CN114931967B - Preparation method and application of catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound - Google Patents

Preparation method and application of catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound Download PDF

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CN114931967B
CN114931967B CN202210754667.5A CN202210754667A CN114931967B CN 114931967 B CN114931967 B CN 114931967B CN 202210754667 A CN202210754667 A CN 202210754667A CN 114931967 B CN114931967 B CN 114931967B
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CN114931967A (en
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谭媛
李秀丽
丁云杰
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Zhejiang Normal University CJNU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention discloses a preparation method of a catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro-compounds, which takes sodium metasilicate and sodium metaaluminate as a silicon source and an aluminum source, synthesizes an AlSBA-15 carrier under certain conditions by adopting a template agent method, then adopts a two-step method to deposit metal salts of non-noble metals Cu and Ni on the AlSBA-15 carrier in steps, and then obtains a supported Cu-Ni catalyst by drying, roasting, hydrogen reduction and other treatments. The prepared Cu-Ni bi-component catalyst has very high activity (100%) and selectivity (99%) in the reaction of preparing corresponding aromatic amine by selective hydrogenation of aromatic nitro-compounds, mild reaction conditions and strong universality, and is suitable for various aromatic nitro-compounds containing different functional groups.

Description

Preparation method and application of catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound
Technical Field
The invention relates to the technical field of catalytic hydrogenation, in particular to a preparation method and application of a catalyst for preparing corresponding aromatic amine by catalyzing selective hydrogenation of aromatic nitro compounds.
Background
Hydrogenation is one of the most important catalytic reactions in fine chemical production. The traditional method generally adopts a metered reducing agent to reduce the compound (comprising a metal-acid system reduction method, a sulfide reduction method or a hydrazine hydrate reduction method and the like), but the process is not only cumbersome, but also pollutes the environment. In contrast, the catalytic hydrogenation method has the characteristics of high atomic efficiency, environmental friendliness and the like, and attracts attention of vast researchers in recent years.
The functionalized aromatic amine compounds are important mass chemicals and are also main raw materials or key intermediates of dyes, medicines, herbicides, polymers, agrochemicals and fine chemicals. The hydrogen is used as the reducing agent, and the aromatic nitro compound is selectively hydrogenated under certain conditions to prepare the corresponding aromatic amine compound, so that the method has the characteristics of cleanness, environmental protection, high efficiency and the like.
However, during catalytic hydrogenation of aromatic nitro compounds, there is often a competing reaction between the nitro group and other functional groups, and thus, selective reduction of the nitro group to an amino group without other side reactions presents a considerable challenge. The use of supported noble metal catalysts to catalyze selective hydrogenation of nitro compounds is currently the focus of attention of many researchers. Among them, the noble metal Pt, pd, ru, au and the like exhibit excellent catalytic performance in the reaction. For example, patent publication No. CN101745382A discloses a Pt catalyst prepared by an impregnation method under a reaction condition of 40℃H 2 After 35min of reaction under the pressure of 3MPa, the conversion rate and the selectivity of p-chloroaniline prepared by the selective hydrogenation of p-chloronitrobenzene can reach 100 percent. Literature (Angew. Chem. Int. Ed.,2017,129 (33): 9879-9883) reports a Pd@beta catalyst with a core-shell structure for the selective hydrogenation of nitrobenzaldehyde at a reaction temperature of 80 ℃, H 2 The reaction is carried out for 2 hours under the pressure of 1MPa, and the conversion rate and the selectivity of the nitrobenzaldehyde are both over 99.9 percent. The literature (science.2006, 313 (5785): 332-334) reported for the first time a supported gold catalyst (Au/TiO) 2 、Au/Fe 2 O 3 ) Catalytic effect in preparing aminostyrene by nitrostyrene selective hydrogenation at reaction temperature of 120 ℃ and H 2 Reacting for 6h under the pressure of 0.9MPa, wherein Au/TiO is prepared 2 Shows the highest conversion (98.5%) and selectivity (95.9%).
