A trimetallic pre-oxidized carbon black supported catalyst and its application

Abstract

The application discloses a three-metal pre-oxidized carbon black supported catalyst and application thereof, and the catalyst takes pre-oxidized carbon black as a carrier, and is loaded with a first metal element, a second metal element and an auxiliary metal element, wherein the first metal element is selected from Ir, Au and Ru, the second metal element is selected from Zn, Zr and V, and the auxiliary metal element is selected from Na, K and Mg. The application is applied to the hydrogenation of 2-hexanone into 2-hexanol, and when the catalytic conversion of 2-hexanone reaches 100%, the selectivity of the product 2-hexanol can reach 100%, the burden of separation and purification of the product can be greatly reduced, and the production cost is lowered; the catalytic reaction process does not use a solvent, the operation temperature is relatively low, and the process is green, low in energy consumption. The catalyst has high activity, the reaction time is relatively short, and the production efficiency can be improved.

Description

Technical Field

[0001] This invention belongs to the field of industrial catalyst technology, specifically relating to a trimetallic pre-oxidized carbon black supported catalyst and its application. Background Technology

[0002] 2-Hexanol is an important chemical raw material, mainly used as a solvent and emulsifier, and can also be used to prepare adipic acid, plasticizers, detergents, etc. 2-Hexanol can be obtained by hydrogenating 2-hexanone; currently, no patents have been found for catalysts related to the hydrogenation of 2-hexanone to 2-hexanol.

[0003] Previous technologies have disclosed catalysts and processes for the hydrogenation of ketones to alcohols. CN1152744C, CN1114490C, and CN1347758A disclose methods for the hydrogenation of 2-octanone to 2-octanol, using a self-made catalyst system (containing copper and nickel catalysts) and a fixed-bed liquid-phase hydrogenation process at a reaction temperature of 100-250℃. The selectivity for 2-octanol is 96%-99.5%. CN1974514A discloses a method for the hydrogenation reduction of 2-octanone to 2-octanol, in which a ferromagnetic hydrogenation catalyst is added to a magnetically stabilized bed reactor, and the reaction is carried out under the following conditions: temperature 70-120℃, pressure 0.3-2.5MPa, liquid hourly space velocity 1-50h⁻¹, hydrogen to 2-octanone solution volume ratio 2-100:1, and magnetic field strength 10-50kA / m. The yield of 2-octanol can reach 70%. Patent CN1083415C uses a pressed CuO-ZnO mixture as a catalyst, achieving a conversion rate and selectivity of 99% for the gas-phase hydrogenation of acetone to isopropanol at a reaction temperature of 150-250℃. Japanese Patent Hei 2-279643 discloses a Ru / Al2O3-catalyzed acetone hydrogenation process that is demanding, requiring a reaction pressure of 9 MPa and significant equipment investment. Japanese Patent Hei-41038 and Soviet Patent SU1118632A introduce acetone hydrogenation methods using Cu-Cr catalysts. Russian Patent RU2047590 uses catalysts containing NiO and CuO, but these catalysts have low conversion rates and poor selectivity. Furthermore, the use of Cr2O3 as an auxiliary agent causes environmental pollution, failing to meet the requirements of green chemistry. CN103030525A discloses a method for preparing isopropanol by liquid-phase hydrogenation of acetone, but the reaction temperature is relatively high, at 100-200℃, with an acetone conversion rate of over 96% and an isopropanol selectivity greater than 95%. CN1962588 discloses a continuous gas-phase hydrogenation reaction of acetone using a nickel-cobalt bimetallic catalyst supported on activated carbon, with a reaction temperature of 100-150℃ and a pressure of 1.0-1.5 MPa, achieving high acetone conversion and isopropanol selectivity. CN103706365 discloses a nickel-copper bimetallic supported catalyst for atmospheric pressure gas-phase fixed-bed hydrogenation of acetone, with a reaction temperature of 100-150℃, achieving 100% isopropanol selectivity and an acetone conversion rate of over 85.5%. CN103706377A and CN103752327A disclose the liquid-phase hydrogenation of acetone to isopropanol using a metal catalyst with Pt, Fe, Sn, and Co as the main components, at a reaction temperature of 100-150℃ and a reaction time of 4 h. USP4,182,721 discloses a method for the catalytic hydrogenation of ketones using a molybdenum-modified skeletal nickel catalyst, although the reaction conditions are relatively mild (60℃, 2.1 MPa), the product selectivity is poor.USP4,459,419 discloses a method for hydrogenating organic ketones or aldehydes using a ruthenium catalyst supported on a molecular sieve, and cites its application in the hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol, but the reaction system requires a high pressure of 12.7 MPa.

