CN105562047A - Preparation method and application of catalyst for natural monoterpene hydrogenation - Google Patents
Preparation method and application of catalyst for natural monoterpene hydrogenation Download PDFInfo
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- CN105562047A CN105562047A CN201610001916.8A CN201610001916A CN105562047A CN 105562047 A CN105562047 A CN 105562047A CN 201610001916 A CN201610001916 A CN 201610001916A CN 105562047 A CN105562047 A CN 105562047A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229930003658 monoterpene Natural products 0.000 title claims abstract description 12
- 235000002577 monoterpenes Nutrition 0.000 title claims abstract description 12
- 150000002773 monoterpene derivatives Chemical class 0.000 title claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 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
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 3
- 229910017119 AlPO Inorganic materials 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 8
- 229940001007 aluminium phosphate Drugs 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- -1 Monoterpene alkene Chemical class 0.000 claims description 6
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N α-pinene Chemical compound CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 abstract 4
- 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 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane group Chemical group C12C(CCC(C1(C)C)C2)C XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 31
- 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 16
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229930006728 pinane Natural products 0.000 description 6
- XOKSLPVRUOBDEW-IWSPIJDZSA-N (1r,4r,5r)-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound C[C@@H]1CC[C@H]2C(C)(C)[C@@H]1C2 XOKSLPVRUOBDEW-IWSPIJDZSA-N 0.000 description 3
- 230000000694 effects Effects 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CZCBTSFUTPZVKJ-UHFFFAOYSA-N rose oxide Chemical compound CC1CCOC(C=C(C)C)C1 CZCBTSFUTPZVKJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930008394 dihydromyrcenol Natural products 0.000 description 1
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction 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
- 229930007744 linalool Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229930007790 rose oxide Natural products 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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)
Abstract
The invention discloses a preparation method and application of a catalyst for natural monoterpene hydrogenation, and belongs to the field of chemical engineering. The catalyst is a supported Ni/AlPO4 catalyst. The preparation method comprises the following steps: mixing phosphoric acid, aluminum hydroxide, triethylamine, and water, transferring the mixture to a hydrothermal kettle, maintaining a certain pH value, carrying out crystallization for 20 to 28 hours at a temperature of 160 to 200 DEG C, after crystallization, filtering, washing and drying the reaction product, burning the reaction product to remove the template so as to obtain an AlPO4 molecular sieve carrier; adding AlPO4 molecular sieves into a nickel nitrate water solution, fully stirring, performing impregnation for 20 to 30 hours, drying for 3 to 10 hours at a temperature of 50 to 80 DEG C, then burning for 2 to 5 hours at a temperature of 300 to 450 DEG C, and introducing hydrogen gas into the system to carry out activation in the presence of a catalyst at a temperature of 300 to 600 DEG C to obtain the supported Ni/AlPO4 catalyst. The obtained catalyst is used for alpha-pinene hydrogenation reactions, the reaction temperature is 120 to 150 DEG C, the reaction time is 50 to 90 minutes, and the using amount of the catalyst is 3 to 9 wt% of the weight of alpha-pinene. The technological method is simple, the cost of the catalyst is low, the thermal stability of the catalyst is high, the catalytic effect is good, and the catalyst is easy to recover.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of the catalyst for Monoterpene alkene hydrogenation, belong to chemical field.
Background technology
Terpenes is that a class is with C
5h
8for the compound of basic composition unit, be extensively present in occurring in nature.Wherein, terebinthine main component--australene is important Monoterpene.It has active chemical property, and prepares the product of multiple high added value by the effect such as hydrogenation, epoxidation.The hydrogenated products of australene is pinane, is a kind of transparence liquid, and can prepare linalool through reactions such as oxidation, reduction and cracking, the latter is important spices, also can be used for the intermediate prepared bergamio and be used as pharmaceuticals industry vitamin E simultaneously.In addition, pinane also can obtain the terpenes fragrance products such as dihydromyrcenol, citronellol, rose oxide, A Fuman and rosemusk by By Direct Pyrolysis.Pinane comprises cis-pinane and trans pinane, and wherein cis-pinane activity is high, in fragrance industry, be used as raw material, and trans pinane then needs removing.But in practical application, because the two is stereoisomer, boiling point only differs 1K, adopt conventional rectification cannot separating-purifying, and trans pinane and downstream product thereof be difficult to be separated.Therefore, need strictly to control hydroconversion condition when firpene catalytic hydrogenation reaction, to improve the suitable inverse ratio of pinane, be important in pinane application process and have very large meaning process.
