CN110639552A - Platinum-based composite carbon-aluminum catalyst and method for continuously producing 2B oil - Google Patents
Platinum-based composite carbon-aluminum catalyst and method for continuously producing 2B oil Download PDFInfo
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- 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
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Abstract
The invention discloses a platinum-based composite carbon-aluminum catalyst for continuously producing 2B oil and a method thereof, wherein the catalyst takes carbon-coated foamed aluminum as a carrier and loads Pt, a second noble metal and a transition metal, the second noble metal is any one of Ru, Au and Pd, the transition metal is any one of Zn, Fe, Sn and Cu, the mass content of Pt in the catalyst is 0.6-1.9%, and the mass contents of the second noble metal and the transition metal are all in the range of 0.1-0.7%. The method takes o-chloro-p-nitrotoluene as a raw material, takes platinum-based composite carbon aluminum as a catalyst, adopts a fixed bed to continuously produce the 2B oil (o-chloro-p-aminotoluene), can control the occurrence of a dechlorination side reaction under the condition of not adding a solvent and an inhibitor, has the advantages that the conversion rate of the raw material reaches 100 percent, the selectivity of a target product is more than 99.9 percent, a dechlorination byproduct is less than 0.1 percent, the catalyst has stable performance, the process saves resources and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of catalytic hydrogenation, and particularly relates to a platinum-based composite carbon-aluminum catalyst and a method for continuously producing 2B oil by using the catalyst.
Background
O-chloro-p-aminotoluene (2B oil) is an important chemical intermediate and is widely used in the fields of medicines, pesticides, dyes and the like. P-aminotoluene is a colorless, glossy, flaky crystal, slightly soluble in water, soluble in ethanol, ether, benzene, hydrochloric acid, toxic, and a strong methemoglobin former. In industry, p-toluidine is mainly used as a dye intermediate and an intermediate of medical pyrimethamine.
At present, the conventional kettle type process is still adopted in the industry to produce o-chloro-p-aminotoluene, and the raw materials are corresponding nitro compounds: the raw material used in industry is a mixture, the content of o-chloro-p-nitrotoluene is about 80%, and the content of p-nitrotoluene is about 20%. The traditional process adopts iron powder reduction to reduce the o-chloro-p-nitrotoluene and the p-nitrotoluene into the o-chloro-p-aminotoluene and the p-aminotoluene, so as to prevent dechlorination, and then the separation and purification of the product are carried out. The intermittent kettle type process has low production efficiency, and the used iron powder catalyst has large process waste water amount and is limited by environmental protection.
Chinese patent 201810911201.5 discloses a method for synthesizing o-chloro-p-aminotoluene by catalytic hydrogenation of o-chloro-p-nitrotoluene, which is still a kettle type technique, Raney's nickel is used as a catalyst, a large amount of methanol is added as a solvent, a certain amount of dechlorination still exists in the reaction, and the purity of the reaction product is 98% after rectification and purification, the reaction temperature and pressure are 95 ℃ and about 2.0 MPa. Chinese patent 201710650447.7 discloses a method for preparing 2B oil by catalytic hydrogenation, which is a tank type technique, using water as solvent and platinum carbon as catalyst, and reacting at 70 ℃ and about 0.8MPa, the conversion rate is 99.61%, the dechlorination by-product can be controlled below 0.16%, probably because of the diffusion problem of the tank type process, the raw material can not be completely converted, the subsequent purification is needed, the reaction dechlorination is higher, and water is generated, so the reaction solution has certain corrosivity, and the addition of sodium hydroxide can neutralize a certain amount of hydrogen chloride, but the reaction can also proceed towards the side reaction of dechlorination. Therefore, the method for producing the 2B oil by adopting the more advanced fixed bed technology has stronger practical significance.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a platinum-based composite carbon-aluminum catalyst and a method for continuously producing 2B oil by using the catalyst, aiming at the defects in the prior art.
In order to solve the technical problems, the catalyst adopted by the invention takes carbon-coated foamed aluminum as a carrier and loads Pt, a second noble metal and a transition metal, wherein the second noble metal is any one of Ru, Au and Pd, the transition metal is any one of Zn, Fe, Sn and Cu, the mass content of Pt in the catalyst is 0.6-1.9%, and the mass contents of the second noble metal and the transition metal are both in the range of 0.1-0.7%; the catalyst is prepared by the following preparation method:
(1) and (3) washing and drying the 10-20-mesh granular foamed aluminum, and then roasting the foamed aluminum in a muffle furnace at 400-500 ℃ for 1-3 h.
