CN114933535A - Preparation method of membrane reactor and method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene - Google Patents

Preparation method of membrane reactor and method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene Download PDF

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CN114933535A
CN114933535A CN202210654795.2A CN202210654795A CN114933535A CN 114933535 A CN114933535 A CN 114933535A CN 202210654795 A CN202210654795 A CN 202210654795A CN 114933535 A CN114933535 A CN 114933535A
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aniline
film
membrane
solution
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CN114933535B (en
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陈远志
王凯
李艳杰
何景豪
牛桂英
王文博
吴雪峰
张宏科
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Wanhua Chemical Ningbo Co Ltd
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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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B01J35/59—Membranes
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/86—Separation

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Abstract

The invention discloses a preparation method of a membrane reactor and a method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene. The membrane reactor uses aniline tar waste to prepare active carbon, uses Covalent Organic Frameworks (COFs) with high hydrothermal stability as membrane materials, and modifies the COFs membrane materials on the framework to prepare the bifunctional membrane catalytic reactor which simultaneously provides a hydrogenation catalytic center and an alkaline catalytic center, thereby realizing resource utilization of the tar waste. Under the synergistic action of separation and catalysis of the membrane catalytic reactor, 4-aminodiphenylamine is continuously generated by side reactions and separated out, and the production of tar byproducts of heavy components of tricyclic and polycyclic aromatic amines is reduced. The invention not only reduces the generation amount of tar heavy components in the aniline production process, but also can obtain the 4-aminodiphenylamine by reaction without additionally adding organic/inorganic alkali, and the membrane catalytic reactor has good use stability and long service cycle.

Description

Preparation method of membrane reactor and method for co-producing aniline and 4-aminodiphenylamine from nitrobenzene
Technical Field
The invention belongs to a hydrogenation catalytic membrane reactor, and particularly relates to a preparation method of a nitrobenzene liquid-phase hydrogenation catalytic membrane reactor and a method for preparing aniline and co-producing 4-aminodiphenylamine.
Background
Aniline is an important organic chemical intermediate, has wide application in the production of fine chemical intermediates such as polyurethane, fuel, medicine, rubber auxiliary agent and the like, and particularly has great market demand as a raw material for producing diphenyl Methyl Diisocyanate (MDI).
The nitrobenzene liquid phase hydrogenation method is the main method for industrially producing aniline at present, and the adopted catalysts mainly comprise two types, namely a noble metal catalyst and a nickel catalyst. The noble metal catalyst mainly adopts Pt, Pd and Au as active components, such as Pt supported catalysts disclosed in CN103316676A, and the catalysts have high catalytic activity, good selectivity and high price; the nickel-based catalyst has low raw material cost, such as the Ni/bentonite catalyst disclosed in CN103288651A, but has more reaction byproducts. In the process of preparing aniline by liquid phase hydrogenation of nitrobenzene, tar-like high-viscosity mixture is generated due to side reactions such as catalytic condensation, hydrogenation and the like, and the tar-like high-viscosity mixture mainly comprises 4-aminodiphenylamine and other high-melting-point and high-boiling-point tricyclic and polycyclic aromatic amine heavy components with larger molecular weight. The generation of heavy component tar not only influences the stable operation of a production device, but also reduces the yield of products, aniline tar is treated by adopting an incineration mode at present, steam can be byproduct, but the resource utilization rate is low, and carbon emission is increased.
The 4-aminodiphenylamine is also called N-phenyl-p-phenylenediamine, called RT base for short, is an important fine chemical intermediate, has wide application in the industries of rubber auxiliaries, dyes, medicines and the like, and is mainly used for producing the p-phenylenediamine rubber antioxidant.
The prior industrial production method of 4-aminodiphenylamine mainly comprises a diphenylamine method, an aniline method, a formanilide method and a nitrobenzene method, wherein the nitrobenzene method has the advantages of high yield, good quality and less three wastes. The nitrobenzene method takes aniline and nitrobenzene as raw materials to synthesize 4-aminodiphenylamine by two-step reaction: under the action of alkali catalyst, 4-nitrosodiphenylamine and 4-nitrodiphenylamine are obtained by condensation, and the obtained mixture is reacted under the action of hydrogenation catalyst to obtain 4-aminodiphenylamine. The base catalyst can be selected from organic base or inorganic base, or organic base and inorganic base mixed catalyst, such as tetraalkyl amine hydroxide, tetraalkyl ammonium salt and alkali metal oxide composite base catalyst disclosed in CN 1721390A; the hydrogenation catalyst is mainly selected from platinum group noble metal catalysts and nickel group catalysts, such as palladium/carbon catalyst for preparing 4-aminodiphenylamine disclosed in CN 106179332A. The recovery process of the liquid alkali catalyst by the nitrobenzene method is complex, the water content needs to be strictly controlled in the reaction process, the catalytic effect of alkali is influenced by excessive water, the decomposition of the catalyst is increased by too little water, and impurities such as methanol generated by decomposition easily poison the hydrogenation catalyst.
The membrane catalytic reactor is a novel technology which integrates catalysis and separation, can provide a large number of catalytic reaction nests, and simultaneously has rich catalytic reaction active sites, wherein the COFs membrane has high thermal stability and chemical stability, is resistant to humidity, acid and alkali corrosion and has a large specific surface area.
