CN106582656A - Synthesis method for nickel-base composite catalyst used for synthesizing n-amylamine from pentanenitrile - Google Patents
Synthesis method for nickel-base composite catalyst used for synthesizing n-amylamine from pentanenitrile Download PDFInfo
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- CN106582656A CN106582656A CN201611120354.5A CN201611120354A CN106582656A CN 106582656 A CN106582656 A CN 106582656A CN 201611120354 A CN201611120354 A CN 201611120354A CN 106582656 A CN106582656 A CN 106582656A
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- catalyst
- composite catalyst
- amylamine
- based composite
- valeronitrile
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 238000001308 synthesis method Methods 0.000 title abstract 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 229960001484 edetic acid Drugs 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 238000003756 stirring Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 11
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 11
- -1 titanium modified aluminium oxide Chemical class 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000009413 insulation Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000005070 sampling Methods 0.000 description 10
- 239000002243 precursor Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- YWKRGLREGGAHDC-UHFFFAOYSA-N dichloro(pentyl)borane Chemical compound CCCCCB(Cl)Cl YWKRGLREGGAHDC-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method for a nickel-base composite catalyst used for synthesizing n-amylamine from pentanenitrile. The synthesis method includes the steps of: 1) dissolving soluble nickel salt in a solvent to prepare a solution; 2) impregnating a moulded carrier having a pore structure in the solution in the step 1) to produce a catalyst precursor; 3) reducing the catalyst precursor; 4) drying the reduced catalyst precursor to produce the nickel-base composite catalyst. In the method, the pH of a reductant solution is controlled to be a proper range of 8-14, so that Ni<2+> can be reduced completely and a moderated reduction rate can be maintained, thereby producing metal nickel particles in nano scale. The synthesis method can prevent agglomeration due to growth of the metal nickel particles, thereby producing high-activity supported nickel-base composite catalyst.
Description
Technical field
The present invention relates to a kind of synthetic method of the Ni-based composite catalyst for synthesizing n-amylamine for valeronitrile, belongs to and becomes more meticulous
The technical field of work.
Background technology
N-amylamine is a kind of important chemical intermediate, be widely used in synthesize medicine, dyestuff, solvent, anticorrosive,
The many-sides such as emulsifying agent, antioxidant, flotation agent and thiofide.
The synthetic method of n-amylamine has many kinds, typically several to have：Valeral method, amide method, valeronitrile method and n-amyl alcohol
Method.Wherein, valeral method selectively about 48%, azide method selectively about 88%, amide method selectively about 81%, valeronitrile method are selected
Rate about 71% and two n-pentyl boron chloride methods selective about 93% etc..Separately：The existing valeronitrile method of our companies uses market purchasing
Nickel-base catalyst and addition alkaline assistant prepare n-amylamine and selectively reach 95% or so.
Above method is disadvantageous in that：
1st, there is considerable amount of accessory substance to produce while every kind of method target product is generated, be required to subsequent purification point
It is not high from, yield and increased cost；
2nd, some methods have used explosion risk article (azide method), raw materials used high cost (two n-pentyls having
Boron chloride method).
The content of the invention
For the above-mentioned technical problem of prior art, it is an object of the invention to provide a kind of synthesize n-amylamine for valeronitrile
The synthetic method of Ni-based composite catalyst, the pH of reductant solution is controlled in 8～14 OK range, to make Ni2+
Reduction is complete, and suitable rate of reduction can be kept again, generates the metal nickel particle of nanoscale, and can prevent metal nickel particle
Reunite because growing up, so as to obtain highly active load-type nickel based composite catalyst.
To reach above-mentioned purpose, the present invention is achieved by the following technical solutions：
A kind of synthetic method of the Ni-based composite catalyst for synthesizing n-amylamine for valeronitrile, comprises the following steps：
(1) soluble nickel salt is dissolved in solvent and is configured to solution；
(2) shaping carrier with pore structure is put in solution obtained in step (1) and is impregnated, obtain catalyst precarsor；
(3) catalyst precarsor in step (2) is reduced；
(4) catalyst precarsor after step (3) reduction is dried, obtains Ni-based composite catalyst.
Described step (1) is that solution is configured in solvent by auxiliary agent, surfactant and soluble nickel salt are miscible；Institute
State auxiliary agent account for Ni-based composite catalyst mass percent be 5～10%, the surfactant accounts for Ni-based composite catalyst
Mass percent is 1～10%.
Described auxiliary agent is the mixture of ethylenediamine tetra-acetic acid, diethylamine and triethylamine, and described surfactant is poly-
One or several mixing of oxirane triblock copolymer, polyethers F-201, PEG-8 00 or PEG20000
Thing, described soluble nickel salt is nickel nitrate, nickel acetate or nickel sulfate.
