CN105618132A - Preparation method and application of aluminum phosphate molecular sieve loaded Ni catalyst - Google Patents
Preparation method and application of aluminum phosphate molecular sieve loaded Ni catalyst Download PDFInfo
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- CN105618132A CN105618132A CN201610001914.9A CN201610001914A CN105618132A CN 105618132 A CN105618132 A CN 105618132A CN 201610001914 A CN201610001914 A CN 201610001914A CN 105618132 A CN105618132 A CN 105618132A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229940001007 aluminium phosphate Drugs 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910017119 AlPO Inorganic materials 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 abstract 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 abstract 1
- 230000004913 activation Effects 0.000 abstract 1
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 17
- XOKSLPVRUOBDEW-DJLDLDEBSA-N (1r,4s,5r)-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound C[C@H]1CC[C@H]2C(C)(C)[C@@H]1C2 XOKSLPVRUOBDEW-DJLDLDEBSA-N 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 229930006728 pinane Natural products 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- -1 Monoterpene alkene Chemical class 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical group [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- 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
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of an aluminum phosphate molecular sieve loaded Ni catalyst and belongs to the field of chemical engineering. The preparation method of the catalyst comprises the following steps of mixing phosphoric acid, aluminum hydroxide, triethanolamine and alpha-pinene according to a certain proportion; placing a mixture into a hydrothermal reactor, and maintaining a certain pH value; ageing for 12 to 60 hours and then crystalizing at 160 to 200DEG C for 20 to 36 hours; after the crystallization is ended, filtering, washing and drying a product, and performing microwave roasting at the temperature of 350 to 550DEG C for 2 to 5 hours to obtain an AlPO4 molecular sieve, and taking the AlPO4 molecular sieve as a carrier; adding the AlPO4 molecular sieve into an aqueous solution of nickel nitrate with the mass percent concentration of 5 to 15 percent according to a certain proportion, performing ultrasonic immersing and then drying and roasting under an infrared lamp to obtain a catalyst precursor; introducing hydrogen at the temperature of 300 to 500DEG C, and performing catalyst activation to obtain a loaded Ni/AlPO4 catalyst. The catalyst disclosed by the invention is used for a hydrogenation reaction of pinene; a process method is simple; the catalyst is lower in cost, excellent in thermal stability, good in catalytic effect and easy for recovery.
Description
Technical field
The present invention relates to the preparation method of a kind of aluminium phosphate molecular sieve supported ni catalyst and application, belong to chemical field.
Background technology
Australene is terebinthine main component, is a kind of Monoterpene alkene. The hydrogenated prepared pinane of australene, the latter is the important intermediate preparing spice and vitamin E, has significantly high surcharge. Pinane includes cis and trans two kinds, mainly needs cis-pinane due to industrial, and the process therefore preparing pinane needs to promote it along inverse ratio. Improve pinane and have multiple along the method for inverse ratio, be wherein that to improve selectivity of catalyst catalytic performance be a kind of important channel.
Australene hydrogenation catalyst conventional at present includes homogeneous composite catalyst and heterogeneous loaded catalyst. Wherein heterogeneous catalyst is widely used, and has reaction controllability is good, product and the advantage such as catalyst is easily separated. The part of loaded catalyst includes the base metals such as noble metal and Ni such as Pd, Ru, and noble metal has high activity, but cost is high; Therefore, supported Ni catalyst has the good suitability.
For loaded catalyst, its performance is had impact by carrier equally, selects suitable carrier to be conducive to the carrying out of reaction. Phosphate aluminium molecular sieve (AlPO4) it is the conventional catalyst carrier of a class, due to the good heat stability of acid phosphorus aluminum skeleton, and have micropore-mesopore structure more, be therefore provided that considerable response area. In prepared by phosphate aluminium molecular sieve, solvent, template can affect its construction features. Using the australene of Colophonium system as solvent, preparing phosphate aluminium molecular sieve, load Ni catalysis carries out hydrogenation reaction with the australene under system, can show outstanding catalytic effect. Its performance advantage includes carrier surface area less demanding, and amount of ligand is less demanding, and under gentle reaction condition, catalyst can keep greater activity etc.
