CN108927173A - A kind of alkynes selective hydrocatalyst and its preparation method and application - Google Patents
A kind of alkynes selective hydrocatalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108927173A CN108927173A CN201810887717.0A CN201810887717A CN108927173A CN 108927173 A CN108927173 A CN 108927173A CN 201810887717 A CN201810887717 A CN 201810887717A CN 108927173 A CN108927173 A CN 108927173A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- alkynes
- palladium
- variety
- butadiene
- Prior art date
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Links
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 108
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 102
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 46
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 30
- 150000001340 alkali metals Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 21
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000004033 plastic Substances 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000009938 salting Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910001593 boehmite Inorganic materials 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 206010013786 Dry skin Diseases 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 238000003483 aging Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 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 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 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 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- KKKAMDZVMJEEHQ-UHFFFAOYSA-N [Sn].[N+](=O)(O)[O-] Chemical compound [Sn].[N+](=O)(O)[O-] KKKAMDZVMJEEHQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000000306 component Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
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- 238000004064 recycling Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
- B01J23/8946—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 alkali or alkaline earth 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth 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
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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
- B01J23/38—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
- B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
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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
- B01J23/8966—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 germanium, tin or lead
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- B01J35/613—
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- B01J35/633—
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- B01J35/635—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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Abstract
The invention belongs to technical field of petrochemical industry, and in particular to a kind of alkynes hydrogenation selectivity catalyst and its preparation method and application.Catalyst is made of active component, co-catalysis component and carrier, active component is palladium, and it is added to the co-catalysis component for being intended to improve catalyst hydrogenation stability and selectivity, co-catalysis component takes different modes to be introduced into catalyst, it realizes the Reasonable Regulation And Control to catalyst surface acidity and promotes the dispersion of active component palladium, to form more active sites.Catalyst of the present invention is suitable for the selective hydrogenation of the material containing alkynes, it is particularly suitable for the selective hydrogenation of the high alkynes content C 4 materials of butadiene extraction device discharge, butadiene and butylene are converted by vinylacetylene and ethyl acetylene, hydrogenated products return to raw material storage tank or butadiene extraction device recycling butadiene and butylene.Catalyst hydrogenation reaction condition of the present invention is mild, and activity and selectivity is high, and especially stability is good, and operation cycle is long, adds hydrogen suitable for high alkynes content material.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of alkynes hydrogenation selectivity catalyst and its preparation side
Method and application.
Background technique
Butadiene is a kind of important basic petrochemical Organic Ingredients and synthetic rubber monomer, is most heavy in C-4-fraction
One of component wanted, the status in petrochemical industry olefin feedstock are only second to ethylene and propylene.The most important source of butadiene is
It is raw material with the mixing carbon four of ethylene unit by-product, it is isolated by the method for solvent extraction.The mixing of ethylene unit by-product
C-4-fraction usually contains the butadiene of 40wt%~60wt%, and the alkynes of 0.5wt%~2.0wt% mainly includes methyl second
Alkynes (MA), ethyl acetylene (EA) and vinylacetylene (VA), it is other for butane (normal butane and iso-butane) and butylene (n-butene,
Isobutene, trans-butene-2 and cis-butene-2).
It is industrial at present mainly use acetonitrile (ACN), N-Methyl pyrrolidone (NMP) or dimethylformamide (DMF) for
Solvent extraction butadiene, the butadiene after extracting can satisfy its requirement as polymerized monomer purity.By cracking severity and split
The influence of the factors such as solution technology, mixing alkynes content in carbon four has the tendency that gradually increasing, and to guarantee butadiene purity, needs to add
Big extracting depth, this causes plant energy consumption to increase, tail gas containing alkynes (main group becomes vinylacetylene, butadiene and butylene) discharge
Amount increases, and butadiene yield decline, device economy is deteriorated.Due to containing a large amount of vinylacetylenes (usually in tail gas containing alkynes
20wt%~35wt%), inflammable and explosive risk is big, and industrial application value is not high, is usually diluted with other C_4 hydrocarbons or methane
After be discharged into torch burning or as low-value fuel sell.If this part tail gas containing alkynes handled, can not only recycle
A large amount of butadiene and butylene, can also eliminate the bring security risk of exhaust emissions containing alkynes, realize the purpose to turn waste into wealth.
Vent gas treatment containing alkynes is mainly the method for using catalysis selective hydrogenation, using high-selectivity hydrogenation catalyst by tail gas
In the vinylacetylene that contains be converted into 1,3-butadiene, ethyl acetylene is converted into butylene, separately has a small amount of butane to generate.After adding hydrogen
The fixed gas of tail gas separation containing alkynes after return raw material storage tank mix or be returned directly to raw material butadiene extraction device recycle fourth
Diene and butylene reduce butadiene loss, utilize tail gas containing alkynes well, and eliminate to improve butadiene purity
The discharge of the tail gas containing alkynes.
Tail gas containing alkynes select hydrogen addition technology key first is that catalyst, it is desirable that catalyst has higher hydrogenation activity, choosing
Selecting property will especially have good run stability, i.e., the alkynes in tail gas is not only removed to reduced levels (can directly return
Butadiene product equipment is returned as extracting raw material), more to ensure that vinylacetylene is converted into 1,3-butadiene as far as possible and is recycled with maximum
Butadiene, while catalyst being required to have higher stability, there are the ability and length of the impurity such as preferable water-fast, solvent, heavy constituent
Run stability to adapt to the requirement of commercial plant long-term operation.
