CN113663727A - Preparation method of supported catalyst with high specific surface area and application of supported catalyst in p-nitroaniline synthesis - Google Patents
Preparation method of supported catalyst with high specific surface area and application of supported catalyst in p-nitroaniline synthesis Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title claims description 10
- 230000015572 biosynthetic process Effects 0.000 title claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 29
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 25
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 22
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000005457 ice water Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 14
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical group [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 2
- 229910021426 porous silicon Inorganic materials 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- LOCWBQIWHWIRGN-UHFFFAOYSA-N 2-chloro-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1Cl LOCWBQIWHWIRGN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- BIXZHMJUSMUDOQ-UHFFFAOYSA-N dichloran Chemical compound NC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl BIXZHMJUSMUDOQ-UHFFFAOYSA-N 0.000 description 1
- AOMZHDJXSYHPKS-UHFFFAOYSA-L disodium 4-amino-5-hydroxy-3-[(4-nitrophenyl)diazenyl]-6-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(N=NC=3C=CC=CC=3)C(O)=C2C(N)=C1N=NC1=CC=C([N+]([O-])=O)C=C1 AOMZHDJXSYHPKS-UHFFFAOYSA-L 0.000 description 1
- DDLNJHAAABRHFY-UHFFFAOYSA-L disodium 8-amino-7-[[4-[4-[(4-oxidophenyl)diazenyl]phenyl]phenyl]diazenyl]-2-phenyldiazenyl-3,6-disulfonaphthalen-1-olate Chemical compound [Na+].[Na+].NC1=C(C(=CC2=CC(=C(C(=C12)O)N=NC1=CC=CC=C1)S(=O)(=O)[O-])S(=O)(=O)[O-])N=NC1=CC=C(C=C1)C1=CC=C(C=C1)N=NC1=CC=C(C=C1)O DDLNJHAAABRHFY-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LHHIALSOMNPUOW-UHFFFAOYSA-N n-chloro-n-phenylnitramide Chemical compound [O-][N+](=O)N(Cl)C1=CC=CC=C1 LHHIALSOMNPUOW-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002994 raw 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a supported catalyst with high specific surface area, which comprises the following steps: dispersing porous nano silicon oxide in deionized water, adding an aniline monomer under the condition of ice-water bath, uniformly mixing, adding an ammonium persulfate solution, stirring for reaction, filtering reaction liquid after the reaction is finished, washing and precipitating by using deionized water, drying, and calcining the dried solid in a muffle furnace under an inert atmosphere to prepare nano silicon oxide coated by a nitrogen-doped carbon layer; and adding the prepared nano silicon oxide coated by the nitrogen-doped carbon layer into the dispersion liquid of the phase transfer catalyst, performing adsorption treatment, and drying to obtain the supported catalyst with high specific surface area. The prepared supported catalyst has large specific surface area and high catalytic activity, greatly improves the yield and purity of a target product when being used for synthesizing p-nitroaniline, has small catalyst consumption, is convenient to recover, and greatly improves the production cost of the product.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of a supported catalyst with high specific surface area and application of the supported catalyst in p-nitroaniline synthesis.
Background
The p-nitroaniline is an important organic synthesis intermediate in the fields of dyes, pesticides, antioxidants and the like, can be directly synthesized into o-chloro-p-nitroaniline, 2, 6-dichloro-p-nitroaniline, p-phenylenediamine, chloronitroaniline and the like, and is further used for preparing azo dyes, such as direct dark green B, acid mordant brown G, acid black 10B and the like.
At present, the domestic production method of p-nitroaniline is mainly the amination method of p-nitrochlorobenzene. P-nitrochlorobenzene and concentrated ammonia react for 15 to 20 hours in a stirring kettle under the conditions of 140 ℃ and 180 ℃, 3.7 to 5.5MPa and large excess of liquid ammonia, and the p-nitroaniline is obtained by crystallization and filtration. The process mainly has the problems of low production efficiency, unstable product quality, poor reliability of equipment amplification and the like. It is pointed out in the literature that a phase transfer catalyst or the like can be introduced to improve the production efficiency, and although the method greatly improves the yield of the product, the catalyst is inconvenient to separate and the amount of the catalyst used is large, which increases the production cost of the product.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the invention provides a preparation method of a supported catalyst with high specific surface area and application thereof in paranitroaniline synthesis.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a supported catalyst with high specific surface area comprises the following steps:
(1) dispersing porous nano silicon oxide in deionized water, adding an aniline monomer under the condition of ice-water bath, uniformly mixing, adding an ammonium persulfate solution, stirring for reaction, filtering reaction liquid after the reaction is finished, washing and precipitating by using deionized water, drying, and calcining the dried solid in a muffle furnace under an inert atmosphere to prepare nano silicon oxide coated by a nitrogen-doped carbon layer;
(2) and adding the prepared nano silicon oxide coated by the nitrogen-doped carbon layer into the dispersion liquid of the phase transfer catalyst, performing adsorption treatment, and drying to obtain the supported catalyst with high specific surface area.
