CN111013561A - Preparation method of catalyst for liquid-phase hydrogenation of nitrobenzene to prepare aniline - Google Patents

Preparation method of catalyst for liquid-phase hydrogenation of nitrobenzene to prepare aniline Download PDF

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CN111013561A
CN111013561A CN201911406309.XA CN201911406309A CN111013561A CN 111013561 A CN111013561 A CN 111013561A CN 201911406309 A CN201911406309 A CN 201911406309A CN 111013561 A CN111013561 A CN 111013561A
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catalyst
nitrobenzene
preparing
palladium
aniline
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安霓虹
戴云生
王红琴
王剑辉
张孟旭
沈亚峰
周伟
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Kunming Sino Platinum Metals Catalyst Co ltd
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Kunming Sino Platinum Metals Catalyst Co ltd
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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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • 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
    • B01J35/393—
    • B01J35/396—
    • B01J35/613—
    • B01J35/633—
    • B01J35/647—
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • 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
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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

Abstract

The invention discloses a preparation method of a catalyst for preparing aniline by liquid phase hydrogenation of nitrobenzene, belonging to the technical field of petrochemical catalytic hydrogenation. The preparation method of the invention avoids the migration and agglomeration in the loading process, the prepared catalyst can ensure that the metal is stably distributed on the carbon carrier, the service life and the activity of the catalyst are improved, and the good catalytic effect is still kept after the catalyst is recycled for many times.

