CN115304489A - Method for synthesizing parachloroaniline through catalytic hydrogenation of parachloronitrobenzene - Google Patents
Method for synthesizing parachloroaniline through catalytic hydrogenation of parachloronitrobenzene Download PDFInfo
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- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 42
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 238000001338 self-assembly Methods 0.000 claims abstract description 4
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- 239000004005 microsphere Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims 1
- 238000002474 experimental method Methods 0.000 claims 1
- 238000004817 gas chromatography Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 238000006298 dechlorination reaction Methods 0.000 abstract description 8
- 239000003112 inhibitor Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 208000012839 conversion disease Diseases 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 33
- 230000009467 reduction Effects 0.000 description 7
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000005181 nitrobenzenes Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
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- 239000002894 chemical waste Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/399—
-
- B01J35/51—
Abstract
The invention discloses a method for synthesizing parachloroaniline through high-selectivity catalytic hydrogenation of parachloronitrobenzene in a liquid phase system. The method comprises the steps of preparing sulfur-doped carbon nano microspheres (S-mC) with high specific surface area and ordered mesoporous structure by using a water phase synergistic self-assembly and subsequent carbonization method; then, dispersing a certain mass of superfine Pt nanoclusters on an S-mC carrier by a dipping-reduction method to prepare a Pt/S-mC catalyst; the catalyst Pt/S-mC is dispersed in an ethanol solvent, hydrogen is used as a hydrogen source to catalyze p-chloronitrobenzene to synthesize p-chloroaniline by hydrogenation, the reaction conversion rate and the selectivity are both higher than 99%, and the dechlorination reaction is obviously inhibited. In the method, the Pt/S-mC catalyst is simple to prepare and operate, short in production period, mild in condition, good in Pt cluster dispersibility and high in atom utilization rate; in the catalytic p-chloronitrobenzene hydrogenation reaction, a dechlorination inhibitor is not required to be added, hydrogen is used as a hydrogen source, the product selectivity is high, the separation is easy, and the method is economic and environment-friendly.
Description
Technical Field
The invention relates to a method for synthesizing parachloroaniline, in particular to a method for synthesizing parachloroaniline by catalyzing parachloronitrobenzene to hydrogenate in a liquid phase system by taking parachloronitrobenzene as a raw material, pt/S-mC as a catalyst and hydrogen as a hydrogen source.
Background
Para-chloroaniline is an important essenceThe refined chemical product and the organic intermediate are widely applied to the synthesis of fine chemicals such as medicines, dyes, pesticides and the like. Parachloroaniline is usually prepared by reduction of parachloronitrobenzene, and the reduction method mainly comprises a sodium sulfide reduction method, a hydrazine hydrate (potassium borohydride) reduction method, an electrochemical reduction method, a catalytic hydrogenation reduction method and the like. When the p-chloronitrobenzene is reduced by the reducing agent, a large amount of chemical waste is generated and serious environmental pollution is caused; the electrochemical reduction method has the defects of needing special equipment, high energy consumption and the like; the catalytic hydrogenation method for synthesizing p-chloroaniline uses hydrogen as a reducing agent, and has little pollution to the environment. However, achieving high selectivity to p-chloroaniline under catalytic hydrogenation conditions is a great challenge because p-chloronitrobenzene contains two functional groups, in-NO 2 Is reduced to-NH 2 At the same time, the carbon-chlorine bond is also broken to produce dechlorination byproducts. Therefore, the development of the catalyst capable of realizing the high-selectivity hydrogenation of the halogenated nitrobenzene under the mild condition has great significance. Currently, there are two main methods for inhibiting hydrodechlorination: firstly, dechlorination inhibitor is added, and secondly, the catalyst is modified. The addition of hydrodechlorination inhibitors such as thiophene, morpholine and diethylamine can reduce the catalyst reactivity and make it difficult to separate the dechlorination inhibitors from the product. Therefore, the activity of the catalyst can be regulated and controlled by adjusting the interaction between the carrier and the active metal component, so that the selectivity of the parachloroaniline is improved.