Although noble metal catalysts exhibit good catalytic effects in selective hydrogenation of aromatic nitro compounds, their high cost and scarce resources limit their industrial application. Therefore, the research on the application of the non-noble metal catalyst in the selective hydrogenation reaction of the aromatic nitro compound has important practical significance. Document (Nature chem.; 2013,5 (6): 537-543) reports a Co-L1/C catalyst for the selective hydrogenation of o-chloronitrobenzene at a reaction temperature of 110 ℃, H 2 The reaction is carried out for 4 hours under the pressure of 5MPa, and the conversion rate and the yield can reach 99 percent. Literature (science.2013, 342(6162) 1073-1076) reports that an Fe-phen/C-800 catalyst is used for selective hydrogenation of pentachloronitrobenzene at 120 ℃ and H 2 The reaction is carried out for 12 hours under the pressure of 5MPa, the substrate is completely converted, and the yield of pentachloroaniline can reach 96 percent. Document (ACS Catal.,2015,5 (8): 4814-4818) reports a Ni/SiO prepared by atomic layer deposition 2 The catalyst is used for fluoronitrobenzene selective hydrogenation, when hydrazine hydrate is used as a hydrogen source and reacts for 8 hours at 100 ℃, the substrate is completely converted, and the selectivity of the fluoroaniline can reach 98.2 percent.
Copper is also an inexpensive metal compared to the above catalyst, however, its activity in hydrogenation is weak, so that the reaction conditions are generally severe, and Cu catalysts are easily deactivated under long-term operation, so that it is an effective strategy to promote its activity and stability in the reaction by alloying Cu with other metals or adding a second component to improve the dispersibility and reducibility of Cu as an active component. The catalytic effect of Cu-Ni, cu-Co catalysts in the gas phase hydrogenation of o-chloronitrobenzene to o-chloroaniline is reported in literature (Catal. Commun.,. 2010,11 (2): 142-145). The catalyst is operated for about 10 hours at the reaction temperature of 310 ℃ and the hydrogen flow rate of 45-60mL/min, the Cu-Ni catalyst shows higher conversion rate (96.6%) and product selectivity (97.8%), and the Cu-Co catalyst has slightly lower conversion rate (87.5%), but the product selectivity can also reach 97.6%. The literature (ChemCatChem, 2012,4 (5): 668-673) reports the catalytic effect of Cu-Al and Cu-Ni-Al catalysts in the hydrogenation of p-chloronitrobenzene, with the selectivity maintained at 100% compared to the single Cu catalyst with the Cu-Ni-Al and Cu-Al catalysts having an increased activity at a reaction temperature of 150 ℃. However, the catalyst prepared by the method still has the problems of poor activity, easy deactivation, harsh reaction conditions and the like, so that the development of an efficient and stable non-noble metal catalytic system is still heavy and far away.
Mesoporous materials play an important role in synthesizing highly dispersed metal catalysts due to controllable pore size, pore volume and high specific surface area. Mesoporous materials are used as carriers of metals and catalytically active species and exhibit good catalytic performance in reactions such as methane reforming (RSC adv.,2016,6 (77): 73887-73896), nitrobenzene hydrogenation (catalyst. Lett.,2009,128 (1-2): 164-170), and methanol oxidation (Carbon, 2009,47 (1): 186-194).
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro-compound, which synthesizes a bimetallic catalyst with mutually promoted Cu and Ni components by using a two-step method, and applies the bimetallic catalyst to the reaction for preparing corresponding aromatic amine by selective hydrogenation of aromatic nitro-compound, and obtains excellent activity (100%) and selectivity (> 99%) under milder conditions.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation method of the catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound comprises the following steps:
(1) Respectively taking sodium metasilicate and sodium metaaluminate as a silicon source and an aluminum source, and adopting a template agent method to synthesize an AlSBA-15 carrier under certain conditions;
(2) Depositing a metal salt precursor containing Ni on the carrier synthesized in the step 1) by adopting a precipitator, filtering, washing and drying to obtain Ni/AlSBA-15;
(3) Depositing a metal salt precursor containing Cu onto the Ni/AlSBA-15 synthesized in the step 2) by adopting a precipitant, and obtaining mNi-nCu/AlSBA-15 through the processes of filtering, washing, drying and the like, wherein m and n are the loading amounts of Ni and Cu respectively;
(4) And (3) placing the mNi-nCu/AlSBA-15 synthesized in the step (3) into a muffle furnace with a certain temperature for roasting, and placing the roasted powder into a hydrogen atmosphere with a certain temperature for reduction, so as to obtain the catalyst which can be directly used for hydrogenation catalytic reaction, wherein the catalyst is marked as mNi-nCu/AlSBA-R, and R is the reduction temperature.
Further, the template is selected from P123, and the relative molecular mass is 8400.
Further, the AlSBA-15 carrier obtained in the step (1) has a Si content of 15-35 wt.% and an Al content of 20-55 wt.%.
Further, the content of Cu as an active component in the mNi-nCu/AlSBA-15 catalyst obtained in the step (3) is 0.01-30 wt.% and the content of Ni is 0.1-20 wt.%.