Disclosure of Invention
The invention aims to provide a preparation method for a nitrobenzene liquid-phase hydrogenation catalytic membrane reactor and a method for preparing aniline and co-producing 4-aminodiphenylamine by the same aiming at the defects in the prior art, which can utilize industrial tar wastes as raw materials to obtain a membrane catalytic reactor with long-term stability and long service life by loading a catalyst on an alkaline COFs C-Zn membrane with high hydrothermal and high chemical stability, and reduce the production cost.
The invention also aims to use the prepared membrane catalyst reactor, and the membrane catalyst reactor can be used for preparing aniline by liquid phase hydrogenation of nitrobenzene, reduces the generation of tar of heavy components of tricyclic and polycyclic aromatic amines in the production process of aniline, coproduces 4-aminodiphenylamine, and reduces the production cost of 4-aminodiphenylamine.
In order to achieve the above purpose and achieve the above technical effects, the technical solution of the present invention is as follows:
a method of making a membrane reactor comprising the steps of:
(1) activating aniline tar with an activating agent, separating, heating, grinding and carbonizing to obtain activated carbon;
(2) mixing and heating a salt solution prepared by alumina and strong acid and the activated carbon obtained in the step (1), adjusting the pH value to be neutral, separating, drying and calcining to obtain an activated carbon-alumina composite carrier;
(3) dipping a dichloromethane mixed solution of COFs C-Zn powder on an active carbon-alumina composite carrier, and reacting to obtain a COFs C-Zn film;
(4) grafting organic alkali on the COFs C-Zn film, washing, soaking with hydrochloric acid to obtain an alkaline COFs C-Zn film;
(5) and dip-coating the basic COFs C-Zn film by adopting an aqueous solution containing Pt salt and an auxiliary agent, and drying.
In the step (1), the mass ratio of the aniline tar to the activator is (1.0-2.1): 1.
In the step (1), the activating agent is one or more aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate and zinc chloride, and the concentration of the activating agent is 40-50 wt%.
In the step (1) of the present invention, the activation condition is stirring and refluxing at 100-120 ℃ for 1-2 h.
In the step (1) of the present invention, the heating condition is heating at 400-550 ℃ for 2-4 h.
In the step (1), the carbonization conditions are as follows: at 600-800 deg.c, water vapor is used as activating medium and the activating time is 5-6 hr.
In the step (1) of the invention, the mass ratio of the amount of the water vapor to the raw material for carbonization in the carbonization is (1.2-1.9): 1.
In the step (2), the salt solution is one or more of nitrate, phosphate and hydrochloride with metal ion concentration of 1.5 wt% -2.1 wt%.
In the step (2) of the invention, the mass ratio of the activated carbon to the salt solution is (0.25-0.75): 1.
In the step (2) of the present invention, the heating is carried out at 80-100 ℃ for 2-4 hours.
In the step (2), the calcining atmosphere is nitrogen, the temperature is 500-600 ℃, and the time is 3-5 h.
In the step (3) of the invention, the mass ratio of the COFs C-Zn powder to the dichloromethane is (0.7-1): 1000.
In the step (3) of the present invention, the reaction condition is 120-155 ℃ for 16-24 h.
The preparation method of the COFs C-Zn powder comprises the following steps: uniformly mixing trihydroxybenzaldehyde, ethylenediamine, o-dichlorobenzene, n-butanol and acetic acid mixed solution, adding zinc acetate solution, reacting, cooling with liquid nitrogen, vacuumizing, reacting under the protection of nitrogen to obtain light yellow COFs C-Zn powder, washing, and drying.
In the preparation method of COFs C-Zn powder, the mass ratio of trihydroxybenzaldehyde to ethylenediamine is 1 (1.38-2.42).
In the preparation method of the COFs C-Zn powder, the volume ratio of o-dichlorobenzene to acetic acid is (3-4) to 1; the volume ratio of the n-butanol to the acetic acid is (8-9) to 1.
In the preparation method of COFs C-Zn powder, the concentration of the zinc acetate solution is 2-4 mol/L. The dosage of the zinc acetate solution is 0.055mL-0.103mL/1mg trihydroxybenzaldehyde.
In the preparation method of the COFs C-Zn powder, the reaction temperature is 100-150 ℃, and the reaction time is 12-72 h.
In the step (4), the organic base is one or more of imidazole, oxazole, pyridine, bipyridine, guanidine, trimethylamine, ethylenediamine and triethylamine.
In the step (4), the grafting comprises the following steps: heating the water solution of organic base at 140-180 deg.c to graft the organic base onto the surface and pore canal of COFs C-Zn film in the form of steam for 5-24 hr.
In the step (4), the concentration of the hydrochloric acid is 2 wt% -10 wt%.
In the step (5) of the present invention, the Pt salt is one or more of platinum nitrate, platinum sulfite and chloroplatinic acid.
In the step (5), the amount of the Pt salt is 1.0-2.5% of the mass of the basic COFs C-Zn film obtained in the step (4) calculated by Pt element.
In step (5) of the present invention, the auxiliary agent is selected from one or more nitrates of Fe and Co. And (5) the dosage of the auxiliary agent is 0.3-0.9% of the mass of the basic COFs C-Zn film obtained in the step (4) by the mass of Fe or Co element.
The membrane reactor is used for catalyzing the liquid phase hydrogenation of nitrobenzene to prepare aniline and coproduce 4-aminodiphenylamine.
A method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene comprises the following steps: aniline and deionized water are mixed evenly and then added into a continuous hydrogenation reaction kettle provided with the membrane reactor, and the mixture is stirred and reacted for a certain time at a certain temperature and pressure.
