CN117384006A - Preparation method of bromobenzene - Google Patents

Preparation method of bromobenzene Download PDF

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CN117384006A
CN117384006A CN202311674715.0A CN202311674715A CN117384006A CN 117384006 A CN117384006 A CN 117384006A CN 202311674715 A CN202311674715 A CN 202311674715A CN 117384006 A CN117384006 A CN 117384006A
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micro
reaction
catalyst
bromobenzene
primary
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CN117384006B (en
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李荣彬
赵守俊
刘万林
张�杰
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Shouguang Chengxin Salt Industry Co ltd
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Shouguang Chengxin Salt Industry Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00867—Microreactors placed in series, on the same or on different supports

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a preparation method of bromobenzene, and belongs to the field of bromobenzene preparation. The preparation method of bromobenzene comprises the following steps: primary micro-reaction, secondary micro-reaction, tertiary micro-reaction and refining. The preparation method of bromobenzene can further improve the purity and the yield of the bromobenzene, reduce the consumption of raw materials and catalysts, avoid the generation of byproduct impurities in the reaction process, simplify the operation process of preparation and purification, and improve the reaction controllability; and purification processes such as water washing impurity removal, layering, drying and the like are not needed, so that the generation of water washing wastewater, solid waste and the like is avoided, and the environmental friendliness is improved.

Description

Preparation method of bromobenzene
Technical Field
The invention relates to the field of bromobenzene preparation, in particular to a bromobenzene preparation method.
Background
Bromobenzene, also known as monobromobenzene, phenylbromine, of formula C 6 H 5 Br is a colorless oily liquid, and has a benzene smell. Bromobenzene is insoluble in water, soluble in methanol and ethylThe organic solvents such as ether and acetone are mainly used in the fields of solvents, analysis reagents, organic synthesis and the like.
In the field of fine chemical engineering, bromobenzene can be used as a raw material of pressure-sensitive dye and heat-sensitive dye and a raw material of diphenyl ether series perfume. In the field of pesticide production, bromobenzene can be used as a pesticide raw material, for example, bromobenzene can be used for producing broad-spectrum, long-acting and low-toxicity pesticide fenpyroximate. In the field of medicine production, bromobenzene can be used as a starting material of medicine molecules to produce medicines with the effects of easing pain, relieving fever, relieving cough and the like. In addition, bromobenzene is commonly used for coupling derivatization in transition metal catalytic reactions in organic synthesis, and can perform coupling reaction with different compounds to synthesize various arylate products.
In the prior art, the preparation method of bromobenzene mainly adopts a bromine bromination method. Specifically, benzene is used as a raw material, bromine is dropwise added for reaction under the catalysis of iron powder or ferric trichloride, bromobenzene and hydrogen bromide are prepared by the reaction, then the bromobenzene is subjected to refining treatment, and tail gas absorption and other treatments are carried out on the hydrogen bromide. The method has the advantages of simple and controllable reaction process, but in the preparation process, the application amount of the catalyst iron powder or ferric trichloride is large, impurities are easy to generate, and the quality of the prepared bromobenzene product is influenced. Meanwhile, the method of directly brominating bromine has the problems of large bromine consumption, large raw material consumption and high production cost; and the byproduct contains impurities such as polybrominated benzene and the like, the content of the byproduct is higher, the subsequent separation and purification operation is complex, and the purity and the yield of the prepared bromobenzene product are affected. Further, because hydrogen bromide is produced in the process of preparing bromobenzene at the same time, the bromobenzene can be distilled and purified later only by adopting alkali solution to carry out refining and purifying processes such as water washing impurity removal, layering, drying and the like, so that the production efficiency is low, a large amount of water washing wastewater and solid waste containing organic pollutants can be produced, the environment friendliness is poor, the post-treatment difficulty is high, and the comprehensive production cost is high.
Chinese patent CN104086353a discloses a process for synthesizing bromobenzene, which uses iron powder as catalyst, and adds bromine into benzene at normal temperature to generate hydrogen chloride gas, and then heats to 70-80 ℃ to carry out bromination reaction; and after the bromination reaction is finished, washing by adopting 5% sodium hydroxide solution in sequence, drying by adopting anhydrous calcium chloride, and then carrying out distillation and purification to obtain bromobenzene. However, the mass ratio of the catalyst iron powder to benzene reaches 1:3, and the excessive addition of the iron powder can cause the quality reduction of bromobenzene products; the consumption of the bromine is large, the reaction economy is poor, and the production cost is high; impurities such as polybrominated benzene and the like can be produced as by-products; meanwhile, in order to remove impurities and purify, a large amount of washing wastewater and solid waste can be generated in the processes of washing impurities, layering and drying the crude bromobenzene product, so that the post-treatment difficulty and the production cost are further improved, and the environment friendliness is poor.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of bromobenzene, which can further improve the purity and yield of the bromobenzene prepared, reduce the consumption of raw materials and catalysts, avoid the generation of byproduct impurities in the reaction process, simplify the operation process of preparation and purification and improve the reaction controllability; and purification processes such as water washing impurity removal, layering, drying and the like are not needed, so that the generation of water washing wastewater, solid waste and the like is avoided, and the environmental friendliness is improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of bromobenzene comprises the following steps: primary micro-reaction, secondary micro-reaction, tertiary micro-reaction and refining.
The primary micro-reaction method comprises the steps of introducing benzene into a pre-cooling tank, cooling to 7-8 ℃, metering by a first flowmeter, and feeding the benzene into a first micro-reactor through a first feeding port of a micro-channel reaction device by a first peristaltic pump; meanwhile, bromine chloride is discharged from a storage steel bottle, is metered by a second flowmeter, and is fed into the first micro-reactor through a second feeding port of the micro-channel reaction device by a second peristaltic pump; controlling the temperature of the first micro-reaction at 7-8 ℃, the vacuum degree of the first micro-reaction at 0.02-0.03MPa, and the material retention time at 480-600s, and obtaining a first micro-reaction liquid after the first micro-reaction;
and hydrogen chloride gas generated in the first micro-reaction process is led out from the first micro-reactor to a tail gas treatment device for tail gas treatment.