Description

Preparation method of catalyst for liquid-phase hydrogenation of nitrobenzene to prepare aniline
Technical Field
The invention belongs to the technical field of catalytic hydrogenation in petrochemical industry, and particularly relates to a preparation method of a catalyst for preparing aniline by liquid-phase hydrogenation of nitrobenzene.
Background
The industrial production of aniline begins in 1857 years, the nitrobenzene iron powder reduction method is adopted at first, and the aniline is gradually replaced by an advanced nitrobenzene catalytic hydrogenation method after the 50 s of the 20 th century because of the defects of huge equipment, serious corrosion, large iron powder consumption, serious three-waste pollution and the like; the phenol ammoniation method was successfully developed in 1962, and the industrial production was realized in 1970. Currently, the production of aniline in the world is mainly based on a nitrobenzene catalytic hydrogenation method.
The nitrobenzene liquid phase catalytic hydrogenation catalyst system is mainly classified into Cu-based, Ni-based (including Ni amorphous alloy catalyst, such as Ni-B or Ni-P catalyst), Pd-based, Pt-based, Au-based and multi-metal (such as PdPt, FeCo, etc.) catalysts, and in addition, metal catalysts such as Co, Ag, Ru, Ir, Rh, etc. according to the types of different active sites. For example, the chinese patent "a process for synthesizing aniline by hydrogenation of nitrobenzene" (application No. 201410526666.0), discloses a Pd, Pt, Rh, Ru or Ni supported catalyst; chinese patent 'a nitrogen-doped carbon material loaded Pd catalyst and a preparation method thereof and application thereof in nitrobenzene catalytic hydrogenation reaction' (application number is 201710125093.4), discloses a Pd supported catalyst. The initial yield of aniline in literature reports is high and can reach more than 99.85%, but specific stability data are rarely disclosed. Meanwhile, the research on nitrobenzene hydrogenation catalysts focuses on initial activity, the problems of oxidative deterioration, poisoning and inactivation, coking and agglomeration, loss, poor reusability and the like of the catalysts cannot be completely solved, and most catalytic systems are only limited to laboratory research.
At present, the domestic production device mainly adopts a liquid phase hydrogenation technology of DuPont company, uses a platinum/palladium catalyst taking carbon as a carrier and iron as a modifier, and the reaction is carried out in a piston type fluidized bed reactor. In the case of the catalyst for preparing aniline by hydrogenation of nitrobenzene, the conversion rate of nitrobenzene is close to 100 percent by combining the catalyst investigated by the literature. The key point of the reaction is how to control the reaction speed, prevent the pore channel from being blocked and prolong the service life of the catalyst.
It has been found that, on one hand, the physicochemical properties of the carbon support greatly affect the physicochemical properties of the finally synthesized catalyst, and on the other hand, the loading manner, component ratio and the like of the active metal component also affect the performance of the catalyst. Therefore, research on reasonable parameters of a catalytic system, such as specific surface area, granularity, bulk density, metal size morphology and the like of a carbon carrier, has important significance in improving the service life and operability of the catalyst while ensuring high yield of the catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for preparing aniline by nitrobenzene liquid-phase hydrogenation. The prepared catalyst has high yield, and the service life and the operability of the catalyst are greatly improved.
The technical scheme of the invention is as follows:
a preparation method of a catalyst for preparing aniline by nitrobenzene liquid phase hydrogenation comprises the following steps:
1) preparing a carbon carrier, namely heating vinasse which is a byproduct in the brewing industry in 0.5mol/L ethylenediamine solution at 90 ℃ in an oil bath, stirring and refluxing for 6 hours, taking out the vinasse, drying the vinasse in an oven, mixing citric acid, aluminum nitrate, phosphoric acid and the vinasse treated by the method according to the mass ratio of 0.5: 1-5: 2: 10-15, adding water, uniformly stirring, dropwise adding 0.5mol/L diluted ammonia water to adjust the pH value of the system to 5.0, continuously stirring for 5 hours, evaporating the mixture on the water bath, carbonizing the mixture at 300 ℃, performing dry distillation at 600-800 ℃, pickling and dealuminizing with 4-6 mol/L nitric acid, washing the mixture with distilled water to be neutral, and drying the mixture in the oven at 110 ℃ to obtain the carbon carrier;
2) preparing a catalyst, namely mixing polyol, ethylene diamine tetraacetic acid and a metal compound according to a mass ratio of 100: 5-8: 2 until the polyol, the ethylene diamine tetraacetic acid and the metal compound are completely dissolved, adjusting the pH value to 10-12 by adopting NaOH, and reducing for 2-4 hours at 120-170 ℃ to obtain a metal colloid particle solution; diluting the metal colloidal particle solution by 2 times with water, adding the carbon carrier prepared in the step 1), performing ultrasonic treatment, and standing in a water bath at 80 ℃ for 12-24 h; finally, filtering and washing to obtain the catalyst for preparing aniline by nitrobenzene liquid phase hydrogenation; the metal compounds are iron salt, palladium salt and platinum compounds, wherein the mass ratio of iron to palladium to platinum is 3-8: 1.
