CN112675840A - Catalyst for nitroaniline and preparation method thereof - Google Patents
Catalyst for nitroaniline and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of nitroaniline, and particularly relates to a catalyst for nitroaniline and a preparation method thereof. The invention solves the problem of low utilization rate of the existing palladium-carbon catalyst, and forms a filter type fixed bed reaction system by using the active carbon hollow sphere with a porous structure as a carrier, thereby reducing the retention of raw materials, preventing the raw materials from being blocked and ensuring the large-area exposure of the active palladium.
Description
Technical Field
The invention belongs to the field of nitroaniline, and particularly relates to a catalyst for nitroaniline and a preparation method thereof.
Background
Nitroaniline includes o-nitroaniline, m-nitroaniline and p-nitroaniline, which are artificially synthesized chemical substances widely applied to the dye-burning industry and are mainly used as intermediates for dye synthesis and intermediates for pharmaceutical chemicals.
Nitro-chlorobenzene ammonolysis is commonly used industrially to prepare nitroaniline directly from nitrochlorobenzene by ammonolysis under high pressure. The process is adopted to prepare the nitroaniline with selectivityHigh product purity, but the process has low production efficiency, generates a large amount of chlorine-containing wastewater in the process, and is not environment-friendly. With the continuous development of catalytic hydrogenation reduction technology, more and more catalytic hydrogenation technology is used for the catalytic reduction of nitrobenzene compounds: (1) hydrogenation reduction technology using skeleton nickel, skeleton ruthenium and the like as catalysts; (2) CO/H using selenium as catalyst2Catalytic reduction technology with O as a reducing agent; (3) Pd/C as catalyst, H2Catalytic reduction technology for reducing agent. The nitroaniline is prepared by reducing dinitrobenzene by catalytic hydrogenation with skeletal nickel, skeletal ruthenium and the like as catalysts, so that higher conversion rate can be obtained, but the reaction end point is difficult to control, and the target product nitroaniline is easy to be subjected to transitional hydrogenation to form phenylenediamine. CO/H using selenium as catalyst2O is used as a reducing agent to catalyze and reduce dinitrobenzene to prepare nitroaniline, higher reaction pressure is needed, and auxiliary agents such as sodium acetate and the like are also needed to be added, so that the product yield is lower. Pd/C as catalyst, H2The catalytic reduction technology which is a reducing agent can make the catalyst show excellent performance in terms of both reactivity and selectivity by controlling the preparation conditions of the catalyst preparation process. However, the Pd/C catalyst is affected by the porous structure of the activated carbon, so that the activity utilization rate of the catalyst is not high.
Disclosure of Invention
Aiming at the problems in the prior art, the invention solves the problem of low utilization rate of the existing palladium-carbon catalyst, and the active carbon hollow sphere with a porous structure is used as a carrier to form a filter type fixed bed reaction system, thereby reducing the retention of raw materials, preventing the raw materials from being blocked and ensuring the large-area exposure of the active palladium.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a catalyst for nitroaniline takes a porous active carbon hollow sphere as a carrier and palladium as an active point of a membrane to form a hollow spherical Pd/C catalyst; active palladium is loaded on the surface of the porous active carbon hollow sphere to form specific surface active points, and meanwhile, the porous active carbon hollow sphere forms a porous structure and is communicated with the hollow sphere center, so that the reactants are not influenced by the adsorption force of the active carbon to form pore blockage in the reaction process, the surface exposed area of the active palladium is greatly improved, and the improvement of the catalytic efficiency is realized.
The preparation method of the porous active carbon hollow sphere comprises the following steps:
step 1, adding ethyl cellulose into absolute ethyl alcohol, uniformly stirring to form viscous liquid, and then putting the viscous liquid into a mold to be pressed at constant temperature to form microspheres; the mass ratio of the ethyl cellulose to the absolute ethyl alcohol is 4:1-2, the stirring speed is 2000r/min, the temperature of the constant-temperature pressing is 90-100 ℃, and the pressure is 0.3-0.4 MPa;
step 2, adding activated carbon into an ethanol water solution, stirring uniformly, slowly adding ethyl cellulose and methyl cellulose, performing ultrasonic dispersion to obtain a suspension dispersion liquid, uniformly spraying the suspension dispersion liquid on the surface of the microsphere, and pressing at constant temperature to form the coated microsphere; the concentration of the activated carbon in the ethanol water solution is 100-200g/L, the volume ratio of water in the ethanol water solution is 20-40%, the adding amount of the ethyl cellulose is 2-4% of the mass of the activated carbon, the adding amount of the methyl cellulose is 2-4% of the mass of the activated carbon, the ultrasonic dispersion temperature is 20-30 ℃, and the ultrasonic frequency is 80-90 kHz; the amount of the spray is 10-30mL/cm2And the spraying amount is formed by repeated spraying-drying operations, and the spraying amount is 1-3mL/cm2The drying temperature is 100-;
step 3, slowly washing the coated microspheres with distilled water, and then placing the coated microspheres into an infrared illumination box for illumination treatment for 3-6 hours to obtain porous active carbon hollow spheres; the washing speed of the distilled water is 2-4mL/min, the temperature is 10-20 ℃, and the illumination intensity of the illumination treatment is 10-30W/cm2The temperature is 130-150 ℃.