In the primary micro-reaction, the molar ratio of benzene to bromine chloride is 1:1.01-1.03; the feeding rate ratio of benzene to bromine chloride is 1:1.49-1.52;
the first microreactor is filled with a catalyst, and the filling amount of the catalyst is 0.7-0.8wt% of the total mass of benzene in the material residence time in one microreactor.
The catalyst is prepared by the following steps: primary compounding, secondary compounding, and tertiary compounding.
The primary compounding method comprises the steps of adding ferric trichloride and titanium tetrachloride into a mixed solvent, and performing ultrasonic dispersion for 20-30min; then stirring and adding sodium acetate at a feeding rate of 0.4-0.5g/min, and continuing stirring for 10-20min after the adding is completed; then transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be increased to 180-190 ℃, preserving heat for 8-10 hours, naturally cooling to normal temperature, separating out solid matters, washing the solid matters with deionized water for 2-3 times, and drying at 85-95 ℃ for 16-18 hours to obtain dried matters; then putting the dried substance into an ethanol solution with the weight being 90-95 times that of the dried substance, stirring for 10-20min, continuously adding ammonia water, performing ultrasonic dispersion for 10-20min, continuously adding tetraethoxysilane, performing ultrasonic dispersion for 5-6h at normal temperature, separating out solid substances, washing the solid substances with deionized water for 2-3 times, and drying at 70-75 ℃ for 22-24h to obtain the primary compound.
In the primary compounding, the weight ratio of the ferric trichloride to the titanium tetrachloride to the sodium acetate to the mixed solvent is 1.4-1.5:0.9-1:3.4-3.5:50-55;
the mixed solvent is a mixture of glycol and deionized water, and the volume ratio of the glycol to the deionized water is 6.5-7:3-3.5;
the volume concentration of the ethanol solution is 82-85%;
the mass concentration of the ammonia water is 24-25wt%;
the weight ratio of the dry matter to the ammonia water to the tetraethoxysilane is 1:5.4-5.5:5-5.2.
The secondary compounding method comprises the steps of adding aluminum chloride and zirconium chloride into N, N-dimethylformamide, stirring for 20-30min, continuously adding primary compound and mesoporous activated carbon, uniformly dispersing by ultrasonic, continuously adding phthalic acid, stirring for 20-30min, transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be 130-140 ℃, keeping the temperature and stirring for 14-15h, naturally cooling to normal temperature, separating out solid matters, washing the solid matters with deionized water for 2-3 times, and placing in an environment with the vacuum degree of 0.05-0.07MPa, and drying at the temperature of 65-70 ℃ for 8-10h to obtain the secondary compound.
In the secondary compounding, the weight ratio of aluminum chloride to zirconium chloride to primary compound to mesoporous activated carbon to phthalic acid to N, N-dimethylformamide is 18-20:20-22:7-8:2-2.2:33-35:1100-1200.
The three-time compounding method is that the secondary compound is put into 5-6 times volume of treatment liquid, stirred and heated to 40-45 ℃, kept at a temperature and stirred for 10-12 hours, the solid is filtered out, washed for 2-3 times by deionized water, placed in an environment with the vacuum degree of 0.08-0.09MPa, dried for 10-12 hours at the temperature of 80-85 ℃, and granulated to the particle size of 0.3-0.35mm, and the catalyst is prepared.
In the three-time compounding, the treatment fluid is an absolute ethanol solution of aluminum tribromide and lanthanum cerium chloride; in the treatment liquid, the mass concentration of aluminum tribromide is 3.2-3.5%, and the mass concentration of lanthanum cerium chloride is 1.5-1.7%.
The method for the secondary micro-reaction comprises the steps of feeding a first micro-reaction liquid obtained by the first micro-reaction into a second micro-reactor, controlling the temperature of the second micro-reaction to be 7-8 ℃, controlling the vacuum degree of the second micro-reaction to be 0.02-0.03MPa, and controlling the material retention time to be 300-420s, so as to obtain a second micro-reaction liquid after the second micro-reaction;
hydrogen chloride gas generated in the second micro-reaction process is led out from the second micro-reactor to a tail gas treatment device for tail gas treatment;
the second microreactor is filled with a catalyst, the catalyst is the same as the catalyst in the first microreactor, and the catalyst filling amount is 50-60wt% of the catalyst mass in the first microreactor.
Feeding a second micro-reaction liquid obtained by the second micro-reaction into a third micro-reactor, controlling the temperature of the third micro-reaction to be 25-30 ℃, controlling the vacuum degree of the third micro-reaction to be 0.02-0.03MPa, and controlling the material retention time to be 180-240s, so as to obtain a third micro-reaction liquid after the third micro-reaction; introducing the third micro-reaction liquid into an intermediate product tank for later use;
the gas generated in the third micro-reaction process is led out from the third micro-reactor to a tail gas treatment device for tail gas treatment;
the third microreactor is filled with a catalyst, the catalyst is the same as the catalyst in the first microreactor, and the filling amount of the catalyst is 50-60wt% of the mass of the catalyst in the first microreactor.
