)C(O)=O DLVZBSZXZDGKQY-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 9
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004939 coking Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 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 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- 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 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 6
- 239000001119 stannous chloride Substances 0.000 description 6
- 235000011150 stannous chloride Nutrition 0.000 description 6
- IKEUZCGOPYSHNN-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]benzoic acid Chemical compound OC(=O)CN(CC(O)=O)C1=CC=CC=C1C(O)=O IKEUZCGOPYSHNN-UHFFFAOYSA-N 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
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- 239000004323 potassium nitrate Substances 0.000 description 5
- 235000010333 potassium nitrate Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- 238000001816 cooling Methods 0.000 description 4
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
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- 239000001273 butane Substances 0.000 description 3
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- 238000011161 development Methods 0.000 description 3
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
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- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
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- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- PEQJBOMPGWYIRO-UHFFFAOYSA-N n-ethyl-3,4-dimethoxyaniline Chemical compound CCNC1=CC=C(OC)C(OC)=C1 PEQJBOMPGWYIRO-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 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
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8973—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony or bismuth
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- 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
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/656—Manganese, technetium or rhenium
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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Abstract
The invention belongs to the technical field of dehydrogenation catalysts, particularly relates to a low-carbon alkane dehydrogenation catalyst, and further discloses a preparation method thereofThe method and the application. The low-carbon alkane dehydrogenation catalyst provided by the invention is prepared from Sn-X-Al2O3The composite carrier is a carrier, and platinum and alkali metal or alkaline earth metal are loaded as effective components, so that the catalyst has high activity, good selectivity and good stability under high-temperature operation conditions; and moreover, the catalyst has strong anti-carbon deposition capability, slow coking rate and excellent regeneration performance, and is suitable for a catalytic system of a low-carbon alkane dehydrogenation process.
Description
Technical Field
The invention belongs to the technical field of dehydrogenation catalysts, and particularly relates to a low-carbon alkane dehydrogenation catalyst, and further discloses a preparation method and application thereof.
Background
Propylene is an important petrochemical basic raw material next to ethylene, and is mainly derived from catalytic cracking of petroleum, steam cracking of naphtha, dehydrogenation of propane (isobutane) and the like. In recent years, the global demand for propylene has rapidly increased due to the pull of downstream propylene industries, and the trend of imbalance in supply and demand for propylene has been increasing year by year. With the great reduction of the price of natural gas relative to the price of crude oil caused by the development and application of the north american shale gas, the process for preparing propylene by propane dehydrogenation is most concerned.
China has abundant light hydrocarbon resources such as liquefied petroleum gas, condensate liquid and the like, wherein the light hydrocarbon resources comprise a large amount of propane, butane and the like, and if propane, butane and the like can be effectively and directly converted into propylene and butylene, petroleum resources can be fully utilized, the problem that low-carbon olefins, particularly propylene, butylene and the like, are insufficient in source is solved, the problem of the source of the low-carbon olefins such as propylene, butylene and the like can be solved, and hydrogen with high added value can be obtained at the same time. Therefore, not only the process for dehydrogenating light alkane suitable for industrial application needs to be developed, but also the catalyst suitable for the process becomes the focus of research.
In order to meet the above-mentioned growing demand for lower olefins, domestic and foreign research and development organizations have developed various lower alkanes such as propane dehydrogenation process in the last century, among which are mainly the Oleflex process of UOP, the Catofin process of ABB Lummus, the Star process of Phillips, the PDH process of Linde, and the like. The Oleflex process of UOP adopts a platinum catalyst continuous regeneration fluidized bed reactor and adopts Sn, K or Li modified Pt/Al2O3The reaction temperature is 550-650 ℃ as the catalyst, and the reaction period isThe process has exceeded the million ton production scale worldwide for 7 days. The Catofin process adopts Cr2O3/Al2O3The reaction temperature is about 600 ℃ for the catalyst, but the catalyst has high inactivation speed and needs to be regenerated every 15 minutes. The Star process of Phillips adopts a plain fixed bed tubular reactor, the catalyst takes zinc aluminate spinel as a carrier and Pt as an active component, the catalyst has the advantages of high selectivity and low isomerization activity, has certain tolerance to olefin, oxygen-containing compounds and a certain amount of sulfur in the raw materials, and is switched to be regenerated after the reaction period is 8 hours.