The preparation method of the catalyst comprises the following steps:
step a, adding porous active carbon hollow spheres into an alkali solution, carrying out low-temperature ultrasonic treatment for 10-20min, then heating and standing for 10-20min, taking out and drying to obtain alkalized active carbon; the alkali solution is sodium hydroxide solution or potassium hydroxide solution, the pH is 10-14, the low-temperature ultrasonic temperature is 2-10 ℃, the ultrasonic frequency is 80-120kHz, and the temperature for heating and standing is 50-70 ℃;
step b, dipping alkaline activated carbon in H2PdCl4Taking out the solution from the water solution, and then putting the solution into a reaction kettle for standing reaction to obtain a precursor catalyst; said H2PdCl4The mass ratio of the water solution is 3-8%, the reaction kettle is filled with water vapor and ammonia gas, the volume ratio of the water vapor to the ammonia gas is 3-4:2, and the temperature is 70-90 ℃;
and c, carrying out reduction reaction on the precursor catalyst for 2-5h by adopting a reducing agent to obtain the catalyst, wherein the reducing agent adopts hydrogen, and the reduction temperature is 80-90 ℃.
The catalyst is used for a catalytic hydrogenation process for preparing nitroaniline from dinitrobenzene.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of low utilization rate of the existing palladium-carbon catalyst, and forms a filter type fixed bed reaction system by using the active carbon hollow sphere with a porous structure as a carrier, thereby reducing the retention of raw materials, preventing the raw materials from being blocked and ensuring the large-area exposure of the active palladium.
2. According to the invention, the alkalization characteristic of the activated carbon is utilized, the palladium particles are adsorbed by matching with the self-adsorption property, and hydrogen bond connection is formed in the strong palladium oxide conversion process, so that the connection stability of the palladium particles and the activated carbon is greatly improved.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A catalyst for nitroaniline is prepared from porous hollow activated carbon spheres as carrier and Pd as active site of membrane through preparing hollow spherical Pd/C catalyst.
The preparation method of the porous active carbon hollow sphere comprises the following steps:
step 1, adding 50g of ethyl cellulose into absolute ethyl alcohol, uniformly stirring to form viscous liquid, and then putting the viscous liquid into a mold to be pressed at constant temperature to form microspheres with the diameter of 2 mm; the mass ratio of the ethyl cellulose to the absolute ethyl alcohol is 4:1, the stirring speed is 1000r/min, the temperature of the constant-temperature pressing is 90 ℃, and the pressure is 0.3 MPa;
step 2, adding activated carbon into 1L of ethanol water solution, stirring uniformly, slowly adding ethyl cellulose and methyl cellulose, performing ultrasonic dispersion to obtain a suspension dispersion liquid, uniformly spraying the suspension dispersion liquid on the surface of the microsphere, and pressing at constant temperature to form a 2.7mm coated microsphere; the concentration of the activated carbon in the ethanol water solution is 100g/L, the volume ratio of water in the ethanol water solution is 20%, the adding amount of the ethyl cellulose is 2% of the mass of the activated carbon, the adding amount of the methyl cellulose is 2% of the mass of the activated carbon, the ultrasonic dispersion temperature is 20 ℃, and the ultrasonic frequency is 80 kHz; the amount of the spray was 10mL/cm2And the spraying amount is formed by repeated spraying-drying operations, and the spraying amount is 1mL/cm2The drying temperature is 100 ℃, the surface is kept in a wet state after the last spraying is finished, and the constant-temperature pressing is carried out, wherein the constant-temperature pressing temperature is 130 ℃, the heating rate is 8 ℃/min, and the pressure is 0.3 MPa;
step 3, slowly washing the coated microspheres for 1 hour by using distilled water, and then placing the coated microspheres into an infrared illumination box for illumination treatment for 3 hours to obtain porous activated carbon hollow spheres with the diameter of 2.7 mm; the washing speed of the distilled water is 2mL/min, the temperature is 10 ℃, and the illumination intensity of the illumination treatment is 10W/cm2The temperature was 130 ℃.