Further, the Ni-containing metal salt in step (2) is selected from the group consisting of nitrate, sulfate, acetate, chloride, or carbonate of Ni; the metal salt containing Cu in step (3) is selected from nitrate, sulfate, acetate, chloride or carbonate of Cu.
Further, the precipitants in step (2) and step (3) are selected from sodium carbonate, sodium bicarbonate, urea, or ammonia water.
Further, sodium metasilicate Na 2 SiO 3 Sodium metaaluminate NaAlO 2 The molar ratio of the template agent P123, the precipitant and the Cu-Ni metal salt is 2.5-1000: 1.5 to 1000:0.05 to 50: 1-30: 1.
more specifically, the preparation method of the catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound comprises the following steps:
(1) Adding a certain amount of sodium metaaluminate into template agent P123, dissolving in water, magnetically stirring at 25-100 ℃, dissolving a certain amount of sodium metasilicate into water, stirring for a period of time under the same condition, regulating the pH value of the sodium metasilicate solution to 5-7 by using HCl, slowly dripping the sodium metaaluminate solution into the sodium metasilicate solution by using a peristaltic pump to obtain a final mixed solution, stirring at 25-100 ℃, and finally filtering, washing and drying the solution to obtain an AlSBA-15 carrier;
(2) Taking a certain amount of Ni (NO) 3 ) 2 ·6H 2 O is dissolved in 25mL deionized water, stirred at 25-100 ℃, alSBA-15 carrier is added, stirring is continued, and Na is used 2 CO 3 Regulating the pH value of the solution to 8.0-12.0, continuously stirring, filtering, washing and drying to obtain mNi/AlSBA-15;
(3) Another amount of Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 25mL of deionized water, stirred for a certain time under the same condition, then mNi/AlSBA-15 is added, stirring is continued, pH is regulated to 8.0-12.0, stirring is continued, and finally mNi-nCu/AlSBA-15 is obtained through filtration, washing and drying, wherein m and n are the loading amounts of Ni and Cu respectively;
(4) And (3) synthesizing mNi-nCu/AlSBA-15, roasting in a muffle furnace with a certain temperature, and reducing the roasted powder in a hydrogen atmosphere with a certain temperature to obtain the catalyst which can be directly used for hydrogenation catalytic reaction, wherein the roasting temperature is 200-800 ℃, the roasting time is 60-360 min, the reduction temperature is 100-800 ℃, the reduction time is 60-360 min, and the obtained catalyst is mNi-nCu/AlSBA-R, wherein R is the reduction temperature.
Further, the reduction temperature in the step (4) is 250-650 ℃.
The invention also aims to provide a method for preparing aromatic amine by selective hydrogenation of aromatic nitro compound, which adopts the following technical scheme:
a method for preparing aromatic amine by selective hydrogenation of aromatic nitro compound comprises loading the prepared catalyst mNi-nCu/AlSBA-R, aromatic nitro compound and solvent into a high-pressure reaction kettle equipped with a magnetic stirring device, replacing the gas in the kettle with hydrogen for 3-6 times, filling a certain pressure, sealing the kettle, heating in a water bath or an oil bath kettle with a certain temperature, starting stirring when the temperature in the kettle reaches a preset temperature, recording the reaction time, cooling the reaction kettle in cooling water with the temperature of 0-30 ℃ after the reaction is finished, and quantitatively analyzing the reaction product by gas chromatography;
or in a continuous fixed bed reactor, loading the prepared catalyst mNi-nCu/AlSBA-R into a constant temperature area of the fixed bed reactor, and introducing N into the reaction system 2 Purging the reaction pipeline for 10-30 min, and switching the reaction gas into H 2 And utilize backpressure valve and mass flowmeter to H in the reaction system 2 The pressure and flow are regulated, the temperature controller with K-type thermocouple is used for regulating the reaction temperature, the system temperature is increased to a specified value, then the system is waited for stabilization, then the aromatic nitro compound or the mixed solution of the aromatic nitro compound and the solvent is pumped into a reaction system through a high-pressure pump, the weight hourly space velocity is regulated, the reaction is started, the liquid product is sampled by a collecting tank and analyzed by gas chromatography, and the tail gas is detected by online gas chromatography.
Further, the aromatic nitro compound is selected from o-nitrophenol, nitrostyrene, nitroacetophenone, nitroacetonitrile, ethyl nitrobenzoate, 3, 4-dichloronitrobenzene, chloronitrobenzene, bromonitrobenzene, or nitrobenzene.