The refining method comprises the steps of filtering a third micro-reaction liquid in an intermediate product tank, introducing the third micro-reaction liquid into an atmospheric distillation device, carrying out heat preservation distillation for 45-60min at the temperature of 138-140 ℃, and removing light component impurities; heating to 155-157 ℃, preserving heat and distilling, controlling the reflux ratio to be 1:2-2.5, and collecting light components to prepare bromobenzene.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of bromobenzene, the primary micro-reaction, the secondary micro-reaction, the tertiary micro-reaction and the refining step are adopted to cooperate, and the micro-reaction temperature, the pressure and the residence time are set in a targeted manner for different reaction stages in the primary micro-reaction, the secondary micro-reaction and the tertiary micro-reaction processes respectively; meanwhile, a catalyst prepared by a specific method is adopted in the primary micro-reaction, the secondary micro-reaction and the tertiary micro-reaction; in the preparation of the catalyst, the primary composite is prepared by adopting ferric oxide, titanium dioxide and silicon dioxide to be matched in the primary composite, so that the primary composite which has a large number of active sites capable of being effectively combined with other catalytic components and has certain catalytic activity is prepared; then combining the primary compound, the mesoporous activated carbon and an aluminum-zirconium metal organic framework to prepare a secondary compound with certain catalytic activity; then, the secondary compound and the treatment fluid containing aluminum tribromide and lanthanum cerium chloride are subjected to tertiary compounding to prepare the catalyst with low addition, good low-temperature catalytic activity and good long-term catalytic performance; the purity and the yield of the prepared bromobenzene can be further improved, the consumption of raw materials and catalysts is reduced, the generation of byproduct impurities in the reaction process is avoided, the operation processes of preparation and purification are simplified, and the reaction controllability is improved; and purification processes such as water washing impurity removal, layering, drying and the like are not needed, so that the generation of water washing wastewater, solid waste and the like is avoided, and the environmental friendliness is improved.
(2) According to the preparation method of bromobenzene, bromine chloride is adopted as a brominating reagent, so that the problems of high bromine consumption, easiness in generating impurities such as polybrominated benzene and the like, high post-treatment difficulty and high production cost existing in the traditional technology of directly brominating with bromine are effectively avoided; meanwhile, the loading of the catalyst in the primary micro-reaction is 0.7-0.8wt% of the total mass of benzene in the material residence time in the primary micro-reaction; the loading of the catalyst in the secondary micro-reaction is 50-60wt% of the mass of the catalyst in the first micro-reactor; the loading of the catalyst in the three times of micro-reactions is 50-60wt% of the mass of the catalyst in the first micro-reactor; can obtain good low-temperature catalytic reaction effect under the condition of low catalyst usage amount and low temperature (7-8 ℃).
(3) According to the preparation method of bromobenzene, the HPLC purity of the bromobenzene is 99.51-99.58wt% and the yield is 94.3-94.7%; and the continuous production of the p-bromobenzene can be realized, the purity and the yield of the prepared bromobenzene can be improved, the reaction efficiency can be further improved, and the continuous mass production of the bromobenzene is facilitated.
(4) According to the preparation method of bromobenzene, the catalyst has good long-term catalytic performance, and after 180 days of continuous use, the HPLC purity of the bromobenzene is 99.37-99.42wt% and the yield is 91.9-92.6%; meanwhile, after 180 days of continuous use, the optimal addition amount of the catalyst in the first micro-reactor is 0.78wt percent, the optimal catalytic temperature value is 7.6 ℃, the catalyst can still adapt to the existing reaction conditions, and the catalytic performance attenuation is reduced.
(5) The preparation method of bromobenzene has the advantages of simple process, easy control and simple post-refining, and effectively reduces the energy consumption for bromobenzene production; and a large amount of waste water and solid waste are not generated in the preparation process, so that the production cost of bromobenzene is further reduced.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A preparation method of bromobenzene comprises the following specific scheme:
1. primary microreaction
Benzene is led into a pre-cooling tank, cooled to 7 ℃, and then metered by a first flowmeter, and fed into a first micro-reactor through a first feed inlet of a micro-channel reaction device by adopting a first peristaltic pump; meanwhile, bromine chloride is discharged from a storage steel bottle, is metered by a second flowmeter, and is fed into the first micro-reactor through a second feeding port of the micro-channel reaction device by a second peristaltic pump; the temperature in the first micro-reactor (namely the first micro-reaction temperature) is controlled to be 7 ℃, the vacuum degree in the first micro-reactor (namely the first micro-reaction pressure) is controlled to be 0.02MPa, the material residence time is 480s, and the first micro-reaction liquid is obtained after the first micro-reaction.
Meanwhile, hydrogen chloride gas generated in the first micro-reaction process is led out from the first micro-reactor to a tail gas treatment device for tail gas treatment.
In one micro-reaction, the molar ratio of benzene to bromine chloride is 1:1.01.
The feed rate ratio of benzene to bromine chloride was 1:1.49; in this example, the benzene feed rate to the first microreactor was 0.1kg/s; bromine chloride was fed to the first microreactor at a feed rate of 0.149kg/s.
The first microreactor is filled with a catalyst, and the filling amount of the catalyst is 0.7 weight percent of the total mass of benzene in the material residence time in one microreactor.
The catalyst is prepared by the following steps:
1) Disposable composite
Adding ferric trichloride and titanium tetrachloride into a mixed solvent, and performing ultrasonic dispersion for 20min; then stirring and adding sodium acetate at a feeding rate of 0.4g/min, and continuing stirring for 10min after the adding is completed; then transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be increased to 180 ℃, preserving heat for 8 hours, naturally cooling to normal temperature, separating out solid matters, washing the solid matters with deionized water for 2 times, and drying at 85 ℃ for 16 hours to obtain dried matters; then putting the dried substance into an ethanol solution with the weight being 90 times that of the dried substance, stirring for 10min, continuously adding ammonia water, performing ultrasonic dispersion for 10min, continuously adding tetraethoxysilane, performing ultrasonic dispersion for 5h at normal temperature, separating out a solid substance, washing the solid substance with deionized water for 2 times, and drying at 70 ℃ for 22h to obtain the primary compound.