The preparation method of the catalyst comprises the following steps:
step a, adding porous activated carbon hollow spheres into an alkali solution, carrying out low-temperature ultrasonic treatment for 10min, then heating and standing for 10min, taking out and drying to obtain alkalized activated carbon; the alkali solution is sodium hydroxide solution, the pH is 10, the low-temperature ultrasonic temperature is 2 ℃, the ultrasonic frequency is 80kHz, and the temperature for heating and standing is 50 ℃;
step b, dipping alkaline activated carbon in H2PdCl4Taking out the solution from the water solution, and then putting the solution into a reaction kettle for standing reaction to obtain a precursor catalyst; said H2PdCl4The mass ratio of the aqueous solution is 3 percent, and the reaction kettle is filled with water vapor andammonia gas, wherein the volume ratio of the water vapor to the ammonia gas is 3:2, and the temperature is 70 ℃;
and c, reducing the precursor catalyst for 2 hours by adopting a reducing agent to obtain the catalyst, wherein the reducing agent adopts hydrogen, and the reduction temperature is 80 ℃.
The catalyst prepared in this example had a particle size of 2.7mm, a hollow diameter of 1.8mm, and a particle size of 10nm for the palladium particles.
150g of p-dinitrobenzene, 200g of methanol and 3g of the catalyst are added into a 500mL high-pressure reaction kettle, nitrogen at 1MPa is substituted for 3 times, then hydrogen at 1MPa is substituted for 3 times, the temperature is raised to 150 ℃, the reaction pressure is controlled to be 2MPa, and the reaction is continued for 1.5 h. And (3) cooling, distilling and recovering the methanol under the protection of nitrogen at normal pressure, and separating to obtain a p-nitroaniline crude product. The product was analyzed for its composition by gas chromatography, with a conversion of 99.6% for dinitrobenzene, a selectivity of 99.3% for p-nitroaniline and a yield of 98.7% for p-nitroaniline.
Example 2
A catalyst for nitroaniline is prepared from porous hollow activated carbon spheres as carrier and Pd as active site of membrane through preparing hollow spherical Pd/C catalyst.
The preparation method of the porous active carbon hollow sphere comprises the following steps:
step 1, adding 50g of ethyl cellulose into absolute ethyl alcohol, uniformly stirring to form viscous liquid, and then putting the viscous liquid into a mold to be pressed at constant temperature to form microspheres with the diameter of 3.8 mm; the mass ratio of the ethyl cellulose to the absolute ethyl alcohol is 2:1, the stirring speed is 2000r/min, the temperature of the constant-temperature pressing is 100 ℃, and the pressure is 0.4 MPa;
step 2, adding activated carbon into 1L of ethanol water solution, stirring uniformly, slowly adding ethyl cellulose and methyl cellulose, performing ultrasonic dispersion to obtain a suspension dispersion liquid, uniformly spraying the suspension dispersion liquid on the surface of the microsphere, and pressing at constant temperature to form a 5mm coated microsphere; the concentration of the activated carbon in the ethanol water solution is 200g/L, the volume ratio of water in the ethanol water solution is 40%, the adding amount of the ethyl cellulose is 4% of the mass of the activated carbon, the adding amount of the methyl cellulose is 4% of the mass of the activated carbon, the ultrasonic dispersion temperature is 20-30 ℃, and the ultrasonic frequency is 90 kHz;the amount of the spray was 30mL/cm2And the spraying amount is formed by repeated spraying-drying operations, and the spraying amount is 3mL/cm2The drying temperature is 120 ℃, the surface is kept in a wet state after the last spraying is finished, and the constant-temperature pressing is carried out, wherein the constant-temperature pressing temperature is 150 ℃, the heating speed is 10 ℃/min, and the pressure is 0.5 MPa;
step 3, slowly washing the coated microspheres for 2 hours by using distilled water, and then placing the coated microspheres into an infrared illumination box for illumination treatment for 6 hours to obtain porous activated carbon hollow spheres of 5 mm; the washing speed of the distilled water is 4mL/min, the temperature is 20 ℃, and the illumination intensity of the illumination treatment is 30W/cm2The temperature was 150 ℃.