In recent years, researchers have developed various catalysts using noble metals or metal alloys as active sites, which are used for catalyzing p-chloronitrobenzene to synthesize p-chloroaniline in different systems. For example, the literature (nat. Catal.,4 (2021) 840-849) reports atomic layer deposition on Au/SiO 2 Depositing a Pt monoatomic layer on the catalyst to obtain an Au @1ML-Pt catalyst which has obvious activity on the hydrogenation reaction of the halogenated nitrobenzene and high reaction selectivity; however, the equipment for the preparation of the catalyst is expensive and the process is complicated. Therefore, there is a need to develop a simple, economical and environment-friendly catalyst preparation method to realize high selectivity and high activity of p-chloronitrobenzene hydrogenation. Of the many noble metals, au and Pt can be used for catalytic hydrogenation reactions. Literature (J.Catal., 242 (2006) 227-230) reportsAu/SiO 2 The p-chloronitrobenzene is subjected to high-selectivity hydrogenation reaction, but the reaction conditions are harsh, and the reaction needs to be carried out at 140 ℃ under the hydrogen pressure of 4.0MPa, because the active site of Au is difficult to dissociate H 2 . Among the catalysts reported in many documents, platinum-based catalysts have strong hydrogen activation capability and are proved to be good active metals for catalytic hydrogenation reactions. Meanwhile, the specific surface area and the pore structure of the carrier also influence the catalytic hydrogenation performance of the active metal sites, and the literature (RSC adv.,10 (2020) 14208-14216) compares Pt/Al 2 O 3 And Pt/Al 2 O 3 The @ NC catalyst can obviously inhibit dechlorination when a nitrogen-containing doped carbon material is used as a carrier; with Pt/Al 2 O 3 When the catalyst is used, the selectivity of parachloroaniline is low. Therefore, the heteroatom-doped porous carrier with high specific surface area is accurately designed, the superfine Pt nanocluster supported catalyst is prepared, and the catalytic synthesis of p-chloroaniline through high-selectivity hydrogenation of p-chloronitrobenzene under mild conditions is of great significance.
Disclosure of Invention
The invention provides a method for synthesizing parachloroaniline by catalytic hydrogenation by taking parachloronitrobenzene as a raw material, which is characterized in that hydrogen is taken as a hydrogen source in a liquid phase system, and a metal catalyst is added to catalyze the parachloronitrobenzene to synthesize the parachloroaniline (shown as the following formula). The method comprises providing an efficient and economical catalyst preparation method, wherein the catalyst is Pt/S-mC and is mixed with Pt/g-C 3 N 4 The catalytic activity of (2) was compared.
The technical scheme is as follows for solving the technical problem of the invention:
a method for synthesizing parachloroaniline by catalytic hydrogenation of parachloronitrobenzene comprises the following steps: adding a certain amount of Pt/S-mC catalyst and p-chloronitrobenzene into a reactor, adding a proper amount of solvent, filling hydrogen into the reactor, setting the reaction temperature, determining reaction products by using a gas chromatograph and a gas chromatograph, and analyzing the conversion rate of the p-chloronitrobenzene and the yield of the p-chloroaniline.
The solvent is absolute ethyl alcohol.
The reaction temperature is 40-80 ℃, and the reaction time is 150 minutes.
The hydrogen pressure is 1atm.
The dosage of the catalyst is 4wt% -8wt% of the mass of the p-chloronitrobenzene.
The catalyst is Pt/S-mC, and the specific preparation method is as follows: the sulfur-doped carbon nano-microsphere (S-mC) with high specific surface area and ordered mesoporous structure is prepared by taking phenol and 4-hydroxythiophenol as a carbon source and a sulfur source, taking the block copolymer F127 as a template agent and removing the template agent through water phase synergistic self-assembly and subsequent carbonization. Then, preparing a catalyst by an impregnation-reduction method, ultrasonically dispersing a certain mass of S-mC carrier in distilled water, dripping an aqueous solution containing a certain mass of chloroplatinic acid into the mixed solution, fully stirring and impregnating, removing the solvent by suction filtration, placing the obtained sample in a tubular furnace, raising the temperature to 300 ℃ by a program, and roasting in a hydrogen/argon mixed gas for 2 hours to obtain the Pt/S-mC catalyst.
The Pt content in the Pt/S-mC catalyst is 1wt% -5wt%.
The reducing mixed gas is H 2 /Ar＝5％。
The invention has the advantages that: 1. the Pt/S-mC catalyst designed by the invention is prepared by water phase synergistic self-assembly, subsequent high-temperature carbonization and a simple dipping-reduction method, and the superfine Pt nanoclusters are uniformly dispersed on the carrier; 2. the catalytic hydrogenation activity is regulated and controlled through the interaction between the carrier and the metal, p-chloronitrobenzene is catalyzed to be hydrogenated and synthesized into p-chloroaniline with high selectivity, the conversion rate and the selectivity are both more than 99 percent, and the dechlorination reaction is obviously inhibited; 3. the catalytic hydrogenation method provided by the invention does not need to add a dechlorination inhibitor in the reaction, and the product is easy to separate, simple to operate, economic and environment-friendly and has better application prospect.
Drawings
FIG. 1 is a scanning electron microscope and a transmission electron microscope image of the S-mC carrier (a-b) and Pt/S-mC catalyst (c) prepared in example 1 of the present invention.
FIG. 2 is a graph showing Pt/g-C prepared in comparative example 1 of the present invention 3 N 4 Transmission electron micrograph of catalyst.