Wherein, the weight ratio of the ferric trichloride, the titanium tetrachloride, the sodium acetate and the mixed solvent is 1.4:0.9:3.4:50.
The mixed solvent is a mixture of glycol and deionized water, and the volume ratio of the glycol to the deionized water is 6.5:3.
The volume concentration of the ethanol solution was 82%.
The mass concentration of the ammonia water was 24wt%.
The weight ratio of the dry matter to the ammonia water to the tetraethoxysilane is 1:5.4:5.
2) Secondary compounding
Adding aluminum chloride and zirconium chloride into N, N-dimethylformamide, stirring for 20min, continuously adding the primary compound and mesoporous activated carbon, uniformly dispersing by ultrasonic, continuously adding phthalic acid, stirring for 20min, transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be 130 ℃, preserving heat and stirring for 14h, naturally cooling to normal temperature, separating out solid matters, washing the solid matters with deionized water for 2 times, placing in an environment with the vacuum degree of 0.05MPa, and drying at 65 ℃ for 8h to obtain the secondary compound.
Wherein the weight ratio of aluminum chloride, zirconium chloride, primary compound, mesoporous activated carbon, phthalic acid and N, N-dimethylformamide is 18:20:7:2:33:1100.
3) Three times of compounding
And (3) putting the secondary compound into a treatment solution with the volume being 5 times that of the secondary compound, stirring and heating to 40 ℃, preserving heat and stirring for 10 hours, filtering out solid matters, washing the solid matters with deionized water for 2 times, placing in an environment with the vacuum degree of 0.08MPa, drying at 80 ℃ for 10 hours, and granulating to obtain the catalyst with the particle size of 0.3 mm.
Wherein the treatment fluid is an absolute ethanol solution of aluminum tribromide and lanthanum cerium chloride; in the treatment liquid, the mass concentration of aluminum tribromide is 3.2%, and the mass concentration of lanthanum cerium chloride is 1.5%.
2. Secondary microreaction
The first micro-reaction liquid obtained by the first micro-reaction is fed into a second micro-reactor, the temperature in the second micro-reactor (namely the second micro-reaction temperature) is controlled to be 7 ℃, the vacuum degree in the second micro-reactor (namely the second micro-reaction pressure) is controlled to be 0.02MPa, the material residence time is 300s, and the second micro-reaction liquid is obtained after the second micro-reaction is carried out.
Meanwhile, hydrogen chloride gas generated in the second micro-reaction process is led out from the second micro-reactor to a tail gas treatment device for tail gas treatment.
The second microreactor is filled with a catalyst, the catalyst is the same as the catalyst in the first microreactor, and the filling amount of the catalyst is 50wt% of the mass of the catalyst in the first microreactor.
3. Three microreaction
Feeding a second micro-reaction liquid obtained by the second micro-reaction into a third micro-reactor, controlling the temperature in the third micro-reactor (namely the third micro-reaction temperature) to be 25 ℃, controlling the vacuum degree in the third micro-reactor (namely the third micro-reaction pressure) to be 0.02MPa, and controlling the material retention time to be 180s, so as to obtain a third micro-reaction liquid after the third micro-reaction; and introducing the third micro-reaction liquid into an intermediate product tank for later use.
Meanwhile, the gas generated in the third micro-reaction process is led out from the third micro-reactor to a tail gas treatment device for tail gas treatment.
The third microreactor is filled with a catalyst, the catalyst is the same as the catalyst in the first microreactor, and the filling amount of the catalyst is 50wt% of the mass of the catalyst in the first microreactor.
4. Refining
Filtering the third micro-reaction liquid in the intermediate product tank, introducing the filtered third micro-reaction liquid into an atmospheric distillation device, and carrying out heat preservation distillation for 45min at the temperature of 138 ℃ to remove light component impurities; heating to 155 ℃, preserving heat and distilling, controlling the reflux ratio to be 1:2, and collecting light components to obtain bromobenzene.
The HPLC purity of bromobenzene obtained in this example was 99.51wt% and the yield was 94.3%.
Example 2
A preparation method of bromobenzene comprises the following specific scheme:
1. primary microreaction
Benzene is led into a pre-cooling tank, cooled to 7.5 ℃, and then metered by a first flowmeter, and fed into a first micro-reactor through a first feed inlet of a micro-channel reaction device by adopting a first peristaltic pump; meanwhile, bromine chloride is discharged from a storage steel bottle, is metered by a second flowmeter, and is fed into the first micro-reactor through a second feeding port of the micro-channel reaction device by a second peristaltic pump; the temperature in the first micro-reactor (namely the first micro-reaction temperature) is controlled to be 7.5 ℃, the vacuum degree in the first micro-reactor (namely the first micro-reaction pressure) is controlled to be 0.025MPa, the material retention time is controlled to be 540s, and the first micro-reaction liquid is obtained after the first micro-reaction.
Meanwhile, hydrogen chloride gas generated in the first micro-reaction process is led out from the first micro-reactor to a tail gas treatment device for tail gas treatment.
In one micro-reaction, the molar ratio of benzene to bromine chloride is 1:1.02.
The feed rate ratio of benzene to bromine chloride was 1:1.51; in this example, the benzene feed rate to the first microreactor was 0.1kg/s; bromine chloride was fed to the first microreactor at a feed rate of 0.151kg/s.
The first microreactor is filled with a catalyst, and the filling amount of the catalyst is 0.75 weight percent of the total mass of benzene in the material residence time in one microreactor.