(2) Grinding dried corn particles into powder, uniformly stirring and mixing the powder with polyethylene glycol powder and alumina sol with the solid content of 20-25%, then placing the calcined foamed aluminum obtained in the step (1) into the obtained mixed solution, soaking for 1-3 h, taking out, placing the mixture into a tubular furnace, heating to 400-500 ℃ under the protection of nitrogen, carrying out constant temperature treatment for 2-4 h, then adding water vapor into nitrogen, heating to 800-900 ℃, continuing to treat for 2-4 h, and cooling to obtain a carbon-coated foamed aluminum carrier; the mass ratio of the dried corn particles to the polyethylene glycol powder to the foamed aluminum to the alumina sol is 2-4: 1:1: 5-12, and the volume ratio of the water vapor to the nitrogen is 10: 90-15: 85.
(3) Adding dinitroso diammine platinum into deionized water according to the composition of the catalyst, heating and stirring until the dinitroso diammine platinum is completely dissolved, then spraying the dinitroso diammine platinum onto a carbon-coated foamed aluminum carrier, drying, soaking the obtained solid product in an aqueous solution containing a second noble metal precursor and a transition metal precursor for 10-12 h, and finally drying in an oven at 120-150 ℃ for 10-12 h to obtain a platinum-based composite carbon-aluminum catalyst; the second noble metal precursor is any one of chloroauric acid, palladium trichloride and ruthenium trichloride, and the transition metal precursor is any one of zinc chloride, ferric trichloride, tin dichloride and copper chloride.
In the platinum-based composite carbon aluminum catalyst, the mass content of Pt is preferably 1.0-1.6%, and the mass content of the second noble metal and the mass content of the transition metal are both in the range of 0.2-0.4%.
In the step (2) of the preparation method of the platinum-based composite carbon-aluminum catalyst, the mass ratio of the dried corn particles, the polyethylene glycol powder, the foamed aluminum and the aluminum sol is preferably 2:1:1: 5-12, wherein the polyethylene glycol is polyethylene glycol 2000 or polyethylene glycol 4000.
In the step (2) of the preparation method of the platinum-based composite carbon-aluminum catalyst, the heating rate is preferably 1-3 ℃/min.
The method for continuously producing the 2B oil by adopting the platinum-based composite carbon-aluminum catalyst comprises the following steps:
(1) filling a platinum-based composite carbon-aluminum catalyst into a fixed bed reactor, introducing hydrogen into the fixed bed reactor filled with the catalyst under the normal pressure condition, raising the temperature of the fixed bed reactor to 300-500 ℃, and reducing the catalyst under the normal pressure condition.
(2) Maintaining a flow of hydrogenContinuously introducing hydrogen into the fixed bed reactor without changing the amount, adjusting the pressure of the hydrogen to 0.9-1.7 MPa, reducing the pressure of the fixed bed reactor to 60-100 ℃, then pumping a nitro material into the fixed bed reactor for carrying out nitro hydrogenation reaction, wherein the nitro material is o-chloro-p-nitrotoluene or a mixture of the o-chloro-p-nitrotoluene and the p-nitrotoluene with the mass ratio of 4:1, and the volume space velocity of the nitro material is 0.3-1.0 h-1。
(3) And (3) separating the material subjected to the nitro hydrogenation reaction in the step (2) by an oil-water separator to obtain an organic phase and a water phase, and separating and purifying the organic phase to obtain pure 2B oil.
In the step (1) and the step (2) of the method for continuously producing the 2B oil, the ratio of the flow rate of the hydrogen to the filling volume of the catalyst is preferably 6-15: 1, wherein the flow rate of the hydrogen is mL/min, and the filling volume of the catalyst is mL.
In the step (1) of the method for continuously producing the 2B oil, the reduction treatment time is preferably 2-8 hours.
In the step (2) of the method for continuously producing the 2B oil, the flow of hydrogen is kept unchanged, the hydrogen is continuously introduced into the fixed bed reactor, the pressure of the hydrogen is preferably adjusted to 1.2-1.5 MPa, the fixed bed reactor is reduced to 80-90 ℃, then a nitro material is pumped into the fixed bed reactor to carry out nitro hydrogenation reaction, and the volume space velocity of the nitro material is 0.5-0.8 h-1。
In the method for continuously producing the 2B oil, the fixed bed reactor adopts a circulating water heating mode to supply heat, all pipelines except the gas-liquid separator have electric tracing heat, and the temperature is 30-50 ℃.