Preferably, in the step (1), the concentration of the ammonium persulfate solution is 1mol/L, and the usage ratio of the nano silicon oxide, the aniline monomer and the ammonium persulfate solution is 1 g: (7-8) ml: 50 ml.
Preferably, in the step (1), the time of the stirring reaction is 7-8 h, and the rotation speed of the stirring reaction is 3000-5000 rpm.
Preferably, in the step (1), during the calcination treatment, the temperature is first raised to 500 ℃ at the rate of 4-5 ℃/min, the temperature is kept for 2h, then the temperature is raised to 8h at the rate of 1 ℃/min, and the temperature is kept for 2-3 h.
Preferably, in the step (2), the phase transfer catalyst is tetrabutylammonium chloride.
Preferably, in the step (2), the concentration of the dispersion of the phase transfer catalyst is 0.15g/ml, and the ratio of the amount of the nano silica coated on the nitrogen-doped carbon layer to the amount of the dispersion of the phase transfer catalyst is 5: 10-15 ml.
Preferably, in the step (2), the adsorption treatment time is 10-15 h; the drying temperature is 80-100 ℃, and the drying time is 10-20 h.
In order to better solve the technical problems, the invention also provides the following technical scheme:
an application of a supported catalyst with high specific surface area in p-nitroaniline synthesis is specifically as follows: loading a supported catalyst with a high specific surface area into a high-pressure reaction kettle, adding p-nitrochlorobenzene and liquid ammonia, heating to 170 ℃, stirring for reaction, filtering the hot reaction liquid, cooling and crystallizing the filtered liquid, filtering, washing the obtained precipitate, and drying to obtain the target product p-nitroaniline.
Preferably, in the above technical solution, the use amount ratio of the supported catalyst with high specific surface area, the p-nitrochlorobenzene, and the liquid ammonia is 5 g: (31-32) g: 165 ml.
Preferably, the rotation speed of the stirring reaction is 800-.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the catalyst adopted by the invention takes porous silicon oxide as a framework material, and then a nitrogen-doped carbon layer is modified on the surface of the porous silicon oxide to increase the anchoring sites of the catalyst, so that the prepared carrier has large specific surface area and good adsorbability, and can effectively adsorb the phase transfer catalyst in the pores of the phase transfer catalyst, and the prepared catalyst has unique active sites, thereby improving the yield of the product.
The invention takes the p-nitrochlorobenzene and the liquid ammonia as raw materials, ammonolysis is carried out under the action of a self-made supported catalyst to prepare a target product, the catalyst is separated by filtering when the reaction is finished, and the filtered liquid is cooled and crystallized to prepare the target product.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
The porous nano-silica used in the following examples had an average particle size of 2- μmm, a porosity of 60%, and an average pore size of 20-30 nm.
Example 1
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, then adding 75ml of aniline monomer under the condition of ice-water bath, uniformly mixing, then adding 50ml of ammonium persulfate solution with the concentration of 1mol/L, stirring at 3000rpm for reaction for 7h, filtering reaction liquid after the reaction is finished, washing and precipitating by adopting deionized water, drying, placing the dried solid in a muffle furnace under the inert atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2h, then heating to 8h at the speed of 1 ℃/min, preserving heat for 2h, and preparing the nano silicon oxide coated by the nitrogen-doped carbon layer;
(2) adding 5g of the nanometer silicon oxide coated with the prepared nitrogen-doped carbon layer into 10ml of tetrabutylammonium chloride dispersion liquid with the concentration of 0.15g/ml, carrying out adsorption treatment for 10h, and then drying at 80 ℃ for 10h to obtain the nanometer silicon oxide with the specific surface area of 502m2Catalyst with high specific surface area/mgAn oxidizing agent;
(3) 5g of supported catalyst with high specific surface area is loaded into a high-pressure reaction kettle, 31.5g of p-nitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred and reacted for 8 hours at 800rpm, the reaction liquid is filtered while being hot, the filtered liquid is cooled, crystallized and filtered, the obtained precipitate is washed and dried, and the target product p-nitroaniline is prepared, wherein the purity is 99.9%, and the yield is 98.3%.