The catalyst is prepared by the following steps:
1) Disposable composite
Adding ferric trichloride and titanium tetrachloride into a mixed solvent, and performing ultrasonic dispersion for 25min; then stirring and adding sodium acetate at a feeding rate of 0.45g/min, and continuing stirring for 15min after the adding is completed; then transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to rise to 185 ℃, preserving heat for 9 hours, naturally cooling to normal temperature, separating out solid matters, washing the solid matters with deionized water for 3 times, and drying at 90 ℃ for 17 hours to obtain dried matters; then putting the dried substance into an ethanol solution with 92 times of weight, stirring for 15min, continuously adding ammonia water, performing ultrasonic dispersion for 15min, continuously adding tetraethoxysilane, performing ultrasonic dispersion for 5.5h at normal temperature, separating out a solid substance, washing the solid substance with deionized water for 3 times, and drying at 72 ℃ for 23h to obtain the primary compound.
Wherein, the weight ratio of the ferric trichloride, the titanium tetrachloride, the sodium acetate and the mixed solvent is 1.45:0.95:3.45:52.
The mixed solvent is a mixture of glycol and deionized water, and the volume ratio of the glycol to the deionized water is 6.8:3.2.
The volume concentration of the ethanol solution was 83.5%.
The mass concentration of the ammonia water was 24.5wt%.
The weight ratio of the dry matter to the ammonia water to the tetraethoxysilane is 1:5.45:5.1.
2) Secondary compounding
Adding aluminum chloride and zirconium chloride into N, N-dimethylformamide, stirring for 25min, continuously adding the primary compound and mesoporous activated carbon, uniformly dispersing by ultrasonic, continuously adding phthalic acid, stirring for 25min, transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be 135 ℃, preserving heat, stirring for 14.5h, naturally cooling to normal temperature, separating out solid matters, washing the solid matters with deionized water for 3 times, placing in an environment with the vacuum degree of 0.06MPa, and drying at 68 ℃ for 9h to obtain the secondary compound.
Wherein the weight ratio of aluminum chloride, zirconium chloride, primary compound, mesoporous activated carbon, phthalic acid and N, N-dimethylformamide is 19:21:7.5:2.1:34:1150.
3) Three times of compounding
And (3) putting the secondary compound into a treatment solution with the volume being 5.5 times that of the secondary compound, stirring and heating to 42 ℃, preserving heat and stirring for 11 hours, filtering out solid matters, washing the solid matters with deionized water for 3 times, placing in an environment with the vacuum degree of 0.085MPa, drying at 82 ℃ for 11 hours, and granulating to obtain the catalyst with the particle size of 0.33 mm.
Wherein the treatment fluid is an absolute ethanol solution of aluminum tribromide and lanthanum cerium chloride; in the treatment liquid, the mass concentration of aluminum tribromide is 3.3%, and the mass concentration of lanthanum cerium chloride is 1.6%.
2. Secondary microreaction
The first micro-reaction liquid obtained by the first micro-reaction is fed into a second micro-reactor, the temperature in the second micro-reactor (namely the second micro-reaction temperature) is controlled to be 7.5 ℃, the vacuum degree in the second micro-reactor (namely the second micro-reaction pressure) is controlled to be 0.025MPa, the material retention time is 360s, and the second micro-reaction liquid is obtained after the second micro-reaction.
Meanwhile, hydrogen chloride gas generated in the second micro-reaction process is led out from the second micro-reactor to a tail gas treatment device for tail gas treatment.
The second microreactor is filled with a catalyst, the catalyst is the same as the catalyst in the first microreactor, and the filling amount of the catalyst is 55wt% of the mass of the catalyst in the first microreactor.
3. Three microreaction
Feeding a second micro-reaction liquid obtained by the second micro-reaction into a third micro-reactor, controlling the temperature in the third micro-reactor (namely the third micro-reaction temperature) to be 28 ℃, controlling the vacuum degree in the third micro-reactor (namely the third micro-reaction pressure) to be 0.025MPa, and controlling the material retention time to be 210s, so as to obtain a third micro-reaction liquid after the third micro-reaction; and introducing the third micro-reaction liquid into an intermediate product tank for later use.
Meanwhile, the gas generated in the third micro-reaction process is led out from the third micro-reactor to a tail gas treatment device for tail gas treatment.
The third microreactor is filled with a catalyst, the catalyst is the same as the catalyst in the first microreactor, and the filling amount of the catalyst is 55wt% of the mass of the catalyst in the first microreactor.
4. Refining
Filtering the third micro-reaction liquid in the intermediate product tank, introducing the filtered third micro-reaction liquid into an atmospheric distillation device, and carrying out heat preservation distillation for 50min at the temperature of 139 ℃ to remove light component impurities; heating to 156 ℃, preserving heat and distilling, controlling the reflux ratio to be 1:2.3, and collecting light components to obtain bromobenzene.
The HPLC purity of bromobenzene obtained in this example was 99.58wt% and the yield was 94.7%.
Example 3
A preparation method of bromobenzene comprises the following specific scheme:
1. primary microreaction
Benzene is led into a pre-cooling tank, cooled to 8 ℃, and then metered by a first flowmeter, and fed into a first micro-reactor through a first feed inlet of a micro-channel reaction device by adopting a first peristaltic pump; meanwhile, bromine chloride is discharged from a storage steel bottle, is metered by a second flowmeter, and is fed into the first micro-reactor through a second feeding port of the micro-channel reaction device by a second peristaltic pump; the temperature in the first micro-reactor (namely the first micro-reaction temperature) is controlled to be 8 ℃, the vacuum degree in the first micro-reactor (namely the first micro-reaction pressure) is controlled to be 0.03MPa, the material residence time is 600s, and the first micro-reaction liquid is obtained after the first micro-reaction.
Meanwhile, hydrogen chloride gas generated in the first micro-reaction process is led out from the first micro-reactor to a tail gas treatment device for tail gas treatment.