The invention has the following beneficial effects:
1. the interaction of the active component Pt of the catalyst, the auxiliary agent, the second noble metal and the transition metal is beneficial to improving the adsorption and activation effects of the catalyst on nitro and reducing the adsorption capacity of the catalyst on chlorine, thereby achieving the purposes of reducing the dechlorination activity of the catalyst and ensuring that the catalyst has stronger nitro hydrogenation capacity; the foamed aluminum has excellent heat conducting performance, can remove huge heat generated by nitro hydrogenation reaction in time, maintain the reaction temperature, avoid temperature runaway, and effectively control the reaction temperature within the required range.
2. The invention adopts a fixed bed continuous process, not only has higher efficiency than an intermittent kettle process, but also avoids the occurrence of side reactions of dechlorination to a certain extent by controlling the contact time of materials and the catalyst and separating the materials from the catalyst after the nitro hydrogenation, and has less dechlorination, less three wastes and good product quality. Wherein the conversion rate of the raw material (the mixture of the o-chloro-p-nitrotoluene and the p-nitrotoluene) is up to 100 percent, the selectivity of the product p-aminotoluene is 100 percent, the selectivity of the o-chloro-p-aminotoluene (2B oil) is more than 99.9 percent, and the dechlorination byproduct is less than 0.1 percent.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Since the nitro compound used as the raw material for the industrial production of o-chloro-p-aminotoluene (2B oil) is a mixture of o-chloro-p-nitrotoluene and p-nitrotoluene at a mass ratio of 4:1, the final object of the present invention is to be put to practical use in industry, and therefore, the raw materials in this ratio are also used in the following examples.
Example 1
1. Preparation of the catalyst
(1) 200g of 10-20-mesh granular foamed aluminum is washed with water, dried and then placed in a muffle furnace for roasting at 400 ℃ for 1 h.
(2) Grinding 200g of dried corn particles into powder, uniformly stirring and mixing with 100g of polyethylene glycol 4000 powder and 1000g of alumina sol with the solid content of 20%, then placing 100g of the calcined foamed aluminum obtained in the step (1) into the obtained mixed solution, soaking for 1h, taking out, placing in a tubular furnace, treating for 3h at 400 ℃ under the protection of nitrogen, then adding water vapor into the nitrogen, controlling the volume ratio of the water vapor to the nitrogen to be 12:88, simultaneously heating to 800 ℃ at the speed of 2 ℃/min, continuing to treat for 2h, and cooling to obtain the carbon-coated foamed aluminum carrier.
(3) Adding 2.03g of dinitroso diammine platinum into 40g of deionized water, heating and stirring until the dinitroso diammine platinum is completely dissolved, then spraying the mixture on 98.3g of carbon-coated foamed aluminum carrier, drying, soaking the obtained solid product in 200mL of aqueous solution containing 0.54g of ruthenium trichloride and 0.87g of ferric trichloride, keeping the solution for 12 hours, and finally drying the product in an oven at 150 ℃ for 12 hours to obtain the 1.2% Pt-0.2% Ru-0.3% Fe/C @ Al catalyst.
2. Continuous production of 2B oil in fixed bed
(1) Filling 1.2% of Pt-0.2% of Ru-0.3% of Fe/C @ Al catalyst into a fixed bed reactor, introducing hydrogen into the fixed bed reactor filled with the catalyst under the normal pressure condition, wherein the ratio of the flow rate of the hydrogen to the filling volume of the catalyst is 15:1, the flow rate unit of the hydrogen is mL/min, the filling volume unit of the catalyst is mL, simultaneously raising the temperature of the fixed bed reactor to 300 ℃, and carrying out reduction treatment on the catalyst for 2 hours under the normal pressure condition.
(2) Keeping the flow of hydrogen unchanged, continuously introducing hydrogen into the fixed bed reactor, adjusting the pressure of the hydrogen to 1.5MPa, reducing the temperature of the fixed bed reactor to 90 ℃, and then pumping the fixed bed reactor with a volume space velocity of 0.5h-1The nitro material raw material is a mixture of o-chloro-p-nitrotoluene and p-nitrotoluene with the mass ratio of 4:1, and the nitro hydrogenation reaction is carried out.