Summary of the invention
It is an object of the invention to provide a kind of support type Ni/AlPO4The preparation method of catalyst, and it is applied to australene Hydrogenation for cis-pinane; Australene is introduced the preparation process of catalyst carrier, and reacts with this catalyst australene, there is catalyst preparation conditions gentleness, the advantages such as technological process is short, and reaction condition is moderate, and catalysis activity is high, good product selectivity.
The preparation method of the loaded catalyst preparing cis-pinane for pinene hydrogenation of the present invention, specifically includes following steps:
(1) be in molar ratio 1:1:0.5 ~ 1.5:20 ~ 60 ratio by phosphoric acid, aluminium hydroxide, triethanolamine, australene mixing, insert in water heating kettle, after ageing 12 ~ 60h at 160 ~ 200 DEG C crystallization 20 ~ 36h, crystallization product filters, washing, dry, rear microwave calcining obtain aluminium phosphate molecular sieve carrier;
(2) aluminium phosphate molecular sieve carrier is joined in the nickel nitrate aqueous solution that mass percent concentration is 25mg/mL ~ 75mg/mL in the ratio of 50 ~ 150mg/mL, at 25 ~ 55 DEG C after ultrasonic immersing 30 ~ 60min, 1 ~ 4h is dried under infrared lamp, then roasting 2 ~ 5h at 300 ~ 500 DEG C, obtains catalyst precursor;
(3) at 300 ~ 500 DEG C, catalyst precursor is activated by logical hydrogen 1 ~ 5h, obtains Ni/AlPO4Catalyst.
Preferably, after the crystallization product that step of the present invention (1) obtains is filtered, with distilled water wash 3 ~ 5 times, dry 12 ~ 48h at 50 ~ 80 DEG C, then microwave calcining 2 ~ 5h at 350 ~ 550 DEG C, obtains AlPO4Molecular sieve carrier.
It is a further object of the present invention to provide described AlPO4Molecular sieve carried Ni catalyst, for the method for catalysis pinene hydrogenation reaction, specifically includes the following step: take australene and be placed in reactor, adds catalyst by 1 ~ 9wt% of australene quality, puts into magnet rotor, and close reactor; Replace 3 times under 0.1 ~ 0.4MPa with nitrogen, then replace 3 times under 0.1 ~ 0.4MPa with hydrogen, leak detection, confirm that reactor seals intact; Opening hydrogen gas valve, regulating pressure in still is 2 ~ 5MPa, opens temperature control instrument, in 110 ~ 150 DEG C, reaction 30 ~ 150min under stir speed (S.S.) 600 ~ 900r/min.
The australene (solvent and reaction raw materials) of present invention use, hydrogen, nitrogen are technical grade, and phosphoric acid, aluminium hydroxide, triethanolamine, nickel nitrate are analytical pure.
Compared to the prior art the present invention has the advantage that:
(1) catalyst catalytic performance that the present invention prepares is excellent, and the selectivity of principal product is good.
(2) the catalyst Heat stability is good that the present invention prepares, preparation process is easy to control, and loading condition easily realizes.
(3) the method for the invention uses microwave calcining, and catalyst order is better.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1
(1) be in molar ratio 1:1:0.5:30 ratio by phosphoric acid, aluminium hydroxide, triethanolamine, australene mixing, insert in water heating kettle, after ageing 12h at 200 DEG C crystallization 20h, with distilled water wash 3 times, dry 48h at 50 DEG C, then microwave calcining 2h at 350 DEG C, obtains AlPO4Molecular sieve carrier.
(2) aluminium phosphate molecular sieve carrier is added to the nickel nitrate aqueous solution that 20mL mass percent concentration is 25mg/mL in the ratio of 50mg/mL, at 55 DEG C after ultrasonic immersing 30min, drying 4h under infrared lamp, then roasting 2h at 300 DEG C, obtains catalyst precursor.
(3) at 300 DEG C, catalyst precursor is activated by logical hydrogen 5h, obtains Ni/AlPO4Catalyst.
