CN105665005B - A kind of preparation method and application of catalyst for firpene asymmetric hydrogenation - Google Patents
A kind of preparation method and application of catalyst for firpene asymmetric hydrogenation Download PDFInfo
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- CN105665005B CN105665005B CN201610001913.4A CN201610001913A CN105665005B CN 105665005 B CN105665005 B CN 105665005B CN 201610001913 A CN201610001913 A CN 201610001913A CN 105665005 B CN105665005 B CN 105665005B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 title claims abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 20
- 230000008025 crystallization Effects 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 19
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- 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 19
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 18
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000001632 sodium acetate Substances 0.000 claims abstract description 18
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017119 AlPO Inorganic materials 0.000 claims abstract description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 11
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-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
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910018104 Ni-P Inorganic materials 0.000 claims description 20
- 229910018536 Ni—P Inorganic materials 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 7
- 239000004411 aluminium Substances 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 19
- 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
- 238000004458 analytical method Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229930006728 pinane Natural products 0.000 description 4
- 238000006555 catalytic reaction Methods 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
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 2
- 239000003795 chemical substances by application 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
- XOKSLPVRUOBDEW-YIZRAAEISA-N (1r,4s,5s)-4,6,6-trimethylbicyclo[3.1.1]heptane Chemical compound C[C@H]1CC[C@H]2C(C)(C)[C@H]1C2 XOKSLPVRUOBDEW-YIZRAAEISA-N 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 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
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012153 distilled water Substances 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
- 239000012535 impurity Substances 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 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
- 230000003313 weakening effect Effects 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
- B01J29/83—Aluminophosphates [APO compounds]
-
- 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
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/83—Aluminophosphates (APO compounds)
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 present invention discloses a kind of preparation method and applications of the catalyst for firpene asymmetric hydrogenation, belongs to chemical field；Catalyst of the present invention is carried non-crystal Ni P/AlPO45 catalyst, its preparation method are：Phosphoric acid, aluminium hydroxide, triethylamine and α firpenes are mixed, it is placed in the water heating kettle of the liner containing PTFE, maintains certain pH value, 12 ~ 60h is after 20 ~ 36h of crystallization at 160 ~ 200 DEG C for ageing, after crystallization terminates, product is filtered, washs, dry, roasting obtains carrier phosphate aluminium molecular sieve AlPO45, in the nickel chloride aqueous solution that concentration is 6g/L ~ 18g/L, add carrier and sodium acetate, it is sufficiently stirred at 25 DEG C, regulation mother liquor pH value 5 ~ 13, puts into sodium hypophosphite, and a small amount of reaction initiator is added, 4 ~ 10h is sufficiently stirred, filtering, carried non-crystal Ni P/AlPO are made after drying45 catalyst；Catalyst of the present invention reacts for pinene hydrogenation, and process is simple, and preparation process energy consumption is low, and catalyst cost is low, good heat stability, catalytic effect are excellent, easy recovery.
Description
Technical field
The present invention relates to a kind of preparation method and applications of the catalyst for firpene asymmetric hydrogenation, more particularly to one
Kind is used for carried non-crystal Ni-P method for preparing catalyst and its application that pinene hydrogenation prepares high-purity cis-pinane, belongs to
Chemical field.
Background technology
Australene is a kind of Monoterpene, is primarily present in turpentine oil.The hydrogenated products of australene are pinanes, Hou Zheshi
Important chemical intermediate, for preparing spices, linalool and vitamin E etc..The pinane obtained by pinene hydrogenation contains cis/trans
Two kinds of stereoisomers, the two boiling point difference 1K, are not easy rectifying separation, but industrially mainly use cis-pinane, trans pinane
Then it is normally used as impurity.Therefore the process for needing to prepare firpene hydrogenation pinane improves, to obtain the pinane of high cis-to-trans ratio
Alkane product.