(3) And (3) separating the material subjected to the nitro hydrogenation reaction in the step (2) by an oil-water separator to obtain an organic phase and a water phase, wherein the organic phase is a mixture of the o-chloro-p-aminotoluene and the p-aminotoluene, and separating and purifying to obtain a pure o-chloro-p-aminotoluene (2B oil) product. The fixed bed reaction device adopts a heating mode of circulating water to supply heat, all pipelines except the gas-liquid separator have electric tracing, and the temperature is 40 ℃. The reaction results are shown in Table 1.
Example 2
1. Preparation of the catalyst
(1) 200g of 10-20 mesh granular foamed aluminum is washed with water, dried and then placed in a muffle furnace for roasting at 400 ℃ for 1 h.
(2) Grinding 200g of dried corn particles into powder, uniformly stirring and mixing with 100g of polyethylene glycol 4000 powder and 1100g of alumina sol with the solid content of 20%, then placing 100g of the calcined foamed aluminum obtained in the step (1) into the obtained mixed solution, soaking for 1h, taking out, placing in a tubular furnace, treating for 3h at 400 ℃ under the protection of nitrogen, then adding water vapor into the nitrogen, controlling the volume ratio of the water vapor to the nitrogen to be 12:88, simultaneously heating to 800 ℃ at the speed of 2 ℃/min, continuing to treat for 4h, and cooling to obtain the carbon-coated foamed aluminum carrier.
(3) Adding 1.86g dinitroso diammine platinum into 35g deionized water, heating and stirring until the dinitroso diammine platinum is completely dissolved, then spraying the mixture on 98.2g carbon-coated foamed aluminum carrier, drying, soaking the obtained solid product in 200mL aqueous solution containing 0.5g palladium chloride and 0.83g zinc chloride, keeping the solution for 12 hours, and finally drying the product in an oven at 150 ℃ for 12 hours to obtain the 1.1% Pt-0.3% Pd-0.4% Zn/C @ Al catalyst.
2. Continuous production of 2B oil in fixed bed
(1) Filling 1.1% of Pt-0.3% of Pd-0.4% of Zn/C @ Al catalyst into a fixed bed reactor, introducing hydrogen into the fixed bed reactor filled with the catalyst under the normal pressure condition, wherein the ratio of the flow rate of the hydrogen to the filling volume of the catalyst is 6:1, the flow rate of the hydrogen is mL/min, the filling volume of the catalyst is mL, simultaneously raising the temperature of the fixed bed reactor to 300 ℃, and carrying out reduction treatment on the catalyst for 3 hours.
(2) Keeping the flow of hydrogen unchanged, continuously introducing hydrogen into the fixed bed reactor, adjusting the pressure of the hydrogen to 1.1MPa, reducing the temperature of the fixed bed reactor to 70 ℃, and then pumping the fixed bed reactor with a volume space velocity of 0.4h-1The nitro material raw material is a mixture of o-chloro-p-nitrotoluene and p-nitrotoluene with the mass ratio of 4:1, and the nitro hydrogenation reaction is carried out.
(3) And (3) separating the material subjected to the nitro hydrogenation reaction in the step (2) by an oil-water separator to obtain an organic phase and a water phase, wherein the organic phase is a mixture of the o-chloro-p-aminotoluene and the p-aminotoluene, and separating and purifying to obtain a pure o-chloro-p-aminotoluene (2B oil) product. The fixed bed reaction device adopts a heating mode of circulating water to supply heat, all pipelines except the gas-liquid separator have electric tracing, and the temperature is 40 ℃. The reaction results are shown in Table 1.
Example 3
1. Preparation of the catalyst
(1) 200g of 10-20 mesh granular foamed aluminum is washed with water, dried and then placed in a muffle furnace for roasting at 400 ℃ for 1 h.
(2) Grinding 200g of dried corn particles into powder, uniformly stirring and mixing with 100g of polyethylene glycol 4000 powder and 1200g of alumina sol with the solid content of 20%, then placing 100g of the calcined foamed aluminum obtained in the step (1) into the obtained mixed solution, soaking for 1h, taking out, placing in a tubular furnace, treating for 2h at 400 ℃ under the protection of nitrogen, then adding water vapor into the nitrogen, controlling the volume ratio of the water vapor to the nitrogen to be 10:90, simultaneously heating to 800 ℃ at the speed of 1 ℃/min, continuing to treat for 3h, and cooling to obtain the carbon-coated foamed aluminum carrier.