The preparation method of the catalyst comprises the following steps:
step a, adding 5mm porous activated carbon hollow spheres into an alkali solution, carrying out low-temperature ultrasonic treatment for 20min, then heating and standing for 20min, taking out and drying to obtain alkalized activated carbon; the alkali solution is potassium hydroxide solution, the pH value is 14, the low-temperature ultrasonic temperature is 10 ℃, the ultrasonic frequency is 120kHz, and the temperature for heating and standing is 70 ℃;
step b, dipping alkaline activated carbon in H2PdCl4Taking out the solution from the water solution, and then putting the solution into a reaction kettle for standing reaction to obtain a precursor catalyst; said H2PdCl4The mass ratio of the aqueous solution is 8%, the reaction kettle is filled with water vapor and ammonia gas, the volume ratio of the water vapor to the ammonia gas is 2:1, and the temperature is 90 ℃;
and c, reducing the precursor catalyst for 5 hours by using a reducing agent to obtain the catalyst, wherein the reducing agent adopts hydrogen, and the reduction temperature is 90 ℃.
The catalyst prepared in this example had a particle size of 5mm, a hollow diameter of 3.5mm, and a particle size of 50nm for the palladium particles.
150g of p-dinitrobenzene, 200g of methanol and 2.5g of the catalyst are added into a 500mL high-pressure reaction kettle, nitrogen at 1MPa is used for 3 times of replacement, then hydrogen at 1MPa is used for 3 times of replacement, the temperature is raised to 150 ℃, the reaction pressure is controlled to be 2MPa, and the reaction is continued for 1.5 h. And (3) cooling, distilling and recovering the methanol under the protection of nitrogen at normal pressure, and separating to obtain a p-nitroaniline crude product. The product was analyzed for its composition by gas chromatography, with a conversion of 99.7% for dinitrobenzene, a selectivity of 99.5% for p-nitroaniline and a yield of 99.0% for p-nitroaniline.
Example 3
A catalyst for nitroaniline is prepared from porous hollow activated carbon spheres as carrier and Pd as active site of membrane through preparing hollow spherical Pd/C catalyst.
The preparation method of the porous active carbon hollow sphere comprises the following steps:
step 1, adding ethyl cellulose into absolute ethyl alcohol, uniformly stirring to form viscous liquid, and then putting the viscous liquid into a mold to be pressed at constant temperature to form microspheres with the thickness of 3 mm; the mass ratio of the ethyl cellulose to the absolute ethyl alcohol is 4:1, the stirring speed is 1500r/min, the temperature of the constant-temperature pressing is 95 ℃, and the pressure is 0.4 MPa;
step 2, adding activated carbon into 1L of ethanol water solution, stirring uniformly, slowly adding ethyl cellulose and methyl cellulose, performing ultrasonic dispersion to obtain a suspension dispersion liquid, uniformly spraying the suspension dispersion liquid on the surface of the microsphere, and pressing at constant temperature to form a 4.3mm coated microsphere; the concentration of the activated carbon in the ethanol water solution is 150g/L, the volume ratio of water in the ethanol water solution is 30%, the adding amount of the ethyl cellulose is 3% of the mass of the activated carbon, the adding amount of the methyl cellulose is 3% of the mass of the activated carbon, the ultrasonic dispersion temperature is 25 ℃, and the ultrasonic frequency is 85 kHz; the amount of the spray was 20mL/cm2And the spraying amount is formed by repeated spraying-drying operations, and the spraying amount is 2mL/cm2The drying temperature is 110 ℃, the surface is kept in a wet state after the last spraying is finished, and the constant-temperature pressing is carried out, wherein the constant-temperature pressing temperature is 140 ℃, the heating speed is 9 ℃/min, and the pressure is 0.4 MPa;
step 3, slowly washing the coated microspheres for 2 hours by using distilled water, and then placing the coated microspheres into an infrared illumination box for illumination treatment for 5 hours to obtain porous activated carbon hollow spheres with the diameter of 4.3 mm; the washing speed of the distilled water is 3mL/min, the temperature is 15 ℃, and the illumination intensity of the illumination treatment is 20W/cm2The temperature was 140 ℃.
The preparation method of the catalyst comprises the following steps:
step a, adding porous activated carbon hollow spheres into an alkali solution, carrying out low-temperature ultrasonic treatment for 15min, then heating and standing for 15min, taking out and drying to obtain alkalized activated carbon; the alkali solution is potassium hydroxide solution, the pH value is 12, the low-temperature ultrasonic temperature is 8 ℃, the ultrasonic frequency is 100kHz, and the temperature for heating and standing is 60 ℃;
step b, dipping alkaline activated carbon in H2PdCl4Taking out the solution from the water solution, and then putting the solution into a reaction kettle for standing reaction to obtain a precursor catalyst; said H2PdCl4The mass ratio of the aqueous solution is 6%, the reaction kettle is filled with water vapor and ammonia gas, the volume ratio of the water vapor to the ammonia gas is 2:1, and the temperature is 80 ℃;
and c, reducing the precursor catalyst for 4 hours by using a reducing agent to obtain the catalyst, wherein the reducing agent adopts hydrogen, and the reduction temperature is 85 ℃.