Further, the solvent is one or more selected from tetrahydrofuran, water, ethanol, methanol, toluene, isopropanol, cyclohexane, dichloromethane and the like.
Further, the reaction conditions are: the temperature is 60-120 ℃, preferably 80-120 ℃; h 2 The pressure is 0.1-6 MPa, preferably 1-4 MPa; the reaction time in the kettle type reactor is 10 min-24 h; the flow rate of hydrogen in the fixed bed reactor is 10-200 mL/min, and the weight hourly space velocity is 0.01-200 h -1 。
Further, the concentration of the aromatic nitro compound is 0.01-5M; the total molar ratio of the aromatic nitro compound to Cu-Ni in the catalyst is 0.6-300: 1.
the beneficial effects of the invention are as follows: the Al-modified SBA-15 mesoporous material is used as a carrier to carry non-noble metals Cu and Ni, and is applied to the selective hydrogenation of aromatic nitro compounds, so that excellent activity (100%) and selectivity (> 99%) are obtained under milder conditions. By depositing Cu and Ni onto AlSBA-15 carrier step by step, aggregation of Cu-Ni components can be effectively limited, and meanwhile, interaction between Cu and Ni plays an important role in stabilizing Cu-Ni active species and enhancing activity and selectivity of the Cu-Ni active species in hydrogenation reaction. The method provides guidance for synthesizing the high-efficiency, high-selectivity and stable non-noble metal catalyst, provides thought for understanding interaction between Cu and Ni, and is expected to replace the noble metal catalyst to be applied to industrial production in the future.
Drawings
In FIG. 1, (a) is a TEM image of an AlSBA-15 supported single metal Cu (5 Cu/AlSBA-300) catalyst, and (b) is a TEM image of a Cu-Ni two-component (5 Ni-2.5 Cu/AlSBA-300) catalyst.
Detailed Description
The invention is further explained below with reference to examples. The following examples are only illustrative of the present invention and are not intended to limit the scope of the invention.
Example 1: preparation method of catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound
(1) Preparation of AlSBA-15 vector: 7.3mmol of sodium metaaluminate NaAlO was taken 2 1.4mmol of template P123 (MW=8400) is added, dissolved in 850mL of water and magnetically stirred at 40 ℃ for 120min, 314mmol of sodium metasilicate Na is additionally taken 2 SiO 3 Dissolving in 2550mL of water, stirring for a period of time under the same conditions, regulating the pH of the sodium metasilicate solution to 5.0 by using 4.0M HCl, slowly dripping the sodium metasilicate solution into the sodium metasilicate solution by using a peristaltic pump to obtain a final mixed solution, then stirring at 40 ℃ for 240min, and finally filtering, washing and drying the solution to obtain the carrier AlSBA-15.
(2) Preparation of Ni/AlSBA-15: 0.5g Ni (NO) was weighed out 3 ) 2 ·6H 2 Dissolving O in 25mL water, magnetically stirring at 80deg.C for 15min, adding 2.0g of AlSBA-15 carrier prepared above, stirring for 10min, and adding 0.1M Na 2 CO 3 Regulating pH of the solution to about 9.5, continuously stirring at 80deg.C for 360min, filtering, washing, and drying to obtain Ni/AlSBA-15 (marked as A);
(3) Preparation of 5Ni-10 Cu/AlSBA-15: 0.76g Cu (NO) was weighed out 3 ) 2 ·3H 2 Dissolving O in 25mL water, magnetically stirring at 80deg.C for 15min, adding A, stirring for 10min, and adding 0.1M Na 2 CO 3 Regulating the pH of the solution to about 9.5, continuously stirring for 360min, filtering, washing and drying to obtain 5Ni-10Cu/AlSBA-15;
(4) Preparation of 5Ni-10Cu/AlSBA-300 catalyst: roasting Ni/AlSBA-15 at 500 deg.C and at 300 deg.C H 2 Reduction under an atmosphere (flow 30 mL/min) gave the final catalyst, designated (5 Ni-10 Cu/AlSBA-300), with an ICP measured Ni loading of 5.5wt.%, cu loading of 10.6wt.%.
Example 2
Preparation of 0.1Ni-10Cu/AlSBA-300 catalyst: in comparison with example 1, the difference is that Ni (NO 3 ) 2 ·6H 2 The mass of O was 0.01g, and the loading of Ni was 0.015wt.% and the loading of Cu was 10.1wt.% as measured by ICP.