(3) Adding 1.69g dinitroso diammine platinum into 32g deionized water, heating and stirring until the dinitroso diammine platinum is completely dissolved, then spraying the mixture on 98.6g of carbon-coated foamed aluminum carrier, drying, soaking the obtained solid product in 200mL of aqueous solution containing 0.34g of chloroauric acid and 0.38g of stannous chloride dihydrate, keeping the solution for 12 hours, and finally drying the product in an oven at 150 ℃ for 12 hours to obtain the 1.0% Pt-0.2% Au-0.2% Sn/C @ Al catalyst.
2. Continuous production of 2B oil in fixed bed
(1) Filling 1.0% of Pt-0.2% of Au-0.2% of Sn/C @ Al catalyst into a fixed bed reactor, introducing hydrogen into the fixed bed reactor filled with the catalyst under the normal pressure condition, wherein the ratio of the flow rate of the hydrogen to the filling volume of the catalyst is 8:1, the flow rate unit of the hydrogen is mL/min, the filling volume unit of the catalyst is mL, simultaneously raising the temperature of the fixed bed reactor to 400 ℃, and carrying out reduction treatment on the catalyst for 5 hours.
(2) Keeping the flow of hydrogen unchanged, continuously introducing hydrogen into the fixed bed reactor, adjusting the pressure of the hydrogen to 0.9MPa, reducing the temperature of the fixed bed reactor to 100 ℃, and then pumping into the fixed bed reactor at a volume space velocity of 1.0h-1The nitro material raw material is a mixture of o-chloro-p-nitrotoluene and p-nitrotoluene with the mass ratio of 4:1, and the nitro hydrogenation reaction is carried out.
(3) And (3) separating the material subjected to the nitro hydrogenation reaction in the step (2) by an oil-water separator to obtain an organic phase and a water phase, wherein the organic phase is a mixture of the o-chloro-p-aminotoluene and the p-aminotoluene, and separating and purifying to obtain a pure o-chloro-p-aminotoluene (2B oil) product. The fixed bed reaction device adopts a heating mode of circulating water to supply heat, all pipelines except the gas-liquid separator have electric tracing, and the temperature is 30 ℃. The reaction results are shown in Table 1.
Example 4
1. Preparation of the catalyst
(1) 200g of 10-20 mesh granular foamed aluminum is washed with water, dried and then placed in a muffle furnace for roasting at 400 ℃ for 1 h.
(2) Grinding 200g of dried corn particles into powder, uniformly stirring and mixing with 100g of polyethylene glycol 4000 powder and 500g of alumina sol with the solid content of 20%, then placing 100g of the calcined foamed aluminum obtained in the step (1) into the obtained mixed solution, soaking for 1h, taking out, placing in a tubular furnace, treating for 2h at 400 ℃ under the protection of nitrogen, then adding water vapor into the nitrogen, controlling the volume ratio of the water vapor to the nitrogen to be 15:85, simultaneously heating to 800 ℃ at the speed of 1 ℃/min, continuing to treat for 2h, and cooling to obtain the carbon-coated foamed aluminum carrier.
(3) Adding 2.37g dinitroso diammine platinum into 36g deionized water, heating and stirring until the dinitroso diammine platinum is completely dissolved, then spraying the mixture on 98.1g carbon-coated foamed aluminum carrier, drying, soaking the obtained solid product in 200mL aqueous solution containing 0.81g ruthenium trichloride and 0.42g copper chloride, keeping the solution for 12 hours, and finally drying the product in an oven at 150 ℃ for 12 hours to obtain the 1.4% Pt-0.3% Ru-0.2% Cu/C @ Al catalyst.
2. Continuous production of 2B oil in fixed bed
(1) Filling 1.4% of Pt-0.3% of Ru-0.2% of Cu/C @ Al catalyst into a fixed bed reactor, introducing hydrogen into the fixed bed reactor filled with the catalyst under the normal pressure condition, wherein the ratio of the flow rate of the hydrogen to the filling volume of the catalyst is 10:1, the flow rate unit of the hydrogen is mL/min, the filling volume unit of the catalyst is mL, simultaneously raising the temperature of the fixed bed reactor to 400 ℃, and carrying out reduction treatment on the catalyst for 4 hours.