At present, dehydrogenation catalysts mainly comprise platinum group and chromium group catalysts, but the chromium group catalysts are limited due to high deactivation rate, frequent regeneration, high toxicity and easy environmental pollution. Therefore, although the cost of the non-toxic platinum-containing catalyst is high, the non-toxic platinum-containing catalyst is highly regarded as being environment-friendly without being replaced by other non-toxic catalysts. Platinum-containing catalysts are a very important class of dehydrogenation catalysts, and alumina is generally used as a carrier, and attempts are made to modify the catalyst by adding various auxiliary agents so as to overcome the defects of poor stability and low selectivity of a single platinum catalyst. At present, the most common modifying components are mainly components selected from tin, germanium, lead, indium, gallium, thallium and mixtures thereof (in particular tin), alkali or alkaline earth metals (in particular potassium), rare earth elements and halogens (such as chlorine) to improve the regeneration stability of the catalyst.
For example, patents USP4786625, USP4506032, USP4914075 and the like in the prior art disclose platinum-containing dehydrogenation catalysts which have alumina as a carrier, a promoter selected from modifier metal components of tin, germanium, rhenium and mixtures thereof and optionally an alkali or alkaline earth metal component, and a low tin/platinum mole ratio on the catalyst, wherein a halogen content of more than 0.2 m% by mass is required and the atomic ratio of alkali or alkaline earth metal to platinum group element is greater than 10. For example, the platinum-containing dehydrogenation catalyst disclosed in chinese patent CN108295846A uses alumina with 5-30% of micropores with pore diameters of 2-15nm and 55-85% of micropores with pore diameters of 15-85nm as a carrier, and 2-propenyl acrylic acid, pyruvic acid and tetronic acid as competitive adsorbents, and the catalyst is suitable for dehydrogenation reaction of low carbon alkane, and has low selectivity when used for dehydrogenation of low carbon alkane.
Thus, although major advances have been made in the art with respect to the development of lower alkane dehydrogenation catalysts, these catalysts still suffer from various problems and deficiencies, such as short single pass operating cycle and frequent regeneration, undesirable propane conversion and propylene selectivity. Therefore, a catalyst with high conversion rate, high selectivity and long one-way operation period needs to be developed, and the method has positive significance for the development of the low-carbon alkane dehydrogenation process.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a low-carbon alkane dehydrogenation catalyst which has good activity and stability, carbon deposition resistance and regeneration performance;
the second technical problem to be solved by the present invention is to provide a preparation method and an application of the light alkane dehydrogenation catalyst.
In order to solve the technical problems, the catalyst for dehydrogenation of the light alkane comprises a composite carrier, and a Pt component and an alkali metal or alkaline earth metal component which are loaded on the surface of the composite carrier;
the catalyst comprises the following components in percentage by mass based on the total amount of the catalyst:
88-99.8 wt% of composite carrier;
0.1-1.0 wt% of Pt component;
0.1-10.0 wt% of alkali metal or alkaline earth metal component;
the composite carrier comprises Sn-X-Al2O3The composite carrier is characterized In that the X component is one or more selected from P, Si, Ge, Ga, As, Sb, In, Pb, Ti, Bi, Fe, Ru and Mn.
The Sn-X-Al2O3In the composite carrier, the X element, Sn and Al are synthesized into the composite carrier with a Sn-X-Al skeleton structure, so that the catalyst has a good stable structure, and meanwhile, the carrier has a proper acidity distribution and pore structure, the adsorption of reactants and the desorption of products are facilitated, and the proper acidity can reduce the catalystThe cracking performance of the catalyst is improved, and the olefin selectivity of the catalyst is improved.
Specifically, the content of the X component is 0.01-10 wt%, and the content of the Sn component is 0.01-1.0 wt%.