The AlPO that the present embodiment prepares4Molecular sieve carried Ni catalyst, for the method for catalysis pinene hydrogenation reaction, specifically includes the following step: take australene and be placed in the reactor containing PTFE liner, adds catalyst by the 9wt% of australene quality, puts into magnet rotor, and close reactor; Replace 3 times under 0.1MPa with nitrogen, then replace 3 times under 0.1MPa with hydrogen, leak detection, confirm that reactor seals intact; Opening hydrogen gas valve, regulating pressure in still is 5MPa, opens temperature control instrument, in 110 DEG C, reaction 150min under stir speed (S.S.) 600r/min.
Analysis result is as follows: the conversion ratio of australene is 98.88%, cis-pinane selectivity 91.17%.
Embodiment 2
(1) be in molar ratio 1:1:1:60 ratio by phosphoric acid, aluminium hydroxide, triethanolamine, australene mixing, insert in water heating kettle, after ageing 40h at 180 DEG C crystallization 28h, with distilled water wash 4 times, dry 30h at 60 DEG C, then microwave calcining 3h at 400 DEG C, obtains AlPO4Molecular sieve carrier.
(2) aluminium phosphate molecular sieve carrier is added to the nickel nitrate aqueous solution that 20mL mass percent concentration is 50mg/mL in the ratio of 100mg/mL, at 25 DEG C after ultrasonic immersing 45min, drying 2h under infrared lamp, then roasting 4h at 400 DEG C, obtains catalyst precursor.
(3) at 400 DEG C, catalyst precursor is activated by logical hydrogen 3h, obtains Ni/AlPO4Catalyst.
The AlPO that the present embodiment prepares4Molecular sieve carried Ni catalyst, for the method for catalysis pinene hydrogenation reaction, specifically includes the following step: take australene and be placed in the reactor containing PTFE liner, adds catalyst by the 4wt% of australene quality, puts into magnet rotor, and close reactor; Replace 3 times under 0.3MPa with nitrogen, then replace 3 times under 0.3MPa with hydrogen, leak detection, confirm that reactor seals intact; Opening hydrogen gas valve, regulating pressure in still is 4MPa, opens temperature control instrument, in 130 DEG C, reaction 150min under stir speed (S.S.) 800r/min.
Analysis result is as follows: the conversion ratio of australene is 97.89%, cis-pinane selectivity 93.25%.
Embodiment 3
(1) be in molar ratio 1:1:1.5:20 ratio by phosphoric acid, aluminium hydroxide, triethanolamine, australene mixing, insert in water heating kettle, after ageing 60h at 160 DEG C crystallization 36h, with distilled water wash 5 times, dry 12h at 80 DEG C, then microwave calcining 5h at 550 DEG C, obtains AlPO4Molecular sieve carrier.
(2) aluminium phosphate molecular sieve carrier is added to the nickel nitrate aqueous solution that 20mL mass percent concentration is 75mg/mL in the ratio of 150mg/mL, at 30 DEG C after ultrasonic immersing 60min, drying 1h under infrared lamp, then roasting 5h at 500 DEG C, obtains catalyst precursor.
(3) at 500 DEG C, catalyst precursor is activated by logical hydrogen 5h, obtains Ni/AlPO4Catalyst.
The AlPO that the present embodiment prepares4Molecular sieve carried Ni catalyst, for the method for catalysis pinene hydrogenation reaction, specifically includes the following step: take australene and be placed in the reactor containing PTFE liner, adds catalyst by the 1wt% of australene quality, puts into magnet rotor, and close reactor; Replace 3 times under 0.4MPa with nitrogen, then replace 3 times under 0.4MPa with hydrogen, leak detection, confirm that reactor seals intact; Opening hydrogen gas valve, regulating pressure in still is 2MPa, opens temperature control instrument, in 150 DEG C, reaction 90min under stir speed (S.S.) 900r/min.
Analysis result is as follows: the conversion ratio of australene is 95.67%, cis-pinane selectivity 93.83%.
Embodiment 4
(1) be in molar ratio 1:1:1.25:30 ratio by phosphoric acid, aluminium hydroxide, triethanolamine, australene mixing, insert in water heating kettle, after ageing 24h at 160 DEG C crystallization 28h, with distilled water wash 5 times, dry 12h at 80 DEG C, then microwave calcining 4h at 450 DEG C, obtains AlPO4Molecular sieve carrier.