(2) Keeping the flow of the hydrogen unchanged, and continuously introducing the hydrogen into the fixed bed reactorAdjusting the hydrogen pressure to 1.7MPa, reducing the temperature of the fixed bed reactor to 80 ℃, and then pumping the fixed bed reactor with a volume space velocity of 0.6h-1The nitro material raw material is a mixture of o-chloro-p-nitrotoluene and p-nitrotoluene with the mass ratio of 4:1, and the nitro hydrogenation reaction is carried out.
(3) And (3) separating the material subjected to the nitro hydrogenation reaction in the step (2) by an oil-water separator to obtain an organic phase and a water phase, wherein the organic phase is a mixture of the o-chloro-p-aminotoluene and the p-aminotoluene, and separating and purifying to obtain a pure o-chloro-p-aminotoluene (2B oil) product. The fixed bed reaction device adopts a heating mode of circulating water to supply heat, all pipelines except the gas-liquid separator have electric tracing, and the temperature is 30 ℃. The reaction results are shown in Table 1.
Example 5
1. Preparation of the catalyst
(1) 200g of 10-20 mesh granular foamed aluminum is washed with water, dried and then placed in a muffle furnace for roasting at 400 ℃ for 1 h.
(2) Grinding 200g of dried corn particles into powder, uniformly stirring and mixing with 100g of polyethylene glycol 4000 powder and 700g of alumina sol with the solid content of 20%, then placing 100g of the calcined foamed aluminum obtained in the step (1) into the obtained mixed solution, soaking for 1h, taking out, placing in a tubular furnace, treating for 4h at 400 ℃ under the protection of nitrogen, then adding water vapor into the nitrogen, controlling the volume ratio of the water vapor to the nitrogen to be 10:90, simultaneously heating to 800 ℃ at the speed of 3 ℃/min, continuing to treat for 4h, and cooling to obtain the carbon-coated foamed aluminum carrier.
(3) Adding 2.03g of dinitroso diammine platinum into 40g of deionized water, heating and stirring until the dinitroso diammine platinum is completely dissolved, then spraying the mixture on 98.1g of carbon-coated foamed aluminum carrier, drying, soaking the obtained solid product in 200mL of aqueous solution containing 0.67g of palladium chloride and 0.63g of zinc chloride, keeping the solution for 12 hours, and finally drying the product in an oven at 150 ℃ for 12 hours to obtain the 1.2 Pt-0.4% Pd-0.3% Zn/C @ Al catalyst.
2. Continuous production of 2B oil in fixed bed
(1) Filling 1.2 Pt-0.4% Pd-0.3% Zn/C @ Al catalyst into a fixed bed reactor, introducing hydrogen into the fixed bed reactor filled with the catalyst under the normal pressure condition, wherein the ratio of the flow rate of the hydrogen to the filling volume of the catalyst is 12:1, the flow rate of the hydrogen is mL/min, the filling volume of the catalyst is mL, simultaneously raising the temperature of the fixed bed reactor to 500 ℃, and carrying out reduction treatment on the catalyst for 6 hours.
(2) Keeping the flow of hydrogen unchanged, continuously introducing hydrogen into the fixed bed reactor, adjusting the pressure of the hydrogen to 1.2MPa, reducing the temperature of the fixed bed reactor to 90 ℃, and then pumping the fixed bed reactor with a volume space velocity of 0.8h-1The nitro material raw material is a mixture of o-chloro-p-nitrotoluene and p-nitrotoluene with the mass ratio of 4:1, and the nitro hydrogenation reaction is carried out.
(3) And (3) separating the material subjected to the nitro hydrogenation reaction in the step (2) by an oil-water separator to obtain an organic phase and a water phase, wherein the organic phase is a mixture of the o-chloro-p-aminotoluene and the p-aminotoluene, and separating and purifying to obtain a pure o-chloro-p-aminotoluene (2B oil) product. The fixed bed reaction device adopts a heating mode of circulating water to supply heat, and all pipelines except the gas-liquid separator have electric tracing at the temperature of 50 ℃. The reaction results are shown in Table 1.
Example 6
1. Preparation of the catalyst
(1) 200g of 10-20 mesh granular foamed aluminum is washed with water, dried and then placed in a muffle furnace for roasting at 400 ℃ for 1 h.
