CN113663727B - Preparation method of supported catalyst with high specific surface area and application of supported catalyst in synthesis of p-nitroaniline - Google Patents
Preparation method of supported catalyst with high specific surface area and application of supported catalyst in synthesis of p-nitroaniline Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 title claims description 8
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 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 35
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 33
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 33
- 239000007788 liquid 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
- 239000012295 chemical reaction liquid Substances 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
- 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
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 239000000047 product 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 11
- 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
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 239000005457 ice water Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 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 9
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 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
- 238000005008 domestic process Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
Classifications
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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
- 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
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- 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 aniline monomer under ice water bath condition, adding ammonium persulfate solution after mixing uniformly, stirring for reaction, filtering reaction liquid after reaction, washing precipitate by adopting deionized water, drying, and calcining the dried solid in a muffle furnace under inert atmosphere to obtain the nano silicon oxide coated by the 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, carrying out adsorption treatment, and then drying to obtain the supported catalyst with high specific surface area. The supported catalyst prepared by the invention has large specific surface area and high catalytic activity, is used for greatly improving the yield and purity of target products when synthesizing p-nitroaniline, has small catalyst dosage, is convenient to recycle, and greatly improves the production cost of the products.
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 synthesizing paranitroaniline.
Background
The p-nitroaniline is an extremely 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 manufacturing azo dyes such as direct blackish green B, acid medium brown G, acid black 10B and the like.
At present, the domestic method for producing paranitroaniline is mainly an amination method of paranitrochlorobenzene. And (3) reacting the paranitrochlorobenzene with concentrated ammonia in a stirred tank for 15-20h at 140-180 ℃ and under the conditions of 3.7-5.5MPa and large excess of liquid ammonia, crystallizing and filtering to obtain the paranitroaniline. The process mainly has the problems of low production efficiency, unstable product quality, poor equipment amplification reliability and the like. It is pointed out that a phase transfer catalyst or the like can be introduced to improve the production efficiency, and the method improves the yield of the product to a great extent, but the catalyst is inconvenient to separate, the use amount is large, and the preparation cost of the product is increased.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects existing in the prior art, the invention provides a preparation method of a supported catalyst with high specific surface area and application thereof in synthesizing paranitroaniline.
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 aniline monomer under ice water bath condition, adding ammonium persulfate solution after mixing uniformly, stirring for reaction, filtering reaction liquid after reaction, washing precipitate by adopting deionized water, drying, and calcining the dried solid in a muffle furnace under inert atmosphere to obtain the nano silicon oxide coated by the 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, carrying out adsorption treatment, and then drying to obtain the supported catalyst with high specific surface area.
As a preferable mode of the above technical scheme, in the step (1), the concentration of the ammonium persulfate solution is 1mol/L, and the dosage ratio of the nano silicon oxide, the aniline monomer and the ammonium persulfate solution is 1g: (7-8) ml:50ml.
As a preferable mode of the technical scheme, in the step (1), the stirring reaction time is 7-8h, and the rotating speed of the stirring reaction is 3000-5000rpm.
As the preferable technical scheme, in the step (1), during the calcination treatment, firstly, the temperature is raised to 500 ℃ at the speed of 4-5 ℃/min, the temperature is kept for 2 hours, then the temperature is raised to 8 hours at the speed of 1 ℃/min, and the temperature is kept for 2-3 hours.
Preferably, in the above technical scheme, in step (2), the phase transfer catalyst is tetrabutylammonium chloride.
As a preferable mode of the above technical scheme, in the step (2), the concentration of the dispersion liquid of the phase transfer catalyst is 0.15g/ml, and the dosage ratio of the dispersion liquid of the nitrogen-doped carbon layer coated nano silicon oxide and the phase transfer catalyst is 5:10-15ml.
As a preferable mode of the technical scheme, in the step (2), the time of the adsorption treatment is 10-15 hours; the drying temperature is 80-100 ℃ and the drying time is 10-20h.
In order to better solve the technical problems, the invention also provides the following technical scheme:
the application of the supported catalyst with high specific surface area in synthesizing paranitroaniline is as follows: loading the supported catalyst with 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 the filtered liquid for crystallization, filtering, washing the obtained precipitate, and drying to obtain the target product p-nitroaniline.
As a preferable mode of the technical scheme, the dosage ratio of the supported catalyst with high specific surface area, the paranitrochlorobenzene and the liquid ammonia is 5g: (31-32) g:165ml.
As the preferable choice of the technical scheme, the rotation speed of the stirring reaction is 800-1500rpm, and the stirring reaction time is 8-10h.
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 the surface of the porous silicon oxide is modified with a nitrogen doped carbon layer to increase the anchoring sites of the catalyst, so that the prepared carrier has large specific surface area and good adsorptivity, can effectively adsorb the phase transfer catalyst in the holes of the catalyst, and has unique active sites, thereby improving the yield of products.
