CN110813352B - Ni2Preparation method of P/NC catalyst, Ni2P/NC catalyst and application thereof - Google Patents
Ni2Preparation method of P/NC catalyst, Ni2P/NC catalyst and application thereof Download PDFInfo
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- CN110813352B CN110813352B CN201911056803.8A CN201911056803A CN110813352B CN 110813352 B CN110813352 B CN 110813352B CN 201911056803 A CN201911056803 A CN 201911056803A CN 110813352 B CN110813352 B CN 110813352B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000003756 stirring Methods 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 30
- IZRBAWXNLPBYKE-UHFFFAOYSA-N cyclohexane dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1CCCCC1 IZRBAWXNLPBYKE-UHFFFAOYSA-N 0.000 claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229960003638 dopamine Drugs 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 13
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 11
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 94
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 69
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 69
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 46
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000047 product Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 49
- 230000000052 comparative effect Effects 0.000 description 48
- 238000003917 TEM image Methods 0.000 description 23
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 229910021392 nanocarbon Inorganic materials 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910015335 Ni2In Inorganic materials 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- -1 phthalate ester Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- B01J35/23—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- 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 the technical field of catalysts, in particular to Ni for producing cyclohexane-1, 2-dioctyl phthalate2Preparation method of P/NC catalyst and Ni2P/NC catalyst and application thereof. Ni of the invention2The preparation method of the P/NC catalyst comprises the steps of mixing water and ethanol, adding the polyoxyethylene polyoxypropylene ether segmented copolymer, and stirring and mixing; adding dopamine, stirring, adding nickel nitrate hexahydrate, and stirring; then adding hydrochloric acid and stirring; continuing to add mesitylene and stirring; slowly dropping ammonia water; and (3) centrifugally separating and washing the prepared solution, and finally drying and phosphorizing and reducing a product prepared by the reaction to obtain the catalyst. Ni prepared by the invention2The P/NC catalyst has large specific surface area, good dispersity and low production cost.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to Ni for producing cyclohexane-1, 2-dioctyl phthalate2Preparation method of P/NC catalyst and Ni2P/NC catalyst and application thereof.
Background
Dioctyl phthalate is a colorless or light yellow oily transparent liquid, is dissolved in most organic solvents and hydrocarbons, is slightly dissolved in glycerol and glycol, has good compatibility with most industrial resins, and is a common industrial raw material. Cyclohexane-1, 2-dioctyl phthalate is an environment-friendly plasticizer which is not phthalate ester, has a structure similar to that of dioctyl phthalate, has the performance of dioctyl phthalate, and has more excellent functions. The concrete expression is as follows: the cyclohexane-1, 2-dioctyl phthalate has small mobility, is colorless and transparent, is completely environment-friendly, can be mutually dissolved with common organic solvents and common plasticizers, has elasticity, transparency and low-temperature performance far superior to those of dioctyl phthalate, and more importantly, the cyclohexane-1, 2-dioctyl phthalate has excellent toxicological characteristics, and the excellent performances enable the cyclohexane-1, 2-dioctyl phthalate to replace phthalate to be used as the plasticizer in the production process of products such as food packaging, medical supplies, toys for children and the like. However, in the prior art, in the production process for preparing the cyclohexane-1, 2-dioctyl diformate, the conversion rate of reactants is low, the selectivity of products is low, and the method is not suitable for large-scale production.
Disclosure of Invention
The invention aims to provide Ni for producing cyclohexane-1, 2-dioctyl diformate2Preparation method of P/NC catalyst and Ni2P/NC catalyst and application thereof in producing cyclohexane-1, 2-dioctyl diformate.
In order to achieve the purpose, the technical scheme of the invention is as follows:
ni2The preparation method of the P/NC catalyst comprises the following steps:
1) mixing water and ethanol, adding polyoxyethylene polyoxypropylene ether block copolymer, and stirring; adding dopamine, stirring, adding nickel nitrate hexahydrate, and stirring; adding hydrochloric acid into the solution, and stirring; continuing to drop mesitylene and stirring; then slowly dropping ammonia water; centrifugally separating and washing the prepared solution, wherein the mass ratio of dopamine to nickel nitrate hexahydrate is 1: 4-5: 1;
2) drying the product prepared in the step 1), introducing hydrogen, adding triphenylphosphine, and ensuring that the liquid hourly space velocity of the triphenylphosphine is 2-10 h-1；
3) Putting the product prepared in the step 2) into nitrogen for passivation to obtain Ni2P/NC catalyst.
In the step 1), the volume ratio of ethanol to water is 0.5: 1-2: 1; adding polyoxyethylene polyoxypropylene ether segmented copolymer, and stirring at the rotating speed of 300-500 r/min for more than 0.5 h; and (3) after dopamine is added, stirring for 2-5 h, after nickel nitrate hexahydrate is added, stirring at the rotating speed of 300-500 r/min, and stirring for more than 1 h.