In one micro-reaction, the molar ratio of benzene to bromine chloride is 1:1.03.
The feed rate ratio of benzene to bromine chloride was 1:1.52; in this example, the benzene feed rate to the first microreactor was 0.1kg/s; bromine chloride was fed to the first microreactor at a feed rate of 0.152kg/s.
The first microreactor is filled with a catalyst, and the filling amount of the catalyst is 0.8 weight percent of the total mass of benzene in the material residence time in one microreactor.
The catalyst is prepared by the following steps:
1) Disposable composite
Adding ferric trichloride and titanium tetrachloride into a mixed solvent, and performing ultrasonic dispersion for 30min; then stirring and adding sodium acetate at a feeding rate of 0.5g/min, and continuing stirring for 20min after the adding is completed; then transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be increased to 190 ℃, preserving heat for 10 hours, naturally cooling to normal temperature, separating out solid matters, washing the solid matters with deionized water for 3 times, and drying at 95 ℃ for 18 hours to obtain dried matters; then putting the dried substance into an ethanol solution with the weight being 95 times that of the dried substance, stirring for 20min, continuously adding ammonia water, performing ultrasonic dispersion for 20min, continuously adding tetraethoxysilane, performing ultrasonic dispersion for 6h at normal temperature, separating out a solid substance, washing the solid substance with deionized water for 3 times, and drying at 75 ℃ for 24h to obtain the primary compound.
Wherein, the weight ratio of the ferric trichloride, the titanium tetrachloride, the sodium acetate and the mixed solvent is 1.5:1:3.5:55.
The mixed solvent is a mixture of glycol and deionized water, and the volume ratio of the glycol to the deionized water is 7:3.5.
The volume concentration of the ethanol solution was 85%.
The mass concentration of the ammonia water was 25wt%.
The weight ratio of the dry matter to the ammonia water to the tetraethoxysilane is 1:5.5:5.2.
2) Secondary compounding
Adding aluminum chloride and zirconium chloride into N, N-dimethylformamide, stirring for 30min, continuously adding the primary compound and mesoporous activated carbon, uniformly dispersing by ultrasonic, continuously adding phthalic acid, stirring for 30min, transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be 140 ℃, keeping the temperature and stirring for 15h, naturally cooling to normal temperature, separating out solid matters, washing the solid matters with deionized water for 3 times, placing in an environment with the vacuum degree of 0.07MPa, and drying at 70 ℃ for 10h to obtain the secondary compound.
Wherein the weight ratio of aluminum chloride, zirconium chloride, primary compound, mesoporous activated carbon, phthalic acid and N, N-dimethylformamide is 20:22:8:2.2:35:1200.
3) Three times of compounding
Adding the secondary compound into a treatment solution with the volume of 6 times, stirring and heating to 45 ℃, preserving heat and stirring for 12 hours, filtering out solid matters, washing the solid matters with deionized water for 3 times, placing in an environment with the vacuum degree of 0.09MPa, drying at the temperature of 85 ℃ for 12 hours, and granulating to obtain the catalyst with the particle size of 0.35 mm.
Wherein the treatment fluid is an absolute ethanol solution of aluminum tribromide and lanthanum cerium chloride; in the treatment liquid, the mass concentration of aluminum tribromide is 3.5%, and the mass concentration of lanthanum cerium chloride is 1.7%.
2. Secondary microreaction
The first micro-reaction liquid obtained by the first micro-reaction is fed into a second micro-reactor, the temperature in the second micro-reactor (namely the second micro-reaction temperature) is controlled to be 8 ℃, the vacuum degree in the second micro-reactor (namely the second micro-reaction pressure) is 0.03MPa, the material residence time is 420s, and the second micro-reaction liquid is obtained after the second micro-reaction is carried out.
Meanwhile, hydrogen chloride gas generated in the second micro-reaction process is led out from the second micro-reactor to a tail gas treatment device for tail gas treatment.
The second microreactor is filled with a catalyst, the catalyst is the same as the catalyst in the first microreactor, and the filling amount of the catalyst is 60wt% of the mass of the catalyst in the first microreactor.
3. Three microreaction
Feeding a second micro-reaction liquid obtained by the second micro-reaction into a third micro-reactor, controlling the temperature in the third micro-reactor (namely the third micro-reaction temperature) to be 30 ℃, controlling the vacuum degree in the third micro-reactor (namely the third micro-reaction pressure) to be 0.03MPa, and controlling the material retention time to be 240s, so as to obtain a third micro-reaction liquid after the third micro-reaction; and introducing the third micro-reaction liquid into an intermediate product tank for later use.
Meanwhile, the gas generated in the third micro-reaction process is led out from the third micro-reactor to a tail gas treatment device for tail gas treatment.
The third microreactor is filled with a catalyst, the catalyst is the same as the catalyst in the first microreactor, and the filling amount of the catalyst is 60wt% of the mass of the catalyst in the first microreactor.
4. Refining
Filtering the third micro-reaction liquid in the intermediate product tank, introducing the filtered third micro-reaction liquid into an atmospheric distillation device, and carrying out heat preservation distillation for 60min at 140 ℃ to remove light component impurities; heating to 157 ℃, preserving heat and distilling, controlling the reflux ratio to be 1:2.5, and collecting light components to prepare bromobenzene.