Specifically, the alkali metal or alkaline earth metal component is selected from at least one of Li, Na, K, Rb, Mg, Ca, Sr and Ba.
The invention also discloses a method for preparing the low-carbon alkane dehydrogenation catalyst, which comprises the steps of soaking and loading the composite carrier in a soaking solution containing a Pt-containing compound and an alkali metal or alkaline earth metal compound according to the selected loading amount, and drying and roasting the loaded product.
Specifically, the preparation method of the low-carbon alkane dehydrogenation catalyst comprises the following steps:
the temperature of the dipping step is 30-80 ℃, and the dipping time is 1-8 h;
the temperature of the drying step is 80-150 ℃, and the drying time is 2-6 h;
the temperature of the roasting step is 250-800 ℃, and the roasting time is 2-8 h.
Specifically, the preparation method of the low-carbon alkane dehydrogenation catalyst comprises the following steps:
the Pt-containing compound comprises platinum, chloroplatinic acid, potassium chloroplatinate and ammonium chloroplatinate;
the alkali metal or alkaline earth metal containing compound comprises carbonates, nitrates, sulfates, hydroxycarbonates, halides of Li, Na, K, Rb, Mg, Ca, Sr, Ba;
the impregnation liquid comprises an aqueous solution or a water-soluble organic solvent.
Preferably, in the preparation method of the low-carbon alkane dehydrogenation catalyst, the impregnation liquid further contains hydroxycarboxylic acids or/and aminocarboxylic acids competitive adsorbents;
in the impregnation liquid, the mass concentration of the competitive adsorbent is 0.1-10 wt%.
Specifically, the competitive adsorbent comprises one or a mixture of more of gluconic acid, polyacrylic acid, maleic acid, alpha-hydroxy acid, beta-hydroxybutyric acid, dihydroxy succinic acid, o-hydroxybenzoic acid, ethylene diamine tetraacetic acid, nitrilotriacetic acid, cyclohexanediamine tetraacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid, ethylene diamine tetraacetic acid, triethylenetetramine hexaacetic acid, o-carboxyaniline-N, N-diacetic acid, 2-hydroxyethyl ethylenediamine triacetic acid, N' -ethyl-bis- [2- (o-hydroxyphenyl) ] -glycine and the like.
In the process of impregnation and loading of the catalyst, a competitive adsorbent is further added, and the competitive adsorbent can be dissolved in water or water-soluble organic solvents (ethanol, acetone, acetic acid and the like) and then added into an impregnation solution; or directly adding the competitive adsorbent into the prepared impregnation liquid, and uniformly mixing; it is preferable to prepare a stable impregnation solution by dissolving the platinum component and the alkali metal or alkaline earth metal component in a solution prepared from water or a water-soluble organic solvent containing a hydroxycarboxylic acid or/and aminocarboxylic acid competitive adsorbent.
Preferably, the weight portion of platinum: alkali metal or alkaline earth metal: competitive adsorbents: water or solvent 1-3: 2-10: 0.5-5: 150-500.
Preferably, Sn-X-Al2O3The composite carrier is immersed in the immersion liquid, and the proportion of the carrier to the immersion liquid is controlled to be 100: 50-200, drying and roasting to obtain the low-carbon alkane dehydrogenation catalyst.
In the invention, the competitive adsorbent is added, so that the active component Pt, alkali metal or alkaline earth metal and the 'anchoring' Pt site on the carrier are combined together to form Pt-Sn-X-alkali metal (alkaline earth metal) active site, the competitive adsorbent in the process forms an effective active complex with the Pt, the alkali metal or the alkaline earth metal, and forms rich, uniform and dispersed active sites in the impregnation process of the catalyst, thereby effectively improving the stability of the catalyst and prolonging the single-cycle operation time of the catalyst.
Specifically, the preparation method of the low-carbon alkane dehydrogenation catalyst further comprises the step of preparing Sn-X-Al of the composite carrier2O3And compounding the carrier, namely mixing an aluminum source material, a tin source material, an acid solution and an X element material, and kneading, molding, drying and roasting to obtain the composite material.