In the step 1), the concentration of hydrochloric acid is 6-12 mol/L, and the hydrochloric acid is dripped into the solution and then stirred at the rotating speed of 300-500 r/min for 0.5-5 h; the mesitylene is dripped at the speed of two drops per second and then stirred for 2-4 hours at the rotating speed of 300-500 r/min.
In the step 1), the concentration of the ammonia water is 6-10 mol/L, and after the ammonia water is slowly dropped into the solution (one drop per second), the solution is stirred at the rotating speed of 300-500 r/min for 2-4 h.
In the step 1), the precipitate after centrifugal separation is alternately washed by adopting an ethanol solution and absolute ethanol, wherein the concentration of the ethanol solution is 60-70%.
In the step 2), the drying temperature is below 60 ℃, the flow rate of introduced hydrogen is 30-50 ml/min, triphenylphosphine is added, the temperature is raised to 380-450 ℃ at the temperature rise rate of 3-5 ℃/min, reaction is carried out for 3-5 h, a heptane solution of triphenylphosphine is added, and the mass ratio of triphenylphosphine to heptane is 0.5: 100-3: 100.
In the step 3), the oxygen content of the nitrogen is lower than 0.1%, and the passivation temperature in the nitrogen is below 50 ℃.
Ni2P/NC catalyst, said Ni2P/NC catalyst made of the above-mentioned Ni2The P/NC catalyst is prepared by a preparation method.
Ni2The application of the P/NC catalyst comprises the following steps: adding dioctyl phthalate, a solvent and a catalyst, introducing hydrogen, wherein the reaction temperature is 110-300 ℃, the hydrogen pressure is 2-10 MPa, the mass ratio of the dioctyl phthalate to the solvent is 1: 100-10: 100, and the liquid hourly space velocity of the dioctyl phthalate is 2-10 h-1The hydrogen-oil ratio is 1-200, and after a period of reaction, the product cyclohexane-1, 2-dioctyl diformate is prepared, wherein the solvent is n-decane and cyclohexaneOr benzene, and the catalyst is the Ni2P/NC catalyst.
The Ni2In the application of the P/NC catalyst, the mass ratio of the dioctyl phthalate to the solvent is 3: 100-5: 100.
The Ni2In the application of the P/NC catalyst, the reaction temperature is 110-160 ℃, and the hydrogen pressure is 2-4 MPa.
The invention has the beneficial effects that:
ni provided in the invention2A P/NC catalyst is prepared through generating petal-shaped N-contained nano carbon spheres by dopamine, adding nickel nitrate hexahydrate and mesitylene to the disperser of alcohol and polyoxyvinyl-polyoxypropenyl ether block copolymer, regulating particle size, synthesizing Ni-contained nano carbon spheres, washing, baking, adding triphenyl phosphine, phosphorizing reduction and synthesizing step-by-step process to obtain Ni2P/NC catalyst.
Ni of the invention2In the preparation method of the P/NC catalyst, a soft template method is adopted, so that the prepared Ni2The specific surface area of the P/NC catalyst is large, and the active component Ni is caused by the complexation of dopamine2The P has good dispersity on the nitrogen-containing nano carbon spheres, and the prepared Ni2The P/NC catalyst is uniformly dispersed.
Ni prepared by the invention2When the P/NC catalyst is used for preparing the cyclohexane-1, 2-dioctyl phthalate, the reaction temperature and the reaction pressure are low, the requirements on a reaction device are low, the energy consumption is low, the final production cost is low, the reaction is mild, the reaction yield is high, and the method is suitable for industrial large-scale production.
Ni prepared by the invention2When the P/NC catalyst is used for preparing cyclohexane-1, 2-dioctyl phthalate, the hydrogenation reaction of dioctyl phthalate is utilized to generate cyclohexane-1, 2-dioctyl phthalate, while the Ni of the invention2The P/NC catalyst has good hydrogenation effect, further promotes the dioctyl phthalate to react to generate cyclohexane-1, 2-dioctyl phthalate, ensures that the conversion rate of the dioctyl phthalate is higher, and the cyclohexane-1The selectivity of the 2-dioctyl phthalate is higher.