At present conventional pinene hydrogenation is prepared in the catalyst of cis-pinane, and the noble metal catalysts such as rhodium, palladium, ruthenium have higher hydrogenation activity, and so its cost is high, and easily causes pinane in product lower along inverse ratio because of wayward reaction rate.Ni catalyst, under certain reaction condition, has good catalytic activity and selective, but strict to reaction condition control overflow, and the reaction time is longer.
Summary of the invention
The object of the present invention is to provide a kind of for the preparation method and application of monoterpene Hydrogenation for the supported Ni catalyst of cis-pinane, react with this catalyst australene, there is technological process short, reaction temperature is moderate, catalyst amount is few, the advantages such as catalytic activity is high, good product selectivity.
The preparation method of the catalyst for Monoterpene alkene hydrogenation of the present invention, specifically comprises the following steps:
(1) by phosphoric acid, aluminium hydroxide, triethylamine and hydromassage, you mix than for the ratio of 1:1:0.5 ~ 1.5:20 ~ 60, insert in the water heating kettle containing PTFE liner, crystallization 20 ~ 28h at 160 ~ 200 DEG C;
(2) after the crystallization product that step (1) obtains filters, with distilled water washing 3 ~ 5 times, dry 3 ~ 10h at 50 ~ 80 DEG C, then at 450 ~ 600 DEG C, roasting 2 ~ 6h sloughs template, obtains AlPO
4molecular sieve carrier;
(3) aluminium phosphate molecular sieve carrier being added to mass percent concentration in the ratio of 50 ~ 150mg/mL is in the nickel nitrate aqueous solution of 25mg/mL ~ 75mg/mL, dry 3 ~ 10h at 50 ~ 80 DEG C is fully stirred after dipping 20 ~ 30h at 40 ~ 70 DEG C, sample is roasting 2 ~ 5h at 300 ~ 450 DEG C, obtain catalyst precursor, this presoma passes into hydrogen 1 ~ 4h and activates at 300 ~ 600 DEG C, obtains Ni/AlPO
4loaded catalyst.
Another object of the present invention is to provide the catalyst of described Monoterpene alkene hydrogenation for the method for catalysis monoterpene hydrogenation reaction, specifically comprise the following steps:
(1) get in the autoclave that australene inserts containing PTFE liner, add catalyst by the 3wt% ~ 9wt% of australene quality, put into magnet rotor, close reactor.
(2) change 3 times under 0.2 ~ 0.4MPa with nitrogen, then use hydrogen to change 3 times under 0.2 ~ 0.4MPa, leak detection, confirm that reactor sealing is intact.
(3) open hydrogen gas valve, regulate pressure in still to be 3 ~ 5MPa, open temperature controller, in 120 ~ 150 DEG C, reaction 50 ~ 90min under stir speed (S.S.) 600 ~ 900r/min.
The australene that the present invention uses, hydrogen, nitrogen are technical grade, and distilled water is self-control, and phosphoric acid, aluminium hydroxide, triethylamine, nickel nitrate are pure for analyzing.
The advantage that compared to the prior art the present invention has:
(1) raw material used in the present invention is convenient source, and the method for synthetic catalyst is simple, and catalyst cost is low.
(2) the method for the invention loading condition is easy to realize, and process is easy to control.
(3) heat endurance of catalyst is higher, and catalytic activity is strong.
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
The preparation of supported Ni catalyst described in the present embodiment, specifically comprises following method:
(1) by the 1:1:0.5:20 mixing in mass ratio of phosphoric acid, aluminium hydroxide, triethylamine and water, insert in the water heating kettle containing PTFE liner, crystallization 28h at 160 DEG C.
(2) after the crystallization product obtained filters, wash 3 times with distilled water, dry 10h at 50 DEG C, then at 450 DEG C, roasting 6h sloughs template, obtains AlPO
4molecular sieve carrier.