In the method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene, the mass ratio of aniline to deionized water is (1.5-2.5) to 1.
In the method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene, the reaction pressure is 2.0-4.0MPaG, the reaction temperature is set to be 100-200 ℃, the stirring speed is 500-1400rpm, the molar ratio of hydrogen to nitrobenzene is (3.84-4.32): 1, and the reaction is carried out for 5-10 h.
Compared with the prior art, the invention has the following positive effects:
(1) the invention adopts the aniline tar waste as the raw material to prepare the activated carbon carrier, thereby reducing the carbon emission while realizing the resource utilization of the tar waste.
(2) The prepared membrane catalytic reactor has dual functions of catalysis and separation, simultaneously has large specific surface area, can provide abundant reaction nests and catalytic active sites, and has long-term stability and longer service cycle.
(3) The prepared membrane catalytic reactor is used for nitrobenzene liquid-phase hydrogenation reaction, the membrane reaction catalyst with hydrogenation and alkaline catalytic centers is designed, the aniline can be continuously promoted to generate, excessive nitrobenzene and aniline react to generate 4-nitrodiphenylamine and 4-nitrosodiphenylamine under the action of the alkaline catalytic sites on the membrane under the action of the alkaline catalytic sites, and finally the 4-aminodiphenylamine is generated under the action of the hydrogenation catalytic sites. The separation effect of the COFs membrane enables the generated 4-aminodiphenylamine to be continuously separated out, the reaction is pushed to be continuously carried out towards the direction of generating the 4-aminodiphenylamine, the generation of side products of heavy components of tricyclic and polycyclic arylamines is reduced, the 4-aminodiphenylamine is obtained by the reaction under the condition of not additionally adding organic/inorganic bases, the problem of decomposition of a basic catalyst in the conventional 4-aminodiphenylamine synthesis process is solved, the catalyst is not required to be recycled and regenerated, and the production cost is reduced.
Detailed Description
The following examples are provided to further illustrate the technical solutions provided by the present invention, but the scope of application of the present invention includes but is not limited to these examples.
The chemicals in the examples are all from national chemical reagent limited and analytically pure.
The content of organic substances such as aniline, p-aminodiphenylamine and the like in the product is determined by 7890A gas chromatography of Agilent, and an FID detector and a DB-5 chromatographic column (30m multiplied by 0.53m multiplied by 1.5 mu m) are adopted, the injection inlet temperature is 280 ℃, the detector temperature is 280 ℃, the flow rate of carrier gas (nitrogen) is 3mL/min, the air flow rate is 400mL/min, and the hydrogen flow rate is 40 mL/min.
Example 1
(1)80g of tar waste at a tower bottom of a product tower of a Wanhuanibo aniline device is added with 80g of sodium hydroxide solution with the mass concentration of 40%, stirred and refluxed for 1h at the temperature of 100 ℃, cooled and filtered, heated for 1h at the temperature of 400 ℃, heated for 3h at the temperature rising rate of 10 ℃/min to 550 ℃, cooled to normal temperature, ground and crushed, heated to 800 ℃ at the temperature rising rate of 10 ℃/min in a carbonization furnace, activated for 5h by taking water vapor as an activating medium (the mass of the water vapor is 1.2:1), and cooled to obtain the activated carbon.
(2) Adding 2.04g of alumina into 50g of dilute nitric acid solution with the mass concentration of 2%, stirring and dissolving, adding 13.5g of ground activated carbon powder, heating to 80 ℃, refluxing for 2h, adjusting the pH to be neutral by using ammonia water, filtering, drying, raising the temperature to 500 ℃ at the heating rate of 10 ℃/min in the atmosphere of high-purity nitrogen, and calcining at high temperature for 3h to obtain the activated carbon-alumina composite carrier.
(3) 14.5mg of trihydroxybenzaldehyde and 20.1mg of ethylenediamine are respectively added into a triangular flask, then a mixed solution of o-dichlorobenzene, n-butanol and acetic acid (the volumes of three solvents are respectively 2.857mL, 6.428mL and 0.714mL) is added into the triangular flask, 1.2mL of 3M zinc acetate solution is added into the triangular flask after uniform mixing, the mixture is cooled by liquid nitrogen and then vacuumized, and the mixture reacts for 72 hours at 120 ℃ under the protection of nitrogen, so that light yellow COFs C-Zn powder is obtained. And washing the obtained light yellow powder by using N, N-dimethylformamide and acetone respectively, and drying for later use.
(4) Dissolving the synthesized COFs C-Zn powder of 10mg in 13.5g of dichloromethane, performing ultrasonic treatment for 10min to obtain a uniform solution, then assembling the uniform solution on an activated carbon-alumina composite carrier in a dip-coating manner, placing the carrier in a polytetrafluoroethylene lining with a support, and reacting at 120 ℃ for 24h to obtain the COFs C-Zn film.
(5) Placing the synthesized COFs C-Zn film in a polytetrafluoroethylene lining with a bracket, wherein the mass ratio of 10g is 1:4, heating the oxazole-water solution at 150 ℃ for 18h, grafting the oxazole-water solution on the surface and in a pore channel of the COFs C-Zn film in a steam mode in the heating process, washing the film by deionized water after grafting is finished, and soaking the film by 6 wt% of dilute hydrochloric acid to obtain the alkaline COFs C-Zn film.