Drawings
FIG. 1 shows Ni prepared in example 1 of the present invention2Transmission Electron Microscopy (TEM) image of P/NC catalyst;
FIG. 2 is Ni prepared in example 2 of the present invention2TEM image of P/NC catalyst;
FIG. 3 is Ni prepared in example 3 of the present invention2TEM image of P/NC catalyst;
FIG. 4 is Ni prepared in example 4 of the present invention2TEM image of P/NC catalyst;
FIG. 5 is a TEM image of the catalyst prepared in comparative example 1 of the present invention;
FIG. 6 is a TEM image of the catalyst prepared in comparative example 2 of the present invention;
FIG. 7 is a TEM image of the catalyst prepared in comparative example 3 of the present invention;
FIG. 8 is a TEM image of the catalyst prepared in comparative example 4 of the present invention;
FIG. 9 is a TEM image of the catalyst prepared in comparative example 5 of the present invention;
FIG. 10 is a TEM image of the catalyst prepared in comparative example 6 of the present invention;
fig. 11 is a TEM image of the catalyst prepared in comparative example 7 of the present invention.
Detailed Description
Example 1
Ni of the present example2The preparation method of the P/NC catalyst comprises the following steps:
1) adding 400ml of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 1:1 into a stirrer, adjusting the rotating speed of the stirrer to be 500r/min, stirring, adding 5g of polyoxyethylene polyoxypropylene ether segmented copolymer, and continuing stirring for 1 h; then adding 2.5g of dopamine, continuously stirring for 2h, weighing 2.5g of nickel nitrate hexahydrate, adding the solution, and continuously stirring for 2 h; then 6ml of hydrochloric acid with the concentration of 12mol/l is added, and the mixture is stirred for 2 hours; slowly dripping (two drops per second) 10ml mesitylene, stirring for 4h, taking 25m ammonia water with the concentration of 6mol/l, dripping (one drop per second) into the solution dropwise, and continuously stirring for 4 h; and finally, performing centrifugal separation, and alternately washing the precipitate after the centrifugal separation for five times by adopting 70% ethanol water solution and absolute ethanol.
2) Putting the product prepared in the step 1) into an oven, baking for 24h at 50 ℃, transferring the product into a fixed bed, introducing hydrogen at the flow rate of 40ml/min, heating to 380 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of triphenylphosphine to heptane is 1: 100; the liquid hourly space velocity of the triphenylphosphine is 2h-1The introducing time is 4h, the reaction time is consistent with that of triphenylphosphine, and then the temperature is reduced.
3) Passivating the product obtained in the step 2) in nitrogen (the oxygen content is lower than 0.1%) at 40 ℃ to obtain Ni2P/NC catalyst, FIG. 1 shows Ni of the present example2TEM image of P/NC catalyst.
Such as Ni2The application of the P/NC catalyst comprises the following steps:
0.2 g of the prepared Ni was weighed2Putting the P/NC catalyst into a fixed bed reactor, adding an n-decane solution of dioctyl phthalate, wherein the mass ratio of the dioctyl phthalate to the n-decane is 1:100, and the liquid hourly space velocity of the dioctyl phthalate is 2h-1And simultaneously introducing hydrogen at the flow rate of 60ml/min, wherein the hydrogen pressure is 2MPa, the temperature in the fixed bed reactor is increased to 150 ℃ from room temperature at the speed of 5 ℃/min, finally preparing a reaction product, and analyzing by adopting gas chromatography to calculate that the conversion rate of the dioctyl phthalate is 99 percent and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 99 percent.
Example 2
Ni of the present example2The preparation method of the P/NC catalyst comprises the following steps:
1) adding 400ml of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 1:1 into a stirrer, adjusting the rotating speed of the stirrer to be 500r/min, stirring, adding 5g of polyoxyethylene polyoxypropylene ether segmented copolymer, and continuing stirring for 1 h; then adding 2.5g of dopamine, continuously stirring for 2h, weighing 1.5g of nickel nitrate hexahydrate, adding the solution, and continuously stirring for 2 h; then 6ml of hydrochloric acid with the concentration of 12mol/l is added, and the mixture is stirred for 2 hours; slowly dripping (two drops per second) 10ml mesitylene, stirring for 4h, taking 25ml ammonia water with the concentration of 6mol/l, dripping (one drop per second) into the solution dropwise, and continuously stirring for 4 h; and finally, performing centrifugal separation, and alternately washing the precipitate after the centrifugal separation for five times by adopting 70% ethanol water solution and absolute ethanol.
2) Putting the product prepared in the step 1) into an oven, baking for 24h at 50 ℃, transferring the product into a fixed bed, introducing hydrogen at the flow rate of 40ml/min, heating to 380 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of triphenylphosphine to heptane is 1:100, respectively; the liquid hourly space velocity of the triphenylphosphine is 2h-1The introducing time is 4h, the reaction time is consistent with that of triphenylphosphine, and then the temperature is reduced.
3) Passivating the product obtained in the step 2) in nitrogen (the oxygen content is lower than 0.1%) at 40 ℃ to obtain Ni2P/NC catalyst, FIG. 2 shows Ni of the present example2TEM image of P/NC catalyst.