(3) aluminium phosphate molecular sieve carrier being added to 30mL mass percent concentration in the ratio of 50mg/mL is in the nickel nitrate aqueous solution of 25mg/mL, dry 3h at 80 DEG C is fully stirred after dipping 30h at 40 DEG C, sample is roasting 5h at 300 DEG C, obtain catalyst precursor, this presoma passes into hydrogen 4h and activates at 300 DEG C, obtains Ni/AlPO
4loaded catalyst.
The Ni/AlPO that the present embodiment prepares
4loaded catalyst is used for catalysis australene Hydrogenation for cis-pinane: specifically comprise following process steps:
Get in the reactor that australene inserts containing PTFE liner, add catalyst by the 3wt% of australene quality, put into magnet rotor, close reactor; Change 3 times at 0.2 mpa with nitrogen, then change 3 times at 0.2 mpa with hydrogen, leak detection, confirm that reactor sealing is intact; Open hydrogen gas valve, regulate pressure in still to be 4MPa, open temperature controller, in 150 DEG C, react 50min under stir speed (S.S.) 800r/min.After reaction terminates, first stop heating stopping stirring, drive reactor after release, by catalyst and product isolated by filtration, product GC analyzes, and catalyst system can be recycled again.
Analysis result is as follows: the conversion ratio of australene is 93.16%, cis-pinane selective 90.07%.
Embodiment 2
The preparation of supported Ni catalyst described in the present embodiment, specifically comprises following method:
(1) by phosphoric acid, aluminium hydroxide, triethylamine and water be in mass ratio mol ratio be 1:1:1:60 ratio mixing, insert in the water heating kettle containing PTFE liner, crystallization 24h at 180 DEG C.
(2), after the crystallization product obtained filters, wash 5 times with distilled water, dry 8h at 60 DEG C, then at 550 DEG C, roasting 4h sloughs template, obtains AlPO
4molecular sieve carrier.
(3) aluminium phosphate molecular sieve carrier being added to 30mL mass percent concentration in the ratio of 100mg/mL is in the nickel nitrate aqueous solution of 50mg/mL, dry 8h at 60 DEG C is fully stirred after dipping 24h at 60 DEG C, sample is roasting 3h at 400 DEG C, obtain catalyst precursor, this presoma passes into hydrogen 2h and activates at 500 DEG C, obtains Ni/AlPO
4loaded catalyst.
The Ni/AlPO that the present embodiment prepares
4loaded catalyst is used for catalysis australene Hydrogenation for cis-pinane: specifically comprise following process steps:
Get in the reactor that australene inserts containing PTFE liner, add catalyst by the 5wt% of australene quality, put into magnet rotor, close reactor; Change 3 times under 0.3MPa with nitrogen, then change 3 times under 0.3MPa with hydrogen, leak detection, confirm that reactor sealing is intact; Open hydrogen gas valve, regulate pressure in still to be 3MPa, open temperature controller, in 140 DEG C, react 60min under stir speed (S.S.) 600r/min.After reaction terminates, first stop heating stopping stirring, drive reactor after release, by catalyst and product isolated by filtration, product GC analyzes, and catalyst system can be recycled again.
Analysis result is as follows: the conversion ratio of australene is 98.17%, cis-pinane selective 94.72%.
Embodiment 3
The preparation of supported Ni catalyst described in the present embodiment, specifically comprises following method:
(1) by phosphoric acid, aluminium hydroxide, triethylamine and water be in mass ratio mol ratio be 1:1:1.5:40 ratio mixing, insert in the water heating kettle containing PTFE liner, crystallization 20h at 200 DEG C.
(2), after the crystallization product obtained filters, wash 4 times with distilled water, dry 3h at 80 DEG C, then at 600 DEG C, roasting 2h sloughs template, obtains AlPO
4molecular sieve carrier.
(3) aluminium phosphate molecular sieve carrier being added to 30mL mass percent concentration in the ratio of 150mg/mL is in the nickel nitrate aqueous solution of 75mg/mL, dry 3h at 80 DEG C is fully stirred after dipping 20h at 70 DEG C, sample is roasting 2h at 450 DEG C, obtain catalyst precursor, this presoma passes into hydrogen 1h and activates at 600 DEG C, obtains Ni/AlPO
4loaded catalyst.