Example 3
Preparation of 5Ni-0.1Cu/AlSBA-300 catalyst: in comparison with example 1, the difference is that Cu (NO 3 ) 2 ·3H 2 The mass of O was 0.01g, and the loading of Ni was 5.5wt.% and the loading of Cu was 0.13wt.% as measured by ICP for the finally prepared catalyst.
Example 4
Preparation of 5Ni-30Cu/AlSBA-300 catalyst: in comparison with example 1, the difference is that Cu (NO 3 ) 2 ·3H 2 The mass of O was 2.28g, and the loading of Ni was 5.3wt.% and the loading of Cu was 29.6wt.% as measured by ICP for the final catalyst.
Example 5
Preparation of 20Ni-5Cu/AlSBA-300 catalyst: the difference compared with example 1 is that Ni (NO) 3 ) 2 ·6H 2 O and Cu (NO) 3 ) 2 ·3H 2 The mass of O was 2.0 and 0.38g, respectively, and the loading of Ni was 20.3wt.% and the loading of Cu was 5.8wt.% as measured by ICP for the finally prepared catalyst.
Example 6
Preparation of 5Cu/AlSBA-300 catalyst: 0.38g Cu (NO) was weighed out 3 ) 2 ·3H 2 O was dissolved in 25mL of water and magnetically stirred at 80℃for 15min, 2.0g of AlSBA-15 carrier prepared in example 1 was added, stirring was continued for 10min, and then 0.1M Na was used 2 CO 3 Regulating pH to about 9.5, stirring at 80deg.C for 360min, filtering, washing, and drying to obtain 5Cu/AlSBA-15, calcining at 500deg.C, and H at 300deg.C 2 Reduction under atmosphere (flow 30 mL/min) gives the final catalyst with a Cu loading of 7.7wt.% as measured by ICP.
Example 7
Preparation of 5Ni/AlSBA-300 catalyst: in comparison with example 7, the difference is that 0.38g Cu (NO 3 ) 2 ·3H 2 O is changed to 0.5g Ni (NO) 3 ) 2 ·6H 2 O, the final catalyst produced had a Ni loading of 5.3wt.% as measured by ICP.
Example 8
Preparation of 5Ni-10Cu/AlSBA-250 catalyst: in comparison with example 1, the difference is that H 2 The temperature of the reduction under the atmosphere was 250 ℃.
Example 9
Preparation of 5Ni-10Cu/AlSBA-600 catalyst: in comparison with example 1, the difference is that H 2 The temperature of the reduction under the atmosphere was 600 ℃.
Example 10
Preparation of 5Ni-10Cu/AlSBA-800 catalyst: in comparison with example 1, the difference is that H 2 The temperature of the reduction under the atmosphere was 800 ℃.
Example 11
Preparation of 5Ni-10Cu/AlSBA-800 catalyst: in comparison with example 1, the difference is that in step (3), 0.76g of Cu (NO 3 ) 2 ·3H 2 O is changed to 0.64g CuSO 4 ·5H 2 O。
Example 12: preparation of p-chloroaniline by selective hydrogenation of p-chloronitrobenzene
Using tetrahydrofuran as solvent to prepare 0.20M p-chloronitrobenzene solution in advance, adding 50mg of 5Ni-10Cu/AlSBA-300 catalyst (total molar quantity of Cu-Ni is 0.12 mmol) prepared in example 1 into a 15mL stainless steel high-pressure reaction kettle, adding 2mL of p-chloronitrobenzene solution and magneton which are prepared in advance, pressurizing to 2.5MPa after removing air in the reaction kettle by hydrogen, and then placing in a 95 ℃ water bath kettle for stirring for 3 hours, analyzing the product, wherein the conversion rate of the reactant is 99.2%, and the selectivity of p-chloroaniline is 99.8%.
Example 13
The difference compared with example 12 is that the substrate is 3, 4-dichloronitrobenzene, the substrate conversion after the reaction is 99.9% and the selectivity for 3, 4-dichloroaniline is 99.9%.
Example 14
The difference compared to example 12 is that the substrate is ethyl 4-nitrobenzoate, the substrate conversion after the reaction is 100.0% and the selectivity to ethyl 4-aminobenzoate is 99.9%.
Example 15
The difference compared to example 12 is that the substrate is p-bromonitrobenzene, the substrate conversion after the reaction is 99.6% and the selectivity to p-bromoaniline is 96.5%.
Example 16
The difference compared to example 12 is that the substrate is o-nitrophenol, the substrate conversion after the reaction is 100.0% and the selectivity to o-aminophenol is 96.3%.
Example 17
The difference compared to example 12 is that the substrate is 4-nitroacetophenone, the substrate conversion after the reaction is 100.0% and the selectivity for 4-aminoacetophenone is 93.0%.