The HPLC purity of bromobenzene obtained in this example was 99.56wt% and the yield was 94.6%.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that: omitting the steps of primary micro-reaction, secondary micro-reaction and tertiary micro-reaction, and modifying the reaction process of benzene and bromine chloride without adopting micro-channel reaction, namely, introducing benzene into a reaction kettle filled with a catalyst (the filling amount of the catalyst is 1.6wt% of the total mass of benzene), cooling to 7.5 ℃, preserving heat and keeping the vacuum degree in the reaction kettle to be 0.025MPa; under the stirring condition, bromine chloride is dripped at the dripping rate of 20kg/h, after the bromine chloride dripping is completed, the heat preservation stirring is continued for 16 hours, the reaction liquid is prepared, and the reaction liquid is introduced into an intermediate product tank, and then the subsequent refining step is carried out. Similarly, the hydrogen chloride gas generated in the reaction process is led out to a tail gas treatment device for tail gas treatment.
According to the yield calculation of 24h in the technical scheme of example 2, under the condition of the same raw material consumption, the total reaction time (comprising the feeding and cooling time of benzene) of benzene and bromine chloride in comparative example 1 exceeds 30.5h, and the production process is batch production, so that continuous production cannot be realized.
The HPLC purity of bromobenzene obtained in comparative example 1 was 98.12wt% and the yield was 88.6%.
It can be seen that the continuous production of bromobenzene cannot be realized after the steps of primary micro-reaction, secondary micro-reaction and tertiary micro-reaction are omitted, and the production efficiency is obviously reduced; and along with the increase of raw material contact time in the reaction process, impurities are easy to generate, so that the reaction yield is reduced, the energy consumption in the refining process is increased, the refining efficiency is reduced, and the purity of the bromobenzene as a final product is influenced.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: in the preparation of the catalyst, a primary compounding step is omitted; and in the secondary compounding step, the use of the primary compound is omitted, and the mesoporous activated carbon is adopted to complement the weight part of the primary compound.
The HPLC purity of bromobenzene obtained in comparative example 2 was 98.40wt% by detection, and the yield was 89.0%.
It can be seen that in the preparation of the catalyst, after omitting the primary compounding step, the combination performance of the mesoporous activated carbon and the metal organic framework material and the combination performance of the catalytic active components in the treatment fluid are reduced to a certain extent, and the catalytic performance and the low-temperature activity of the catalyst are degraded, which is particularly shown as obvious reduction of the yield and the purity of the prepared bromobenzene.
Comparative example 3
The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) In the preparation of the catalyst, a secondary compounding step is omitted; in the three-time compounding step, the primary compound and mesoporous activated carbon with the weight ratio of 7.5:2.1 are adopted to replace the secondary compound, and are put into the treatment fluid; 2) The addition of cerium chloride was omitted from the treatment solution.
The HPLC purity of bromobenzene obtained in comparative example 3 was 98.93wt% and the yield was 91.3%.
It can be seen that in the preparation of the catalyst, after omitting the secondary compounding step, the combination performance of the primary compound and the mesoporous activated carbon with the catalytic active components in the treatment liquid is also reduced to a certain extent, and the catalytic performance and the low-temperature activity of the catalyst are declined, which is particularly shown by the obvious reduction of the yield and the purity of the prepared bromobenzene.
Further, after 180 days of continuous preparation of bromobenzene by adopting the technical schemes of examples 1-3 and comparative examples 2-3, the HPLC purity and yield of bromobenzene obtained were detected and counted, and specific results are shown in the following table:
further, the catalysts used for 180 days continuously in example 2, comparative example 2 and comparative example 3 were subjected to catalytic performance detection, respectively, to determine the optimal addition amount of each catalyst in one micro-reaction at 7.5 ℃ (the mass of the catalyst is the percentage of the total mass of benzene in the material residence time in one micro-reaction); and determining an optimal catalytic temperature value for each catalyst. The specific results are shown in the following table:
it can be seen that the catalyst adopted in the preparation process of bromobenzene has better long-term catalytic performance, and the catalytic performance is less attenuated after 180 days of continuous use. In the preparation of the catalyst, the catalyst has larger catalytic performance attenuation after omitting relevant steps, and the catalyst is particularly characterized by the reduction of purity and yield index of the prepared bromobenzene, and obvious increase of the optimal addition amount and the optimal catalytic temperature value of the catalyst.
According to the preparation method of bromobenzene, the primary micro-reaction, the secondary micro-reaction, the tertiary micro-reaction and the refining step are adopted to cooperate, and the micro-reaction temperature, the pressure and the residence time are set in a targeted manner for different reaction stages in the primary micro-reaction, the secondary micro-reaction and the tertiary micro-reaction processes respectively; meanwhile, a catalyst prepared by a specific method is adopted in the primary micro-reaction, the secondary micro-reaction and the tertiary micro-reaction; in the preparation of the catalyst, the primary composite is prepared by adopting ferric oxide, titanium dioxide and silicon dioxide to be matched in the primary composite, so that the primary composite which has a large number of active sites capable of being effectively combined with other catalytic components and has certain catalytic activity is prepared; then combining the primary compound, the mesoporous activated carbon and an aluminum-zirconium metal organic framework to prepare a secondary compound with certain catalytic activity; then, the secondary compound and the treatment fluid containing aluminum tribromide and lanthanum cerium chloride are subjected to tertiary compounding to prepare the catalyst with low addition, good low-temperature catalytic activity and good long-term catalytic performance; the purity and the yield of the prepared bromobenzene can be further improved, the consumption of raw materials and catalysts is reduced, the generation of byproduct impurities in the reaction process is avoided, the operation processes of preparation and purification are simplified, and the reaction controllability is improved; and purification processes such as water washing impurity removal, layering, drying and the like are not needed, so that the generation of water washing wastewater, solid waste and the like is avoided, and the environmental friendliness is improved.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The preparation method of bromobenzene is characterized by comprising the following steps: primary micro-reaction, secondary micro-reaction, tertiary micro-reaction and refining;