It is the suitable catalyst of selection that pinane, which is improved, along an important method of inverse ratio.Wherein loaded catalyst is because being easy to
It is isolated more applications.For loaded catalyst, suitable carrier is selected to be advantageous to improve catalyst performance.Phosphorus aluminium point
Son sieve（AlPO4-5）It is a kind of conventional catalyst carrier, possesses huge surface area and excellent heat endurance.In phosphorus aluminium point
During sub- sieve series is standby, solvent, template can influence its design feature.Solvent is made using australene, prepares phosphate aluminium molecular sieve as load
Body, catalytic effect of the catalysis part to australene hydrogenation reaction can be effectively improved.
Hydrogenation reaction custom catalystses part is noble metal and the Ni series catalysts such as Ru, Rh.Precious metal catalyst
Excellent but cost is high, and the selective catalysis ability of Ni catalyst is then poor, and it is bad to react controllability.Urged using Ni-P alloys
Agent can improve the presence of catalytic performance, wherein P components, can adjust Ni decentralization well, anti-so as to be more conducive to control
Answer speed.In addition, with Ni existing for alloy form, magnetic obtains very big weakening, and practicality greatly enhances.
Another factor for influenceing catalyst performance is thing phase, and generally, amorphous catalyst performance is better than crystalline-state catalyst.
Ni-P alloys using one-step synthesis method are amorphous states, and performance is better than crystalline-state catalyst in itself.It is and excellent based on phosphate aluminium molecular sieve
Heat endurance, the Ni-P alloys after load are not easy crystallization, can keep the outstanding performance of amorphous catalyst at high temperature.And by
There is P presence in carrier and part, the catalyst property is more stable, difficult for drop-off.Catalyst preparation process has more
The advantages that energy consumption is low, and method is simple.
The content of the invention
The present invention provides a kind of Ni-P/AlPO that high-purity cis-pinane is prepared for firpene asymmetric hydrogenation4- 5 catalysis
The preparation method and application of agent；The catalyst australene hydrogenation reaction, catalyst heat endurance short with technological process
Well, the advantages that catalytic activity is high, and product e.e. values are high.
The preparation method of catalyst of the present invention for firpene asymmetric hydrogenation, specifically includes following steps：
（1）By phosphorus source, silicon source, template and solvent in molar ratio 1:1:0.4~1.6:20 ~ 60 mixing, insert water heating kettle
In, 12 ~ 60h is after 20 ~ 36h of crystallization at 160 ~ 200 DEG C for ageing；After obtained crystallization product is filtered, with distillation water washing 3
~ 5 times, 12 ~ 48h is dried at 50 ~ 80 DEG C, then 1 ~ 5h of microwave calcining at 450 ~ 650 DEG C, obtains AlPO4- 5 molecular sieves, production
Thing is as catalyst carrier.
（2）In 5 ~ 15g/L ratio by AlPO4The nickel chloride aqueous solution that -5 molecular sieves input concentration is 6g/L ~ 18g/L,
Then it is 1 by nickel chloride and sodium acetate mol ratio:1 ratio adds sodium acetate, is sufficiently stirred under normal temperature, and regulation mother liquor pH value 5 ~
13, it is 1 by Ni and P mol ratios:2 ~ 5 ratio input sodium hypophosphite, and initiator is added, under 160 ~ 600rad/min fully
4 ~ 10h is stirred, filtering, Amorphous Ni-P Alloy/AlPO is made after drying4- 5 catalyst.
Preferably, step of the present invention（1）Described in phosphorus source, silicon source, template and solvent be respectively phosphoric acid, aluminium hydroxide,
Triethylamine and australene.
Preferably, step of the present invention（2）Described in reaction initiator be potassium borohydride, addition<0.15g/L.
Preferably, step of the present invention（2）Described in drying condition be nitrogen protect dry.
Another object of the present invention is to provide the firpene asymmetric hydrogenation Ni-P/AlPO4- 5 catalyst are used to be catalyzed
The method of pinene hydrogenation reaction, specifically includes the following steps：
（1）Take australene to be placed in reactor, add catalyst by 1 ~ 9wt% of australene quality, be put into magnet rotor, close
Upper reactor.
（2）Changed 3 times under 0.2 ~ 0.4MPa with nitrogen, then changed 3 times under 0.2 ~ 0.4MPa with hydrogen, hunted leak, really
It is intact to recognize reactor sealing.