Specifically, an aluminum source, a tin source and an acid solution are added, and then an element X is added to form a sol or a mixture, wherein the aluminum oxide comprises the following components in parts by weight: tin: acid: x: 100 parts of water: 0.01-10.0: 3.0-9.0: 0.1-10.0: 60-200, kneading, extruding into strips or oil column forming, drying and roasting to obtain Sn-X-Al2O3And (3) a composite carrier.
Specifically, in the preparation of the carrier, the acid is selected from one or more of hydrochloric acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, nitric acid and sulfuric acid.
Specifically, in the preparation of the carrier, the Sn source is selected from one or more of tin, stannic chloride, stannous chloride, metastannic acid, potassium stannate and stannous acetate.
Specifically, in the preparation of the carrier, the aluminum source is selected from one or more of pseudo-boehmite, aluminum hydroxide, aluminum hydroxychloride, aluminum nitrate, sodium metaaluminate and aluminum trichloride.
Specifically, in the preparation of the carrier, the preparation conditions of the composite carrier are as follows: drying at 80-150 deg.C for 2-8h, and further calcining at 500-1200 deg.C for 3-8 h.
The Sn-X-Al2O3In the composite carrier, the addition of the X element enables the Sn-X-Al skeleton structure to be uniformly dispersed in the carrier, so that the local uneven distribution of active components is effectively avoided, the dispersity of the active components is improved, the acidity of alumina is reduced due to the addition of the X component, and the carbon deposition resistance of the catalyst is improved. Sn-X-Al2O3The Sn-X-Al framework structure which is uniformly dispersed in the composite carrier forms an active site which can anchor noble metal platinum, so that the dispersion degree of the platinum can be improved when the catalyst is prepared and impregnated with the platinum, an effective active dehydrogenation active center is formed with the platinum, and the activity and the stability of the catalyst are improved in the process.
The invention also discloses application of the low-carbon alkane dehydrogenation catalyst in a low-carbon alkane dehydrogenation process, and further preferably in propane, butane and isobutane dehydrogenation processes.
The low-carbon alkane dehydrogenation catalyst provided by the invention is prepared from Sn-X-Al2O3The composite carrier is a carrier, and platinum and alkali metal or alkaline earth metal are loaded as effective components, so that the catalyst has high activity, good selectivity and good stability under high-temperature operation conditions; and moreover, the catalyst has strong anti-carbon deposition capability, slow coking rate and excellent regeneration performance, and is suitable for a catalytic system of a low-carbon alkane dehydrogenation process.
Detailed Description
Example 1
Taking 8ml of stannous chloride aqueous solution containing 0.05g/ml of tin, adding 0.4g of 85% phosphoric acid and 0.2g of gallium nitrate, fully and uniformly mixing with 200g of dilute hydrochloric acid solution containing 3%, adding 200g of aluminum hydroxide powder into the solution, uniformly mixing in a sol tank to form sol, forming in an oil column to obtain small balls, drying for 4h at 130 ℃, roasting for 4h at 900 ℃, cooling and screening the small balls to obtain the carrier A1.
50g of the A1 composite carrier pellet is taken and placed in impregnation equipment, 3.0ml of chloroplatinic acid aqueous solution containing 0.05g/ml of platinum and 1.0ml of potassium chloride solution containing 0.4g/ml of potassium are taken and added into 35g of deionized water solution containing 0.4g of EDTA to prepare impregnation liquid, the carrier is subjected to vacuum impregnation loading at 60 ℃ by adopting a vacuum impregnation method, the impregnation time is 4h, then the carrier is dried at 100 ℃ for 2h, and the carrier is roasted at 550 ℃ for 4h, so that the catalyst C1 is obtained.
Example 2
5ml of an aqueous solution of tin tetrachloride containing 0.05g/ml of tin was taken, and 0.1g of TlCl and 0.2g of InCl were added3And after fully and uniformly mixing, adding 150g of aqueous solution, fully and uniformly mixing, adding 200g of aluminum nitrate into the solution, uniformly mixing in a sol tank to form sol, forming in an oil column to obtain small balls, drying at 110 ℃ for 4h, roasting at 800 ℃ for 6h, cooling, and screening to obtain the carrier A2.