Example 18
The difference compared to example 12 is that the substrate is 4-nitrophenylacetonitrile, the substrate conversion after the reaction is 100% and the selectivity for 4-aminophenylacetonitrile is 89.0%.
Example 19
The difference compared with example 12 is that the substrate is 3-nitrostyrene, the reaction time is 2h, the conversion of the substrate after the reaction is 94.8%, and the selectivity of 3-aminostyrene is 99.9%.
Example 20
The difference compared with example 12 is that the catalyst is the 0.1Ni-10Cu/AlSBA-300 catalyst synthesized in example 2, the conversion of the substrate after the reaction is 12.1%, and the selectivity to chloroaniline is 80.9%.
Example 21
The difference compared with example 12 is that the catalyst is 5Ni-0.1Cu/AlSBA-300 catalyst synthesized in example 3, the conversion of the substrate after reaction is 3.1%, and the selectivity to chloroaniline is 21.3%.
Example 22
The difference compared with example 12 is that the catalyst is the 5Ni-30Cu/AlSBA-300 catalyst synthesized in example 4, the conversion of the substrate after the reaction is 99.7%, and the selectivity to chloroaniline is 99.8%.
Example 23
The difference compared with example 12 is that the catalyst is 20Ni-5Cu/AlSBA-300 catalyst synthesized in example 5, the conversion of the substrate after the reaction is 87.6%, and the selectivity to chloroaniline is 92.5%.
Example 24
The difference compared with example 12 is that the catalyst is the 5Cu/AlSBA-300 catalyst synthesized in example 6, the conversion rate of the substrate after the reaction is 45.3%, and the selectivity to chloroaniline is 98.5%.
Example 25
The difference compared with example 12 is that the catalyst is the 5Ni/AlSBA-300 catalyst synthesized in example 7, the conversion rate of the substrate after the reaction is 0, and the selectivity to chloroaniline is 0.
Example 26
The difference compared with example 12 is that the catalyst is the 5Ni-10Cu/AlSBA-250 catalyst synthesized in example 8, the conversion of the substrate after the reaction is 95.5%, and the selectivity to chloroaniline is 96.4%.
Example 27
The difference compared with example 12 is that the catalyst is the 5Ni-10Cu/AlSBA-600 catalyst synthesized in example 9, the conversion of the substrate after the reaction is 100%, and the selectivity to chloroaniline is 92%.
Example 28
The difference compared with example 12 is that the catalyst is the 5Ni-10Cu/AlSBA-800 catalyst synthesized in example 10, the conversion of the substrate after the reaction is 20.1%, and the selectivity to chloroaniline is 85.7%.
Example 29
The difference compared to example 12 is that the reaction time is 1h, the conversion of the substrate after the reaction is 86.3% and the selectivity to chloroaniline is 98.2%.
Example 30
The difference compared to example 12 is that the reaction time is 10min, the conversion of the substrate after the reaction is 8.5% and the selectivity to p-chloroaniline is 93.0%.
Example 31
The difference compared with example 12 is that the reaction time is 1h, the hydrogen pressure is 1MPa, the conversion of the substrate after the reaction is 25.4%, and the selectivity to p-chloroaniline is 50.7%.
Example 32
The difference compared with example 12 is that the reaction time is 1h, the hydrogen pressure is 1.5MPa, the conversion of the substrate after the reaction is 32.3%, and the selectivity to p-chloroaniline is 63.8%.
Example 33
The difference compared with example 12 is that the reaction time is 1h, the hydrogen pressure is 6MPa, the conversion of the substrate after the reaction is 99.5%, and the selectivity to p-chloroaniline is 70.7%.
Example 34
The difference compared to example 12 is that the reaction temperature is 80℃and the substrate conversion after the reaction is 70.6% and the selectivity to chloroaniline is 85.2%.
Example 35
The difference compared to example 12 is that the reaction temperature is 120℃and the conversion of the substrate after the reaction is 100% and the selectivity to p-chloroaniline is 94.7%.
Example 36
The difference compared with example 12 is that the substrate concentration is 1M, the reaction time is 12h, the conversion of the substrate after the reaction is 87.9%, and the selectivity to chloroaniline is 98.1%.
Example 37
The difference compared to example 12 is that the substrate concentration is 5M, the reaction time is 24h, the substrate conversion after the reaction is 79.8%, and the p-chloroaniline selectivity is 98.7%.
Example 38
The difference compared to example 12 is that the substrate concentration is 0.1M, the reaction time is 1h, the conversion of the substrate after the reaction is 99.4%, and the selectivity to p-chloroaniline is 99.9%.