Such as Ni2The application of the P/NC catalyst comprises the following steps:
0.2 g of the prepared Ni was weighed2Putting the P/NC catalyst into a fixed bed reactor, adding an n-decane solution of dioctyl phthalate, wherein the mass ratio of the dioctyl phthalate to the n-decane is 1:100, and the liquid hourly space velocity of the dioctyl phthalate is 2h-1The reaction of the dioctyl phthalate is a continuous reaction, hydrogen is introduced at the same time at the flow rate of 60ml/min, the hydrogen pressure is 2MPa, the temperature in the reactor is increased to 150 ℃ from room temperature at the speed of 5 ℃/min, and finally a reaction product is prepared, and the gas chromatography is adopted for analysis, so that the conversion rate of the dioctyl phthalate is 99 percent, and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 98 percent.
Example 3
Ni of the present example2The preparation method of the P/NC catalyst comprises the following steps:
1) adding 600ml of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 2:1 into a stirrer, adjusting the rotating speed of the stirrer to 300r/min, stirring, adding 5g of polyoxyethylene polyoxypropylene ether segmented copolymer, and continuing stirring for 1 h; then adding 1g of dopamine, continuously stirring for 2 hours, weighing 4g of nickel nitrate hexahydrate, adding the solution, and continuously stirring for 2 hours; then 6ml of hydrochloric acid with the concentration of 12mol/L is added, and the mixture is stirred for 2 hours; slowly dripping (two drops per second) 10ml mesitylene, stirring for 4h, taking 25ml ammonia water with the concentration of 6mol/L, dripping (one drop per second) into the solution dropwise, and continuously stirring for 3 h; and finally, performing centrifugal separation, and alternately washing the precipitate after the centrifugal separation for five times by adopting 70% ethanol water solution and absolute ethanol.
2) Putting the product prepared in the step 1) into an oven, baking for 24h at 50 ℃, transferring the product into a fixed bed, introducing hydrogen at the flow rate of 40ml/min, heating to 380 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of triphenylphosphine to heptane is 1:100, respectively; the liquid hourly space velocity of the triphenylphosphine is 6h-1The introducing time is 4h, the reaction time is consistent with that of triphenylphosphine, and then the temperature is reduced.
3) Passivating the product obtained in the step 2) in nitrogen (the oxygen content is lower than 0.1%) at 40 ℃ to obtain Ni2P/NC catalyst, FIG. 3 shows Ni of the present example2TEM image of P/NC catalyst.
Such as Ni2The application of the P/NC catalyst comprises the following steps:
weighing 1g of the prepared Ni2Putting the P/NC catalyst into a fixed bed reactor, adding an n-decane solution of dioctyl phthalate, wherein the mass ratio of the dioctyl phthalate to the n-decane is 1:100, and the liquid hourly space velocity of the dioctyl phthalate is 10h-1And simultaneously introducing hydrogen at the flow rate of 60ml/min, wherein the hydrogen pressure is 2MPa, the temperature in the fixed bed reactor is increased to 110 ℃ from room temperature at the speed of 5 ℃/min, and finally, a reaction product is prepared, and the gas chromatography is adopted for analysis, so that the conversion rate of the dioctyl phthalate is 98 percent, and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 98 percent.
Example 4
This implementationExample Ni2The preparation method of the P/NC catalyst comprises the following steps:
1) adding 400ml of mixed solution consisting of absolute ethyl alcohol and water according to the volume ratio of 1:1 into a stirrer, adjusting the rotating speed of the stirrer to 400r/min, stirring, adding 5g of polyoxyethylene polyoxypropylene ether segmented copolymer, and continuing stirring for 1 h; then 12.5g of dopamine is added and continuously stirred for 2 hours, 2.5g of nickel nitrate hexahydrate is weighed, and the solution is added and continuously stirred for 2 hours; then 6ml of hydrochloric acid with the concentration of 12mol/L is added, the mixture is stirred for 2 hours, 10ml of mesitylene is slowly dripped (two drops per second), the mixture is stirred for 4 hours, 25ml of ammonia water with the concentration of 6mol/L is taken, the mixture is dripped (one drop per second) into the solution, and the stirring is continued for 4 hours; and finally, performing centrifugal separation, and alternately washing the precipitate after the centrifugal separation for five times by adopting 70% ethanol water solution and absolute ethanol.
2) Putting the product prepared in the step 1) into an oven, baking for 24h at 50 ℃, transferring the product into a fixed bed, introducing hydrogen at the flow rate of 40ml/min, heating to 450 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of triphenylphosphine to heptane is 1:100, respectively; the liquid hourly space velocity of the triphenylphosphine is 2h-1The introducing time is 4h, the reaction time is consistent with that of triphenylphosphine, and then the temperature is reduced.