(2) Grinding 200g of dried corn particles into powder, uniformly stirring and mixing with 100g of polyethylene glycol 4000 powder and 900g of alumina sol with the solid content of 20%, then placing 100g of the calcined foamed aluminum obtained in the step (1) into the obtained mixed solution, soaking for 1h, taking out, placing in a tubular furnace, treating for 4h at 400 ℃ under the protection of nitrogen, then adding water vapor into the nitrogen, controlling the volume ratio of the water vapor to the nitrogen to be 15:85, simultaneously heating to 800 ℃ at the speed of 3 ℃/min, continuing to treat for 3h, and cooling to obtain the carbon-coated foamed aluminum carrier.
(3) Adding 2.71g dinitroso diammine platinum into 38g deionized water, heating and stirring until the dinitroso diammine platinum is completely dissolved, then spraying the mixture on 97.8g carbon-coated foamed aluminum carrier, drying, soaking the obtained solid product in 200mL aqueous solution containing 0.34g chloroauric acid and 1.16g ferric trichloride, keeping the solution for 12 hours, and finally drying the product in an oven at 150 ℃ for 12 hours to obtain the 1.6% Pt-0.2% Au-0.4% Fe/C @ Al catalyst.
2. Continuous production of 2B oil in fixed bed
(1) Filling 1.6% of Pt-0.2% of Au-0.4% of Fe/C @ Al catalyst into a fixed bed reactor, introducing hydrogen into the fixed bed reactor filled with the catalyst under the normal pressure condition, wherein the ratio of the flow rate of the hydrogen to the filling volume of the catalyst is 13:1, the flow rate unit of the hydrogen is mL/min, the filling volume unit of the catalyst is mL, simultaneously raising the temperature of the fixed bed reactor to 500 ℃, and carrying out reduction treatment on the catalyst for 8 hours.
(2) Keeping the flow of hydrogen unchanged, continuously introducing hydrogen into the fixed bed reactor, adjusting the pressure of the hydrogen to 1.4MPa, reducing the temperature of the fixed bed reactor to 60 ℃, and then pumping the fixed bed reactor with a volume space velocity of 0.3h-1The nitro material raw material is a mixture of o-chloro-p-nitrotoluene and p-nitrotoluene with the mass ratio of 4:1, and the nitro hydrogenation reaction is carried out.
(3) And (3) separating the material subjected to the nitro hydrogenation reaction in the step (2) by an oil-water separator to obtain an organic phase and a water phase, wherein the organic phase is a mixture of the o-chloro-p-aminotoluene and the p-aminotoluene, and separating and purifying to obtain a pure o-chloro-p-aminotoluene (2B oil) product. The fixed bed reaction device adopts a heating mode of circulating water to supply heat, and all pipelines except the gas-liquid separator have electric tracing at the temperature of 50 ℃. The reaction results are shown in Table 1.
TABLE 1 results of catalytic reactions of examples 1 to 6
As can be seen from Table 1, the catalyst and the fixed bed process of the present invention have the conversion rate of the nitro compounds (o-chloro-p-nitrotoluene and p-nitrotoluene) as the raw materials close to 100%, the selectivity of o-chloro-p-aminotoluene is more than 99.7%, and the dechlorination byproduct is less than 0.3%.