(6) And (2) uniformly stirring 41g of 2 wt% platinum nitrate solution until the platinum nitrate solution is completely dissolved, adding 52g of 1 wt% ferric nitrate solution, uniformly stirring, assembling on a 20g alkaline COFs C-Zn film in a dip-coating manner to obtain a membrane catalytic reactor, and drying for later use.
(7) 200g of aniline and 100g of deionized water are mixed and uniformly stirred and added into a 1L continuous hydrogenation reaction kettle with a 16g membrane reactor, the reaction pressure is set to be 2.5MPaG, the reaction temperature is set to be 100 ℃, the stirring speed is 900rpm, the nitrobenzene feeding quantity is 2.5mL/min, the hydrogen feeding quantity is 2.4NL/min, the molar ratio of hydrogen to nitrobenzene is 4.32:1, and the analysis result of the product after 10h of reaction is shown in Table 1.
Example 2
(1) Adding 80g of 50% sodium hydroxide solution into 120g of tar waste at a tower bottom of a warfarin device product, stirring and refluxing for 2h at 110 ℃, cooling and filtering, heating for 1h at 400 ℃, heating to 550 ℃ at a heating rate of 10 ℃/min for 2h, cooling to normal temperature, grinding and crushing, heating to 800 ℃ at a heating rate of 10 ℃/min in a carbonization furnace, activating for 5h by using water vapor as an activating medium (the mass of the water vapor is 1.9:1) and cooling to obtain the activated carbon.
(2) Adding 1.73g of alumina into 50g of dilute nitric acid solution with the mass concentration of 2%, stirring and dissolving, adding 13.5g of ground activated carbon powder, heating to 80 ℃, refluxing for 4h, adjusting the pH to be neutral by using ammonia water, filtering, drying, raising the temperature to 500 ℃ at the heating rate of 10 ℃/min in the atmosphere of high-purity nitrogen, and calcining at high temperature for 4h to obtain the activated carbon-alumina composite carrier.
(3) 14.5mg of trihydroxybenzaldehyde and 35.1mg of ethylenediamine are respectively added into a triangular flask, then a mixed solution of o-dichlorobenzene, n-butanol and acetic acid (the volumes of the three solvents are 2.142mL, 6.428mL and 0.714mL respectively) is added into the triangular flask, after uniform mixing, 0.8mL of 3M zinc acetate solution is added into the triangular flask, liquid nitrogen is cooled and vacuumized, and reaction is carried out for 72 hours at 120 ℃ under the protection of nitrogen, so that light yellow COFs C-Zn powder is obtained. And washing the obtained light yellow powder with N, N-dimethylformamide and acetone respectively, and drying for later use.
(4) Dissolving the synthesized COFs C-Zn powder of 10mg in 10g of dichloromethane, performing ultrasonic treatment for 10min to obtain a uniform solution, then assembling the uniform solution on an activated carbon-alumina composite carrier in a dip-coating manner, placing the activated carbon-alumina composite carrier in a polytetrafluoroethylene lining with a support, and reacting at 120 ℃ for 24h to obtain the COFs C-Zn film.
(5) Placing the synthesized COFs C-Zn film in a polytetrafluoroethylene lining with a bracket, wherein the mass ratio of 10g is 1:4, heating the pyridine-water solution at 150 ℃ for 18h, grafting the pyridine-water solution on the surface and in the pore channels of the COFs C-Zn film in a steam mode in the heating process, washing the film by deionized water after grafting is finished, and soaking the film by using 6 wt% of dilute hydrochloric acid to obtain the alkaline COFs C-Zn film.
(6) Uniformly stirring 16.4g of 2 wt% platinum nitrate solution until the platinum nitrate solution is completely dissolved, adding 26g of 1 wt% ferric nitrate solution, uniformly stirring, assembling on a 20g alkaline COFs C-Zn film in a dip-coating manner to obtain a membrane catalytic reactor, and drying for later use.
(7) 150g of aniline and 100g of deionized water are mixed and uniformly stirred and added into a 1L continuous hydrogenation reaction kettle with a 16g membrane reactor, the reaction pressure is set to be 2.5MPaG, the reaction temperature is set to be 100 ℃, the stirring speed is 500rpm, the nitrobenzene feeding quantity is 2.5mL/min, the hydrogen feeding quantity is 2.2NL/min, the molar ratio of hydrogen to nitrobenzene is 4.01:1, and the analysis result of the product after 10h of reaction is shown in Table 1.
Example 3
(1)80g of tar waste at a tower bottom of a product tower of a Wanhuanibo aniline device is added with 80g of 45 mass percent sodium hydroxide solution, stirred and refluxed for 1h at 120 ℃, cooled and filtered, heated for 1h at 400 ℃, heated for 3h at the temperature rising rate of 10 ℃/min to 550 ℃, cooled to normal temperature, ground and crushed, heated to 600 ℃ at the temperature rising rate of 10 ℃/min in a carbonization furnace, activated for 6h by taking water vapor as an activating medium (the mass of the water vapor is 1.2:1), and cooled to obtain the activated carbon.
(2) Adding 2.04g of alumina into 50g of dilute nitric acid solution with the mass concentration of 2%, stirring and dissolving, adding 26.0g of ground activated carbon powder, heating to 100 ℃, refluxing for 2 hours, adjusting the pH to be neutral by using ammonia water, filtering, drying, heating to 600 ℃ at the heating rate of 10 ℃/min in the atmosphere of high-purity nitrogen, and calcining at high temperature for 5 hours to obtain the activated carbon-alumina composite carrier.