（3）Hydrogen gas valve is opened, it is 2 ~ 5MPa to adjust pressure in kettle, opens temperature controller, in 110 ~ 150 DEG C, stirring speed
30 ~ 150min is reacted under 600 ~ 900r/min of rate.
The australene that the present invention uses（Solvent and reaction raw materials）, hydrogen, nitrogen be technical grade, distilled water is self-control, phosphorus
Acid, aluminium hydroxide, triethylamine, nickel chloride, sodium hypophosphite, sodium acetate, potassium borohydride are pure to analyze.
Compared to the prior art the present invention has the advantage that：
（1）The amorphous catalyst that the present invention is prepared, performance are significantly improved compared to crystalline-state catalyst.
（2）The catalyst cost that the present invention is prepared is low, and preparation condition is gentle, preparation process is easily controllable and energy consumption
It is low.
（3）The catalyst good heat stability that the present invention is prepared, is not easy crystallization.
（4）The catalyst choice catalytic capability that the present invention is prepared is strong, high to the e.e. values of goal response.
Embodiment
The present invention is described in further detail with reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1
（1）By phosphoric acid, aluminium hydroxide, triethylamine and australene in molar ratio 1:1:0.4:20 mixing, are inserted in water heating kettle,
12h is aged after crystallization 20h at 200 DEG C；After obtained crystallization product is filtered, with water washing is distilled 3 times, done at 80 DEG C
Dry 12h, then the microwave calcining 5h at 450 DEG C, obtains AlPO4- 5 molecular sieves, product is as catalyst carrier；
（2）In 5g/L ratio by AlPO4The nickel chloride aqueous solution that -5 molecular sieves input 200mL concentration is 6g/L, then
It is 1 by nickel chloride and sodium acetate mol ratio:1 ratio adds sodium acetate, is sufficiently stirred under normal temperature, regulation mother liquor pH value 5, by by
Ni and P mol ratios are 1:5 ratio input sodium hypophosphite, adds initiator potassium borohydride, under 160rad/min by 0.05g/L
10h is sufficiently stirred, filtering, Amorphous Ni-P Alloy/AlPO is made after drying4- 5 catalyst.
Amorphous Ni-P Alloy/AlPO that the present invention is prepared4- 5 catalyst are used for the method for firpene asyininetric hydrogenation,
Specifically include following steps：
（1）Take australene to be placed in the reactor of the liner containing PTFE, add catalyst by the 5wt% of australene quality, be put into
Magnet rotor, close reactor；
（2）Changed 3 times, then changed at 0.2 mpa with hydrogen 3 times at 0.2 mpa with nitrogen, hunted leak, confirm reactor
Seal intact；
（3）Hydrogen gas valve is opened, it is 5MPa to adjust pressure in kettle, temperature controller is opened, in 150 DEG C, stir speed (S.S.) 600r/
30min is reacted under min.
Analysis result is as follows：Australene conversion ratio 98.61%, cis-pinane 95.19%, e.e. of selectivity values 90.37%.
Embodiment 2
（1）By phosphoric acid, aluminium hydroxide, triethylamine and australene in molar ratio 1:1:0.9:40 mixing, are inserted in water heating kettle,
40h is aged after crystallization 30h at 180 DEG C；After obtained crystallization product is filtered, with water washing is distilled 4 times, done at 60 DEG C
Dry 30h, then the microwave calcining 3h at 550 DEG C, obtains AlPO4- 5 molecular sieves, product is as catalyst carrier；
（2）In 15g/L ratio by AlPO4The nickel chloride aqueous solution that -5 molecular sieves input 200mL concentration is 18g/L, so
It is afterwards 1 by nickel chloride and sodium acetate mol ratio:1 ratio adds sodium acetate, is sufficiently stirred under normal temperature, regulation mother liquor pH value 13,
It is 1 by by Ni and P mol ratios:3 ratio input sodium hypophosphite, adds initiator potassium borohydride, in 400rad/ by 0.15g/L
6h is sufficiently stirred under min, filtering, Amorphous Ni-P Alloy/AlPO is made after drying4- 5 catalyst.