50g of the A2 composite carrier pellet is taken and placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.05g/ml of platinum and 0.5ml of potassium stannate solution containing 0.04g/ml of potassium are taken and added into 50g of deionized water solution containing 0.5g of gluconic acid and 0.3g of ethylene diamine tetrapropionic acid to prepare impregnation liquid, the carrier is impregnated at 60 ℃ for 3 hours, and then the carrier is dried at 110 ℃ for 4 hours and roasted at 450 ℃ for 4 hours, so that the catalyst C2 is obtained.
Example 3
Dissolving 0.05g/ml tin in 6ml 1% hydrochloric acid water solution, and adding 0.1g BiCl3And 0.2g FeCl3Adding 120g of 1% dilute hydrochloric acid solution, fully and uniformly mixing, uniformly mixing with 200g of pseudo-boehmite powder, kneading, extruding, forming, drying for 5h at 100 ℃, and then roasting for 3h at 1000 ℃ to obtain the carrier A3.
50g of the prepared A3 composite carrier is taken and placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.04g/ml of platinum and 1.5ml of potassium nitrate solution containing 0.04g/ml of potassium are taken and added into 40g of deionized water solution containing 0.8g of o-carboxyaniline-N, N-diacetic acid to prepare impregnation liquid, the A3 composite carrier is impregnated at room temperature for 6 hours, and then the A3578 composite carrier is dried at 100 ℃ for 6 hours and calcined at 350 ℃ for 6 hours to obtain the catalyst C3.
Example 4
Taking 8ml of stannous acetate aqueous solution containing 0.05g/ml of tin, and then adding 0.1g of RuCl3And 0.2g of MnCl2Adding 120g of 1% dilute hydrochloric acid solution, fully and uniformly mixing, uniformly mixing with 200g of pseudo-boehmite powder, kneading, extruding, forming, drying for 4h at 120 ℃, and then roasting for 4h at 850 ℃ to obtain the carrier A4.
50g of the prepared A4 composite carrier is taken and placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.04g/ml of platinum and 1.5ml of lithium nitrate solution containing 0.04g/ml of lithium are taken and added into 40g of deionized water solution containing 0.9g of ethylene glycol diethyl ether diamine tetraacetic acid to prepare impregnation liquid, the A4 composite carrier is impregnated at room temperature for 5 hours, then the mixture is dried at 95 ℃ for 6 hours and calcined at 550 ℃ for 6 hours, and the catalyst C4 is obtained.
Example 5
Taking 10ml of potassium stannate aqueous solution containing 0.05g/ml of tin, adding 0.1g of TiCl3 and 0.2g of 0.2g H3PO4, adding 120g of 1% dilute chloric acid solution, fully and uniformly mixing, uniformly mixing with 200g of aluminum hydroxychloride powder, kneading, extruding, forming, drying at 110 ℃ for 4h, and roasting at 890 ℃ for 4h to obtain the carrier A5.
50g of the prepared A5 composite carrier is taken and placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.06g/ml of platinum and 3.0ml of magnesium sulfate solution containing 0.04g/ml of magnesium are taken and added into 40g of deionized water solution containing 0.5g of cyclohexanediaminetetraacetic acid to prepare impregnation liquid, the A5 composite carrier is impregnated in vacuum at the temperature of 60 ℃ for 8h, then the A3578 composite carrier is dried at the temperature of 105 ℃ for 5h and calcined at the temperature of 600 ℃ for 5h, and the catalyst C5 is obtained.
Example 6
Dissolving tin containing 0.05g/ml of tin in 10ml of 2% HCl aqueous solution, adding 0.2g of GeCl4, adding 120g of 2% dilute sulfuric acid solution, fully and uniformly mixing, uniformly mixing with 200g of aluminum hydroxide powder, kneading, extruding, forming, drying at 110 ℃ for 4h, and then roasting at 890 ℃ for 4h to obtain the carrier A6.