3) Passivating the product obtained in the step 2) in nitrogen (the oxygen content is lower than 0.1%) at 40 ℃ to obtain Ni2P/NC catalyst, FIG. 4 shows Ni of the present example2TEM image of P/NC catalyst.
Such as Ni2The application of the P/NC catalyst comprises the following steps:
0.5 g of the prepared Ni was weighed2Putting the P/NC catalyst into a fixed bed reactor, adding dioctyl phthalate and cyclohexane, wherein the mass ratio of the dioctyl phthalate to the cyclohexane is 5:100, and the liquid hourly space velocity of the dioctyl phthalate is 6h-1The introduction time of the dioctyl phthalate is 2h, hydrogen is introduced at the flow rate of 60ml/min, the pressure of the hydrogen is 2MPa, the temperature in the fixed bed reactor is increased to 300 ℃ from room temperature at the speed of 5 ℃/min, and finally a reaction product is prepared,the conversion rate of dioctyl phthalate is 98% and the selectivity of cyclohexane-1, 2-dioctyl phthalate is 98% by calculation through gas chromatography analysis.
Comparative example 1
The traditional method is adopted to prepare the catalyst containing the nickel phosphide active component, namely the equivalent impregnation method is adopted to prepare Ni2P/NC。
Firstly, 2g of nitrogen-containing mesoporous carbon is dried, 4ml of deionized water is used for dissolving 2.5g of nickel nitrate to prepare a nickel nitrate solution, then the nickel nitrate solution is added into the nitrogen-containing mesoporous carbon, and the nitrogen-containing mesoporous carbon is stood for drying and transferred into a fixed bed reactor for reduction and phosphorization.
Introducing hydrogen at the flow rate of 40ml/min, raising the temperature to 380 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of the triphenylphosphine to the heptane is 1: 100; the liquid hourly space velocity of the triphenylphosphine is 2h-1And (3) introducing for 4h, wherein the reaction time is consistent with that of triphenylphosphine, then cooling, and introducing nitrogen (the oxygen content is lower than 0.1%) for passivation when the temperature is reduced to 40 ℃ to obtain the catalyst. Fig. 5 shows a TEM image of the catalyst of this comparative example.
Weighing 0.2 g of the reduced and passivated catalyst, putting the weighed catalyst into a fixed bed reactor, adding an n-decane solution of dioctyl phthalate, wherein the mass ratio of the dioctyl phthalate to the n-decane is 1:100, and the liquid hourly space velocity of the dioctyl phthalate is 2h-1The introduction time of the dioctyl phthalate is 2h, hydrogen is introduced at the same time at the flow rate of 60ml/min, the hydrogen pressure is 2MPa, the temperature in the fixed bed reactor is increased to 150 ℃ from room temperature at the speed of 5 ℃/min, and finally a reaction product is prepared, and the gas chromatography is adopted for analysis, so that the conversion rate of the dioctyl phthalate is 86 percent, and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 83 percent.
Comparative example 2
Take 2g of SiO2Drying, dissolving 2.5g of nickel nitrate in 4ml of deionized water to prepare a nickel nitrate solution, and adding the nickel nitrate solution into SiO2And standing, drying and transferring into a fixed bed for reduction and phosphorization.
Introducing hydrogen at the flow rate of 40ml/min, raising the temperature to 380 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of the triphenylphosphine to the heptane is 1: 100; the liquid hourly space velocity of the triphenylphosphine is 2h-1And introducing for 4h, wherein the reaction time is consistent with that of triphenylphosphine, then cooling, and introducing nitrogen (the oxygen content is lower than 0.1%) for passivation when the temperature is reduced to 40 ℃. Fig. 6 shows a TEM image of the catalyst prepared in this comparative example.
Weighing 0.2 g of the reduced and passivated catalyst, putting the weighed catalyst into a fixed bed reactor, adding an n-decane solution of dioctyl phthalate, wherein the mass ratio of the dioctyl phthalate to the n-decane is 1:100, and the liquid hourly space velocity of the dioctyl phthalate is 2h-1The introduction time of the dioctyl phthalate is 2h, hydrogen is introduced at the same time at the flow rate of 60ml/min, the hydrogen pressure is 2MPa, the temperature in the fixed bed reactor is increased to 150 ℃ from room temperature at the speed of 5 ℃/min, and finally a reaction product is prepared, and the gas chromatography is adopted for analysis, so that the conversion rate of the dioctyl phthalate is 83 percent, and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 87 percent.
Comparative example 3
2g of TiO are taken2Drying, dissolving 2.5g of nickel nitrate in 4ml of deionized water to prepare a nickel nitrate solution, and adding the nickel nitrate solution into TiO2And standing, drying and transferring into a fixed bed for reduction and phosphorization.