Example 39
The selective hydrogenation of p-chloronitrobenzene is carried out in a continuous fixed bed reactor, 0.5g of the 5Ni-10Cu/AlSBA-300 catalyst prepared in example 1 is weighed and filled into a constant temperature zone of the fixed bed reactor, and N is introduced into a reaction system 2 Purging the reaction pipeline, and switching the reaction gas into H after 10min 2 And utilize backpressure valve and mass flowmeter to H in the reaction system 2 Pressure and flow are regulated, H 2 The pressure was controlled to 2MPa and the flow rate was 50mL/min. The temperature controller with K-type thermocouple is used to regulate the reaction temperature, the system temperature is raised to 100 ℃, then the system is waited for to stabilize, and then p-chloronitrobenzene solution (tetrahydrofuran solvent) with a certain concentration is pumped into the reaction system by a high-pressure pump, the weight hourly space velocity is 0.2h -1 After a period of reaction time, the liquid product in the condensing tank is collected and analyzed by gas chromatography, tail gas is detected by online gas chromatography, and the chromatographic result shows that the conversion rate of the substrate in the liquid product after the reaction is 98.4%, and the selectivity of the p-chloroaniline is 99.1%.

Claims (13)

1. The preparation method of the catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound is characterized by comprising the following steps:
(1) The AlSBA-15 carrier is synthesized by taking sodium metasilicate and sodium metaaluminate as a silicon source and an aluminum source respectively and adopting a template agent method under certain conditions, and specifically comprises the following steps: adding a certain amount of sodium metaaluminate into template agent P123, dissolving in water, magnetically stirring at 25-100 ℃, dissolving a certain amount of sodium metasilicate into water, stirring for a period of time under the same condition, regulating the pH value of the sodium metasilicate solution to 5-7 by using HCl, slowly dripping the sodium metaaluminate solution into the sodium metasilicate solution by using a peristaltic pump to obtain a final mixed solution, stirring at 25-100 ℃, and finally filtering, washing and drying the solution to obtain an AlSBA-15 carrier;
(2) Depositing a metal salt precursor containing Ni on the carrier synthesized in the step 1) by adopting a precipitator, filtering, washing and drying to obtain Ni/AlSBA-15;
(3) Depositing a metal salt precursor containing Cu onto the Ni/AlSBA-15 synthesized in the step 2) by adopting a precipitant, and obtaining mNi-nCu/AlSBA-15 through filtering, washing and drying processes, wherein m and n are the loading amounts of Ni and Cu respectively;
(4) And (3) placing the mNi-nCu/AlSBA-15 synthesized in the step (3) into a muffle furnace with a certain temperature for roasting, and placing the roasted powder into a hydrogen atmosphere with a certain temperature for reduction, so as to obtain the catalyst which can be directly used for hydrogenation catalytic reaction, wherein the catalyst is marked as mNi-nCu/AlSBA-R, and R is the reduction temperature.
2. The method for preparing the catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 1, wherein the template agent in the step (1) is selected from P123, and the relative molecular mass is 8400; the content of Si in the obtained AlSBA-15 carrier is 15-35 wt.% and the content of Al is 20-55 wt.%; the content of active component Cu in the mNi-nCu/AlSBA-15 catalyst obtained in the step (3) is 5.8-30 wt.% and the content of Ni is 5.3-20 wt.%.
3. The method for preparing the catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 1, wherein the metal salt containing Ni in the step (2) is selected from nitrate, sulfate, acetate, chloride or carbonate of Ni; the metal salt containing Cu in the step (3) is selected from nitrate, sulfate, acetate, chloride or carbonate of Cu; the precipitants in the step (2) and the step (3) are selected from sodium carbonate, sodium bicarbonate, urea or ammonia water.
4. The method for preparing the catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 1, wherein sodium metasilicate Na 2 SiO 3 Sodium metaaluminate NaAlO 2 The molar ratio of the template agent P123, the precipitant and the Cu-Ni metal salt is 2.5-1000: 1.5 to 1000:0.05 to 50: 1-30: 1.