50g of the prepared A6 composite carrier is taken and placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.06g/ml of platinum and 2.0ml of calcium sulfate solution containing 0.04g/ml of calcium are taken and added into 40g of deionized water solution of 0.5g of ethylenediamine tetrapropionic acid to prepare impregnation liquid, the A6 composite carrier is impregnated in vacuum at room temperature for 6 hours, then the A3578 composite carrier is dried for 5 hours at 115 ℃, and is calcined for 4 hours at 500 ℃ to obtain the catalyst C6.
Example 7
50g of the A1 composite carrier pellet prepared in the above manner is placed in an impregnation device. Taking 3ml of chloroplatinic acid aqueous solution containing 0.05g/ml of platinum and 1.0ml of potassium chloride solution containing 0.4g/ml of potassium, adding 35g of deionized water to prepare impregnation liquid, impregnating the impregnation liquid on an A1 composite carrier at 60 ℃ for 4 hours by adopting a vacuum impregnation method, drying the impregnation liquid at 100 ℃ for 2 hours, and roasting the impregnation liquid at 550 ℃ for 4 hours to obtain the catalyst C7.
Comparative example 1
Taking 8ml of stannous chloride aqueous solution containing 0.05g/ml of tin, uniformly mixing the stannous chloride aqueous solution with 200g of dilute hydrochloric acid solution containing 3%, then adding 200g of aluminum hydroxide powder, uniformly mixing the aluminum hydroxide powder and the sol in a sol tank to form sol, forming the sol in an oil column to obtain small balls, drying the small balls for 4 hours at 130 ℃, roasting the small balls for 4 hours at 900 ℃, cooling and screening the small balls to obtain the carrier DA 1.
50g of the prepared DA1 composite carrier pellet is taken and placed in impregnation equipment, 3ml of chloroplatinic acid aqueous solution containing 0.05g/ml of platinum and 1.0ml of potassium chloride solution containing 0.04g/ml of potassium are taken, 35g of deionized water is added to prepare impregnation liquid, the impregnation liquid is impregnated on an alumina carrier at 60 ℃ by adopting a vacuum impregnation method for 4 hours, then the alumina carrier is dried at 100 ℃ for 2 hours, and is calcined at 550 ℃ for 4 hours, and the catalyst DC1 is obtained.
Comparative example 2
Dissolving tin containing 0.05g/ml of tin in 5ml of aqueous solution, fully and uniformly mixing the solution with 150g of aqueous solution, adding 200g of aluminum nitrate, uniformly mixing the solution in a sol tank to form sol, forming the sol in an oil column to obtain pellets, drying the pellets for 4 hours at 110 ℃, roasting the pellets for 6 hours at 800 ℃, cooling and screening the pellets to obtain the carrier DA 2.
50g of the prepared DA2 composite carrier pellet is taken and placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.05g/ml of platinum and 0.5ml of potassium stannate solution containing 0.04g/ml of potassium are taken and added with 50g of deionized water to prepare impregnation liquid, and the carrier is impregnated at 60 ℃ for 3 hours. Then drying for 4h at 110 ℃, and roasting for 4h at 450 ℃ to obtain the catalyst DC 2.
Comparative example 3
Dissolving tin containing 0.05g/ml of tin in 6ml of 1% hydrochloric acid aqueous solution, uniformly mixing with 120g of 1% diluted hydrochloric acid solution, adding 200g of pseudo-boehmite powder, uniformly mixing, kneading, extruding, forming, drying at 100 ℃ for 5 hours, and roasting at 1000 ℃ for 3 hours to obtain the carrier DA 3.
50g of the prepared DA3 carrier is taken and placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.05g/ml of platinum and 1.5ml of potassium nitrate solution containing 0.04g/ml of potassium are taken and added with 40g of deionized water to prepare impregnation liquid, the impregnation liquid is impregnated in the F1 carrier at room temperature for 6h, then the carrier is dried at 100 ℃ for 6h and calcined at 350 ℃ for 6h to obtain the catalyst DC 3.