[0004] In summary, existing hydrogenation processes for ketone compounds operate at high temperatures, require demanding equipment conditions, or fail to simultaneously achieve high conversion rates and product selectivity. Therefore, developing a heterogeneous catalyst that can react at lower operating temperatures, without solvents, and exhibits high activity and product selectivity could alleviate the burden on product separation and purification processes, reduce energy consumption, and significantly lower production costs. Low-energy and high-efficiency production aligns with the requirements of green chemistry. Summary of the Invention

[0005] The purpose of this invention is to overcome the defects of the prior art and provide a trimetallic pre-oxidized carbon black supported catalyst.

[0006] Another object of the present invention is to provide the application of the above-mentioned trimetallic pre-oxidized carbon black supported catalyst.

[0007] The technical solution of the present invention is as follows:

[0008] A trimetallic pre-oxidized carbon black supported catalyst uses pre-oxidized carbon black as a support, on which a first metal element, a second metal element, and an auxiliary metal element are loaded. The first metal element is selected from Ir, Au, and Ru; the second metal element is selected from Zn, Zr, and V; and the auxiliary metal element is selected from Na, K, and Mg.

[0009] The above pre-oxidation process is as follows: carbon black is mixed with an aqueous oxidant solution and stirred at 60-100℃ for 1-3 hours. After filtration and washing until neutral, it is vacuum dried at 75-85℃ for 10-14 hours, calcined at 200-600℃ for 1-3 hours under an argon atmosphere, and then cooled to room temperature at a heating rate of 2-10℃ / min. The solute in the above aqueous oxidant solution is nitric acid or hydrogen peroxide.

[0010] In a preferred embodiment of the present invention, the flow rate of argon gas in the argon atmosphere is 20-70 mL / min.

[0011] In a preferred embodiment of the present invention, the heating rate of the calcination is 2-10 °C / min.

[0012] In a preferred embodiment of the present invention, the loading amount of the first metal element is 0.1-1.5 wt.%, the loading amount of the second metal element is 0.5-1.7 wt.%, and the loading amount of the auxiliary metal element is 0.5-1.5 wt.%.

[0013] The application of the above-mentioned trimetallic pre-oxidized carbon black supported catalyst in the hydrogenation of 2-hexanone to 2-hexanol.

[0014] In a preferred embodiment of the present invention, an intermittent high-pressure autoclave liquid-phase hydrogenation process is used, without the use of solvents.

[0015] More preferably, in the intermittent high-pressure autoclave liquid-phase hydrogenation process, the hydrogen pressure is 0.5-5.5 MPa, the reaction temperature is 30-80℃, the catalyst feed rate / substrate is 0.001-0.01 g / mL, and the reaction time is 0.5-2 h.

[0016] A method for hydrogenating 2-hexanone to 2-hexanol, using the above-mentioned trimetallic pre-oxidized carbon black supported catalyst.

[0017] In a preferred embodiment of the present invention, an intermittent high-pressure autoclave liquid-phase hydrogenation process is used, without the use of solvents.

[0018] More preferably, in the intermittent high-pressure autoclave liquid-phase hydrogenation process, the hydrogen pressure is 0.5-5.5 MPa, the reaction temperature is 30-80℃, the catalyst feed rate / substrate is 0.001-0.01 g / mL, and the reaction time is 0.5-2 h.

[0019] The beneficial effects of this invention are:

[0020] 1. The trimetallic pre-oxidized carbon black supported catalyst of this invention operates at a low temperature and consumes less energy when applied to liquid-phase hydrogenation processes. It also operates at moderate pressure and requires minimal equipment investment.

[0021] 2. The catalytic reaction process of this invention does not use solvents, making the process environmentally friendly. The catalyst exhibits high activity, and the reaction time is short, which can improve production efficiency.

[0022] 3. This invention achieves 100% catalytic conversion of 2-hexanone while maintaining 100% selectivity for the product 2-hexanol, which greatly reduces the burden of product separation and purification and lowers production costs.