In the present invention, the polyhydric alcohol is preferably one or more of ethylene glycol, glycerin, and 1, 2-propylene glycol, and further preferably ethylene glycol; the ferric salt is preferably one or more of ferric nitrate, ferric chloride and ferric sulfate, and further preferably ferric nitrate nonahydrate; the palladium salt is preferably one or more of palladium chloride, palladium nitrate and palladium acetate, and is further preferably palladium chloride; the platinum compound is preferably one or more of chloroplatinic acid, potassium tetrachloroplatinate and potassium hexachloroplatinate, and further preferably chloroplatinic acid.
In the invention, the concentration of NaOH used in the step 2) is preferably 10-15 wt%; the time of ultrasonic treatment is preferably 3-5 h.
In the invention, the mass ratio of the carbon carrier in the step 2) to the metal in the metal compound is preferably 95: 5-15.
Has the advantages that:
1. the carbon carrier prepared by the method has a specific pore structure and surface functional groups, so that on one hand, metal can be stably distributed on the carbon carrier, migration and agglomeration in a loading process are avoided, the service life and activity of the catalyst are improved, and a good catalytic effect is still kept after the carbon carrier is recycled for multiple times; and the carbon carrier has strong lipophilicity, is favorable for diffusion in aniline and nitrobenzene, and improves the uniform mixing degree of gas-solid-liquid three phases.
2. The catalyst prepared by the method can effectively eliminate the influence of internal diffusion and ensure the filtering performance of the catalyst; by controlling the preparation parameters of the metal particles, the size of the metal particles can be effectively regulated and controlled so as to achieve the optimal catalytic effect; meanwhile, most of metal particles are distributed on the surface of the carbon, so that the metal particles are prevented from entering the pore channel, and the utilization rate of the metal is improved.
3. The catalyst of the invention is suitable for liquid phase hydrogenation of nitrobenzene. The nitrobenzene has high hydrogenation activity and good stability at 50-150 ℃.
Description of the drawings:
FIG. 1 shows N of carbon supports prepared in examples 1 to 32Adsorption and desorption curves.
Fig. 2 is a TEM image of the catalyst prepared in example 6.
Fig. 3 is a catalytic stability experiment of the catalyst prepared in example 6.
Detailed Description
The preparation of the support and the catalyst of the present invention is carried out according to the above procedures, and is described in detail below by way of examples. These examples are given for the purpose of illustration only and are not intended to be limiting.
Example 1
Preparation of the carrier: 300g of vinasse is heated in an oil bath at 90 ℃ in 0.5mol/L of ethylenediamine solution, stirred and refluxed for 6 hours, and then taken out and dried in a drying oven. Placing 5g of citric acid, 12g of aluminum nitrate, 20g of phosphoric acid and 150g of sample in a three-necked bottle, adding 250mL of water, stirring uniformly, dropwise adding 0.5mol/L of dilute ammonia water, adjusting the pH value to 5.0, continuously stirring for 5h, and evaporating on a water bath. Then treating the mixture for 5min at 300 ℃ in air atmosphere, roasting the mixture for 6h at 800 ℃ in argon atmosphere and adding 4mol/L of HNO3Treating the solution for 4 hours, washing the solution to be neutral by distilled water, and drying the solution in an oven at 110 ℃ to obtain the carbon carrier. The physical parameters of the carbon carrier are as follows: average specific surface area of 48m2G, average pore diameter of 11nm and average pore volume of 0.16cm3G, bulk density 0.17g/cm3。
Preparation of the catalyst: mixing 200g of ethylene glycol, 14g of ethylenediamine tetraacetic acid, 3.24g of ferric nitrate nonahydrate, 1.10g of palladium nitrate and 0.27g of chloroplatinic acid until the mixture is completely dissolved, adjusting the pH value to 10 by adopting 10 wt% of NaOH, and reducing for 1h at 150 ℃ to obtain a metal colloid particle solution; adding 200mL of water, mixing, adding 9g of carbon carrier, performing ultrasonic treatment for 2h, and standing in a water bath kettle at 80 ℃ for 12 h; and finally, filtering and washing to obtain the target catalyst.
Example 2
Preparation of the carrier: 300g of vinasse is heated in an oil bath at 90 ℃ in 0.5mol/L of ethylenediamine solution, stirred and refluxed for 6 hours, and then taken out and dried in a drying oven. Placing 5g of citric acid, 18g of aluminum nitrate, 20g of phosphoric acid and 130g of sample in a three-necked bottle, adding 250mL of water, stirring uniformly, dropwise adding 0.5mol/L of dilute ammonia water, adjusting the pH value to 5.0, continuously stirring for 5h, and evaporating on a water bath. Then treating for 5min at 300 ℃ in air atmosphere, roasting for 6h at 600 ℃ in argon atmosphere and adding 6mol/L HNO3Treating the solution for 4 hours, washing the solution to be neutral by distilled water, and drying the solution in an oven at 110 ℃ to obtain the carbon carrier. The physical parameters of the carbon carrier are as follows: average specific surface area 68m2G, average pore diameter of 10nm and average pore volume of 0.19cm3G, bulk density 0.19g/cm3。
Preparation of the catalyst: mixing 200g of ethylene glycol, 14g of ethylenediamine tetraacetic acid, 3.24g of ferric nitrate nonahydrate, 1.10g of palladium nitrate and 0.27g of chloroplatinic acid until the mixture is completely dissolved, adjusting the pH value to 10 by adopting 10 wt% of NaOH, and reducing for 1h at 150 ℃ to obtain a metal colloid particle solution; adding 200mL of water, mixing, adding 9g of carbon carrier, performing ultrasonic treatment for 2h, and standing in a water bath kettle at 80 ℃ for 12 h; and finally, filtering and washing to obtain the target catalyst.
Example 3