(3) 14.5mg of trihydroxybenzaldehyde and 27.5mg of ethylenediamine are respectively added into a triangular flask, then a mixed solution of o-dichlorobenzene, n-butanol and acetic acid (the volumes of the three solvents are respectively 2.499mL, 5.712mL and 0.714mL) is added into the triangular flask, 1.0mL of 3M zinc acetate solution is added into the triangular flask after uniform mixing, the mixture is cooled by liquid nitrogen and then vacuumized, and the mixture is reacted for 72 hours at 100 ℃ under the protection of nitrogen, so that light yellow COFs C-Zn powder is obtained. And washing the obtained light yellow powder with N, N-dimethylformamide and acetone respectively, and drying for later use.
(4) Dissolving the synthesized COFs C-Zn powder of 10mg in 13.5g of dichloromethane, performing ultrasonic treatment for 10min to obtain a uniform solution, then assembling the uniform solution on an activated carbon-alumina composite carrier in a dip-coating manner, placing the carrier in a polytetrafluoroethylene lining with a support, and reacting at 135 ℃ for 24h to obtain the COFs C-Zn film.
(5) Placing the synthesized COFs C-Zn film in a polytetrafluoroethylene lining with a bracket, wherein the mass ratio of 10g is 1:4, heating the aqueous solution at 150 ℃ for 18h, grafting the aqueous solution onto the surface and in the pore channels of the COFs C-Zn film in a steam mode in the heating process, washing the film by deionized water after grafting is finished, and soaking the film by using 6 wt% of dilute hydrochloric acid to obtain the alkaline COFs C-Zn film.
(6) 32.7g of 2 wt% platinum nitrate solution is uniformly stirred until the platinum nitrate solution is completely dissolved, 52g of 1 wt% ferric nitrate solution is added, the mixture is uniformly stirred and assembled on a 20g alkaline COFs C-Zn film in a dip-coating mode to obtain a membrane catalytic reactor, and the membrane catalytic reactor is dried for later use.
(7) 200g of aniline and 100g of deionized water are mixed and uniformly stirred and added into a 1L continuous hydrogenation reaction kettle with a 16g membrane reactor, the reaction pressure is set to be 2.0MPaG, the reaction temperature is set to be 100 ℃, the stirring speed is 900rpm, the nitrobenzene feeding quantity is 2.5mL/min, the hydrogen feeding quantity is 2.1NL/min, the molar ratio of hydrogen to nitrobenzene is 3.84:1, and the analysis result of the product is shown in Table 1 after 10 hours of reaction.
Example 4
(1) Adding 80g of 45 mass percent sodium hydroxide solution into 160g of tar waste at a tower bottom of a warfarin device product, stirring and refluxing for 1.5h at 100 ℃, cooling and filtering, heating for 1h at 400 ℃, heating to 550 ℃ at the heating rate of 10 ℃/min for 3h, cooling to normal temperature, grinding and crushing, heating to 800 ℃ at the heating rate of 10 ℃/min in a carbonization furnace, activating for 5h by using water vapor as an activating medium (the mass of the water vapor is 1.5:1) and cooling to obtain the activated carbon.
(2) Adding 1.43g of alumina into 50g of dilute nitric acid solution with the mass concentration of 2%, stirring and dissolving, adding 13.5g of ground activated carbon powder, heating to 90 ℃, refluxing for 3h, adjusting the pH to be neutral by using ammonia water, filtering and drying, raising the temperature to 550 ℃ at the heating rate of 10 ℃/min in the atmosphere of high-purity nitrogen, and calcining at high temperature for 3h to obtain the activated carbon-alumina composite carrier.
(3) 14.5mg of trihydroxybenzaldehyde and 20.1mg of ethylenediamine are respectively added into a triangular flask, then a mixed solution of o-dichlorobenzene, n-butanol and acetic acid (the volumes of the three solvents are respectively 2.857mL, 6.069mL and 0.714mL) is added into the triangular flask, 1.5mL of 3M zinc acetate solution is added into the triangular flask after uniform mixing, the mixture is cooled by liquid nitrogen and then vacuumized, and the mixture is reacted for 72 hours at 120 ℃ under the protection of nitrogen, so that light yellow COFs C-Zn powder is obtained. And washing the obtained light yellow powder with N, N-dimethylformamide and acetone respectively, and drying for later use.
(4) Dissolving the synthesized COFs C-Zn powder of 10mg in 14.2g of dichloromethane, performing ultrasonic treatment for 10min to obtain a uniform solution, then assembling the uniform solution on an activated carbon-alumina composite carrier in a dip-coating manner, placing the carrier in a polytetrafluoroethylene lining with a support, and reacting at 155 ℃ for 24h to obtain the COFs C-Zn film.
(5) Placing the synthesized COFs C-Zn film in a polytetrafluoroethylene lining with a bracket, wherein the mass ratio of 10g is 1:4, heating the trimethylamine-water solution at 150 ℃ for 18h, grafting the trimethylamine-water solution on the surface and in the pore channels of the COFs C-Zn film in a steam mode in the heating process, washing the film by deionized water after grafting is finished, and soaking the film by using 6 wt% of dilute hydrochloric acid to obtain the alkaline COFs C-Zn film.
(6) And (2) uniformly stirring 41g of 2 wt% platinum nitrate solution until the platinum nitrate solution is completely dissolved, adding 78g of 1 wt% ferric nitrate solution, uniformly stirring, assembling on a 20g of alkaline COFs C-Zn film in a dip-coating manner to obtain a membrane catalytic reactor, and drying for later use.