Amorphous Ni-P Alloy/AlPO that the present invention is prepared4- 5 catalyst are used for the method for firpene asyininetric hydrogenation,
Specifically include following steps：
（1）Take australene to be placed in the reactor of the liner containing PTFE, add catalyst by the 1wt% of australene quality, be put into
Magnet rotor, close reactor；
（2）Changed 3 times under 0.3MPa with nitrogen, then changed 3 times under 0.3MPa with hydrogen, hunted leak, confirm reactor
Seal intact；
（3）Hydrogen gas valve is opened, it is 3MPa to adjust pressure in kettle, temperature controller is opened, in 110 DEG C, stir speed (S.S.) 700r/
150min is reacted under min.
Analysis result is as follows：Australene conversion ratio 94.57%, cis-pinane 96.86%, e.e. of selectivity values 93.73%.
Embodiment 3
（1）By phosphoric acid, aluminium hydroxide, triethylamine and australene in molar ratio 1:1: 1.6:60 mixing, insert water heating kettle
In, 60h is after crystallization 36h at 160 DEG C for ageing；After obtained crystallization product is filtered, with water washing is distilled 5 times, in 50 DEG C
Lower dry 48h, then the microwave calcining 1h at 650 DEG C, obtains AlPO4- 5 molecular sieves, product is as catalyst carrier；
（2）In 10g/L ratio by AlPO4The nickel chloride aqueous solution that -5 molecular sieves input 200mL concentration is 12g/L, so
It is afterwards 1 by nickel chloride and sodium acetate mol ratio:1 ratio adds sodium acetate, is sufficiently stirred under normal temperature, regulation mother liquor pH value 8, presses
It is 1 by Ni and P mol ratios:2 ratio input sodium hypophosphite, adds initiator potassium borohydride, in 600rad/min by 0.10g/L
Under be sufficiently stirred 4h, filtering, Amorphous Ni-P Alloy/AlPO is made after drying4- 5 catalyst.
Amorphous Ni-P Alloy/AlPO that the present invention is prepared4- 5 catalyst are used for the method for firpene asyininetric hydrogenation,
Specifically include following steps：
（1）Take australene to be placed in the reactor of the liner containing PTFE, add catalyst by the 9wt% of australene quality, be put into
Magnet rotor, close reactor；
（2）Changed 3 times under 0.4MPa with nitrogen, then changed 3 times under 0.4MPa with hydrogen, hunted leak, confirm reactor
Seal intact；
（3）Hydrogen gas valve is opened, it is 2MPa to adjust pressure in kettle, temperature controller is opened, in 150 DEG C, stir speed (S.S.) 900r/
150min is reacted under min.
Analysis result is as follows：Australene conversion ratio 94.59%, cis-pinane 96.73%, e.e. of selectivity values 93.47%.
Embodiment 4
（1）By phosphoric acid, aluminium hydroxide, triethylamine and australene in molar ratio 1:1:1.1:40 mixing, are inserted in water heating kettle,
20h is aged after crystallization 20h at 180 DEG C；After obtained crystallization product is filtered, with water washing is distilled 3 times, done at 80 DEG C
Dry 24h, then the microwave calcining 3h at 550 DEG C, obtains AlPO4- 5 molecular sieves, product is as catalyst carrier；
（2）In 8g/L ratio by AlPO4The nickel chloride aqueous solution that -5 molecular sieves input 200mL concentration is 9.6g/L, so
It is afterwards 1 by nickel chloride and sodium acetate mol ratio:1 ratio adds sodium acetate, is sufficiently stirred under normal temperature, regulation mother liquor pH value 11,
It is 1 by Ni and P mol ratios:4 ratio input sodium hypophosphite, adds initiator potassium borohydride, in 160rad/min by 0.08g/L
Under be sufficiently stirred 10h, filtering, Amorphous Ni-P Alloy/AlPO is made after drying4- 5 catalyst.