Example 2
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, then adding 75ml of aniline monomer under the condition of ice-water bath, uniformly mixing, then adding 50ml of ammonium persulfate solution with the concentration of 1mol/L, stirring at 5000rpm for reaction for 7h, filtering reaction liquid after the reaction is finished, washing and precipitating by adopting deionized water, drying, placing the dried solid in a muffle furnace under the inert atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2h, then heating to 8h at the speed of 1 ℃/min, preserving heat for 3h, and preparing the nano silicon oxide coated by the nitrogen-doped carbon layer;
(2) adding 5g of the nano silicon oxide coated with the prepared nitrogen-doped carbon layer into 15ml of tetrabutylammonium chloride dispersion liquid with the concentration of 0.15g/ml, carrying out adsorption treatment for 10h, and then drying at 100 ℃ for 10h to obtain the nano silicon oxide with the specific surface area of 503m2A high specific surface area supported catalyst per mg;
(3) 5g of supported catalyst with high specific surface area is loaded into a high-pressure reaction kettle, 31.5g of p-nitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred and reacted for 8 hours at 1500rpm, the reaction liquid is filtered while being hot, the filtered liquid is cooled, crystallized and filtered, the obtained precipitate is washed and dried, and the target product p-nitroaniline is prepared, wherein the purity is 99.9%, and the yield is 99.1%.
Example 3
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, then adding 75ml of aniline monomer under the condition of ice-water bath, uniformly mixing, then adding 50ml of ammonium persulfate solution with the concentration of 1mol/L, stirring at 3500rpm for reaction for 7h, filtering reaction liquid after the reaction is finished, washing and precipitating by adopting deionized water, drying, placing the dried solid in a muffle furnace under the inert atmosphere, firstly heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2h, then heating to 8h at the speed of 1 ℃/min, preserving heat for 2h, and preparing the nano silicon oxide coated by the nitrogen-doped carbon layer;
(2) adding 5g of the nanometer silicon oxide coated with the nitrogen-doped carbon layer into 11ml of tetrabutylammonium chloride dispersion liquid with the concentration of 0.15g/ml, performing adsorption treatment for 115h, and drying at 100 deg.C for 20h to obtain a specific surface area of 502m2A high specific surface area supported catalyst per mg;
(3) 5g of supported catalyst with high specific surface area is loaded into a high-pressure reaction kettle, 31.5g of p-nitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred and reacted for 8 hours at 900rpm, the reaction liquid is filtered while being hot, the filtered liquid is cooled, crystallized and filtered, the obtained precipitate is washed and dried, and the target product p-nitroaniline is prepared, wherein the purity is 99.9%, and the yield is 98.8%.
Example 4
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, then adding 75ml of aniline monomer under the condition of ice-water bath, uniformly mixing, then adding 50ml of ammonium persulfate solution with the concentration of 1mol/L, stirring at 4000rpm for reaction for 7h, filtering reaction liquid after the reaction is finished, washing and precipitating by adopting deionized water, drying, placing the dried solid in a muffle furnace under the inert atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2h, then heating to 8h at the speed of 1 ℃/min, preserving heat for 3h, and preparing the nano silicon oxide coated by the nitrogen-doped carbon layer;
(2) adding 5g of the nanometer silicon oxide coated with the prepared nitrogen-doped carbon layer into 12ml of tetrabutylammonium chloride dispersion liquid with the concentration of 0.15g/ml, carrying out adsorption treatment for 12h, and then drying at 100 ℃ for 15h to obtain the product with the specific surface area of 501m2A high specific surface area supported catalyst per mg;
(3) 5g of supported catalyst with high specific surface area is loaded into a high-pressure reaction kettle, 31.5g of p-nitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred and reacted for 8 hours at 1000rpm, the reaction liquid is filtered while being hot, the filtered liquid is cooled, crystallized and filtered, the obtained precipitate is washed and dried, and the target product p-nitroaniline is prepared, wherein the purity is 99.9%, and the yield is 98.8%.