(7) 250g of aniline and 100g of deionized water are mixed and then uniformly stirred and added into a 1L continuous hydrogenation reaction kettle provided with a 16g membrane reactor, the reaction pressure is set to be 2.5MPaG, the reaction temperature is set to be 150 ℃, the stirring speed is 900rpm, the nitrobenzene feeding quantity is 2.5mL/min, the hydrogen feeding quantity is 2.1NL/min, the molar ratio of hydrogen to nitrobenzene is 3.84:1, and the analysis result of the product is shown in Table 1 after 8 hours of reaction.
Example 5
(1)80g of tar waste at a tower bottom of a product tower of a Wanhuanibo aniline device is added with 80g of sodium hydroxide solution with the mass concentration of 40%, stirred and refluxed for 1h at the temperature of 100 ℃, cooled and filtered, heated for 1h at the temperature of 400 ℃, heated for 4h at the temperature rising rate of 10 ℃/min to 550 ℃, cooled to normal temperature, ground and crushed, heated to 700 ℃ at the temperature rising rate of 10 ℃/min in a carbonization furnace, activated for 6h by taking water vapor as an activating medium (the mass of the water vapor is 1.2:1), and cooled to obtain the activated carbon.
(2) Adding 2.04g of alumina into 50g of dilute nitric acid solution with the mass concentration of 2%, stirring and dissolving, adding 40.1g of ground activated carbon powder, heating to 80 ℃, refluxing for 2h, adjusting the pH to be neutral by using ammonia water, filtering, drying, raising the temperature to 500 ℃ at the heating rate of 10 ℃/min in the atmosphere of high-purity nitrogen, and calcining at high temperature for 3h to obtain the activated carbon-alumina composite carrier.
(3) 14.5mg of trihydroxybenzaldehyde and 35.1mg of ethylenediamine are respectively added into a triangular flask, then a mixed solution of o-dichlorobenzene, n-butanol and acetic acid (the volumes of the three solvents are 2.142mL, 6.428mL and 0.714mL respectively) is added into the triangular flask, 1.2mL of 3M zinc acetate solution is added into the triangular flask after uniform mixing, the mixture is cooled by liquid nitrogen and then vacuumized, and the mixture is reacted for 72 hours at 150 ℃ under the protection of nitrogen, so that light yellow COFs C-Zn powder is obtained. And washing the obtained light yellow powder with N, N-dimethylformamide and acetone respectively, and drying for later use.
(4) Dissolving the synthesized COFs C-Zn powder of 10mg in dichloromethane of 12.5g, performing ultrasonic treatment for 10min to obtain a uniform solution, then assembling the uniform solution on an activated carbon-alumina composite carrier in a dip-coating manner, placing the activated carbon-alumina composite carrier in a polytetrafluoroethylene lining with a support, and reacting at 120 ℃ for 24h to obtain the COFs C-Zn film.
(5) Placing the synthesized COFs C-Zn film in a polytetrafluoroethylene lining with a bracket, wherein the mass ratio of 10g is 1:4, heating the triethylamine-water solution at 150 ℃ for 18h, grafting the triethylamine-water solution on the surface and in the pore channels of the COFs C-Zn film in a steam mode in the heating process, washing the film by deionized water after grafting is finished, and soaking the film by 6 wt% of dilute hydrochloric acid to obtain the basic COFs C-Zn film.
(6) And (2) uniformly stirring 41g of 2 wt% platinum nitrate solution until the platinum nitrate solution is completely dissolved, adding 52g of 1 wt% ferric nitrate solution, uniformly stirring, assembling on a 20g alkaline COFs C-Zn film in a dip-coating manner to obtain a membrane catalytic reactor, and drying for later use.
(7) 200g of aniline and 100g of deionized water are mixed and then uniformly stirred and added into a 1L continuous hydrogenation reaction kettle provided with a 16g membrane reactor, the reaction pressure is set to be 4.0MPaG, the reaction temperature is set to be 200 ℃, the stirring speed is 1400rpm, the nitrobenzene feeding quantity is 2.5mL/min, the hydrogen feeding quantity is 2.1NL/min, the molar ratio of hydrogen to nitrobenzene is 3.84:1, and the analysis result of the product is shown in Table 1 after 10 hours of reaction.
Example 6
(1) Adding 80g of 40 mass percent sodium hydroxide solution into 100g of tar waste at a tower bottom of a warfarin device product, stirring and refluxing for 1h at 100 ℃, cooling and filtering, heating for 1h at 400 ℃, heating to 550 ℃ at the heating rate of 10 ℃/min for 3h, cooling to normal temperature, grinding and crushing, heating to 800 ℃ at the heating rate of 10 ℃/min in a carbonization furnace, activating for 5h by using water vapor as an activating medium (the mass of the water vapor is 1.2:1) and cooling to obtain the activated carbon.
(2) Adding 2.04g of alumina into 50g of dilute nitric acid solution with the mass concentration of 2%, stirring and dissolving, adding 13.5g of ground activated carbon powder, heating to 80 ℃, refluxing for 2h, adjusting the pH to be neutral by using ammonia water, filtering, drying, heating to 500 ℃ at the heating rate of 10 ℃/min in the atmosphere of high-purity nitrogen, and calcining at high temperature for 3h to obtain the activated carbon-alumina composite carrier.