Preparation of the carrier: 300g of vinasse is heated in an oil bath at 90 ℃ in 0.5mol/L of ethylenediamine solution, stirred and refluxed for 6 hours, and then taken out and dried in a drying oven. Placing 7.5g of citric acid, 15g of aluminum nitrate, 30g of phosphoric acid and 150g of sample in a three-necked bottle, adding 250mL of water, stirring uniformly, dropwise adding 0.5mol/L of dilute ammonia water, adjusting the pH value to 5.0, continuously stirring for 5h, and evaporating on a water bath. Then treating the mixture for 5min at 300 ℃ in air atmosphere, roasting the mixture for 6h at 800 ℃ in argon atmosphere and adding 4mol/L of HNO3Treating the solution for 4 hours, washing the solution to be neutral by distilled water, and drying the solution in an oven at 110 ℃ to obtain the carbon carrier. The physical parameters of the carbon carrier are as follows: average specific surface area of 62m2G, average pore diameter of 12nm and average pore volume of 0.21cm3G, bulk density 0.18g/cm3。
Preparation of the catalyst: mixing 200g of ethylene glycol, 14g of ethylenediamine tetraacetic acid, 3.24g of ferric nitrate nonahydrate, 1.10g of palladium nitrate and 0.27g of chloroplatinic acid until the mixture is completely dissolved, adjusting the pH value to 10 by adopting 10 wt% of NaOH, and reducing for 1h at 150 ℃ to obtain a metal colloid particle solution; adding 200mL of water, mixing, adding 9g of carbon carrier, performing ultrasonic treatment for 2h, and standing in a water bath kettle at 80 ℃ for 12 h; and finally, filtering and washing to obtain the target catalyst.
Example 4
Preparation of the carrier: prepared according to the method of example 1.
Preparation of the catalyst: mixing 200g of ethylene glycol, 11g of ethylenediamine tetraacetic acid, 3.61g of ferric nitrate nonahydrate, 0.98g of palladium nitrate and 0.27g of chloroplatinic acid until the materials are completely dissolved, adjusting the pH value to 12 by adopting 15 wt% of NaOH, and reducing for 4 hours at 120 ℃ to obtain a metal colloid particle solution; adding 200mL of water, mixing, adding 9g of carbon carrier, performing ultrasonic treatment for 2h, and standing in a water bath kettle at 80 ℃ for 12 h; and finally, filtering and washing to obtain the target catalyst.
Example 5
Preparation of the carrier: prepared according to the method of example 2.
Preparation of the catalyst: mixing 200g of ethylene glycol, 13g of ethylenediamine tetraacetic acid, 3.61g of ferric nitrate nonahydrate, 0.67g of palladium chloride and 0.27g of chloroplatinic acid until the mixture is completely dissolved, adjusting the pH value to 10 by adopting 10 wt% of NaOH, and reducing for 2 hours at 170 ℃ to obtain a metal colloid particle solution; adding 200mL of water, mixing, adding 9g of carbon carrier, performing ultrasonic treatment for 4h, and standing in a water bath kettle at 80 ℃ for 12 h; and finally, filtering and washing to obtain the target catalyst.
Example 6
Preparation of the carrier: prepared according to the method of example 3.
Preparation of the catalyst: mixing 200g of ethylene glycol, 13g of ethylenediamine tetraacetic acid, 3.61g of ferric nitrate nonahydrate, 0.75g of palladium chloride and 0.13g of chloroplatinic acid until the materials are completely dissolved, adjusting the pH value to 10 by adopting 15 wt% of NaOH, and reducing for 2 hours at 150 ℃ to obtain a metal colloid particle solution; adding 200mL of water, mixing, adding 9g of carbon carrier, performing ultrasonic treatment for 4h, and standing in a water bath kettle at 80 ℃ for 24 h; and finally, filtering and washing to obtain the target catalyst.
Example 7
Preparation of the carrier: prepared according to the method of example 3.
Preparation of the catalyst: mixing 200g of ethylene glycol, 14g of ethylene diamine tetraacetic acid, 2.41g of ferric chloride hexahydrate, 0.75g of palladium chloride and 0.13g of chloroplatinic acid until the materials are completely dissolved, adjusting the pH value to 12 by adopting 10 wt% of NaOH, and reducing for 4 hours at 150 ℃ to obtain a metal colloid particle solution; adding 200mL of water, mixing, adding 9g of carbon carrier, performing ultrasonic treatment for 2h, and standing in a water bath kettle at 80 ℃ for 24 h; and finally, filtering and washing to obtain the target catalyst.
Example 8
The catalyst prepared in the embodiment 1-7 is used for preparing aniline by nitrobenzene hydrogenation, and the reaction conditions are as follows: 10mL of nitrobenzene solution, 25mL of ethanol solution, 15mL of deionized water, 0.02g of catalyst and H2The reaction is carried out in a 100mL high-pressure reaction kettle under the pressure of 3.0MPa and the reaction temperature of 110 ℃, and the reaction is stopped when the pressure is reduced by 1.0 MPa. The catalyst and the reaction liquid were separated by centrifugation, the liquid product was analyzed by gas chromatography, and the reaction results are shown in table 1. As can be seen from Table 1, when the catalyst prepared by the invention is used for catalyzing the reaction of preparing aniline by hydrogenating nitrobenzene, the conversion rate of nitrobenzene is more than 99.8 percent, and the selectivity of aniline is more than 98.5 percent.
The catalyst prepared in example 6 was used for nitrobenzene hydrogenation catalyst stability testing, and compared with the imported nitrobenzene hydrogenation catalyst 4.5% PD-0.5% PT-5% FE/C. The catalyst was recycled 8 times, and the reaction results are shown in fig. 3. As can be seen from FIG. 3, the catalytic activity of the catalyst prepared by the invention is basically kept unchanged after being recycled for a plurality of times, which proves that the catalyst prepared by the invention has higher stability, and compared with 4.5% PD-0.5% PT-5% FE/C, the aniline selectivity is obviously reduced after being recycled for 4 times.
TABLE 1 performance of each catalyst in catalytic hydrogenation of nitrobenzene to prepare aniline
Catalyst and process for preparing same Reaction time (min) Nitrobenzene conversion (%) Aniline selectivity (%)
Example 1 1.75 99.9 98.5
Example 2 1.80 99.8 99.0
Example 3 1.73 99.9 98.8
Example 4 1.81 99.9 98.9
Example 5 1.79 99.9 99.3
Example 6 1.80 99.9 99.9
Example 7 1.82 99.8 99.5