[0023] 4. The preparation and production method of the trimetallic pre-oxidized carbon black supported catalyst of the present invention is relatively simple and easy to implement, and is suitable for mass production. Detailed Implementation

[0024] The technical solution of the present invention will be further explained and described below through specific embodiments.

[0025] Example 1

[0026] 100 mL of 15% nitric acid solution was mixed with 1 g of carbon black and heated at 100 °C with continuous stirring for 3 h. The mixture was then filtered, washed until neutral, and dried under vacuum at 80 °C for 12 h. The dried carbon black was then calcined at 200 °C for 3 h under an argon atmosphere with an argon flow rate of 20 mL / min and a heating rate of 5 °C / min.

[0027] Weigh 0.02 g of ruthenium trichloride hydrate, 0.03 g of zinc nitrate hexahydrate, and 0.8 g of PVA, and add them to 50 mL of deionized water. After stirring for 20 min, adjust the pH to 10 with sodium hydroxide. Add 0.6 g of the above-treated carbon black and 3 mL of hydrazine hydrate. The hydrazine hydrate is added at a dropping rate of 10 drops / min. Stir continuously for 3 h. After filtration and washing, dry under vacuum at 80 °C for 12 h. Then, heat to 500 °C in hydrogen at a gas flow rate of 50 mL / min, hold at the temperature for 3 h, and then cool to room temperature to obtain Ru-Zn / C.

[0028] 0.016 g of potassium nitrate was weighed and placed in 50 mL of deionized water, and stirred for 30 min. The above Ru-Zn / C was added to the above solution, and stirred continuously for 2 h. Ammonia was added dropwise until the pH = 10. The solution was then filtered and washed until neutral, dried under vacuum at 80 °C for 12 h, and then heated to 300 °C at 5 °C / min under a hydrogen atmosphere. After holding at the temperature for 2 h, the temperature was lowered to room temperature at a gas flow rate of 70 mL / min to obtain the trimetallic pre-oxidized carbon black supported catalyst.

[0029] The trimetallic pre-oxidized carbon black supported catalyst prepared in this example was applied to the hydrogenation of 2-hexanone to 2-hexanol: the catalyst feed / substrate ratio was 0.01 g / mL, the reaction was carried out in a batch high-pressure reactor at a reaction temperature of 50 °C for 1.5 h, a hydrogen pressure of 5.0 MPa, and a stirring rate of 500 rpm. The conversion rate of 2-hexanone hydrogenation was measured to be 43.3%, and the selectivity for 2-hexanol was 96.9%.

[0030] Example 2

[0031] The pretreatment conditions for the carbon black used in Example 1 were modified: 100 mL of 5% nitric acid solution was mixed with 1 g of carbon black and heated at 60°C with continuous stirring for 3 h. The mixture was then filtered, washed until neutral, and vacuum dried at 80°C for 12 h. The dried carbon black was then calcined at 200°C for 3 h under an argon atmosphere with an argon flow rate of 20 mL / min and a heating rate of 5°C / min. The rest of the process was the same as in Example 1.

[0032] The trimetallic pre-oxidized carbon black supported catalyst prepared in this example was applied to the hydrogenation of 2-hexanone to 2-hexanol: the catalyst feed / substrate ratio was 0.01 g / mL, the reaction was carried out in a batch high-pressure reactor at a reaction temperature of 50 °C for 1.5 h, a hydrogen pressure of 5.0 MPa, and a stirring rate of 500 rpm. The conversion rate of 2-hexanone hydrogenation was measured to be 87.9%, and the selectivity of 2-hexanol reached 98.8%.

[0033] Example 3

[0034] 100 mL of 15% hydrogen peroxide solution was mixed with 1 g of carbon black and heated at 100 °C with continuous stirring for 3 h. After filtration and washing until neutral, the mixture was vacuum dried at 80 °C for 12 h. The dried carbon black was then calcined at 200 °C for 3 h under an argon atmosphere with an argon flow rate of 20 mL / min and a heating rate of 5 °C / min.