According to the method, paranitrochlorobenzene and liquid ammonia are used as raw materials, a target product is prepared through ammonolysis under the action of a self-made supported catalyst, the catalyst is separated through hot filtration after the reaction is finished, and the filtered liquid is cooled and crystallized to prepare the target product.
Detailed Description
The invention is further illustrated below with reference to examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The porous nano-silica used in the examples below had an average particle diameter of 2 to mu mm, a porosity of 60% and an average pore size of 20 to 30nm.
Example 1
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, adding 75ml of aniline monomer under the condition of ice water bath, adding 50ml of ammonium persulfate solution with the concentration of 1mol/L after uniform mixing, stirring at 3000rpm for reaction for 7 hours, filtering reaction liquid after reaction, washing precipitate by adopting deionized water, drying, placing the dried solid in a muffle furnace under inert atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2 hours, then heating to 8 hours at the speed of 1 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon layer coated nano silicon oxide;
(2) Adding 5g of the nano silicon oxide coated by 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 drying at 80 ℃ for 10h to obtain the nano silicon oxide with the specific surface area of 502m 2 High specific surface area supported catalyst per mg;
(3) 5g of a supported catalyst with high specific surface area is filled into a high-pressure reaction kettle, 31.5g of paranitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred for 8 hours at 800rpm, the reaction liquid is filtered while the reaction liquid is hot, the filtered liquid is cooled for crystallization, the filtered liquid is filtered, the obtained precipitate is washed and dried, and the target product paranitroaniline with the purity of 99.9% and the yield of 98.3% is prepared.
Example 2
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, adding 75ml of aniline monomer under the condition of ice water bath, adding 50ml of ammonium persulfate solution with the concentration of 1mol/L after uniform mixing, stirring at 5000rpm for reaction for 7 hours, filtering reaction liquid after reaction, washing precipitate by adopting deionized water, drying, placing the dried solid in a muffle furnace under inert atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2 hours, then heating to 8 hours at the speed of 1 ℃/min, and preserving heat for 3 hours to obtain the nitrogen-doped carbon layer coated nano silicon oxide;
(2) Adding 5g of the nano silicon oxide coated by 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 drying at 100 ℃ for 10h to obtain the nano silicon oxide with the specific surface area of 503m 2 High specific surface area supported catalyst per mg;
(3) 5g of a supported catalyst with high specific surface area is filled into a high-pressure reaction kettle, 31.5g of paranitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred for 8 hours at 1500rpm, the reaction liquid is filtered while the reaction liquid is hot, the filtered liquid is cooled for crystallization, the filtered liquid is filtered, the obtained precipitate is washed and dried, and the target product paranitroaniline with the purity of 99.9% and the yield of 99.1% is prepared.
Example 3
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, adding 75ml of aniline monomer under the condition of ice water bath, adding 50ml of ammonium persulfate solution with the concentration of 1mol/L after uniform mixing, stirring at 3500rpm for reaction for 7 hours, filtering reaction liquid after reaction, washing precipitate by adopting deionized water, drying, placing the dried solid in a muffle furnace under inert atmosphere, firstly heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, then heating to 8 hours at the speed of 1 ℃/min, and preserving heat for 2 hours to obtain the nitrogen-doped carbon layer coated nano silicon oxide;
(2) Adding 5g of the nano silicon oxide coated by the prepared nitrogen-doped carbon layer into 11ml of tetrabutylammonium chloride dispersion liquid with the concentration of 0.15g/ml, carrying out adsorption treatment for 115 hours, and then drying at 100 ℃ for 20 hours to obtain the nano silicon oxide with the specific surface area of 502m 2 High specific surface area supported catalyst per mg;
(3) 5g of a supported catalyst with high specific surface area is filled into a high-pressure reaction kettle, 31.5g of paranitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred for 8 hours at 900rpm, the reaction liquid is filtered while the reaction liquid is hot, the filtered liquid is cooled for crystallization, the filtered liquid is filtered, the obtained precipitate is washed and dried, and the target product paranitroaniline with the purity of 99.9% and the yield of 98.8% is prepared.
Example 4
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, adding 75ml of aniline monomer under the condition of ice water bath, adding 50ml of ammonium persulfate solution with the concentration of 1mol/L after uniform mixing, stirring at 4000rpm for reaction for 7 hours, filtering reaction liquid after reaction, washing precipitate by adopting deionized water, drying, placing the dried solid in a muffle furnace under inert atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2 hours, then heating to 8 hours at the speed of 1 ℃/min, and preserving heat for 3 hours to obtain the nitrogen-doped carbon layer coated nano silicon oxide;
(2) Adding 5g of the nano silicon oxide coated by 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 nano silicon oxide with the specific surface area of 501m 2 High specific surface area supported catalyst per mg;
(3) 5g of a supported catalyst with high specific surface area is filled into a high-pressure reaction kettle, 31.5g of paranitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred for 8 hours at 1000rpm, the reaction liquid is filtered while the reaction liquid is hot, the filtered liquid is cooled for crystallization, the filtered liquid is filtered, the obtained precipitate is washed and dried, and the target product paranitroaniline with the purity of 99.9% and the yield of 98.8% is prepared.