Comparative example 4
50g of the DA1 composite carrier pellet prepared above is placed in an impregnation device. Taking 4ml of chloroplatinic acid aqueous solution containing 0.05g/ml of platinum and 1.0ml of potassium chloride solution containing 0.04g/ml of potassium, adding 0.8g of EDTA, then adding 35g of deionized water to prepare an impregnation solution, impregnating the impregnation solution on an alumina carrier at 60 ℃ for 4 hours by adopting a vacuum impregnation method, drying the impregnation solution at 100 ℃ for 2 hours, and roasting the impregnation solution at 550 ℃ for 4 hours to obtain the catalyst DC 4.
Comparative example 5
The catalyst of this comparative example was supported in the same manner as in example 3 except that the corresponding active ingredient was supported directly on alumina as a carrier, and the catalyst was designated as DC 5.
Taking 120g of 1% dilute hydrochloric acid solution, uniformly mixing with 200g of pseudo-boehmite powder, kneading, extruding, forming, drying for 5h at 100 ℃, and then roasting for 3h at 1000 ℃ to obtain the carrier DA 5.
50g of DA5 alumina carrier is taken and placed in an impregnation device, 4ml of chloroplatinic acid aqueous solution containing 0.04g/ml of platinum and 1.5ml of potassium nitrate solution containing 0.04g/ml of potassium are taken and added into 40g of deionized water solution containing 0.8g of o-carboxyaniline-N, N-diacetic acid to prepare impregnation liquid, the A3 composite carrier is impregnated at room temperature for 6h, and then the catalyst DC5 is obtained after the drying at 100 ℃ for 6h and the roasting at 350 ℃ for 6 h.
Comparative example 6
The loading scheme of the catalyst in the comparative example is the same as that in example 3, the difference is only that the alumina is directly used as the carrier, stannous chloride and gallium nitrate are added into the original impregnation liquid to carry out Sn and Ga element loading, and the obtained catalyst is marked as DC 6.
50g of DA5 alumina carrier is taken and placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.04g/ml of platinum, 6ml of stannous chloride aqueous solution containing 0.05g/ml of tin, 1ml of gallium nitrate solution containing 0.05g/ml of gallium and 1.5ml of potassium nitrate solution containing 0.04g/ml of potassium are taken and added into 40g of deionized water solution of o-carboxyaniline-N, N-diacetic acid to prepare impregnation liquid, the A3 composite carrier is impregnated at room temperature for 6h, then dried at 100 ℃ for 6h, and calcined at 350 ℃ for 6h to obtain the catalyst DC 6.
Comparative example 7
The catalyst scheme of this comparative example is the same as that of example 3, except that the carrier is supported by the DA1 carrier prepared in comparative example 1, and gallium nitrate is added to the original impregnation solution to carry out Ga element loading, and the obtained catalyst is designated as DC 7.
50g of the prepared DA1 composite carrier pellet is placed in impregnation equipment, 4ml of chloroplatinic acid aqueous solution containing 0.04g/ml of platinum, 1.5ml of potassium nitrate solution containing 0.04g/ml of potassium and 1ml of gallium nitrate solution containing 0.05g/ml of gallium are taken and added into 40g of deionized water solution of o-carboxyaniline-N, N-diacetic acid to prepare impregnation liquid, the DA1 composite carrier is impregnated at room temperature for 6 hours, then the drying is carried out at 100 ℃ for 6 hours, and the roasting is carried out at 350 ℃ for 6 hours to obtain the catalyst DC 7.
Examples of the experiments
The catalysts are respectively used for dehydrogenation catalytic performance experiments, hydrogen at 530 ℃ is used for reduction activation for 2h before dehydrogenation reaction of the catalysts, and then the mass space velocity of propane is 3.0h at the reaction temperature of 610 DEG C-1，H2/C3H8The molar ratio is 1: 2, the activity evaluation was carried out on a micro-reactor, the 192-hour reaction results are shown in table 1, and the evaluation results of the catalyst after the coke-burning regeneration are shown in tables 2 and 3.