(2) ratio of aluminium phosphate molecular sieve carrier 60mg/mL is added to the nickel nitrate aqueous solution of 20mL mass percent concentration 30mg/mL,, at 30 DEG C after ultrasonic immersing 50min, under infrared lamp, dry 2h, then roasting 3h at 450 DEG C, obtains catalyst precursor.
(3) at 500 DEG C, catalyst precursor is activated by logical hydrogen 2h, obtains Ni/AlPO4Catalyst.
The AlPO that the present embodiment prepares4Molecular sieve carried Ni catalyst, for the method for catalysis pinene hydrogenation reaction, specifically includes the following step: take australene and be placed in the reactor containing PTFE liner, adds catalyst by the 3wt% of australene quality, puts into magnet rotor, and close reactor; Replace 3 times under 0.4MPa with nitrogen, then replace 3 times under 0.4MPa with hydrogen, leak detection, confirm that reactor seals intact; Opening hydrogen gas valve, regulating pressure in still is 3MPa, opens temperature control instrument, in 130 DEG C, reaction 90min under stir speed (S.S.) 900r/min.
Analysis result is as follows: the conversion ratio of australene is 90.91%, cis-pinane selectivity 94.75%.
Embodiment 5
(1) be in molar ratio 1:1:0.75:50 ratio by phosphoric acid, aluminium hydroxide, triethanolamine, australene mixing, insert in water heating kettle, after ageing 36h at 180 DEG C crystallization 36h, with distilled water wash 5 times, dry 48h at 70 DEG C, then microwave calcining 3h at 400 DEG C, obtains AlPO4Molecular sieve carrier.
(2) aluminium phosphate molecular sieve carrier is added to the nickel nitrate aqueous solution that 20mL mass percent concentration is 60mg/mL in the ratio of 120mg/mL,, at 30 DEG C after ultrasonic immersing 60min, under infrared lamp, dry 1h, then roasting 5h at 400 DEG C, obtains catalyst precursor.
(3) at 400 DEG C, catalyst precursor is activated by logical hydrogen 3h, obtains Ni/AlPO4Catalyst.
The AlPO that the present embodiment prepares4Molecular sieve carried Ni catalyst, for the method for catalysis pinene hydrogenation reaction, specifically includes the following step: take australene and be placed in the reactor containing PTFE liner, adds catalyst by the 5wt% of australene quality, puts into magnet rotor, and close reactor; Replace at 0.2 mpa with nitrogen 3 times, then replace at 0.2 mpa with hydrogen 3 times, leak detection, confirm that reactor seals intact; Opening hydrogen gas valve, regulating pressure in still is 4MPa, opens temperature control instrument, in 140 DEG C, reaction 70min under stir speed (S.S.) 800r/min.
Analysis result is as follows: the conversion ratio of australene is 93.87%, cis-pinane selectivity 93.77%.
Embodiment 6
(1) be in molar ratio 1:1:1:50 ratio by phosphoric acid, aluminium hydroxide, triethanolamine, australene mixing, insert in water heating kettle, after ageing 60h at 160 DEG C crystallization 20h, with distilled water wash 5 times, dry 12h at 80 DEG C, then microwave calcining 4h at 550 DEG C, obtains AlPO4Molecular sieve carrier.
(2) aluminium phosphate molecular sieve carrier is added to the nickel nitrate aqueous solution that 20mL mass percent concentration is 40mg/mL in the ratio of 80mg/mL, at 30 DEG C after ultrasonic immersing 60min, drying 3h under infrared lamp, then roasting 5h at 500 DEG C, obtains catalyst precursor.
(3) at 450 DEG C, catalyst precursor is activated by logical hydrogen 2h, obtains Ni/AlPO4Catalyst.