[0035] Weigh 0.015 g of chloroiridic acid, 0.02 g of hydrated zirconium nitrate and 0.2 g of CTAB, add them to 50 mL of deionized water, stir for 20 min, adjust the pH to 10 with sodium hydroxide, add 0.6 g of the above-treated carbon black and 3 mL of hydrated hydrazine, the hydrazine hydrate is added at a dropping rate of 10 drops / min, stir continuously for 3 h, filter and wash until neutral, vacuum dry at 80 °C for 12 h, then heat to 500 °C in hydrogen at a gas flow rate of 50 mL / min, keep at the temperature for 3 h and cool to room temperature to obtain Ir-Zr / C.

[0036] 0.06 g of magnesium nitrate hexahydrate was weighed and placed in 50 mL of deionized water, and stirred for 30 min. The above Ir-Zr / C was added to the above solution, and stirred continuously for 2 h. Ammonia was added dropwise until pH = 10. The solution was filtered and washed until neutral, and dried under vacuum at 80 °C for 12 h. Then, the temperature was increased to 400 °C at 5 °C / min under a hydrogen atmosphere, held at the temperature for 2 h, and then cooled to room temperature at a gas flow rate of 70 mL / min to obtain the trimetallic pre-oxidized carbon black supported catalyst.

[0037] The trimetallic pre-oxidized carbon black supported catalyst prepared in this example was applied to the hydrogenation of 2-hexanone to 2-hexanol: the catalyst feed / substrate ratio was 0.01 g / mL, the reaction was carried out in a batch high-pressure reactor at a reaction temperature of 50 °C for 1.5 h, a hydrogen pressure of 5.0 MPa, and a stirring rate of 500 rpm. The conversion rate of 2-hexanone hydrogenation was measured to be 72.5%, and the selectivity for 2-hexanol was 100%.

[0038] Example 4

[0039] The pretreatment conditions of the carbon black used in Example 3 were changed. 100 mL of 5% hydrogen peroxide solution was mixed with 1 g of carbon black and heated at 80°C with continuous stirring for 3 hours. After filtration and washing until neutral, the mixture was vacuum dried at 80°C for 12 hours. The dried carbon black was then calcined at 200°C for 3 hours under an argon atmosphere with an argon flow rate of 20 mL / min and a heating rate of 5°C / min. The rest of the process was the same as in Example 3.

[0040] The trimetallic pre-oxidized carbon black supported catalyst prepared in this example was applied to the hydrogenation of 2-hexanone to 2-hexanol: the catalyst feed / substrate ratio was 0.01 g / mL, the reaction was carried out in a batch high-pressure reactor at a reaction temperature of 50°C for 1.5 h, a hydrogen pressure of 5.0 MPa, and a stirring rate of 500 rpm. The conversion rate of 2-hexanone hydrogenation was 100%, and the selectivity for 2-hexanol was 100%.

[0041] Example 5

[0042] 100 mL of 10% nitric acid solution was mixed with 1 g of carbon black and heated at 80 °C with continuous stirring for 3 h. The mixture was then filtered, washed until neutral, and vacuum dried at 80 °C for 12 h. The dried carbon black was then calcined at 200 °C for 3 h under an argon atmosphere with an argon flow rate of 20 mL / min and a heating rate of 5 °C / min.

[0043] Weigh 0.015 g of ruthenium trichloride hydrate, 0.02 g of zirconium nitrate hydrate, and 0.8 g of PVA, add them to 50 mL of deionized water, stir for 40 min, adjust the pH to 10 with sodium hydroxide, add 10 mL of 5 mol / L ascorbic acid aqueous solution, stir continuously for 1 h, add 0.6 g of the above-treated carbon black, stir continuously for 3 h, filter and wash until neutral, vacuum dry at 80 °C for 12 h, then heat to 500 °C in hydrogen at 2 °C / min with a gas flow rate of 50 mL / min, hold at the temperature for 3 h and then cool to room temperature to obtain Ru-Zr / C.

[0044] 0.016 g of potassium nitrate was weighed and placed in 50 mL of deionized water, and stirred for 30 min. The above Ru-Zr / C was added to the above solution, and stirred continuously for 2 h. Ammonia was added dropwise until the pH = 10. The solution was filtered and washed until neutral, and dried under vacuum at 80 °C for 12 h. Then, the temperature was increased to 400 °C at 5 °C / min under a hydrogen atmosphere, held at the temperature for 2 h, and then cooled to room temperature at a gas flow rate of 70 mL / min to obtain the trimetallic pre-oxidized carbon black supported catalyst.