5. the method for preparing the catalyst for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to any one of claims 1 to 4, comprising the following steps:
(1) Adding a certain amount of sodium metaaluminate into template agent P123, dissolving in water, magnetically stirring at 25-100 ℃, dissolving a certain amount of sodium metasilicate into water, stirring for a period of time under the same condition, regulating the pH value of the sodium metasilicate solution to 5-7 by using HCl, slowly dripping the sodium metaaluminate solution into the sodium metasilicate solution by using a peristaltic pump to obtain a final mixed solution, stirring at 25-100 ℃, and finally filtering, washing and drying the solution to obtain an AlSBA-15 carrier;
(2) Taking a certain amount of Ni (NO) 3 ) 2 ·6H 2 O is dissolved in 25mL deionized water, stirred at 25-100 ℃, alSBA-15 carrier is added, stirring is continued, and Na is used 2 CO 3 Regulating the pH value of the solution to 8.0-12.0, continuously stirring, filtering, washing and drying to obtain mNi/AlSBA-15;
(3) Another amount of Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 25mL of deionized water, stirred for a certain time under the same condition, then mNi/AlSBA-15 is added, stirring is continued, pH is regulated to 8.0-12.0, stirring is continued, and finally mNi-nCu/AlSBA-15 is obtained through filtration, washing and drying, wherein m and n are the loading amounts of Ni and Cu respectively;
(4) Placing mNi-nCu/AlSBA-15 synthesized in the step (3) into a muffle furnace with a certain temperature for roasting, and placing the roasted powder into a hydrogen atmosphere with a certain temperature for reduction, so that the catalyst which can be directly used for hydrogenation catalytic reaction is obtained, wherein the roasting temperature is 200-800 ℃, the roasting time is 60-360 min, the reduction temperature is 100-650 ℃, the reduction time is 60-360 min, and the obtained catalyst is mNi-nCu/AlSBA-R, wherein R is the reduction temperature.
6. The method for preparing a catalyst for aromatic amine preparation by selective hydrogenation of aromatic nitro compound according to claim 5, wherein the reduction temperature of the step (4) is 250-650 ℃.
7. A method for preparing aromatic amine by using the catalyst prepared by the method of any one of claims 1-6 for selective hydrogenation of aromatic nitro compounds, which is characterized by comprising the steps of loading the prepared catalyst mNi-nCu/AlSBA-R, aromatic nitro compounds and solvent into a high-pressure reaction kettle provided with a magnetic stirring device, replacing gas in the kettle for 3-6 times by hydrogen, filling a certain pressure, sealing the kettle, placing the kettle in a water bath or an oil bath kettle with a certain temperature for heating, starting stirring when the temperature in the kettle reaches a preset temperature, starting to record the reaction time, placing the reaction kettle in cooling water with the temperature of 0-30 ℃ after the reaction is finished, and quantitatively analyzing a reaction product by using gas chromatography;
or in a continuous fixed bed reactor, loading the prepared catalyst mNi-nCu/AlSBA-R into a constant temperature area of the fixed bed reactor, and introducing N into the reaction system 2 Purging the reaction pipeline for 10-30 min, and switching the reaction gas into H 2 And utilize backpressure valve and mass flowmeter to H in the reaction system 2 The pressure and flow are regulated, the temperature controller with K-type thermocouple is used for regulating the reaction temperature, the system temperature is increased to a specified value, then the system is waited for stabilization, then the aromatic nitro compound or the mixed solution of the aromatic nitro compound and the solvent is pumped into a reaction system through a high-pressure pump, the weight hourly space velocity is regulated, the reaction is started, the liquid product is sampled by a collecting tank and analyzed by gas chromatography, and the tail gas is detected by online gas chromatography.
8. The method for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 7, wherein the aromatic nitro compound is selected from o-nitrophenol, nitrostyrene, nitroacetophenone, nitroacetonitrile, ethyl nitrobenzoate, 3, 4-dichloronitrobenzene, chloronitrobenzene, bromonitrobenzene or nitrobenzene.
9. The method for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 7, wherein the solvent is one or more selected from tetrahydrofuran, water, ethanol, methanol, toluene, isopropanol, cyclohexane, dichloromethane, etc.
10. The method for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 7, wherein the reaction conditions are as follows: the temperature is 80-120 ℃; h 2 The pressure is 2-6 MPa; the reaction time in the kettle type reactor is 1 to 24 hours; the flow rate of hydrogen in the fixed bed reactor is 10-200 mL/min, and the weight hourly space velocity is 0.01-200 h -1 。
11. The method for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 10, wherein the temperature is 95-120 ℃.
12. The method for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 10, wherein the H is 2 The pressure is 2-4 MPa.
13. The method for preparing aromatic amine by selective hydrogenation of aromatic nitro compound according to claim 10, wherein the concentration of aromatic nitro compound is 0.01-5M; the total molar ratio of the aromatic nitro compound to the catalyst Cu-Ni is 0.6-300: 1.
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