(3) 14.5mg of trihydroxybenzaldehyde and 20.1mg of ethylenediamine are respectively added into a triangular flask, then a mixed solution of o-dichlorobenzene, n-butanol and acetic acid (the volumes of the three solvents are respectively 2.857mL, 6.428mL and 0.714mL) is added into the triangular flask, 1.2mL of 3M zinc acetate solution is added into the triangular flask after uniform mixing, the mixture is cooled by liquid nitrogen and then vacuumized, and the mixture is reacted for 72 hours at 120 ℃ under the protection of nitrogen, so that light yellow COFs C-Zn powder is obtained. And washing the obtained light yellow powder with N, N-dimethylformamide and acetone respectively, and drying for later use.
(4) Dissolving the synthesized COFs C-Zn powder of 10mg in 13.5g of dichloromethane, performing ultrasonic treatment for 10min to obtain a uniform solution, then assembling the uniform solution on an activated carbon-alumina composite carrier in a dip-coating manner, placing the carrier in a polytetrafluoroethylene lining with a support, and reacting at 120 ℃ for 24h to obtain the COFs C-Zn film.
(5) Placing the synthesized COFs C-Zn film in a polytetrafluoroethylene lining with a bracket, wherein the mass ratio of 10g is 1:4, heating the solution at 150 ℃ for 18h, grafting the solution on the surface and in the pore channels of the COFs C-Zn film in a steam mode in the heating process, washing the film by deionized water after grafting is finished, and soaking the film by using 6 wt% of dilute hydrochloric acid to obtain the alkaline COFs C-Zn film.
(6) And (2) uniformly stirring 41g of 2 wt% platinum nitrate solution until the platinum nitrate solution is completely dissolved, adding 52g of 1 wt% ferric nitrate solution, uniformly stirring, assembling on a 20g alkaline COFs C-Zn film in a dip-coating manner to obtain a membrane catalytic reactor, and drying for later use.
(7) 200g of aniline and 100g of deionized water are mixed and uniformly stirred and added into a 1L continuous hydrogenation reaction kettle with a 16g membrane reactor, the reaction pressure is set to be 2.5MPaG, the reaction temperature is set to be 100 ℃, the stirring speed is 1000rpm, the nitrobenzene feeding quantity is 2.5mL/min, the hydrogen feeding quantity is 2.1NL/min, the molar ratio of hydrogen to nitrobenzene is 3.84:1, and the analysis result of the product after 5h of reaction is shown in Table 1.
Comparative examples 1 to 1
In contrast to example 1, step (5) used water instead of the oxazole-water solution, the remainder being the same as example 1.
Comparative examples 1 to 2
(1)80g of tar waste at a tower bottom of a product tower of a Wanhuanibo aniline device is added with 80g of sodium hydroxide solution with the mass concentration of 40%, stirred and refluxed for 1h at the temperature of 100 ℃, cooled and filtered, heated for 1h at the temperature of 400 ℃, heated for 3h at the temperature rising rate of 10 ℃/min to 550 ℃, cooled to normal temperature, ground and crushed, heated to 800 ℃ at the temperature rising rate of 10 ℃/min in a carbonization furnace, activated for 5h by taking water vapor as an activating medium (the mass of the water vapor is 1.2:1), and cooled to obtain the activated carbon.
(2) Adding 2.04g of alumina into 50g of dilute nitric acid solution with the mass concentration of 2%, stirring and dissolving, adding 13.5g of ground activated carbon powder, heating to 80 ℃, refluxing for 2h, adjusting the pH to be neutral by using ammonia water, filtering, drying, raising the temperature to 500 ℃ at the heating rate of 10 ℃/min in the atmosphere of high-purity nitrogen, and calcining at high temperature for 3h to obtain the activated carbon-alumina composite carrier.
(3) Placing the synthesized activated carbon-alumina composite carrier in a polytetrafluoroethylene lining with a support, heating 10g of oxazole-water solution with the mass ratio of 1:4 at 150 ℃ for 18h, grafting the oxazole-water solution onto the surface and in a pore channel of the carrier in a steam mode in the heating process, washing the film with deionized water after grafting is finished, and soaking the film with 6 wt% of dilute hydrochloric acid to obtain the alkaline composite carrier.
(4) And (2) uniformly stirring 41g of 2 wt% platinum nitrate solution until the platinum nitrate solution is completely dissolved, adding 52g of 1 wt% ferric nitrate solution, uniformly stirring, assembling on 20g of composite carrier in a dip-coating manner to obtain the catalytic reactor, and drying for later use.
(5) 200g of aniline and 100g of deionized water are mixed and then uniformly stirred and added into a 1L continuous hydrogenation reaction kettle provided with a 16g membrane reactor, the reaction pressure is set to be 2.5MPaG, the reaction temperature is set to be 100 ℃, the stirring speed is 900rpm, the nitrobenzene feeding quantity is 2.5mL/min, the hydrogen feeding quantity is 2.4NL/min, the molar ratio of hydrogen to nitrobenzene is 4.32:1, and the analysis result of the product is shown in Table 1 after 10 hours of reaction.
Comparative examples 1 to 3
(1) 200g of aniline and 100g of deionized water are mixed and then uniformly stirred and added into a 1L continuous hydrogenation reaction kettle provided with a 16g aniline device and the existing nitrobenzene hydrogenation catalyst (1.5 percent of Pt-C), the reaction pressure is set to be 2.5MPaG, the reaction temperature is set to be 100 ℃, the stirring speed is 900rpm, the nitrobenzene feeding amount is 2.5mL/min, the hydrogen feeding amount is 2.4NL/min, the molar ratio of hydrogen to nitrobenzene is 4.32:1, and the analysis result of the product is shown in Table 1 after 10 hours of reaction.