The current selective hydrogenation catalyst of tail gas containing alkynes is mainly noble metal catalyst and non-precious metal catalyst, have merely with
Palladium or copper are the single-metal reforming catalyst of active component, or with palladium and copper etc. are the multimetal reforming catalyst of active component.Copper is urged
When agent is used to select acetylene hydrogenation, selectivity is higher, but due to reaction temperature height, alkadienes and alkynes polymer easily generated are heavy
Product is in catalyst surface, therefore catalyst inactivation is fast, and service life is short.Palladium catalyst activity is higher than copper catalyst, use condition
It mitigates, thus the service life is long, but selectivity is more slightly worse than copper catalyst, and palladium is easy to be complexed with alkynes, causes the loss of palladium,
Generally improve the interaction of palladium and alkynes by adding the method for auxiliary agent, extends the service life of catalyst.
United States Patent (USP) US3,898,298 discloses a kind of Pd/Al2O3Catalyst, active component palladium content be 0.05~
0.2wt%, carrier are aluminium oxide, which is commonly used in the C 4 materials containing alkynes of alkynes content lower (being less than 1.0wt%)
Selection plus hydrogen, vinylacetylene hydrogenation rate is usually more than 90%, but 1,3-butadiene adds hydrogen loss rate larger.
United States Patent (USP) US4,547,600 disclose a kind of Pd, Ag bimetallic catalyst, which is used for low alkynes content
When (vinylacetylene about 1.95%) material adds hydrogen, catalyst hydrogenation activity is high, and vinylacetylene content can be down to the left side 300ppm
The right side, and when being used for medium alkynes content (vinylacetylene about 4.10%) material and adding hydrogen, vinylacetylene conversion ratio are only 70% left
It is right.Simultaneously after the catalyst runs more than 700 hours, palladium is lost seriously, and turnover rate is up to 10%, therefore the catalyst is not suitable for
Alkynes content more high material adds hydrogen.
Patent CN201110205694.9 discloses a kind of four selective acetylene hydrocarbon hydrogenation nickel of carbon and copper bimetallic catalyst, nickel and
Copper is impregnated on carrier using the aqueous solution of soluble-salt, and due to active component content height, catalyst is to water, solvent and recombination
Divide the tolerance of equal impurity stronger, but the adiabatic temperature rise reacted is higher, reactor outlet temperature is more than 80 DEG C, this can aggravate
The polymerization of alkynes and alkadienes influences catalyst long-term operation.The catalyst is equally only applicable in the low material of alkynes content and adds
Hydrogen.
Patent 03159237.6 discloses the utilization method of butadiene product equipment residue, is added using one section, double sections or multistage
Hydrogen technique will recycle butadiene, 1- butylene after containing the processing of alkynes material or as fuel, wherein selective acetylene hydrocarbon hydrogenation is urged for butadiene
Agent is using palladium copper silver or palladium-copper catalyst.Every section of reactor of the technique has a large amount of product to be recycled, recycle stock with
The recycle ratio 10~30 of fresh material, systemic circulation ratio increase plant energy consumption.The process catalyst butadiene selective is poor, alkynes
It is converted mainly into butylene, the technique and catalyst of the patent disclosure are not suitable for alkynes and add hydrogen retrieval butadiene.
Patent CN103787811B discloses a kind of method of hydrotreating of butadiene tail gas, using hydrocarbon liquid phase by butadiene tail gas
Ethylene cracking material is used as by two-stage hydrogenation after absorption.One-stage hydrogenation uses Raney nickel, and the systemic circulation ratio of 8-30, two sections are adopted
With nickel-molybdenum catalyst high-temperature hydrogenation.Not only energy consumption is high for this method, but also hydrogenation products can only be used as ethylene cracking material.
Patent CN201410771106.1 discloses a kind of selective acetylene hydrocarbon hydrogenation method, uses niobia-alumina to carry
The palladium lead catalyst of body, it is desirable that alkynes content is not high to alkynes content in hydrogenation material no more than 25% in C 4 materials containing alkynes
In 10%, when alkynes content is higher, it is diluted using carbon-4.
Patent CN1,321,544A disclose a kind of for selecting the multimetal reforming catalyst of acetylene hydrogenation, and active component is copper
And the promoter metals such as Ag, Pb, Bi, Zr, Pt can also be added in palladium, the processing of or mixtures thereof carrier alkali metal, alkaline-earth metal.It urges
Agent can only handle the C-4-fraction that alkynes content is lower than 1.3wt%.Catalyst Cu content is higher, processing alkynes content compared with
When high material, operation temperature is higher, and catalyst choice and stability can be poor.