Introducing hydrogen at the flow rate of 40ml/min, raising the temperature to 380 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of the triphenylphosphine to the heptane is 1: 100; the liquid hourly space velocity of the triphenylphosphine is 2h-1The introducing time is 4h, the reaction time is consistent with that of triphenylphosphine, then the temperature is reduced, and when the temperature is reduced to 40 ℃, nitrogen (the oxygen content is lower than 0.1%) is introduced for passivation. Fig. 7 shows a TEM image of the catalyst prepared in this comparative example.
Weighing 0.2 g of the reduced and passivated catalyst, putting the weighed catalyst into a fixed bed reactor, adding a n-decane solution of dioctyl phthalate, wherein the mass ratio of the dioctyl phthalate to the n-decane is 1:100, and the catalyst is prepared by adding a catalyst of the dioctyl phthalateThe liquid hourly space velocity of the dioctyl phthalate is 2h-1The introduction time of the dioctyl phthalate is 2h, hydrogen is introduced at the same time at the flow rate of 60ml/min, the hydrogen pressure is 2MPa, the temperature in the reactor is increased to 150 ℃ from room temperature at the speed of 5 ℃/min, and finally a reaction product is prepared, and the gas chromatography is adopted for analysis, so that the conversion rate of the dioctyl phthalate is 82 percent, and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 87 percent.
Comparative example 4
2g of Al are taken2O3Drying, dissolving 2.5g of nickel nitrate in 4ml of deionized water to prepare a nickel nitrate solution, and adding Al into the nickel nitrate solution2O3And standing, drying and transferring into a fixed bed for reduction and phosphorization.
Introducing hydrogen at the flow rate of 40ml/min, raising the temperature to 380 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of the triphenylphosphine to the heptane is 1: 100; the liquid hourly space velocity of the triphenylphosphine is 2h-1The introducing time is 4h, the reaction time is consistent with that of triphenylphosphine, then the temperature is reduced, and when the temperature is reduced to 40 ℃, nitrogen (the oxygen content is lower than 0.1%) is introduced for passivation. Fig. 8 shows a TEM image of the catalyst prepared in this comparative example.
Weighing 0.2 g of the reduced and passivated catalyst, putting the weighed catalyst into a fixed bed reactor, adding an n-decane solution of dioctyl phthalate, wherein the mass ratio of the dioctyl phthalate to the n-decane is 1:100, and the liquid hourly space velocity of the dioctyl phthalate is 2h-1The flow-in time of the dioctyl phthalate is 2h, hydrogen is simultaneously led in at the flow rate of 60ml/min, the pressure of the hydrogen is 2MPa, the temperature in the fixed bed reactor is raised to 150 ℃ from room temperature at the speed of 5 ℃/min, a reaction product is finally prepared, and the gas chromatography is adopted for analysis, so that the conversion rate of the dioctyl phthalate is 79 percent, and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 84 percent.
Comparative example 5
2g of CeO are taken2Drying, dissolving 2.5g of nickel nitrate in 4ml of deionized water to prepare a nickel nitrate solution, and adding CeO into the nickel nitrate solution2In the middle, standing, drying andmoving the mixture into a fixed bed for reduction and phosphorization.
Introducing hydrogen at the flow rate of 40ml/min, raising the temperature to 380 ℃ at the heating rate of 3 ℃/min, and adding a heptane solution of triphenylphosphine, wherein the mass ratio of the triphenylphosphine to the heptane is 1: 100; the liquid hourly space velocity of the triphenylphosphine is 2h-1The introducing time is 4h, the reaction time is consistent with that of triphenylphosphine, then the temperature is reduced, and when the temperature is reduced to 40 ℃, nitrogen (the oxygen content is lower than 0.1%) is introduced for passivation. Fig. 9 shows a TEM image of the catalyst prepared in this comparative example.
Weighing 0.2 g of the reduced and passivated catalyst, putting the weighed catalyst into a fixed bed reactor, adding an n-decane solution of dioctyl phthalate, wherein the mass ratio of the dioctyl phthalate to the n-decane is 1:100, and the liquid hourly space velocity of the dioctyl phthalate is 2h-1The introducing time of the dioctyl phthalate is 2 hours, hydrogen is introduced at the same time at the flow rate of 60ml/min, the hydrogen pressure is 2MPa, the temperature in the fixed bed reactor is increased to 150 ℃ from room temperature at the speed of 5 ℃/min, and finally a reaction product is prepared, and the gas chromatography is adopted for analysis, so that the conversion rate of the dioctyl phthalate is 60 percent, and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 70 percent.
Comparative example 6
The comparative example is different from example 1 in that, in the process of preparing the catalyst, ammonia water is dropped at a speed of ten drops per second instead of dropping ammonia water at a speed of one drop per second in example 1, other steps are the same as example 1, and are not repeated here, and fig. 10 shows a TEM image of the catalyst prepared in the comparative example. Finally, the reaction product is analyzed by gas chromatography, and the conversion rate of the dioctyl phthalate is 81 percent and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 79 percent by calculation.