the primary micro-reaction method comprises the steps of cooling benzene to 7-8 ℃, and feeding the benzene and bromine chloride into a first micro-reactor at the same time; controlling the temperature of the first micro-reaction at 7-8 ℃, the vacuum degree of the first micro-reaction at 0.02-0.03MPa, and the material retention time at 480-600s, and obtaining a first micro-reaction liquid after the first micro-reaction;
the first micro-reactor is filled with a catalyst;
the method for the secondary micro-reaction comprises the steps of feeding a first micro-reaction liquid into a second micro-reactor, controlling the temperature of the second micro-reaction at 7-8 ℃, controlling the vacuum degree of the second micro-reaction at 0.02-0.03MPa, and controlling the material retention time at 300-420s, so as to obtain a second micro-reaction liquid after the second micro-reaction;
the second microreactor is filled with a catalyst which is the same as the catalyst of the primary microreaction;
feeding the second micro-reaction liquid into a third micro-reactor, controlling the temperature of the third micro-reaction at 25-30 ℃, controlling the vacuum degree of the third micro-reaction at 0.02-0.03MPa, and controlling the material retention time at 180-240s, so as to obtain the third micro-reaction liquid after the third micro-reaction;
the third micro-reactor is filled with a catalyst which is the same as the catalyst of the primary micro-reaction;
the catalyst is prepared by the following steps: primary compounding, secondary compounding and tertiary compounding;
the primary compounding method comprises the steps of adding ferric trichloride and titanium tetrachloride into a mixed solvent, and uniformly dispersing; stirring and adding sodium acetate, and stirring uniformly; then transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be increased to 180-190 ℃, preserving heat, naturally cooling to normal temperature, separating out solid matters, washing the solid matters by deionized water, and drying to obtain a dried matter; adding the dried substance into ethanol solution, stirring uniformly, then continuously adding ammonia water, dispersing uniformly, continuously adding tetraethoxysilane, performing ultrasonic dispersion for 5-6 hours at normal temperature, separating out solid substances, washing the solid substances with deionized water, and drying to obtain a primary compound;
the secondary compounding method comprises the steps of adding aluminum chloride and zirconium chloride into N, N-dimethylformamide, stirring uniformly, continuously adding a primary compound and mesoporous activated carbon, dispersing uniformly, continuously adding phthalic acid, stirring uniformly, transferring into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, controlling the temperature of the high-pressure reaction kettle to be 130-140 ℃, preserving heat, stirring, naturally cooling to normal temperature, separating out solid matters, washing the solid matters by deionized water, and drying in vacuum to obtain a secondary compound;
the method for three-time compounding comprises the steps of adding the secondary compound into treatment liquid, stirring and heating to 40-45 ℃, preserving heat and stirring, filtering out solid matters, washing the solid matters by deionized water, drying in vacuum, and granulating to obtain a catalyst;
in the three-time compounding, the treatment fluid is an absolute ethanol solution of aluminum tribromide and lanthanum cerium chloride.
2. The method for preparing bromobenzene as claimed in claim 1, wherein the refining method is that the third micro-reaction liquid is filtered and then is led into an atmospheric distillation device, and the impurity is removed by heat preservation distillation under the temperature condition of 138-140 ℃; heating to 155-157 ℃, preserving heat and distilling, controlling the reflux ratio to be 1:2-2.5, and collecting light components to prepare bromobenzene.
3. The method for preparing bromobenzene according to claim 1, wherein the molar ratio of benzene to bromine chloride in the one-time microreaction is 1:1.01-1.03; the feeding rate ratio of benzene to bromine chloride is 1:1.49-1.52;
the catalyst loading in the first microreactor is 0.7-0.8wt% of the total mass of benzene in the material residence time in the primary microreactor.
4. The method for producing bromobenzene according to claim 3, characterized in that in the secondary microreactor, the loading of the catalyst in the second microreactor is 50 to 60% by weight of the catalyst in the first microreactor;
in the three microreactions, the loading of the catalyst in the third microreactor is 50-60wt% of the mass of the catalyst in the first microreactor.
5. The method for preparing bromobenzene according to claim 1, characterized in that the feeding rate of sodium acetate in the one-time compounding is 0.4-0.5g/min;
the heat preservation time is 8-10h under the temperature condition of 180-190 ℃.
6. The method for preparing bromobenzene according to claim 1, wherein the weight ratio of ferric trichloride, titanium tetrachloride, sodium acetate and mixed solvent in the primary compounding is 1.4-1.5:0.9-1:3.4-3.5:50-55;
the mixed solvent is a mixture of glycol and deionized water, and the volume ratio of the glycol to the deionized water in the mixed solvent is 6.5-7:3-3.5.
7. The method for preparing bromobenzene according to claim 1, characterized in that the weight ratio of the dry matter to the ethanol solution in the primary compounding is 1:90-95;
the volume concentration of the ethanol solution is 82-85%;
the mass concentration of the ammonia water is 24-25wt%;
the weight ratio of the dry matter to the ammonia water to the tetraethoxysilane is 1:5.4-5.5:5-5.2.
8. The method for preparing bromobenzene according to claim 1, wherein the heat preservation stirring time at 130-140 ℃ in the secondary compounding is 14-15h;
the weight ratio of the aluminum chloride to the zirconium chloride to the primary compound to the mesoporous activated carbon to the phthalic acid to the N, N-dimethylformamide is 18-20:20-22:7-8:2-2.2:33-35:1100-1200.
9. The method for preparing bromobenzene according to claim 1, wherein the volume ratio of secondary complex to treatment fluid in the tertiary complex is 1:5-6;
the heat preservation stirring time is 10-12h under the temperature condition of 40-45 ℃;
the mass concentration of aluminum tribromide in the treatment liquid is 3.2-3.5%, and the mass concentration of lanthanum cerium chloride is 1.5-1.7%.
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