In described step (2), after catalyst precarsor is taken out from the container for fill solution, remaining nickel salt in container
Mass fraction≤10% of the soluble nickel salt total amount of addition is accounted for, after dipping is complete, the catalyst precursor for obtaining is dried,
Baking temperature is 50～100 DEG C.
In described step (3), catalyst precarsor is reduced in the reductant solution under inert gas shielding, wherein,
The pH of reductant solution is 8～14, and concentration is 0.01～0.1g/ml.
Beneficial effects of the present invention are as follows：
The present invention controls the pH of reductant solution in 8～14 OK range when Ni-based composite catalyst is prepared,
Ni can either be made2+Reduction is complete, and suitable rate of reduction can be kept again, generates the metal nickel particle of nanoscale, and can prevent
Only metal nickel particle is reunited because growing up, so as to obtain highly active loading type nickel-based catalyst.
The Ni-based composite catalyst of the present invention has when in use significant difference with the Ni-based supported catalyst of market purchasing：It is not required to
Addition alkaline assistant can suppress the generation of diamylamine and triamylamine, and selective more than 99%.And several types of market purchasing
Number nickel-base catalyst when being not added with alkaline assistant the selectivity of n-amylamine only have 75% or so level, add after auxiliary agent its best
Level also less than 95%.
Specific embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Embodiment 1 and 2：The preparation of Ni-based composite catalyst
Used catalyst carrier is and purchases from the market in example 1 below -6, only lives so that titanium is modified in embodiment 1-6
As a example by property alumina support, silica supports：
Embodiment 1
(1) preparation of solvable nickel salt solution：In weighing the beaker of nickel nitrate 300g input 1L, addition 150ML deionized waters,
150ML absolute ethyl alcohols, stir molten clear；Add auxiliary agent ethylenediamine tetra-acetic acid 5g, diethylamine 15g, triethylamine 20g, surfactant
PEG800 5g, PEG100005g stirring is molten clear standby；
(2) preparation of catalyst precarsor：The titanium modified aluminium oxide supports 600g of outsourcing is put in above-mentioned normal temperature solution
Aeration-drying at 80 ± 1 DEG C is taken out in baking oven after 2 days 2 nights of dipping, and to obtain precursor 700g standby；
(3) catalyst precarsor reduction：100g precursors are fitted in the reactor of 2L, the sodium borohydride of 0.05mol/l is put into
Solution buries precursor, adds a small amount of NaOH to adjust pH14, opens and is reacted at 70 ± 1 DEG C of stirring intensification, has reacted after 2 hours
Entirely；
(4) catalyst precarsor after reduction is filtered and is dried at 80 ± 1 DEG C, obtain the new valeronitrile reduction of support type special
Ni-based composite catalyst about 100g.
Embodiment 2
(1) preparation of solvable nickel salt solution：In weighing the beaker of nickel nitrate 300g input 1L, addition 150ML deionized waters,
150ML absolute ethyl alcohols, stir molten clear；Add auxiliary agent ethylenediamine tetra-acetic acid 5g, diethylamine 15g, triethylamine 20g, surfactant
PEG800 5g, PEG100005g stirring is molten clear standby；
(2) preparation of catalyst precarsor：Large aperture silica supports (particle diameter 1-3mm) 600g of outsourcing is put into
State and aeration-drying at 80 ± 1 DEG C is taken out in baking oven after impregnating 2 days 2 nights in normal temperature solution to obtain precursor 700g standby；
(3) catalyst precarsor reduction：100g precursors are fitted in the reactor of 2L, the sodium borohydride of 0.05mol/l is put into
Solution buries precursor, adds a small amount of NaOH to adjust PH14, opens and is reacted at 70 ± 1 DEG C of stirring intensification, has reacted after 2 hours
Entirely；
(4) catalyst precarsor after reduction is filtered and is dried at 80 ± 1 DEG C, obtain the new valeronitrile reduction of support type special
Ni-based composite catalyst about 100g.
In embodiment 1 and 2, directly shaping carrier is impregnated in the solution containing soluble nickel salt, the work in catalyst
Property component in the pore structure of shaping carrier can high degree of dispersion, thus dipping after without the need for heat treatment, can be effectively prevented from live
Property component sinter at relatively high temperatures, avoid active metal particles from becoming big and affect catalytic performance；Catalyst after dipping
The load-type nickel based composite catalyst of shaping is directly prepared after precursor reduction, and without the need for subsequent forming work of the prior art
Skill, reduces waste of the active component nickel in forming process, the utilization rate of Raney nickel is improved, without follow-up roasting journey
Sequence, is effectively prevented from the agglomeration of active component, so as to be effectively improved the catalytic of load-type nickel based composite catalyst
Energy.