The Ni/AlPO that the present embodiment prepares
4loaded catalyst is used for catalysis australene Hydrogenation for cis-pinane: specifically comprise following process steps:
Get in the reactor that australene inserts containing PTFE liner, the 9wt% being australene quality by catalyst amount adds catalyst, puts into magnet rotor, and close reactor; Change 3 times under 0.4MPa with nitrogen, then change 3 times under 0.4MPa with hydrogen, leak detection, confirm that reactor sealing is intact; Open hydrogen gas valve, regulate pressure in still to be 5MPa, open temperature controller, in 120 DEG C, react 90min under stir speed (S.S.) 900r/min.After reaction terminates, first stop heating stopping stirring, drive reactor after release, by catalyst and product isolated by filtration, product GC analyzes, and catalyst system can be recycled again.
Analysis result is as follows: the conversion ratio of australene is 99.16%, cis-pinane selective 89.33%.
Embodiment 4
The preparation of supported Ni catalyst described in the present embodiment, specifically comprises following method:
(1) by phosphoric acid, aluminium hydroxide, triethylamine and water be in mass ratio mol ratio be 1:1:0.75:50 ratio mixing, insert in the water heating kettle containing PTFE liner, crystallization 24h at 170 DEG C.
(2), after the crystallization product that step (1) obtains filters, wash 5 times with distilled water, dry 8h at 60 DEG C, then at 550 DEG C, roasting 4h sloughs template, obtains AlPO
4molecular sieve carrier.
(3) aluminium phosphate molecular sieve carrier being added to 30mL mass percent concentration in the ratio of 100mg/mL is in the nickel nitrate aqueous solution of 25mg/mL, dry 4h at 80 DEG C is fully stirred after dipping 24h at 60 DEG C, sample is roasting 3h at 450 DEG C, obtain catalyst precursor, this presoma passes into hydrogen 2h and activates at 450 DEG C, obtains Ni/AlPO
4loaded catalyst.
The Ni/AlPO that the present embodiment prepares
4loaded catalyst is used for catalysis australene Hydrogenation for cis pinane: specifically comprise following process steps:
Get in the reactor that australene inserts containing PTFE liner, add catalyst by the 3wt% of australene quality, put into magnet rotor, close reactor; Change 3 times under 0.4MPa with nitrogen, then change 3 times under 0.4MPa with hydrogen, leak detection, confirm that reactor sealing is intact; Open hydrogen gas valve, regulate pressure in still to be 4MPa, open temperature controller, in 130 DEG C, react 80min under stir speed (S.S.) 700r/min.After reaction terminates, first stop heating stopping stirring, drive reactor after release, by catalyst and product isolated by filtration, product GC analyzes, and catalyst system can be recycled again.
Analysis result is as follows: the conversion ratio of australene is 95.63%, cis-pinane selective 88.79%.
Embodiment 5
The preparation of supported Ni catalyst described in the present embodiment, specifically comprises following method:
(1) by phosphoric acid, aluminium hydroxide, triethylamine and hydromassage, you mix than for the ratio of 1:1:1.25:30, insert in the water heating kettle containing PTFE liner, crystallization 20h at 190 DEG C.
(2), after the crystallization product obtained filters, wash 3 times with distilled water, dry 5h at 80 DEG C, then at 600 DEG C, roasting 2h sloughs template, obtains AlPO
4molecular sieve carrier.
(3) aluminium phosphate molecular sieve carrier being added to 30mL mass percent concentration in the ratio of 100mg/mL is in the nickel nitrate aqueous solution of 75mg/mL, dry 10h at 80 DEG C is fully stirred after dipping 30h at 50 DEG C, sample is roasting 5h at 400 DEG C, obtain catalyst precursor, this presoma passes into hydrogen 3h and activates at 500 DEG C, obtains Ni/AlPO
4loaded catalyst.
The Ni/AlPO that the present embodiment prepares
4loaded catalyst is used for catalysis australene Hydrogenation for cis pinane: specifically comprise following process steps:
Get in the reactor that australene inserts containing PTFE liner, add catalyst by the 7wt% of australene quality, put into magnet rotor, close reactor; Change 3 times under 0.3MPa with nitrogen, then change 3 times under 0.3MPa with hydrogen, leak detection, confirm that reactor sealing is intact; Open hydrogen gas valve, regulate pressure in still to be 4MPa, open temperature controller, in 120 DEG C, react 70min under stir speed (S.S.) 800r/min.After reaction terminates, first stop heating stopping stirring, drive reactor after release, by catalyst and product isolated by filtration, product GC analyzes, and catalyst system can be recycled again.