Comparative example 7
The comparative example is different from example 1 in that the rotation speed of the stirrer is 100r/min instead of 500r/min in example 1 in the reaction process of preparing the catalyst, the other steps are the same as example 1 and are not repeated, and fig. 11 shows a TEM image of the catalyst prepared in the comparative example. Finally, the reaction product is analyzed by gas chromatography, and the conversion rate of the dioctyl phthalate is 60 percent and the selectivity of the cyclohexane-1, 2-dioctyl phthalate is 70 percent by calculation.
Results of the experiment
1) The gas chromatography data in examples 1 to 4 and comparative examples 1 to 7 were analyzed, and the results are shown in table 1:
TABLE 1 comparison of Dioctyl phthalate hydrogenation Performance in examples and comparative examples
| Conversion of dioctyl phthalate | Selectivity of cyclohexane-1, 2-dioctyl diformate | |
| Example 1 | 99 | 99 |
| Example 2 | 99 | 98 |
| Example 3 | 98 | 98 |
| Example 4 | 98 | 98 |
| Comparative example 1 | 86 | 83 |
| Comparative example 2 | 83 | 87 |
| Comparative example 3 | 82 | 87 |
| Comparative example 4 | 79 | 84 |
| Comparative example 5 | 60 | 70 |
| Comparative example 6 | 81 | 79 |
| Comparative example 7 | 84 | 83 |
As shown in Table 1, in examples 1 to 4, since the petal-shaped nitrogen-containing nanocarbon spheres were produced using dopamine, nickel nitrate hexahydrate and mesitylene were added to the nitrogen-containing nanocarbon spheres and the particle size thereof was adjusted in the presence of a dispersant such as ethanol or a polyoxyethylene polyoxypropylene ether block copolymer to synthesize a nickel-rich nanocarbon sphere precursor, wherein nickel was uniformly distributed on the nitrogen-containing nanocarbon spheres, followed by washing and drying, phosphorization reduction with a heptane solution of triphenylphosphine, and Ni was obtained by stepwise synthesis2P/NC catalyst, because of the large specific surface area of the catalyst preparedThe dispersity is good, when the catalyst prepared in the examples 1-4 is added in the hydrogenation reaction of dioctyl phthalate, the conversion rate of dioctyl phthalate is more than 98%, and the selectivity of prepared cyclohexane-1, 2-dioctyl phthalate is more than 98%; in comparative examples 1 to 5, the catalyst prepared by the traditional equivalent impregnation method has small specific surface area and poor dispersion degree, and when the catalyst prepared in comparative examples 1 to 5 is added in the dioctyl phthalate hydrogenation reaction, the conversion rate of the dioctyl phthalate is less than 86 percent, and the selectivity of the prepared cyclohexane-1, 2-dioctyl phthalate is less than 87 percent; in the comparative example 6, the dropping speed of the ammonia water is too fast in the reaction process of preparing the catalyst, so that the active ingredients in the catalyst are easy to agglomerate, and thus, when the catalyst prepared in the comparative example 6 is added in the hydrogenation reaction of the dioctyl phthalate, the conversion rate of the dioctyl phthalate is 81 percent, and the selectivity of the prepared cyclohexane-1, 2-dioctyl phthalate is 79 percent; in comparative example 7, since the stirring speed of the stirrer was too small during the reaction for preparing the catalyst, the particles of the prepared catalyst were large and were not uniformly dispersed, and when the catalyst prepared in comparative example 7 was added in the hydrogenation reaction of dioctyl phthalate, the conversion of dioctyl phthalate was 84% and the selectivity of cyclohexane-1, 2-dioctyl phthalate was 83%.
2) The catalysts obtained in examples 1 to 4 and comparative examples 1 to 7 were measured for specific surface area by nitrogen adsorption and desorption method, and the results are shown in Table 2:
TABLE 2 specific surface area of catalysts prepared in examples and comparative examples
| Specific surface area (m 2/g) | Specific surface area (m 2/g) | ||
| Example 1 | 424 | Comparative example 1 | 310 |
| Example 2 | 400 | Comparative example 2 | 289 |
| Example 3 | 334 | Comparative example 3 | 287 |
| Example 4 | 378 | Comparative example 4 | 297 |
| Comparative example 5 | 270 | ||
| Comparative example 6 | 260 | ||
| Comparative example 7 | 315 |
As can be seen from Table 2, in examples 1 to 4, the catalysts were prepared by using the soft template method, so that Ni prepared by the present invention2The P/NC catalyst has large specific surface area.