The catalyst prepared in this example had a particle size of 4.3m, a hollow diameter of 2.9mm, and a particle size of palladium particles of 30 nm.
150g of p-dinitrobenzene, 200g of methanol and 3g of the catalyst are added into a 500mL high-pressure reaction kettle, nitrogen at 1MPa is substituted for 3 times, then hydrogen at 1MPa is substituted for 3 times, the temperature is raised to 150 ℃, the reaction pressure is controlled to be 2MPa, and the reaction is continued for 1.5 h. And (3) cooling, distilling and recovering the methanol under the protection of nitrogen at normal pressure, and separating to obtain a p-nitroaniline crude product. The product was analyzed for its composition by gas chromatography, with a conversion of 99.6% for dinitrobenzene, a selectivity of 99.3% for p-nitroaniline and a yield of 98.9% for p-nitroaniline.
In summary, the invention has the following advantages:
1. the invention solves the problem of low utilization rate of the existing palladium-carbon catalyst, and forms a filter type fixed bed reaction system by using the active carbon hollow sphere with a porous structure as a carrier, thereby reducing the retention of raw materials, preventing the raw materials from being blocked and ensuring the large-area exposure of the active palladium.
2. According to the invention, the alkalization characteristic of the activated carbon is utilized, the palladium particles are adsorbed by matching with the self-adsorption property, and hydrogen bond connection is formed in the strong palladium oxide conversion process, so that the connection stability of the palladium particles and the activated carbon is greatly improved.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (8)
1. A catalyst for nitroaniline, characterized in that: porous active carbon hollow spheres are used as carriers, palladium is used as an active point of a membrane, and a hollow spherical Pd/C catalyst is formed.
2. The catalyst for nitroaniline according to claim 1, characterized in that: the preparation method of the porous active carbon hollow sphere comprises the following steps:
step 1, adding ethyl cellulose into absolute ethyl alcohol, uniformly stirring to form viscous liquid, and then putting the viscous liquid into a mold to be pressed at constant temperature to form microspheres;
step 2, adding activated carbon into an ethanol water solution, stirring uniformly, slowly adding ethyl cellulose and methyl cellulose, performing ultrasonic dispersion to obtain a suspension dispersion liquid, uniformly spraying the suspension dispersion liquid on the surface of the microsphere, and pressing at constant temperature to form the coated microsphere;
and 3, slowly washing the coated microspheres by using distilled water, and then placing the coated microspheres into an infrared illumination box for illumination treatment for 3-6 hours to obtain the porous active carbon hollow spheres.
3. The catalyst for nitroaniline according to claim 1, characterized in that: the preparation method of the catalyst comprises the following steps:
step a, adding porous active carbon hollow spheres into an alkali solution, carrying out low-temperature ultrasonic treatment for 10-20min, then heating and standing for 10-20min, taking out and drying to obtain alkalized active carbon;
step b, dipping alkaline activated carbon in H2PdCl4Taking out the aqueous solution and putting the aqueous solution into a reaction kettleStanding for reaction to obtain a precursor catalyst;
and c, carrying out reduction reaction on the precursor catalyst for 2-5h by adopting a reducing agent to obtain the catalyst.
4. The catalyst for nitroaniline according to claim 3, characterized in that: the alkali solution in the step a is sodium hydroxide solution or potassium hydroxide solution, the pH value is 10-14, the low-temperature ultrasonic temperature is 2-10 ℃, and the ultrasonic frequency is 80-120 kHz.
5. The catalyst for nitroaniline according to claim 3, characterized in that: the temperature for raising the temperature and standing in the step a is 50-70 ℃.
6. The catalyst for nitroaniline according to claim 3, characterized in that: h in said step b2PdCl4The mass ratio of the water solution is 3-8%, the reaction kettle is filled with water vapor and ammonia gas, the volume ratio of the water vapor to the ammonia gas is 3-4:2, and the temperature is 70-90 ℃.
7. The catalyst for nitroaniline according to claim 3, characterized in that: the reducing agent in the step c adopts hydrogen, and the reducing temperature is 80-90 ℃.
8. The catalyst for nitroaniline according to claim 1, characterized in that: the catalyst is used for a catalytic hydrogenation process for preparing nitroaniline from dinitrobenzene.
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