CN101,428,228A disclose a kind of selective hydrocatalyst and preparation method thereof, using aluminium oxide as carrier,
Include active component palladium, Cu additives, auxiliary agent X1With auxiliary agent X2, in terms of total catalyst weight 100%: containing palladium 0.1~0.5%, copper
0.1~6%, X10.5~15%, X20.5~5%, 0~2% in cobalt, nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium, neodymium one
Kind or a variety of promoter metals；Wherein X1Selected from IVA element, X2Selected from or mixtures thereof alkali metal, alkaline-earth metal.It is helped in catalyst
Agent element is introduced by impregnated carrier or catalyst precarsor to realize, catalyst is rich in alkynes after being suitable for Butadiene Extraction
The selection acetylene hydrogenation of hydrocarbon salvage stores, but the C 4 materials that alkynes content is high, butadiene content is low can only be handled.
The main reason for coking is to lead to another one of the major reasons of catalyst inactivation, generates coking is first is that catalyst
Selectivity is bad, and the side reactions such as alkynes and diene polymerization are too many, second is that reaction temperature is too high or adiabatic temperature rise is too high, lead
Unsaturated hydrocarbons is caused to polymerize aggravation at high temperature.Once generating colloid, then activated centre or blocking catalyst duct can be covered, thus
Catalyst activity, selectivity and stability are reduced, and eventually leads to catalyst inactivation and can not operate normally.
The prior art is the catalyst of active component due to vulnerable to the impurity such as water, solvent and heavy constituent in hydrogenation material using palladium
Interference is poor to hydrogenation activity especially run stability, to improve this case, introduces variety classes by the method for dipping
Auxiliary agent to promote the dispersion of palladium, and generates synergistic effect with palladium and improves catalyst choice and stability.In the prior art,
When the soluble-salt impregnated carrier of used additives, due to carrier pore structure itself inhomogeneities and be difficult to realize immersion condition control
Consistency the problems such as, non-uniform Distribution is presented in auxiliary agent in the catalyst, is not in full use, causes with the synergistic effect of palladium
Catalyst hydrogenation activity, selectivity and stability are extremely difficult to balance.Especially IB and/or IVA element, especially Cu, Ag,
The introducing of the elements such as Si, Sn, Pb, since content is much higher than palladium content, infusion process is not preferred embodiment.
Summary of the invention:
In view of the defects existing in the prior art, the present invention provides a kind of alkynes hydrogenation selectivity catalyst and preparation method thereof
And application.Catalyst of the present invention is when introducing the elements such as Cu, Ag, Si, Sn, Pb of IB and/or IVA, according to these elements and palladium
Interaction mechanism and purpose to be achieved and select different incorporation ways, i.e., a part use solid-liquid phase dipping
Mode introduces, and a part is introduced using the liquid-liquid phase in carrier preparation, and the ratio that reasonable distribution two parts introduce,
Balance is found between catalyst activity, selectivity and stability, it is therefore an objective to keep the distribution of adjuvant component in the carrier more uniform,
When especially adjuvant component content is high, this effect is more obvious, to improve the hydrogenation activity and selectivity (height of catalyst
Up to 60% or more), stability (1000h operating activity do not reduce substantially, and coking rate, less than 1.5%, palladium base is not originally lost).
Importantly, catalyst of the present invention is due to active high, selectivity is good, therefore hydroconversion condition is mild, inlet temperature, insulation temperature
Liter, operating pressure and recycle ratio are low, and the C 4 materials containing alkynes particularly suitable for high alkynes content add hydrogen, contain particularly suitable for high butadiene
The C 4 materials containing alkynes of amount add hydrogen, the material containing alkynes after catalyst of the present invention and process, can be returned directly to extracting dress
It puts back into and receives butadiene and butylene, increase production butadiene and butylene, eliminate exhaust emissions containing alkynes, improve device economic benefit.
The alkynes selective hydrocatalyst for realizing the object of the invention, according to weight percent, with 0.1~0.8% metal
Palladium is active component, and it is to be modified added with 0~5% alkali metal and/or alkaline earth oxide that 90~99% aluminium oxide, which are carrier,
Auxiliary agent, 0.05~10%IB and/or IVA element oxide are co-catalysis component；Wherein in catalyst components, palladium, alkali metal
And/or alkaline-earth metal is introduced in a manner of impregnating, in a manner of impregnating, another part exists a part in IB and/or IVA element
Introducing when preparing carrier；Specific surface area of catalyst is 20~100m20.15~0.75ml/g of/g, Kong Rongwei.
Wherein, the support shapes are spherical shape, tooth spherical shape, bar shaped, cloverleaf pattern or pass through extrusion, tabletting or spin etc.
The other shapes carrier that mode obtains, preferablyCloverleaf pattern orSpherical shape, tooth it is spherical.
The alkali metal is one of Li, K, Rb, Cs or a variety of, preferably Li, K, additive amount is 0.05~
2.5%, preferably 0.5~1.5%.
The alkaline-earth metal is one of Mg, Ca, Sr, Ba or a variety of, preferably Mg, Sr, additive amount is 0.05~
2.5%, preferably 0.5~1.5%.
The IB element is one of Cu, Ag, Au or a variety of, and a part of the IB element is Ag and/or Au
It is introduced in a manner of dipping, additive amount is 0.1~3.0%, preferably 0.5~2.0%；Another part is that Cu is preparing aluminium oxide
It is introduced when carrier, additive amount 0.5~10%, preferably 1.5~6.0%.