Claims (5)

1. A preparation method of a catalyst for preparing aniline by nitrobenzene liquid phase hydrogenation comprises the following steps:
1) preparing a carbon carrier, namely heating vinasse which is a byproduct in the brewing industry in 0.5mol/L ethylenediamine solution at 90 ℃ in an oil bath, stirring and refluxing for 6 hours, taking out the vinasse, drying the vinasse in an oven, mixing citric acid, aluminum nitrate, phosphoric acid and the vinasse treated by the method according to the mass ratio of 0.5: 1-5: 2: 10-15, adding water, uniformly stirring, dropwise adding 0.5mol/L diluted ammonia water to adjust the pH value of the system to 5.0, continuously stirring for 5 hours, evaporating the mixture on the water bath, carbonizing the mixture at 300 ℃, performing dry distillation at 600-800 ℃, pickling and dealuminizing with 4-6 mol/L nitric acid, washing the mixture with distilled water to be neutral, and drying the mixture in the oven at 110 ℃ to obtain the carbon carrier;
2) preparing a catalyst, namely mixing polyol, ethylene diamine tetraacetic acid and a metal compound according to a mass ratio of 100: 5-8: 2 until the polyol, the ethylene diamine tetraacetic acid and the metal compound are completely dissolved, adjusting the pH value to 10-12 by adopting NaOH, and reducing for 2-4 hours at 120-170 ℃ to obtain a metal colloid particle solution; diluting the metal colloidal particle solution by 2 times with water, adding the carbon carrier prepared in the step 1), performing ultrasonic treatment, and standing in a water bath at 80 ℃ for 12-24 h; finally, filtering and washing to obtain the catalyst for preparing aniline by nitrobenzene liquid phase hydrogenation; the metal compounds are iron salt, palladium salt and platinum compounds, wherein the mass ratio of iron to palladium to platinum is 3-8: 1.
2. The method for preparing the catalyst for liquid phase hydrogenation of nitrobenzene to aniline according to claim 1, wherein the polyol in step 2) is one or more of ethylene glycol, glycerol, 1, 2-propanediol, further preferably ethylene glycol; the ferric salt is one or more of ferric nitrate, ferric chloride and ferric sulfate, and ferric nitrate nonahydrate is further preferred; the palladium salt is one or more of palladium chloride, palladium nitrate and palladium acetate, and palladium chloride is further preferred; the platinum compound is one or more of chloroplatinic acid, potassium tetrachloroplatinate and potassium hexachloroplatinate, and the chloroplatinic acid is further preferred.
3. The method for preparing the catalyst for liquid-phase hydrogenation of nitrobenzene to aniline according to claim 1, wherein the iron salt in step 2) is iron nitrate nonahydrate; the palladium salt is palladium chloride; the platinum compound is chloroplatinic acid.
4. The preparation method of the catalyst for liquid phase hydrogenation of nitrobenzene to aniline according to claim 1, wherein the concentration of NaOH used in step 2) is 10-15 wt%; the ultrasonic treatment time is 3-5 h.
5. The method for preparing the catalyst for preparing the aniline by the liquid phase hydrogenation of the nitrobenzene according to claim 1, wherein the mass ratio of the carbon carrier to the metal in the metal compound in the step 2) is 95: 5-15.
CN201911406309.XA 2019-12-31 2019-12-31 Preparation method of catalyst for liquid-phase hydrogenation of nitrobenzene to prepare aniline Pending CN111013561A (en)

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CN101816956A (en) * 2010-04-20 2010-09-01 武汉理工大学 Method for improving dispersion of nano metal grains on surface of graphitized carbon carrier
CN105435808A (en) * 2014-08-20 2016-03-30 中国石油化工股份有限公司 Carbon black noble metal catalyst preparation method
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CN114471544A (en) * 2022-02-25 2022-05-13 天脊煤化工集团股份有限公司 Catalyst and application thereof in aniline preparation

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