Example 5
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, then adding 75ml of aniline monomer under the condition of ice-water bath, uniformly mixing, then adding 50ml of ammonium persulfate solution with the concentration of 1mol/L, stirring at 4500rpm for reaction for 8h, filtering reaction liquid after the reaction is finished, washing and precipitating by adopting deionized water, drying, placing the dried solid in a muffle furnace under the inert atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2h, then heating to 8h at the speed of 1 ℃/min, preserving heat for 3h, and preparing the nano silicon oxide coated by the nitrogen-doped carbon layer;
(2) adding 5g of the nano silicon oxide coated with the prepared nitrogen-doped carbon layer into 13ml of tetrabutylammonium chloride dispersion liquid with the concentration of 0.15g/ml, carrying out adsorption treatment for 14h, and then drying at 90 ℃ for 15h to obtain the nano silicon oxide with the specific surface area of 503m2A high specific surface area supported catalyst per mg;
(3) 5g of supported catalyst with high specific surface area is loaded into a high-pressure reaction kettle, 31.5g of p-nitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred and reacted for 8 hours at 1500rpm, the reaction liquid is filtered while being hot, the filtered liquid is cooled, crystallized and filtered, the obtained precipitate is washed and dried, and the target product p-nitroaniline is prepared, wherein the purity is 99.9%, and the yield is 99.0%.
Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (10)
1. A preparation method of a supported catalyst with high specific surface area is characterized by comprising the following steps:
(1) dispersing porous nano silicon oxide in deionized water, adding an aniline monomer under the condition of ice-water bath, uniformly mixing, adding an ammonium persulfate solution, stirring for reaction, filtering reaction liquid after the reaction is finished, washing and precipitating by using deionized water, drying, and calcining the dried solid in a muffle furnace under an inert atmosphere to prepare nano silicon oxide coated by a nitrogen-doped carbon layer;
(2) and adding the prepared nano silicon oxide coated by the nitrogen-doped carbon layer into the dispersion liquid of the phase transfer catalyst, performing adsorption treatment, and drying to obtain the supported catalyst with high specific surface area.
2. The method for preparing the supported catalyst with high specific surface area according to claim 1, wherein in the step (1), the concentration of the ammonium persulfate solution is 1mol/L, and the dosage ratio of the nano silica to the aniline monomer to the ammonium persulfate solution is 1 g: (7-8) ml: 50 ml.
3. The method as claimed in claim 1, wherein in step (1), the stirring reaction time is 7-8 h, and the rotation speed of the stirring reaction is 3000-5000 rpm.
4. The method for preparing the supported catalyst with high specific surface area according to claim 1, wherein in the step (1), during the calcination treatment, the temperature is first raised to 500 ℃ at a rate of 4-5 ℃/min, and the temperature is kept for 2h, and then raised to 8h at a rate of 1 ℃/min, and the temperature is kept for 2-3 h.
5. The method for preparing the supported catalyst with high specific surface area according to claim 1, wherein in the step (2), the phase transfer catalyst is tetrabutylammonium chloride.
6. The method for preparing the supported catalyst with high specific surface area according to claim 1, wherein in the step (2), the concentration of the dispersion liquid of the phase transfer catalyst is 0.15g/ml, and the ratio of the nano silicon oxide coated by the nitrogen-doped carbon layer to the dispersion liquid of the phase transfer catalyst is 5: 10-15 ml.
7. The method for preparing the supported catalyst with high specific surface area according to claim 1, wherein in the step (2), the adsorption treatment time is 10-15 h; the drying temperature is 80-100 ℃, and the drying time is 10-20 h.
8. The application of the supported catalyst with high specific surface area prepared by the method according to any one of claims 1 to 7 in the synthesis of p-nitroaniline is characterized by comprising the following specific steps: loading a supported catalyst with a high specific surface area into a high-pressure reaction kettle, adding p-nitrochlorobenzene and liquid ammonia, heating to 170 ℃, stirring for reaction, filtering the hot reaction liquid, cooling and crystallizing the filtered liquid, filtering, washing the obtained precipitate, and drying to obtain the target product p-nitroaniline.
9. The application of the supported catalyst with high specific surface area in the synthesis of paranitroaniline according to claim 8, wherein the dosage ratio of the supported catalyst with high specific surface area, the paranitrochlorobenzene and the liquid ammonia is 5 g: (31-32) g: 165 ml.
10. The application of the supported catalyst with high specific surface area in p-nitroaniline synthesis as in claim 8, wherein the rotation speed of the stirring reaction is 800-1500 rpm, and the stirring reaction time is 8-10 h.
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