Embodiment 3-6：N-amylamine is prepared using Ni-based composite catalyst obtained in embodiment 1 and 2
Embodiment 3
Valeronitrile 500ml is put in the autoclave of 1L, Ni-based composite catalyst 25g obtained in embodiment 1 and 2 is put into, is led to
Nitrogen is replaced three times, opens stirring, logical hydrogen and 100 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.Inhale the obvious rear insulation reaction of hydrogen
Sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 488ml, n-amylamine 99.79%, diamylamine
0.13%th, triamylamine 0.08%.
Embodiment 4
Valeronitrile 500ml is put in the autoclave of 1L, Ni-based composite catalyst 20g obtained in embodiment 1 and 2 is put into, is led to
Nitrogen is replaced three times, opens stirring, logical hydrogen and 100 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.Inhale the obvious rear insulation reaction of hydrogen
Sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 488ml, n-amylamine 99.82%, diamylamine
0.11%th, triamylamine 0.07%.
Embodiment 5
Valeronitrile 500ml is put in the autoclave of 1L, Ni-based composite catalyst 20g obtained in embodiment 1 and 2 is put into, is led to
Nitrogen is replaced three times, opens stirring, logical hydrogen and 100 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.Inhale the obvious rear insulation reaction of hydrogen
Sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 481ml, n-amylamine 99.36%, diamylamine
0.43%th, triamylamine 0.21%.
Embodiment 6
Valeronitrile 500ml is put in the autoclave of 1L, Ni-based composite catalyst 20g obtained in embodiment 1 and 2 is put into, is led to
Nitrogen is replaced three times, opens stirring, logical hydrogen and 100 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.Inhale the obvious rear insulation reaction of hydrogen
Sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 488ml, n-amylamine 99.52%, diamylamine
0.36%th, triamylamine 0.12%.
In embodiment 3-6, Ni-based composite catalyst can apply mechanically more than ten times.Reaction equation is as follows：
Comparative example 1-6：Processing step is identical with embodiment 3-6, but prepares positive penta using commercially available Ni-based supported catalyst
Amine
Comparative example 1
Valeronitrile 500ml, the Ni-based supported catalyst 25g of market purchasing are put in the autoclave of 1L, is led to nitrogen and is replaced three times, opened
Stirring, logical ammonia are to internal pressure 0.5Kg/cm2Lead to hydrogen again and 100 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.After suction hydrogen is obvious
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 478ml, n-amylamine
94.81%th, diamylamine 3.73%, triamylamine 1.46%.
Comparative example 2
Valeronitrile 500ml, the Ni-based supported catalyst 25g of market purchasing are put in the autoclave of 1L, is led to nitrogen and is replaced three times, opened
Stirring, logical ammonia are to internal pressure 0.5Kg/cm2Lead to hydrogen again and 100 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.After suction hydrogen is obvious
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 488ml, n-amylamine
94.50%th, diamylamine 4.73%, triamylamine 0.77%.
Comparative example 3
Valeronitrile 500ml, the Ni-based supported catalyst 25g of market purchasing are put in the autoclave of 1L, is led to nitrogen and is replaced three times, opened
Stirring, logical ammonia are to internal pressure 0.5Kg/cm2Lead to hydrogen again and 100 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.After suction hydrogen is obvious
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 490ml, n-amylamine
94.12%th, diamylamine 5.43%, triamylamine 0.45%.
Comparative example 4
Valeronitrile 500ml, the Ni-based supported catalyst 25g of market purchasing are put in the autoclave of 1L, is led to nitrogen and is replaced three times, opened
Stirring, logical ammonia are to internal pressure 0.1Kg/cm2Lead to hydrogen again and 110 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.After suction hydrogen is obvious
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 481ml, n-amylamine
95.31%th, diamylamine 3.63%, triamylamine 1.06%.
Comparative example 5
Valeronitrile 500ml, the Ni-based supported catalyst 25g of market purchasing are put in the autoclave of 1L, is led to nitrogen and is replaced three times, opened
Stirring, logical ammonia are to internal pressure 0.1Kg/cm2Lead to hydrogen again and 110 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.After suction hydrogen is obvious
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 468ml, n-amylamine
95.21%th, diamylamine 4.56%, triamylamine 0.23%.
Comparative example 6
Valeronitrile 500ml, the Ni-based supported catalyst 25g of market purchasing are put in the autoclave of 1L, is led to nitrogen and is replaced three times, opened
Stirring, logical ammonia are to internal pressure 0.1Kg/cm2Lead to hydrogen again and 110 ± 5 DEG C of reactions are slowly warmed up to desirable pressure.After suction hydrogen is obvious
Insulation reaction sampling in 1 hour can't detect valeronitrile i.e. cooling discharge, leaches catalyst and obtains reactant liquor 468ml, n-amylamine
95.51%th, diamylamine 3.46%, triamylamine 1.03%.