In addition, as can be seen from the TEM images of FIGS. 1 to 11 with respect to examples 1 to 4 and comparative examples 1 to 7, the present invention is producing Ni2In the process of P/NC catalyst, active component Ni is caused by adding dopamine and complexation between dopamine and active component2The P has good dispersity on the nitrogen-containing nano carbon spheres.
Various other modifications and changes may be made by those skilled in the art based on the above-described technical solutions and concepts, and all such modifications and changes should fall within the scope of the claims of the present invention.
Claims (10)
1. Ni for producing cyclohexane-1, 2-dioctyl phthalate2The preparation method of the P/NC catalyst is characterized by comprising the following steps:
1) mixing water and ethanol, adding polyoxyethylene polyoxypropylene ether segmented copolymer, and stirring and mixing; adding dopamine, stirring, adding nickel nitrate hexahydrate, and stirring; then adding hydrochloric acid and stirring; continuing to drop mesitylene and stirring; then slowly dropping ammonia water into the solution; centrifugally separating and washing the prepared solution, wherein the mass ratio of dopamine to nickel nitrate hexahydrate is 1: 4-5: 1;
2) drying the product prepared in the step 1), introducing hydrogen, adding triphenylphosphine, and ensuring that the liquid hourly space velocity of the triphenylphosphine is 2-10 h-1；
3) Putting the product prepared in the step 2) into nitrogen for passivation to obtain Ni2P/NC catalyst.
2. Ni for producing cyclohexane-1, 2-dicaprylyl dimethyl according to claim 12The preparation method of the P/NC catalyst is characterized in that in the step 1), the volume ratio of ethanol to water is 0.5: 1-2: 1.
3. ni for producing cyclohexane-1, 2-dicaprylyl dicarboxylate according to claim 12The preparation method of the P/NC catalyst is characterized in that in the step 1), after dopamine is added, stirring is carried out for 2-5 hours, and after nickel nitrate hexahydrate is added, stirring is carried out at the rotating speed of 300-500 r/min.
4. Ni for producing cyclohexane-1, 2-dicaprylyl dimethyl according to claim 12The preparation method of the P/NC catalyst is characterized in that in the step 1), the concentration of hydrochloric acid is 6-12 mol/L, and after the hydrochloric acid is dripped into the solution, the solution is stirred for 0.5-5 h at the rotating speed of 300-500 r/min.
5. Ni for producing cyclohexane-1, 2-dicaprylyl dimethyl according to claim 12The preparation method of the P/NC catalyst is characterized in that in the step 1), after mesitylene is added, the mixture is stirred for 2-4 hours at a rotating speed of 300-500 r/min.
6. Ni for producing cyclohexane-1, 2-dicaprylyl dimethyl according to claim 12The preparation method of the P/NC catalyst is characterized in that in the step 1), the concentration of the ammonia water is 6-10 mol/L, and the ammonia water is slowly dripped into the solution and then stirred for 2-4 hours at the rotating speed of 300-500 r/min.
7. Ni for producing cyclohexane-1, 2-dicaprylyl dimethyl according to claim 12The preparation method of the P/NC catalyst is characterized in that in the step 1), the precipitate after centrifugal separation is alternately washed by adopting ethanol solution and absolute ethyl alcohol, and the ethanol solutionThe concentration of (A) is 60-70%.
8. Ni for producing cyclohexane-1, 2-dicaprylyl dimethyl according to claim 12The preparation method of the P/NC catalyst is characterized in that in the step 2), the drying temperature is below 60 ℃, the flow rate of introduced hydrogen is 30-50 ml/min, the temperature is raised to 380-450 ℃ at the temperature rise rate of 3-5 ℃/min, the reaction is carried out for 3-5 h, and then a heptane solution of triphenylphosphine is added, wherein the mass ratio of triphenylphosphine to heptane is 0.5: 100-3: 100.
9. Ni for producing cyclohexane-1, 2-dioctyl phthalate2P/NC catalyst, characterized in that the Ni2P/NC catalyst consisting of Ni according to any of claims 1 to 82The P/NC catalyst is prepared by a preparation method.
10. Ni for producing cyclohexane-1, 2-dioctyl phthalate2The application of the P/NC catalyst is characterized by comprising the following steps: adding dioctyl phthalate, a solvent and a catalyst, introducing hydrogen, wherein the reaction temperature is 110-300 ℃, the hydrogen pressure is 2-10 MPa, the mass ratio of the dioctyl phthalate to the solvent is 1: 100-10: 100, and the liquid hourly space velocity of the dioctyl phthalate is 2-10 h-1The hydrogen-oil ratio is 1-200, and after reacting for a period of time, the product cyclohexane-1, 2-dioctyl diformate is prepared, wherein the Ni is2The P/NC catalyst is Ni as described in claim 92The P/NC catalyst, the solvent is any one of n-decane, cyclohexane or benzene.
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