Example 5
(1) Dispersing 10g of porous nano silicon oxide in 500ml of deionized water, adding 75ml of aniline monomer under the condition of ice water bath, adding 50ml of ammonium persulfate solution with the concentration of 1mol/L after uniform mixing, stirring at 4500rpm for reaction for 8 hours, filtering reaction liquid after reaction, washing precipitate by adopting deionized water, drying, placing the dried solid in a muffle furnace under inert atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min, preserving heat for 2 hours, then heating to 8 hours at the speed of 1 ℃/min, and preserving heat for 3 hours to obtain the nano silicon oxide coated with the nitrogen-doped carbon layer;
(2) Adding 5g of the nano silicon oxide coated by 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 503m 2 High specific surface area supported catalyst per mg;
(3) 5g of a supported catalyst with high specific surface area is filled into a high-pressure reaction kettle, 31.5g of paranitrochlorobenzene and 165ml of liquid ammonia are added, the temperature is raised to 170 ℃, the reaction is stirred for 8 hours at 1500rpm, the reaction liquid is filtered while the reaction liquid is hot, the filtered liquid is cooled for crystallization, the filtered liquid is filtered, the obtained precipitate is washed and dried, and the target product paranitroaniline with the purity of 99.9% and the yield of 99.0% is prepared.
Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (9)
1. The preparation method of the supported catalyst with high specific surface area for synthesizing paranitroaniline is characterized by comprising the following steps:
(1) Dispersing porous nano silicon oxide in deionized water, adding aniline monomer under ice water bath condition, adding ammonium persulfate solution after mixing uniformly, stirring for reaction, filtering reaction liquid after reaction, washing precipitate by adopting deionized water, drying, and calcining the dried solid in a muffle furnace under inert atmosphere to obtain the nano silicon oxide coated by the nitrogen-doped carbon layer; the dosage ratio of the nano silicon oxide, the aniline monomer and the ammonium persulfate solution is 1g: (7-8) ml:50ml;
(2) Adding the prepared nano silicon oxide coated by the nitrogen-doped carbon layer into a dispersion liquid of a phase transfer catalyst, carrying out adsorption treatment, and then drying to obtain the supported catalyst with high specific surface area, wherein the phase transfer catalyst is tetrabutylammonium chloride.
2. The method for preparing a supported catalyst with a high specific surface area for use in p-nitroaniline synthesis according to claim 1, wherein in the step (1), the concentration of the ammonium persulfate solution is 1mol/L.
3. The method for preparing a supported catalyst with high specific surface area for synthesizing para-nitroaniline according to claim 1, wherein in the step (1), the stirring reaction time is 7-8 hours, and the rotating speed of the stirring reaction is 3000-5000rpm.
4. The method for preparing a supported catalyst with high specific surface area for synthesizing paranitroaniline 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, the temperature is kept for 2 hours, then raised to 8 hours at a rate of 1 ℃/min, and the temperature is kept for 2-3 hours.
5. The method for preparing a supported catalyst with high specific surface area for synthesizing paranitroaniline 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 dosage ratio of the dispersion liquid of the nitrogen-doped carbon layer coated nano silicon oxide and the phase transfer catalyst is 5g:10-15ml.
6. The method for preparing a supported catalyst with high specific surface area for use in p-nitroaniline synthesis according to claim 1, wherein in the step (2), the time of the adsorption treatment is 10-15 hours; the drying temperature is 80-100 ℃ and the drying time is 10-20h.
7. The use of a supported catalyst of high specific surface area prepared according to any one of claims 1 to 6 in the synthesis of p-nitroaniline, characterized in that it comprises: loading the supported catalyst with 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 the filtered liquid for crystallization, filtering, washing the obtained precipitate, and drying to obtain the target product p-nitroaniline.
8. The use of the supported catalyst with high specific surface area in the synthesis of paranitroaniline according to claim 7, wherein the dosage ratio of the supported catalyst with high specific surface area to paranitrochlorobenzene to liquid ammonia is 5g: (31-32) g:165ml.
9. The use of the supported catalyst with high specific surface area according to claim 7 in synthesizing paranitroaniline, wherein the rotation speed of the stirring reaction is 800-1500rpm, and the stirring reaction time is 8-10h.
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