TABLE 1 results of the reactions of the examples and comparative examples
Conversion rate/% Aniline/%) 4-aminodiphenylamine/%) Cyclohexanone/ppm Heavy fraction tar/%)
Example 1 99.80 88.56 11.4 478 0.04
Example 2 99.20 89.31 10.5 312 0.19
Example 3 98.70 88.50 11.4 278 0.10
Example 4 97.90 87.42 12.2 268 0.38
Example 5 98.40 88.00 11.9 363 0.10
Example 6 97.60 89.76 10.2 252 0.04
Comparative examples 1 to 1 92.30 97.24 0.84 856 1.92
Comparative examples 1 to 2 83.50 96.44 0.63 932 2.93
Comparative examples 1 to 3 96.91 97.20 0.65 656 2.09
As can be seen from the data in Table 1, the membrane reactor prepared by modifying the group with the dual catalytic functions of hydrogenation and alkalinity on the framework of the COFs membrane material can greatly reduce the generation of heavy component byproducts of tricyclic and polycyclic aromatic amine substances in the hydrogenation process of nitrobenzene, and achieve the effect of co-producing 4-aminodiphenylamine. Therefore, the invention can provide rich theoretical guidance for preparing the catalytic reactor for high-yield aniline and co-producing 4-aminodiphenylamine, and lays a solid foundation for the industrialization of the membrane catalytic reactor. The present invention is not limited to the above embodiments, which are only illustrative and not restrictive, and those skilled in the art can make many changes without departing from the spirit and scope of the present invention.

Claims (10)

1. A method of making a membrane reactor comprising the steps of:
(1) activating aniline tar with an activating agent, separating, heating, grinding and carbonizing to obtain activated carbon;
(2) mixing and heating a salt solution prepared by alumina and strong acid and the activated carbon obtained in the step (1), adjusting the pH value to be neutral, separating, drying and calcining to obtain an activated carbon-alumina composite carrier;
(3) dipping a dichloromethane mixed solution of COFs C-Zn powder on an activated carbon-alumina composite carrier, and reacting to obtain a COFs C-Zn film;
(4) grafting organic base on the COFs C-Zn film, washing, and soaking in hydrochloric acid to obtain an alkaline COFs C-Zn film;
(5) and dip-coating the basic COFs C-Zn film by adopting an aqueous solution containing Pt salt and an auxiliary agent, and drying.
2. The method according to claim 1, wherein in step (1), the mass ratio of aniline tar to activator is (1.0-2.1): 1; the activating agent is one or more aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate and zinc chloride, and the concentration of the activating agent is 40-50 wt%; the activation condition is stirring and refluxing for 1-2h at the temperature of 100-120 ℃.
3. The method as claimed in claim 1, wherein in the step (1), the heating is performed at a temperature of 400-550 ℃ for 2-4 h; the carbonization condition is that the temperature is 800 ℃ at 600-; the mass ratio of the amount of the water vapor to the carbonized raw material is (1.2-1.9): 1.
4. The method according to claim 1, wherein in the step (2), the salt solution is one or more of nitrate, phosphate and hydrochloride with a metal ion concentration of 1.5-2.1 wt%; the mass ratio of the active carbon to the salt solution is (0.25-0.75) to 1; the calcining atmosphere is nitrogen, the temperature is 500-600 ℃, and the time is 3-5 h.
5. The method as claimed in claim 1, wherein in the step (3), the reaction condition is 120-155 ℃ for 16-24 h.
6. The method according to claim 1, wherein in the step (3), the COFs C-Zn powder is prepared by a method comprising the following steps: uniformly mixing trihydroxybenzaldehyde, ethylenediamine, o-dichlorobenzene, n-butanol and acetic acid mixed solution, adding zinc acetate solution, reacting, cooling with liquid nitrogen, vacuumizing, reacting under the protection of nitrogen to obtain light yellow COFs C-Zn powder, washing, and drying.
7. The method according to claim 1, wherein in the step (4), the organic base is one or more of imidazole, oxazole, pyridine, bipyridine, guanidine, trimethylamine, ethylenediamine and triethylamine, and is preferably oxazole.
8. The method according to claim 1, wherein in the step (4), the grafting comprises the following steps: heating the water solution of organic base at 140-180 deg.c to graft the organic base onto the surface and pore canal of COFs C-Zn film in the form of steam for 5-24 hr.
9. The method according to claim 1, wherein in the step (5), the amount of the Pt salt is 1.0% -2.5% of the mass of the basic COFs C-Zn film obtained in the step (4) calculated by Pt element; in the step (5), the auxiliary agent is selected from one or more of nitrates of Fe and Co; and (3) the dosage of the auxiliary agent is 0.3-0.9% of the mass of the basic COFs C-Zn film obtained in the step (4) by the mass of Fe or Co element.
10. A method for coproducing aniline and 4-aminodiphenylamine from nitrobenzene comprises the following steps: aniline and deionized water are mixed uniformly and then added into a continuous hydrogenation reaction kettle provided with the membrane reactor of any one of claims 1-9 to react for 5-10h at the temperature of 100-200 ℃ and under the pressure of 2.0-4.0 MPaG.
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