The AlPO that the present embodiment prepares4Molecular sieve carried Ni catalyst, for the method for catalysis pinene hydrogenation reaction, specifically includes the following step: take australene and be placed in the reactor containing PTFE liner, adds catalyst by the 9wt% of australene quality, puts into magnet rotor, and close reactor; Replace 3 times under 0.3MPa with nitrogen, then replace 3 times under 0.3MPa with hydrogen, leak detection, confirm that reactor seals intact; Opening hydrogen gas valve, regulating pressure in still is 2MPa, opens temperature control instrument, in 150 DEG C, reaction 50min under stir speed (S.S.) 700r/min.
Analysis result is as follows: the conversion ratio of australene is 97.20%, cis-pinane selectivity 91.44%.
Claims (3)
1. an AlPO4The preparation method of molecular sieve carried Ni catalyst, it is characterised in that specifically include following steps:
(1) be in molar ratio 1:1:0.5 ~ 1.5:20 ~ 60 ratio by phosphoric acid, aluminium hydroxide, triethanolamine, australene mixing, insert in water heating kettle, after ageing 12 ~ 60h at 160 ~ 200 DEG C crystallization 20 ~ 36h, crystallization product filters, washing, dry, rear microwave calcining obtain aluminium phosphate molecular sieve carrier;
(2) aluminium phosphate molecular sieve carrier is joined in the nickel nitrate aqueous solution that mass percent concentration is 25mg/mL ~ 75mg/mL in the ratio of 50 ~ 150mg/mL, at 25 ~ 55 DEG C after ultrasonic immersing 30 ~ 60min, 1 ~ 4h is dried under infrared lamp, then roasting 2 ~ 5h at 300 ~ 500 DEG C, obtains catalyst precursor;
(3) at 300 ~ 500 DEG C, catalyst precursor is activated by logical hydrogen 1 ~ 5h, obtains Ni/AlPO4Catalyst.
2. AlPO according to claim 14The preparation method of molecular sieve carried Ni catalyst, it is characterised in that: washing process described in step (1) is for using distilled water wash 3 ~ 5 times, and drying condition is dry 12 ~ 48h at 50 ~ 80 DEG C; Microwave calcining condition is microwave calcining 2 ~ 5h at 350 ~ 550 DEG C.
3. the AlPO described in claim 1 or 24Molecular sieve carried Ni catalyst is for the method for catalysis pinene hydrogenation reaction, it is characterised in that specifically include the following step: take australene and be placed in reactor, adds catalyst by 1 ~ 9wt% of australene quality, puts into magnet rotor, and close reactor; Replace 3 times under 0.1 ~ 0.4MPa with nitrogen, then replace 3 times under 0.1 ~ 0.4MPa with hydrogen, leak detection, confirm that reactor seals intact; Opening hydrogen gas valve, regulating pressure in still is 2 ~ 5MPa, opens temperature control instrument, in 110 ~ 150 DEG C, reaction 30 ~ 150min under stir speed (S.S.) 600 ~ 900r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107252672A (en) * | 2017-07-21 | 2017-10-17 | 云南中烟工业有限责任公司 | A kind of modified phosphate aluminium molecular sieve filter tip adsorption material and preparation method and application |
| CN111960911A (en) * | 2020-07-23 | 2020-11-20 | 青岛科技大学 | Method for preparing cis-pinane by hydrogenating alpha-pinene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125864A (en) * | 2010-12-16 | 2011-07-20 | 昆明理工大学 | Supported catalyst for hydrogenation of alpha-pinene and preparation method and uses thereof |
| US8975463B1 (en) * | 2009-08-31 | 2015-03-10 | The United States Of America As Represented By The Secretary Of The Navy | Efficient conversion of pure and mixed terpene feedstocks to high density fuels |
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2016
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| CN107252672A (en) * | 2017-07-21 | 2017-10-17 | 云南中烟工业有限责任公司 | A kind of modified phosphate aluminium molecular sieve filter tip adsorption material and preparation method and application |
| CN111960911A (en) * | 2020-07-23 | 2020-11-20 | 青岛科技大学 | Method for preparing cis-pinane by hydrogenating alpha-pinene |
| CN111960911B (en) * | 2020-07-23 | 2022-05-13 | 青岛科技大学 | Method for preparing cis-pinane by hydrogenating alpha-pinene |
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| CN105618132B (en) | 2018-04-24 |
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