The IVA element is one of Si, Ge, Sn, Pb or a variety of, and a part of the IVA element is Pb
And/or Ge is introduced in a manner of impregnating, additive amount 0.2~3.5%, preferably 0.4~2.5%；Another part is Si and/or Sn
The introducing when preparing alumina support, additive amount are 2.0~10%, preferably 3.0~5.0%.
The preparation method of alkynes selective hydrocatalyst of the invention, follows the steps below:
A, prepared by carrier:
150~250gAl of concentration is diluted with water in silicon source2O3/ L, is added with stirring precipitating reagent, in 50~100 DEG C of plastics, washes
Wash, filter, be beaten, then in 50~100 DEG C of agings, using boehmite is made after filter, drying, roasting, in plastic and
/ or pulping process in IB element Cu and/or IVA elements Si is added and/or Sn obtains soluble salt solutions；
Above-mentioned boehmite is taken, nitric acid, citric acid, sesbania powder and water mixer kneader is added, then forms, 80~150
DEG C dry 10-12 hours, 750~1100 DEG C roasting 8-12 hours, finished product alumina support；
B, support modification:
Take finished product alumina support, measure its water absorption rate, according to water absorption rate and modifier content, prepare alkali metal and/or
Alkaline-earth metal aqueous solution, adjusts solution ph, and finished product alumina support is poured into solution and is impregnated, ageing, 80~150 DEG C it is dry
Dry 6~8h, 4-8 hours obtained modified aluminium oxide supports of 750~1100 DEG C of roastings；
C, catalyst preparation:
According to each component content in catalyst and modified support water absorption rate, palladium solution and/or IB elements A g and/or Au are prepared
Soluble salt solutions and/or IVA elements Pb and/or Ge soluble salt solutions, pH value is adjusted to 2.5 after mixing~
6.0, load weighted modified support is placed in solution and is impregnated, ageing, 80~150 DEG C drying 6~8 hours, 350~600 DEG C roast
It burns 6~8 hours, finished product catalyst.
Wherein, the silicon source is one of aluminium hydroxide, aluminum sulfate, aluminium chloride, aluminum nitrate, sodium metaaluminate or more
Kind；The precipitating reagent is one of sodium metaaluminate, carbon dioxide, sodium carbonate, urea, ammonium carbonate, ammonium hydrogen carbonate or a variety of；
The soluble-salt of the copper is selected from one of copper nitrate, copper sulphate, copper chloride or a variety of；The soluble-salt of the Si selects
From one of sodium metasilicate, sodium metasilicate, silica solution or a variety of；The soluble-salt of the Sn be selected from stannic chloride, stannous chloride,
One of nitric acid tin is a variety of.
The palladium solution is palladium chloride, palladium nitrate or palladium acetate solution.
The alkali metal is one of Li, K, Rb, Cs or a variety of, and preferably Li and/or K, alkali metal are with solubility
The form of salt introduces；Alkaline-earth metal is one of Mg, Ca, Sr, Ba or a variety of, preferably Mg and/or Sr, and alkaline-earth metal is with can
The form of soluble introduces.
The pH value of maceration extract ammonium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate solution adjust.
Alkynes selective hydrocatalyst of the invention, the selection for alkynes in C-4-fraction containing alkynes add hydrogen, according to
Lower step carries out:
Vinylacetylene and the hydrogenated reaction member of ethyl acetylene are converted into butadiene and butylene, and hydrogenated products divide from product
Butadiene extraction device is returned from unit, recycle butadiene and butylene or is mixed into the unit of exhaust collection containing alkynes with raw material, then
It is secondary to be liquefied and purified, reactor be bubble type insulation fix bed reactor, hydrogenation reaction use two-stage hydrogenation technique, each section
20~80 DEG C of reactor inlet temperature, preferably 30-60 DEG C, 0.45~1.5MPa of operating pressure, preferably 0.60~1.0MPa, hydrogen
Gas/alkynes molar ratio 0.5~2.5, preferably 0.8~1.5,0.4~2.5h of fresh material air speed-1, preferably 0.8~1.5h-1, product
It is 2~8, preferably 3~6 with fresh material ratio.
Alkynes selective hydrocatalyst of the invention is used for isothermal fixed bed reactors.
Compared with prior art, the features of the present invention and beneficial effect are:
The present invention mainly solves the coking problem of catalyst from the following aspect: first is that by addition alkali metal and/or alkali
Earth metal modifying agent modification regulation support surface acidity, is greatly reduced the highly acid center easily polymerizeing, second is that addition auxiliary agent and work
Property Metal Palladium forms stronger interaction, to weaken catalyst initial activity, because the coking of initial reaction stage is to catalyst activity
Influence is more significant, by using certain means, while promoting palladium more preferably to disperse between cocatalyst component and carrier
Stronger effect is formed, synergistic effect is generated, the side reactions such as coking are reduced while improving selectivity, in terms of implementation result,
The catalyst of this patent preparation has reached this effect.
Catalyst of the present invention, since IB the and/or IVA element oxide as co-catalysis component is to introduce in different ways
, it can partially promote the dispersion of palladium, improve hydrogenation activity, partially form alloy or solid solution, enhancing palladium and co-catalysis group with palladium
Divide, the interaction between palladium and carrier, to improve hydrogenation selectivity and run stability, palladium is inhibited to be lost.