Amorphous Ni-P Alloy/AlPO that the present invention is prepared4- 5 catalyst are used for the method for firpene asyininetric hydrogenation,
Specifically include following steps：
（1）Take australene to be placed in the reactor of the liner containing PTFE, add catalyst by the 5wt% of australene quality, be put into
Magnet rotor, close reactor；
（2）Changed 3 times, then changed at 0.2 mpa with hydrogen 3 times at 0.2 mpa with nitrogen, hunted leak, confirm reactor
Seal intact；
（3）Hydrogen gas valve is opened, it is 5MPa to adjust pressure in kettle, temperature controller is opened, in 140 DEG C, stir speed (S.S.) 600r/
60min is reacted under min.
Analysis result is as follows：Australene conversion ratio 97.03%, cis-pinane 97.24%, e.e. of selectivity values 94.48%.
Embodiment 5
（1）By phosphoric acid, aluminium hydroxide, triethylamine and australene in molar ratio 1:1:0.9:30 mixing, are inserted in water heating kettle,
40h is aged after crystallization 30h at 180 DEG C；After obtained crystallization product is filtered, with water washing is distilled 4 times, done at 60 DEG C
Dry 30h, then the microwave calcining 1h at 500 DEG C, obtains AlPO4- 5 molecular sieves, product is as catalyst carrier；
（2）In 12g/L ratio by AlPO4The nickel chloride aqueous solution that -5 molecular sieves input 200mL concentration is 14.4g/L,
Then it is 1 by nickel chloride and sodium acetate mol ratio:1 ratio adds sodium acetate, is sufficiently stirred under normal temperature, regulation mother liquor pH value 9,
It is 1 by by Ni and P mol ratios:3 ratio input sodium hypophosphite, adds initiator potassium borohydride, in 400rad/ by 0.12g/L
6h is sufficiently stirred under min, filtering, Amorphous Ni-P Alloy/AlPO is made after drying4- 5 catalyst.
Amorphous Ni-P Alloy/AlPO that the present invention is prepared4- 5 catalyst are used for the method for firpene asyininetric hydrogenation,
Specifically include following steps：
（1）Take australene to be placed in the reactor of the liner containing PTFE, add catalyst by the 3wt% of australene quality, be put into
Magnet rotor, close reactor；
（2）Changed 3 times under 0.3MPa with nitrogen, then changed 3 times under 0.3MPa with hydrogen, hunted leak, confirm reactor
Seal intact；
（3）Hydrogen gas valve is opened, it is 4MPa to adjust pressure in kettle, temperature controller is opened, in 120 DEG C, stir speed (S.S.) 700r/
90min is reacted under min.
Analysis result is as follows：Australene conversion ratio 94.55%, cis-pinane 96.49%, e.e. of selectivity values 92.99%.
Embodiment 6
（1）By phosphoric acid, aluminium hydroxide, triethylamine and australene in molar ratio 1:1: 1.2:50 mixing, insert water heating kettle
In, 60h is after crystallization 36h at 160 DEG C for ageing；After obtained crystallization product is filtered, with water washing is distilled 5 times, in 50 DEG C
Lower dry 48h, then the microwave calcining 1h at 650 DEG C, obtains AlPO4- 5 molecular sieves, product is as catalyst carrier；
（2）In 6g/L ratio by AlPO4The nickel chloride aqueous solution that -5 molecular sieves input 200mL concentration is 7.2g/L, so
It is afterwards 1 by nickel chloride and sodium acetate mol ratio:1 ratio adds sodium acetate, is sufficiently stirred under normal temperature, regulation mother liquor pH value 8, presses
It is 1 by Ni and P mol ratios:2 ratio input sodium hypophosphite, adds initiator potassium borohydride, in 600rad/min by 0.06g/L
Under be sufficiently stirred 4h, filtering, Amorphous Ni-P Alloy/AlPO is made after drying4- 5 catalyst.