TABLE 1 evaluation results of catalyst for 1 st cycle
TABLE 2 evaluation results of catalyst in cycle 2
TABLE 3 evaluation results of catalyst in cycle 3
As can be seen from the data in the table, the catalyst of the invention has the advantages of reaction temperature of 610 ℃, propane mass space velocity of 3.0h-1，H2/C3H8The molar ratio is 1: 2 on a microreaction device, the propylene yield was 38.5% after 192 hours of evaluationThe carbon content is less than 2.0%. The results show that the catalyst has excellent low-carbon alkane dehydrogenation activity and propylene yield, has good anti-carbon deposition performance, ensures the stability of the catalyst under the high-temperature operation condition, and has good performance after the catalyst is regenerated by conventional regeneration.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The low-carbon alkane dehydrogenation catalyst is characterized by comprising a composite carrier, and a Pt component and an alkali metal or alkaline earth metal component which are loaded on the surface of the composite carrier;
the catalyst comprises the following components in percentage by mass based on the total amount of the catalyst:
88.0-99.8 wt% of composite carrier;
0.1-1.0 wt% of Pt component;
0.1-10.0 wt% of alkali metal or alkaline earth metal component;
the composite carrier comprises Sn-X-Al2O3The composite carrier is characterized In that the X component is one or more selected from P, Si, Ge, Ga, As, Sb, In, Pb, Ti, Bi, Fe, Ru and Mn.
2. The light alkane dehydrogenation catalyst of claim 1, wherein the composite support comprises from 0.01 wt% to 10 wt% of the X component and from 0.01 wt% to 1.0 wt% of the Sn component.
3. The light alkane dehydrogenation catalyst of claim 1 or 2, wherein the alkali or alkaline earth metal component is selected from the group consisting of Li, Na, K, Rb, Mg, Ca, Sr, Ba.
4. A method for preparing the light alkane dehydrogenation catalyst according to any one of claims 1 to 3, comprising the steps of impregnating the composite carrier in an impregnation solution containing a Pt-containing compound and an alkali metal or alkaline earth metal compound at a selected loading amount to carry out impregnation loading, and drying and calcining the loaded product.
5. The method for preparing the light alkane dehydrogenation catalyst according to claim 4, wherein:
the temperature of the dipping step is 30-80 ℃, and the dipping time is 1-8 h;
the temperature of the drying step is 80-150 ℃, and the drying time is 2-6 h;
the temperature of the roasting step is 250-800 ℃, and the roasting time is 2-8 h.
6. The method for preparing the light alkane dehydrogenation catalyst according to claim 4 or 5, wherein:
the Pt-containing compound comprises platinum, chloroplatinic acid, potassium chloroplatinate and ammonium chloroplatinate;
the alkali metal or alkaline earth metal containing compound comprises carbonates, nitrates, sulfates, hydroxycarbonates, halides of Li, Na, K, Rb, Mg, Ca, Sr, Ba;
the impregnation liquid comprises an aqueous solution or a water-soluble organic solvent.
7. The method for preparing the low carbon alkane dehydrogenation catalyst according to any one of claims 4 to 6, wherein the impregnation solution further contains a hydroxycarboxylic acid or/and aminocarboxylic acid competitive adsorbent;
in the impregnation liquid, the mass concentration of the competitive adsorbent is 0.1-10 wt%.
8. The method of claim 7, wherein the competitive adsorbent comprises one or more selected from gluconic acid, polyacrylic acid, maleic acid, alpha-hydroxy acid, beta-hydroxybutyric acid, dihydroxybutanoic acid, o-hydroxybenzoic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, ethyleneglycoldiethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, o-carboxyanilide-N, N-diacetic acid, 2-hydroxyethylethylenediaminetriacetic acid, N' -ethyl-bis- [2- (o-hydroxyphenyl) ] -glycine, and the like.
9. The method for preparing the light alkane dehydrogenation catalyst according to any one of claims 4-8, further comprising preparing the composite carrier from Sn-X-Al2O3And compounding the carrier, namely mixing an aluminum source material, a tin source material, an acid solution and an X element material, and kneading, molding, drying and roasting to obtain the composite material.
10. Use of the light alkane dehydrogenation catalyst of any of claims 1-3 in a light alkane dehydrogenation process.
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