Present invention is characterized in that catalyst hydrogenation activity of the invention is high, good, the impurity such as water resistant, solvent of selectivity
Can be strong, run stability is excellent, and method for preparing catalyst is simple to operation.1000h evaluation rear catalyst performance does not reduce substantially,
Less than 1.5%, palladium base is not originally lost coking rate.Be applicable in butadiene extraction device alkynes content it is high carbon containing alkynes four selection add hydrogen or
The selection of the high carbon containing alkynes of person's butadiene content four plus hydrogen, convert butadiene for vinylacetylene, and ethyl acetylene is converted into butylene,
Hydrogenation products can return to extraction device and directly recycle butadiene and butylene, or return to extraction device raw material storage tank, mixed with raw material
It is fed after conjunction together as extraction device.
Catalyst of the present invention has the advantage that first is that hydrogenation activity and selectivity realize preferable balance, solves
The mismatch problem of the highly selective difference of activity existing for catalyst or selective high activity difference.Second is that catalyst is with higher
Stabilized hydrogenation, colloid production quantity is few, and water-fast, solvent and heavy constituent fluctuation ability are strong.Third is that catalyst use condition is mild, add
Hydrogen reaction has preferable Hydrogenation, especially recycle ratio low under room temperature, lower pressure, and product internal circulating load is few, reduces
Impact to catalyst, and reduce plant energy consumption.Fourth is that active component palladium dispersion degree is high, turnover rate is low, and operation cycle is long.Fifth is that
Catalyst of the present invention is applicable not only to the high raw material of alkynes content and adds hydrogen, and the carbon containing alkynes four that particularly suitable butadiene content is high
Material adds hydrogen, can effectively improve butadiene potential content in butadiene product equipment charging, reduce the influence to butadiene extraction device.
Alkali metal and/or alkaline-earth metal primarily serve modification support surface acidity and improve thermal stability effect, IB and/
Or IVA element oxide primarily serves promotion activity, improves selectivity and reduces coking, improves anti-impurity ability and extends fortune
Turn the effect of stability.
Detailed description of the invention
Fig. 1 is alkynes selective hydrocatalyst of the invention for the selection of alkynes in C-4-fraction containing alkynes plus the stream of hydrogen
Cheng Tu.
Specific embodiment:
Embodiment is set forth below and the present invention is described in detail in conjunction with attached drawing, but the present invention is not by these embodiments
Limitation.
Embodiment 1-10
The alkynes selective hydrocatalyst carrier of Examples 1 to 10 is Al2O3, each component is as shown in table 1, prepares
Journey are as follows:
A, prepared by carrier:
Compound concentration is 200gAl2O3/ L sodium aluminate solution 1L is heated to 70 DEG C, compound concentration 80gAl2O3/ L sulphur
Sour aluminum solutions 2L, is heated to 70 DEG C；
1.0L distilled water is added in plastic cans, is heated to 70 DEG C, above two slurries are added in cocurrent, pH value 8.0 is kept,
Temperature 70 C carry out plastic, during plastic be added concentration be 0.05mol/L Cu salting liquid and/or Sn salting liquid and/or
Si salting liquid；
In pH value 8.0, temperature 70 C aging 60min after cemented into bundles.After aging, 65 DEG C of deionized waters are injected,
The slurries after aging are beaten under 200rpm stirring rate, washed, are filtered, filter cake is obtained after 100 DEG C of dry 3h containing Cu
And/or the boehmite of Sn and/or Si；
B, support modification:
It is mediated after boehmite obtained above, nitric acid, citric acid, water etc. are mixed, extruded moulding, 120 DEG C of dryings
Carrier is made in 4h, 600 DEG C of roasting 6h, then impregnates a certain amount of alkali metal and/or alkaline-earth metal salt solution, 120 DEG C of dryings
The carrier of alkali metal containing and/or alkaline-earth metal is made in 4h, 1100 DEG C of roasting 4h；
C, catalyst preparation:
The solution of palladium nitrate, silver nitrate and/or plumbi nitras is prepared, impregnated carrier after pH value, 120 DEG C of dry 4h, 500 are adjusted
DEG C roasting 8h be made catalyst.
Embodiment 11-20
The alkynes selective hydrocatalyst carrier of embodiment 11~20 is Al2O3, each component is as shown in table 1, prepares
Journey are as follows:
A, prepared by carrier:
Compound concentration is 200gAl in plastic cans2O3/ L aluminum nitrate solution 1L, compound concentration 80gAl2O3/ L aluminum sulfate
Solution 1L is uniformly mixed and is heated to 75 DEG C；
CO is passed through into plastic cans2Gas, keeps pH value 8.0~8.5,75 DEG C of progress plastics of temperature, after cemented into bundles
PH value 8.0, temperature 70 C aging 60min；
Aging terminates, and injects 75 DEG C of deionized waters, is beaten under 200rpm stirring rate after washing, while being added dense
The Cu salting liquid and/or Sn salting liquid and/or Si salting liquid that degree is 0.05mol/L, are filtered, filter cake is 120 after being beaten 60min
The boehmite containing Cu and/or Sn and/or Si is obtained after DEG C dry 8h；
B, support modification:
It is mediated after boehmite obtained above, nitric acid, citric acid, water etc. are mixed, extruded moulding, 120 DEG C of dryings
Carrier is made in 4h, 650 DEG C of roasting 8h；Then a certain amount of alkali metal and/or alkaline-earth metal salt solution, 120 DEG C of dryings are impregnated
The carrier of alkali metal containing and/or alkaline-earth metal is made in 4h, 1060 DEG C of roasting 6h；
C, catalyst preparation:
The solution for preparing palladium acetate, silver nitrate and/or lead acetate respectively adjusts impregnated carrier after solution ph, and 120 DEG C dry
Catalyst is made in dry 4h, 450 DEG C of roasting 8h.