Amorphous Ni-P Alloy/AlPO that the present invention is prepared4- 5 catalyst are used for the method for firpene asyininetric hydrogenation,
Specifically include following steps：
（1）Take australene to be placed in the reactor of the liner containing PTFE, add catalyst by the 9wt% of australene quality, be put into
Magnet rotor, close reactor；
（2）Changed 3 times under 0.4MPa with nitrogen, then changed 3 times under 0.4MPa with hydrogen, hunted leak, confirm reactor
Seal intact；
（3）Hydrogen gas valve is opened, it is 3MPa to adjust pressure in kettle, temperature controller is opened, in 140 DEG C, stir speed (S.S.) 900r/
60min is reacted under min.
Analysis result is as follows：Australene conversion ratio 92.09%, cis-pinane 97.60%, e.e. of selectivity values 95.20%.
Claims (4)
1. the preparation method of a kind of catalyst for firpene asymmetric hydrogenation, it is characterised in that specifically include following steps：
（1）By phosphorus source, silicon source, template and solvent in molar ratio 1:1:0.4~1.6:20 ~ 60 mixing, are inserted in water heating kettle, old
Change 12 ~ 60h after 20 ~ 36h of crystallization at 160 ~ 200 DEG C；After obtained crystallization product is filtered, with distillation water washing 3 ~ 5 times,
12 ~ 48h is dried at 50 ~ 80 DEG C, then 1 ~ 5h of microwave calcining at 450 ~ 650 DEG C, obtains AlPO4- 5 molecular sieves, product are made
For catalyst carrier；
（2）In 5 ~ 15g/L ratio by AlPO4The nickel chloride aqueous solution that -5 molecular sieves input concentration is 6g/L ~ 18g/L, is then pressed
Nickel chloride is 1 with sodium acetate mol ratio:1 ratio adds sodium acetate, is sufficiently stirred under normal temperature, regulation mother liquor pH value 5 ~ 13, presses
Ni and P mol ratios are 1:2 ~ 5 ratio input sodium hypophosphite, and initiator is added, it is sufficiently stirred 4 under 160 ~ 600rad/min
~ 10h, filtering, Amorphous Ni-P Alloy/AlPO is made after drying4- 5 catalyst；
Step（2）Described in reaction initiator be potassium borohydride, addition<0.15g/L.
2. it is used for the preparation method of the catalyst of firpene asymmetric hydrogenation according to claim 1, it is characterised in that：Step
（1）Described in phosphorus source, silicon source, template and solvent be respectively phosphoric acid, aluminium hydroxide, triethylamine and australene.
3. the preparation method of the catalyst according to claim 1 for firpene asymmetric hydrogenation, it is characterised in that：Step（2）
Described in drying condition be nitrogen protect dry.
4. the catalyst that preparation method described in claim 1 ~ 3 any one is prepared is used for the side for being catalyzed pinene hydrogenation reaction
Method, it is characterised in that specifically include the following steps：
（1）Take australene to be placed in reactor, add catalyst by 1 ~ 9wt% of australene quality, be put into magnet rotor, close anti-
Answer kettle；
（2）Changed 3 times under 0.2 ~ 0.4MPa with nitrogen, then changed 3 times under 0.2 ~ 0.4MPa with hydrogen, hunted leak, confirmed anti-
Answer kettle sealing intact；
（3）Hydrogen gas valve is opened, it is 2 ~ 5MPa to adjust pressure in kettle, temperature controller is opened, in 110 ~ 150 DEG C, stir speed (S.S.) 600
30 ~ 150min is reacted under ~ 900r/min.
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| CN102671711A (en) * | 2012-04-13 | 2012-09-19 | 昆明理工大学 | Supported nano amorphous alloy catalyst and preparation method and application |
| 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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| 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 |
| CN102671711A (en) * | 2012-04-13 | 2012-09-19 | 昆明理工大学 | Supported nano amorphous alloy catalyst and preparation method and application |
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| Kinetics of the Liquid-Phase Hydrogenation of (-)-a-Pinene over Electrolessly-Deposited Ni-P/y-A1203 Catalyst;Sun-Hua KO等;《Ind. Eng. Chem. Res.》;19931231;第32卷;第1579-1587页 * |
| 非晶态骨架Ni-P/玻璃纤维催化蒎烯加氢;杜朝军等;《工业催化》;20040630;第12卷(第6期);第30-32页 * |
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