The reaction equation of comparative example 1-6 is as follows：
Its reaction equation is identical with embodiment 3-6, but its catalyst is commercially available Ni-based supported catalyst, and this is Ni-based negative
Carried catalyst is the Ni-based supported catalyst of powder of model SN-5000P of the triumphant new material Science and Technology Ltd. production of upper Hisoon.
Comparative example 7
N-amylamine is prepared using traditional preparation technology.
The conversion ratio of embodiment 3-6 is 100%, selectively reaches more than 99%, and the conversion ratio of comparative example 1-6 is 100%,
But it is selectively only 95% or so, and the selectivity of comparative example 7 is only between 70-80%.Therefore, the present invention is obtained Ni-based multiple
Close catalyst and there is obvious advantage.
Above-described embodiment is only used for illustrating the inventive concept of the present invention, rather than the restriction to rights protection of the present invention,
All changes for carrying out unsubstantiality to the present invention using this design, all should fall into protection scope of the present invention.
Claims (5)
1. it is a kind of for valeronitrile synthesize n-amylamine Ni-based composite catalyst synthetic method, it is characterised in that including following step
Suddenly：
(1) soluble nickel salt is dissolved in solvent and is configured to solution；
(2) shaping carrier with pore structure is put in solution obtained in step (1) and is impregnated, obtain catalyst precarsor；
(3) catalyst precarsor in step (2) is reduced；
(4) catalyst precarsor after step (3) reduction is dried, obtains Ni-based composite catalyst.
2. the synthetic method that valeronitrile synthesizes the Ni-based composite catalyst of n-amylamine is used for as claimed in claim 1, it is characterised in that：
Described step (1) is that solution is configured in solvent by auxiliary agent, surfactant and soluble nickel salt are miscible；The auxiliary agent is accounted for
The mass percent of Ni-based composite catalyst is 5～10%, and the surfactant accounts for the quality percentage of Ni-based composite catalyst
Than for 1～10%.
3. the synthetic method that valeronitrile synthesizes the Ni-based composite catalyst of n-amylamine is used for as claimed in claim 2, it is characterised in that：
Described auxiliary agent is the mixture of ethylenediamine tetra-acetic acid, diethylamine and triethylamine, and described surfactant is PEO
One or several mixtures of triblock copolymer, polyethers F-201, PEG-8 00 or PEG20000, it is described
Soluble nickel salt is nickel nitrate, nickel acetate or nickel sulfate.
4. the synthetic method that valeronitrile synthesizes the Ni-based composite catalyst of n-amylamine is used for as claimed in claim 1, it is characterised in that：
In described step (2), after catalyst precarsor is taken out from the container for fill solution, remaining nickel salt accounts for addition in container
Mass fraction≤10% of soluble nickel salt total amount, after dipping is complete, the catalyst precursor for obtaining is dried, baking temperature
For 50～100 DEG C.
5. the synthetic method that valeronitrile synthesizes the Ni-based composite catalyst of n-amylamine is used for as claimed in claim 1, it is characterised in that：
In described step (3), catalyst precarsor is reduced in the reductant solution under inert gas shielding, wherein, reducing agent is molten
The pH of liquid is 8～14, and concentration is 0.01～0.1g/ml.
Priority Applications (1)
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| CN1035284A (en) * | 1988-02-25 | 1989-09-06 | 河南省科学院化学研究所 | The preparation method of fat primary amine |
| CN1810766A (en) * | 2006-01-04 | 2006-08-02 | 四川大学 | Nitrile reducing process to prepare amine |
| CN102614880A (en) * | 2012-01-12 | 2012-08-01 | 西北师范大学 | Preparation and application of carbon-supported amorphous metallic nickel |
| CN104801333A (en) * | 2015-03-03 | 2015-07-29 | 新奥科技发展有限公司 | Preparation method of supported nickel-based catalyst |
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| CN1035284A (en) * | 1988-02-25 | 1989-09-06 | 河南省科学院化学研究所 | The preparation method of fat primary amine |
| CN1810766A (en) * | 2006-01-04 | 2006-08-02 | 四川大学 | Nitrile reducing process to prepare amine |
| CN102614880A (en) * | 2012-01-12 | 2012-08-01 | 西北师范大学 | Preparation and application of carbon-supported amorphous metallic nickel |
| CN104801333A (en) * | 2015-03-03 | 2015-07-29 | 新奥科技发展有限公司 | Preparation method of supported nickel-based catalyst |
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