Embodiment 21-30
The alkynes selective hydrocatalyst carrier of embodiment 21~30 is Al2O3, each component is as shown in table 1, prepares
Journey are as follows:
A, prepared by carrier:
Compound concentration is 200gAl2O3/ L aluminum nitrate solution 1L, compound concentration 80gAl2O3/ L aluminum sulfate solution 1L, will
50 DEG C are heated to after two kinds of solution mixing；
The mixed solution of sodium carbonate and ammonium hydrogen carbonate is prepared in plastic cans and is heated to 60 DEG C, by aluminum nitrate and aluminum sulfate
Mixed solution be added in plastic cans, keep pH value 8.0~8.5, temperature 60 C carry out plastic, be added during plastic dense
The Cu salting liquid and/or Sn salting liquid and/or Si salting liquid that degree is 0.05mol/L；
In pH value 8.0, temperature 60 C aging 60min after cemented into bundles.After aging, 75 DEG C of deionization washings are injected
It washs, is then beaten under 200rpm stirring rate, while adding Cu salting liquid and/or Sn that concentration is 0.05mol/L
Salting liquid and/or Si salting liquid, continue be beaten 60min after wash, filter, filter cake obtained after 130 DEG C of dry 8h contain Cu and/or
The boehmite of Sn and/or Si；
B, support modification:
It is mediated after boehmite obtained above, nitric acid, citric acid, water etc. are mixed, extruded moulding, 120 DEG C of dryings
Carrier is made in 4h, 650 DEG C of roasting 8h, then impregnates a certain amount of alkali metal and/or alkaline-earth metal salt solution, 120 DEG C of dryings
The carrier of alkali metal containing and/or alkaline-earth metal is made in 4h, 950 DEG C of roasting 6h；
C, catalyst preparation:
Then the solution for preparing palladium nitrate, silver nitrate and/or plumbi nitras respectively, adjusts impregnated carrier after solution ph, and 120
DEG C dry 4h, the obtained catalyst of 600 DEG C of roasting 8h.
The alkynes selective hydrocatalyst of Examples 1 to 30, the selection for alkynes in C-4-fraction containing alkynes add hydrogen, such as
Shown in Fig. 1, follow the steps below:
Vinylacetylene and the hydrogenated reaction member of ethyl acetylene are converted into butadiene and butylene, and hydrogenated products divide from product
Butadiene extraction device is returned from unit, recycle butadiene and butylene or is mixed into the unit of exhaust collection containing alkynes with raw material, then
It is secondary to be liquefied and purified, reactor be bubble type insulation fix bed reactor, hydrogenation reaction use two-stage hydrogenation technique, each section
20~80 DEG C of reactor inlet temperature, preferably 30-60 DEG C, 0.45~1.5MPa of operating pressure, preferably 0.60~1.0MPa, hydrogen
Gas/alkynes molar ratio 0.5~2.5, preferably 0.8~1.5,0.4~2.5h of fresh material air speed-1, preferably 0.8~1.5h-1, product
It is 2~8, preferably 3~6 with fresh material ratio.
Comparative example 1-5
1~5 component of comparative example is as shown in table 1, takes Al2O3Then carrier impregnates a certain amount of alkali metal in 550 DEG C of roasting 8h
And/or the carrier of alkali metal containing and/or alkaline-earth metal is made in alkaline-earth metal salt solution, 120 DEG C of dry 4h, 1060 DEG C of roasting 6h；
Then impregnate it is a certain amount of containing Cu and/or containing Sn and/or solution containing Si, 120 DEG C of dry 4h, 500 DEG C roast after impregnate nitric acid again
Catalyst is made in palladium, silver nitrate and/or plumbi nitras, 120 DEG C of dry 4h, 500 DEG C of roasting 8h.
Comparative example 6-10
6~10 component of comparative example is as shown in table 1, by boehmite, nitric acid, citric acid, water, contains Cu and/or containing Sn
And/or alumina support is made in the mixer kneader of solution containing Si, extruded moulding, 120 DEG C of dryings, 550 DEG C of roasting 4h；Then it impregnates
Alkali metal containing and/or alkali is made in a certain amount of alkali metal and/or alkaline-earth metal salt solution, 120 DEG C of dry 4h, 1000 DEG C of roasting 6h
The carrier of earth metal；Then a certain amount of palladium nitrate, silver nitrate and/or plumbi nitras, 120 DEG C of dry 4h, 500 DEG C of roasting 8h are impregnated
Catalyst is made.