Detailed Description
Example 1
A method for synthesizing a Pt/S-mC catalyst comprises the following specific steps: 0.3g of phenol and 0.4g of 4-hydroxythiophenol were first dissolved in 0.1M aqueous NaOH solution. After stirring for 10min, 3.2mL of 37% formaldehyde solution was added dropwise, and the mixture was stirred at 70 ℃ and 350 rpm for 1 hour. Subsequently, 0.96g of the block copolymer F127 was dissolved in 15mL of distilled water, added to the above mixed solution, and stirred at 66 ℃ for 2 hours. Then 50mL of distilled water are added and stirred at 70 ℃ for 16-18h until precipitation occurs. After the precipitate was dissolved, 62mL of distilled water was added, and the mixture was transferred to a hydrothermal reactor and reacted at 130 ℃ for 24 hours. The resulting mixed solution was filtered and washed with distilled water 3 times to obtain a yellow sample. And finally, carbonizing the solid sample at 380 ℃ for 6h, then heating to 800 ℃ at the speed of 1 ℃/min, and roasting for 3h to obtain the S-mC carrier material. And then, ultrasonically dispersing 100mg of S-mC in 50mL of distilled water for 30min, dropwise adding a chloroplatinic acid aqueous solution, violently stirring at room temperature for 24 hours, removing the solvent by suction filtration, placing the obtained sample in a tubular furnace, heating to 300 ℃ at the speed of 5 ℃/min, and roasting in a hydrogen/argon mixed gas for 2 hours to obtain the Pt/S-mC catalyst, wherein the Pt content in the catalyst is 1-5%.
Example 2
A method for synthesizing parachloroaniline by catalytic hydrogenation of parachloronitrobenzene comprises the following specific steps: 10mg of Pt/S-mC catalyst (1%) was charged in a 10mL reactor, 78.8mg of p-chloronitrobenzene and 3mL of ethanol were added thereto, and the reactor was purged with hydrogen gas to displace the air therein, and then the mixture was allowed to react at 80 ℃ for 150 minutes under a hydrogen atmosphere. The conversion rate of p-chloronitrobenzene is 47.5 percent and the selectivity of p-chloroaniline is 99.1 percent by using a gas chromatograph.
Example 3
A method for synthesizing p-chloroaniline from p-chloronitrobenzene through catalytic hydrogenation specifically comprises the following steps: 10mg of a Pt/S-mC catalyst (3%), 78.8mg of p-chloronitrobenzene and 3mL of ethanol were placed in a 10mL reactor, and after displacing the air in the reactor by introducing hydrogen gas, the reactor was allowed to react at 80 ℃ for 150 minutes in a hydrogen atmosphere. The conversion rate of p-chloronitrobenzene is 99.9 percent and the selectivity of p-chloroaniline is 99.3 percent by using a gas chromatograph.
Example 4
A method for synthesizing parachloroaniline by catalytic hydrogenation of parachloronitrobenzene comprises the following specific steps: 10mg of 5% Pt/S-mC catalyst, 78.8mg of p-chloronitrobenzene, and 3mL of ethanol were placed in a 10mL reactor, and after displacing the air in the reactor by introducing hydrogen gas, the reactor was allowed to react at 80 ℃ for 150 minutes under a hydrogen atmosphere. The conversion rate of p-chloronitrobenzene is 99.9 percent and the selectivity of p-chloroaniline is 98.0 percent by using a gas chromatograph.
Example 5
Centrifuging the mixed solution after the reaction in the embodiment 3 to remove the solvent and the reactant, washing the mixed solution with absolute ethyl alcohol for multiple times, drying the obtained solid catalyst in a vacuum drying oven at 30 ℃ overnight, and then carrying out catalyst reusability test on the recovered catalyst according to the method in the embodiment 3; after 5 times of recovery and repeated use, the conversion rate of p-chloronitrobenzene is still 99.9 percent, and the selectivity of p-chloroaniline is 98.8 percent, which shows that the catalyst recovered by 5 times of circulation still has high catalytic activity, and the superfine Pt nanoclusters are stably anchored on the carrier S-mC.