Claims (10)
1. A platinum-based composite carbon aluminum catalyst for continuously producing 2B oil is characterized in that: the catalyst takes carbon-coated foamed aluminum as a carrier, and loads Pt, a second noble metal and a transition metal, wherein the second noble metal is any one of Ru, Au and Pd, the transition metal is any one of Zn, Fe, Sn and Cu, the mass content of Pt in the catalyst is 0.6-1.9%, and the mass contents of the second noble metal and the transition metal are both in the range of 0.1-0.7%; the catalyst is prepared by the following preparation method:
(1) washing and drying 10-20-mesh granular foamed aluminum, and then roasting in a muffle furnace at 400-500 ℃ for 1-3 h;
(2) grinding dried corn particles into powder, uniformly stirring and mixing the powder with polyethylene glycol powder and alumina sol with the solid content of 20-25%, then placing the calcined foamed aluminum obtained in the step (1) into the obtained mixed solution, soaking for 1-3 h, taking out, placing the mixture into a tubular furnace, heating to 400-500 ℃ under the protection of nitrogen, carrying out constant temperature treatment for 2-4 h, then adding water vapor into nitrogen, heating to 800-900 ℃, continuing to treat for 2-4 h, and cooling to obtain a carbon-coated foamed aluminum carrier; wherein the mass ratio of the dried corn particles to the polyethylene glycol powder to the foamed aluminum to the alumina sol is 2-4: 1:1: 5-12, and the volume ratio of the water vapor to the nitrogen is 10: 90-15: 85;
(3) adding dinitroso diammine platinum into deionized water according to the composition of the catalyst, heating and stirring until the dinitroso diammine platinum is completely dissolved, then spraying the dinitroso diammine platinum onto a carbon-coated foamed aluminum carrier, drying, soaking the obtained solid product in an aqueous solution containing a second noble metal precursor and a transition metal precursor for 10-12 h, and finally drying in an oven at 120-150 ℃ for 10-12 h to obtain a platinum-based composite carbon-aluminum catalyst; the second noble metal precursor is any one of chloroauric acid, palladium chloride and ruthenium trichloride, and the transition metal precursor is any one of zinc chloride, ferric trichloride, tin dichloride and copper chloride.
2. The platinum-based composite carbon aluminum catalyst according to claim 1, characterized in that: the mass content of Pt in the catalyst is 1.0-1.6%, and the mass content of the second noble metal and the transition metal are both in the range of 0.2-0.4%.
3. The platinum-based composite carbon aluminum catalyst according to claim 1, characterized in that: in the step (2), the mass ratio of the dried corn particles to the polyethylene glycol powder to the foamed aluminum to the aluminum sol is 2:1:1: 5-12.
4. The platinum-based composite carbon aluminum catalyst according to claim 1 or 3, characterized in that: the polyethylene glycol is polyethylene glycol 2000 or polyethylene glycol 4000.
5. The platinum-based composite carbon aluminum catalyst according to claim 1, characterized in that: in the step (2), the temperature rise rate is 1-3 ℃/min.
6. A method for continuously producing 2B oil by using the platinum-based composite carbon-aluminum catalyst of claim 1, which is characterized in that:
(1) filling a platinum-based composite carbon-aluminum catalyst into a fixed bed reactor, introducing hydrogen into the fixed bed reactor filled with the catalyst under the normal pressure condition, raising the temperature of the fixed bed reactor to 300-500 ℃, and reducing the catalyst under the normal pressure condition;
(2) keeping the flow of hydrogen unchanged, continuously introducing hydrogen into the fixed bed reactor, adjusting the pressure of the hydrogen to 0.9-1.7 MPa, reducing the pressure of the fixed bed reactor to 60-100 ℃, then pumping a nitro material into the fixed bed reactor for carrying out nitro hydrogenation reaction, wherein the nitro material is o-chloro-p-nitrotoluene or a mixture of the o-chloro-p-nitrotoluene and the p-nitrotoluene with the mass ratio of 4:1, and the volume space velocity of the nitro material is 0.3-1.0 h-1；
(3) And (3) separating the material subjected to the nitro hydrogenation reaction in the step (2) by an oil-water separator to obtain an organic phase and a water phase, and separating and purifying the organic phase to obtain pure 2B oil.
7. The method for continuously producing 2B oil according to claim 6, wherein: in the step (1) and the step (2), the ratio of the flow rate of the hydrogen to the filling volume of the catalyst is 6-15: 1, wherein the flow rate unit of the hydrogen is mL/min, and the filling volume unit of the catalyst is mL.
8. The method for continuously producing 2B oil according to claim 6, wherein: in the step (1), the time of the reduction treatment is 2-8 h.
9. The method for continuously producing 2B oil according to claim 6, wherein: in the step (2), keeping the flow of hydrogen unchanged, continuously introducing the hydrogen into the fixed bed reactor, adjusting the pressure of the hydrogen to 1.2-1.5 MPa, reducing the pressure of the fixed bed reactor to 80-90 ℃, then pumping a nitro material into the fixed bed reactor, and carrying out nitro hydrogenation reaction, wherein the volume space velocity of the nitro material is 0.5-0.8 h-1。
10. The method for continuously producing 2B oil according to claim 6, wherein: the fixed bed reactor adopts a circulating water heating mode to supply heat, all pipelines have electric tracing heat except a gas-liquid separator, and the temperature is 30-50 ℃.
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