The catalytic capability of catalyst obtained by Examples 1 to 30 and comparative example 1~10 is evaluated, evaluation condition
Are as follows: using insulation bubbling fixed bed reactors, single hop or two-stage hydrogenation technique, 30~45 DEG C of reactor inlet temperature, reaction pressure
Power 0.8~1.0MPa, H2/ VA molar ratio 0.75~2.0,1.0~2.0h of fresh material liquid hourly space velocity (LHSV)-1, loaded catalyst
50ml。
Reaction process process: C-4-fraction rises to reaction pressure after measuring pump-metered, mixed after preheated with hydrogen from
Reactor lower part enters catalyst bed, carries out gas-liquid separation after reaction product is cooling, the fixed gas emptying after separation, liquid row
Enter products pot.When using two-stage hydrogenation, one-stage hydrogenation product is directly entered second stage reactor, second stage reactor root without isolation
Hydrogen is incorporated according to alkynes content in product.
Catalyst reduction: before evaluation, 120 DEG C, 1.0MPa, lead to hydrogen reducing 8 hours, hydrogen gas space velocity 100h-1。
Catalyst regeneration: the catalyst after 1000h is evaluated unloads, and roasts 4 hours for 550 DEG C of blowing air in Muffle furnace.
Using gas chromatographic analysis raw material and product form.
Alkynes hydrogenation rate and butadiene selective are calculated as follows in the present embodiment:
Embodiment and the specific evaluation condition of comparative example catalyst and it the results are shown in Table 1.
1 embodiment and comparative example evaluating catalyst result of table
Using two-stage hydrogenation technique, catalyst made from embodiment 14 is seated in one, second stage reactor respectively, it is each anti-
Answer device loading catalyst 50ml.At 30 DEG C of reactor inlet temperature, operating pressure 0.95Mpa, one section of H2/ VA (mol)=1.0,
Two sections of H2/ VA (mol)=0.8,1.2~1.5h of fresh material air speed-1Under the conditions of, add up evaluation 1000 hours, catalyst performance is commented
Valence the results are shown in Table 2.
2 embodiment of table, 14 catalyst 1000h evaluation result
Catalyst, regenerated catalyst and fresh catalyst analysis test result after evaluation in 1000 hours are shown in Table 3.
3 embodiment of table, 14 catalyst test result
| Fresh dose | After 1000h evaluation | Regenerative agent | |
| Palladium content (wt%) | 0.40 | - | 0.395 |
| Specific surface area (m2/g) | 52.5 | 40.8 | 50.4 |
| Coking rate (wt%) | - | 1.45 | - |
It can be seen that conversion ratio and the comparison of the catalyst for the preparation that the present invention is city from the Comparative result of 1~table of table 3
Example is suitable, and selectivity is more preferable, and the palladium content and specific surface area after long-time use are without significant changes, it was demonstrated that its stability is excellent
It is different.
Claims (13)
1. a kind of alkynes selective hydrocatalyst, it is characterised in that according to weight percent, be with 0.1~0.8% Metal Palladium
Active component, 90~99% aluminium oxide are carrier, are that modification helps added with 0~5% alkali metal and/or alkaline earth oxide
Agent, 0.05~10%IB and/or IVA element oxide are co-catalysis component；Wherein in catalyst components, palladium, alkali metal and/
Or alkaline-earth metal is introduced in a manner of impregnating, a part in IB and/or IVA element in a manner of impregnating, making by another part
It is introduced when standby carrier；Specific surface area of catalyst is 20~100m20.15~0.75ml/g of/g, Kong Rongwei.
2. a kind of alkynes selective hydrocatalyst according to claim 1, it is characterised in that the support shapes are
Spherical shape, tooth spherical shape, bar shaped, cloverleaf pattern or the other shapes carrier obtained by modes such as extrusion, tabletting or spin, preferablyCloverleaf pattern orSpherical shape, tooth it is spherical.
3. a kind of alkynes selective hydrocatalyst according to claim 1, it is characterised in that the alkali metal be Li,
K, one of Rb, Cs or a variety of, preferably Li, K, additive amount are 0.05~2.5%, preferably 0.5~1.5%.
4. a kind of alkynes selective hydrocatalyst according to claim 1, it is characterised in that the alkaline-earth metal is
One of Mg, Ca, Sr, Ba or a variety of, preferably Mg, Sr, additive amount are 0.05~2.5%, preferably 0.5~1.5%.
5. a kind of alkynes selective hydrocatalyst according to claim 1, it is characterised in that the IB element be Cu,
One of Ag, Au or a variety of, a part of the IB element are that Ag and/or Au are introduced in a manner of impregnating, and additive amount is
0.1~3.0%, preferably 0.5~2.0%；Another part is Cu introducing when preparing alumina support, additive amount 0.5~
10%, preferably 1.5~6.0%.
6. a kind of alkynes selective hydrocatalyst according to claim 1, it is characterised in that the IVA element is
One of Si, Ge, Sn, Pb or a variety of, a part of the IVA element are that Pb and/or Ge are introduced in a manner of impregnating, and are added
Dosage 0.2~3.5%, preferably 0.4~2.5%；Another part is Si and/or the Sn introducing when preparing alumina support, is added
Dosage is 2.0~10%, preferably 3.0~5.0%.