Comparative example 1
Synthetic Pt/g-C 3 N 4 The method of the catalyst comprises the following specific steps: 100mg of g-C 3 N 4 Dispersing in 50mL of distilled water, performing ultrasonic treatment for 30min to uniformly disperse the solution, dropwise adding chloroplatinic acid aqueous solution, vigorously stirring for 24 hours, removing the solvent by suction filtration, placing the obtained sample in a tubular furnace, heating to 300 ℃ at the speed of 5 ℃/min, and roasting in a hydrogen/argon mixed gas for 2 hours to obtain Pt/g-C 3 N 4 The catalyst has a Pt content of 3%. Pt/g-C 3 N 4 The method for catalyzing p-chloronitrobenzene hydrogenation by the catalyst is the same as the embodiment 3, and the specific method is as follows: 3% of Pt/g-C prepared in the above comparative example 1 3 N 4 The catalyst was used in the p-chloronitrobenzene hydrogenation reaction, was 10mg 3% of Pt/g-C 3 N 4 Catalyst and process for preparing same78.8mg of p-chloronitrobenzene and 3mL of ethanol were placed in a 10mL reactor, and after introducing hydrogen gas to displace the air in the reactor, the reactor was allowed to react for 150 minutes at 80 ℃ under a hydrogen atmosphere. The conversion rate of p-chloronitrobenzene is 99.9 percent and the selectivity of p-chloroaniline is only 73.2 percent by using a gas chromatograph.
Claims (7)
1. A method for synthesizing parachloroaniline by catalytic hydrogenation of parachloronitrobenzene is characterized by comprising the following steps: preparing sulfur-doped carbon nano microspheres (S-mC) with high specific surface area and ordered mesoporous structure by taking phenol and 4-hydroxythiophenol as a carbon source and a sulfur source and taking a block copolymer F127 as a template agent through a method of water phase synergistic self-assembly and subsequent carbonization for removing the template agent; then ultrasonically dispersing a certain mass of S-mC carrier in distilled water by an impregnation-reduction method, dripping an aqueous solution containing a certain mass of chloroplatinic acid into the mixture, fully stirring and impregnating, removing the solvent by suction filtration, placing the obtained sample in a tubular furnace, raising the temperature to 300 ℃ by a program, and roasting and reducing the sample in a hydrogen/argon mixed gas for 2 hours to obtain a Pt/S-mC catalyst; adding a Pt/S-mC catalyst, p-chloronitrobenzene and an absolute ethyl alcohol solvent into a reactor, introducing hydrogen to replace air in the reactor, reacting for 150 minutes at 80 ℃, and catalyzing the p-chloronitrobenzene to synthesize the p-chloroaniline through high-selectivity hydrogenation.
2. The process for producing p-chloroaniline according to claim 1, characterized in that: the content of Pt in the Pt/S-mC catalyst is 1-5wt%, the ultrafine Pt nanoclusters in the Pt/S-mC catalyst are uniformly dispersed on a carrier, and the average particle size of the ultrafine Pt nanoclusters is 1.42nm.
3. The process for producing p-chloroaniline according to claim 1, wherein: in the preparation method of the Pt/S-mC catalyst, the reducing atmosphere is H 2 Ar =5%, and the rate of temperature rise is 5 ℃/min.
4. The process for producing p-chloroaniline according to claim 1, wherein: the solvent of the p-chloronitrobenzene hydrogenation reaction is absolute ethyl alcohol, the reaction temperature is 40-80 ℃, and the reaction time is 150 minutes.
5. The process for producing p-chloroaniline according to claim 1, wherein: in the p-chloronitrobenzene hydrogenation reaction, hydrogen is used as a reducing agent, the hydrogen pressure is 1atm, and the dosage of a catalyst Pt/S-mC is 4-8wt% of the p-chloronitrobenzene.
6. The process for producing p-chloroaniline according to claim 1, wherein: the conversion rate of the p-chloronitrobenzene is up to 99.9 percent and the selectivity of the p-chloroaniline is up to 99.3 percent by utilizing gas chromatography and mass chromatograph detection.
7. The process for producing p-chloroaniline according to claim 1, wherein: in the synthesis of p-chloroaniline by hydrogenation of p-chloronitrobenzene catalyzed by the catalyst Pt/S-mC, the conversion rate of the p-chloronitrobenzene is still 99.9 percent and the selectivity of the p-chloroaniline is 98.8 percent after 5 times of recovery experiments.
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| CN202210799201.7A CN115304489A (en) | 2022-07-06 | 2022-07-06 | Method for synthesizing parachloroaniline through catalytic hydrogenation of parachloronitrobenzene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116459857A (en) * | 2023-04-24 | 2023-07-21 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
| CN116651442A (en) * | 2023-06-15 | 2023-08-29 | 西北工业大学 | Surface-confined atomic-level dispersed Pt@SiO 2 -N catalyst, preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116459857A (en) * | 2023-04-24 | 2023-07-21 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
| CN116459857B (en) * | 2023-04-24 | 2024-04-19 | 安徽大学 | High-selectivity catalyst Co/NS800, preparation method thereof and method for selectively hydrogenating p-chloronitrobenzene in heterogeneous system |
| CN116651442A (en) * | 2023-06-15 | 2023-08-29 | 西北工业大学 | Surface-confined atomic-level dispersed Pt@SiO 2 -N catalyst, preparation method and application thereof |
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