Analysis result is as follows: the conversion ratio of australene is 91.56%, cis-pinane selective 89.71%.
Embodiment 6
The preparation of supported Ni catalyst described in the present embodiment, specifically comprises following method:
(1) by phosphoric acid, aluminium hydroxide, triethylamine and hydromassage, you mix than for the ratio of 1:1:1:30, insert in the water heating kettle containing PTFE liner, crystallization 20h at 180 DEG C.
(2), after the crystallization product obtained filters, wash 3 times with distilled water, dry 8h at 60 DEG C, then at 550 DEG C, roasting 4h sloughs template, obtains AlPO
4molecular sieve carrier.
(3) aluminium phosphate molecular sieve carrier being added to 30mL mass percent concentration in the ratio of 100mg/mL is in the nickel nitrate aqueous solution of 50mg/mL, dry 3h at 80 DEG C is fully stirred after dipping 30h at 40 DEG C, sample is roasting 5h at 350 DEG C, obtain catalyst precursor, this presoma passes into hydrogen 2h and activates at 500 DEG C, obtains Ni/AlPO
4loaded catalyst.
The Ni/AlPO that the present embodiment prepares
4loaded catalyst is used for catalysis australene Hydrogenation for cis pinane: specifically comprise following process steps:
Get in the reactor that australene inserts containing PTFE liner, add catalyst by the 3wt% of australene quality, put into magnet rotor, close reactor; Change 3 times at 0.2 mpa with nitrogen, then change 3 times at 0.2 mpa with hydrogen, leak detection, confirm that reactor sealing is intact; Open hydrogen gas valve, regulate pressure in still to be 5MPa, open temperature controller, in 150 DEG C, react 60min under stir speed (S.S.) 800r/min.After reaction terminates, first stop heating stopping stirring, drive reactor after release, by catalyst and product isolated by filtration, product GC analyzes, and catalyst system can be recycled again.
Analysis result is as follows: the conversion ratio of australene is 94.39%, cis-pinane selective 91.20%.
Claims (2)
1., for a preparation method for the catalyst of Monoterpene alkene hydrogenation, it is characterized in that, specifically comprise the following steps:
(1) by phosphoric acid, aluminium hydroxide, triethylamine and hydromassage, you mix than for the ratio of 1:1:0.5 ~ 1.5:20 ~ 60, insert in the water heating kettle containing PTFE liner, crystallization 20 ~ 28h at 160 ~ 200 DEG C;
(2) after the crystallization product that step (1) obtains filters, with distilled water washing 3 ~ 5 times, dry 3 ~ 10h at 50 ~ 80 DEG C, then at 450 ~ 600 DEG C, roasting 2 ~ 6h sloughs template, obtains AlPO
4molecular sieve carrier;
(3) aluminium phosphate molecular sieve carrier being added to mass percent concentration in the ratio of 50 ~ 150mg/mL is in the nickel nitrate aqueous solution of 25mg/mL ~ 75mg/mL, dry 3 ~ 10h at 50 ~ 80 DEG C is fully stirred after dipping 20 ~ 30h at 40 ~ 70 DEG C, sample is roasting 3 ~ 8h at 300 ~ 450 DEG C, obtain catalyst precursor, this presoma passes into hydrogen 1 ~ 4h and activates at 300 ~ 600 DEG C, obtains Ni/AlPO
4loaded catalyst.
2. the catalyst of Monoterpene alkene hydrogenation according to claim 1 is used for the method for catalysis monoterpene hydrogenation reaction, it is characterized in that, specifically comprises the following steps:
(1) get in the autoclave that australene inserts containing PTFE liner, add catalyst by the 3wt% ~ 9wt% of australene quality, put into magnet rotor, close reactor;
(2) change 3 times under 0.2 ~ 0.4MPa with nitrogen, then use hydrogen to change 3 times under 0.2 ~ 0.4MPa, leak detection, confirm that reactor sealing is intact;
(3) open hydrogen gas valve, regulate pressure in still to be 2 ~ 5MPa, open temperature controller, in 120 ~ 150 DEG C, reaction 50 ~ 90min under stir speed (S.S.) 600 ~ 900r/min.
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