7. the preparation method of alkynes selective hydrocatalyst as described in claim 1, it is characterised in that according to the following steps
It carries out:
A, prepared by carrier:
150~250gAl of concentration is diluted with water in silicon source2O3/ L, is added with stirring precipitating reagent, 50~100 DEG C of plastics, washing,
Filtering, mashing, then in 50~100 DEG C of agings, using boehmite is made after filter, drying, roasting, in plastic and/or
IB element Cu and/or IVA elements Si is added in pulping process and/or Sn obtains soluble salt solutions；
Above-mentioned boehmite is taken, nitric acid, citric acid, sesbania powder and water mixer kneader is added, then forms, 80~150 DEG C dry
It is 10-12 hours dry, 750~1100 DEG C roasting 8-12 hours, finished product alumina support；
B, support modification:
Finished product alumina support is taken, its water absorption rate is measured, according to water absorption rate and modifier content, prepares alkali metal and/or alkaline earth
Aqueous metal solution adjusts solution ph, and finished product alumina support is poured into solution and is impregnated, ageing, 80~150 DEG C of dryings 6
~8h, 4-8 hours obtained modified aluminium oxide supports of 750~1100 DEG C of roastings；
C, catalyst preparation:
According to each component content in catalyst and modified support water absorption rate, for preparing palladium solution and/or IB elements A g and/or Au can
The soluble salt solutions of dissolubility salting liquid and/or IVA elements Pb and/or Ge, are adjusted to 2.5~6.0 for pH value after mixing,
Load weighted modified support is placed in solution and is impregnated, ageing, 80~150 DEG C drying 6~8 hours, 350~600 DEG C roast 6~
8 hours, finished product catalyst.
8. the preparation method of alkynes selective hydrocatalyst according to claim 7, it is characterised in that the silicon source
For one of aluminium hydroxide, aluminum sulfate, aluminium chloride, aluminum nitrate, sodium metaaluminate or a variety of；The precipitating reagent is meta-aluminic acid
One of sodium, carbon dioxide, sodium carbonate, urea, ammonium carbonate, ammonium hydrogen carbonate are a variety of；The soluble-salt of the copper is selected from
One of copper nitrate, copper sulphate, copper chloride are a variety of；It is molten that the soluble-salt of the Si is selected from sodium metasilicate, sodium metasilicate, silicon
One of glue is a variety of；The soluble-salt of the Sn is selected from one of stannic chloride, stannous chloride, nitric acid tin or a variety of.
9. the preparation method of alkynes selective hydrocatalyst according to claim 7, it is characterised in that the palladium is molten
Liquid is palladium chloride, palladium nitrate or palladium acetate solution.
10. the preparation method of alkynes selective hydrocatalyst according to claim 7, it is characterised in that the alkali gold
Belonging to is one of Li, K, Rb, Cs or a variety of, preferably Li and/or K, and alkali metal is introduced in the form of soluble-salt；Alkaline earth gold
Belonging to is one of Mg, Ca, Sr, Ba or a variety of, preferably Mg and/or Sr, and alkaline-earth metal is introduced in the form of soluble-salt.
11. the preparation method of alkynes selective hydrocatalyst according to claim 7, it is characterised in that the dipping
The pH value of liquid ammonium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate solution adjust.
12. a kind of alkynes selective hydrocatalyst, it is characterised in that the selection for alkynes in C-4-fraction containing alkynes adds hydrogen, presses
It is carried out according to following steps:
Vinylacetylene and the hydrogenated reaction member of ethyl acetylene are converted into butadiene and butylene, and hydrogenated products separate single from product
Member returns to butadiene extraction device, recycles butadiene and butylene or mixes into the unit of exhaust collection containing alkynes with raw material, again into
Row liquefaction and purification, reactor are bubble type insulation fix bed reactor, and hydrogenation reaction uses two-stage hydrogenation technique, each section of reaction
20~80 DEG C of device inlet temperature, preferably 30-60 DEG C, 0.45~1.5MPa of operating pressure, preferably 0.60~1.0MPa, hydrogen/
Alkynes molar ratio 0.5~2.5, preferably 0.8~1.5,0.4~2.5h of fresh material air speed-1, preferably 0.8~1.5h-1, product and new
Fresh material ratio is 2~8, preferably 3~6.
13. a kind of alkynes selective hydrocatalyst, which is characterized in that be used for isothermal fixed bed reactors.
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| CN109806885A (en) * | 2019-01-07 | 2019-05-28 | 北京理工大学 | A kind of monatomic catalyst of Pdx/Cu and preparation method thereof adding hydrogen for C4 selection |
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| WO2023134779A1 (en) * | 2022-01-17 | 2023-07-20 | 湖南长炼新材料科技股份公司 | Hydrogenation catalyst and preparation method therefor, and method for preparing isohexanediol and methyl isobutyl carbinol |
| CN115124402A (en) * | 2022-08-16 | 2022-09-30 | 武汉科林化工集团有限公司 | Preparation method of catalyst for preparing styrene by selective hydrogenation of phenylacetylene |
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