[0045] The trimetallic pre-oxidized carbon black supported catalyst prepared in this example was applied to the hydrogenation of 2-hexanone to 2-hexanol: the catalyst feed / substrate ratio was 0.01 g / mL, the reaction was carried out in a batch high-pressure reactor at a reaction temperature of 50°C for 2 h, a hydrogen pressure of 5.0 MPa, and a stirring rate of 500 rpm. The conversion rate of 2-hexanone hydrogenation was measured to be 68.3%, and the selectivity of 2-hexanol was 97.6%.

[0046] Example 6

[0047] 100 mL of 10% hydrogen peroxide solution was mixed with 1 g of carbon black and heated at 80 °C with continuous stirring for 3 h. After filtration and washing until neutral, the mixture was vacuum dried at 80 °C for 12 h. The dried carbon black was then calcined at 200 °C for 3 h under an argon atmosphere with an argon flow rate of 20 mL / min and a heating rate of 5 °C / min.

[0048] Weigh 0.015 g of chloroiridic acid, 0.015 g of ammonium metavanadate, and 0.2 g of CTAB, add them to 50 mL of deionized water, stir for 40 min, adjust the pH to 10 with sodium hydroxide, add 10 mL of 5 mol / L ascorbic acid aqueous solution, continue stirring for 1 h, then add 0.6 g of the above-treated carbon black, continue stirring for 3 h, filter and wash until neutral. Vacuum dry at 80 °C for 12 h, then heat to 500 °C in hydrogen at a rate of 2 °C / min and a gas flow rate of 50 mL / min, hold at this temperature for 3 h, and then cool to room temperature to obtain Ir-V / C.

[0049] 0.024 g of sodium nitrate was weighed and placed in 50 mL of deionized water, and stirred for 30 min. The above Ir-V / C was added to the above solution, and the mixture was stirred continuously for 2 h. Ammonia was added dropwise until the pH = 10. The solution was then filtered and washed until neutral, dried under vacuum at 80 °C for 12 h, and then heated to 300 °C at 5 °C / min under a hydrogen atmosphere. The temperature was held for 2 h and then cooled to room temperature at a gas flow rate of 70 mL / min to obtain the trimetallic pre-oxidized carbon black supported catalyst.

[0050] The trimetallic pre-oxidized carbon black supported catalyst prepared in this example was applied to the hydrogenation of 2-hexanone to 2-hexanol: the catalyst feed / substrate ratio was 0.01 g / mL, the reaction was carried out in a batch high-pressure reactor at a reaction temperature of 50°C for 2 h, a hydrogen pressure of 5.0 MPa, and a stirring rate of 500 rpm. The conversion rate of 2-hexanone hydrogenation was measured to be 80.6%, and the selectivity for 2-hexanol was 100%.

[0051] The above description is merely a preferred embodiment of the present invention, and therefore should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made in accordance with the scope of the patent and the contents of the specification should still fall within the scope of the present invention.

Claims

1. The application of a trimetallic pre-oxidized carbon black supported catalyst in the hydrogenation of 2-hexanone to 2-hexanol, characterized in that: A batch autoclave liquid-phase hydrogenation process is adopted without the use of solvents. During the batch autoclave liquid-phase hydrogenation process, the hydrogen pressure is 0.5-5.5 MPa, the reaction temperature is 30-80℃, the catalyst feed rate / substrate is 0.001-0.01 g / mL, and the reaction time is 0.5-2 h. The preparation method of this trimetallic pre-oxidized carbon black supported catalyst includes the following steps: (1) Mix 100 mL of 15% hydrogen peroxide solution with 1 g of carbon black and heat. Stir continuously at 100 °C for 3 h. Then filter and wash until neutral and vacuum dry at 80 °C for 12 h. Calcine the dried carbon black at 200 °C for 3 h under an argon atmosphere with an argon flow rate of 20 mL / min and a heating rate of 5 °C / min. (2) Weigh 0.015g of chloroiridic acid, 0.02g of hydrated zirconium nitrate and 0.2g of CTAB, put them into 50mL of deionized water, stir for 20 min, adjust the pH to 10 with sodium hydroxide, add 0.6g of the above-treated carbon black and 3mL of hydrated hydrazine, the dropping rate of hydrated hydrazine is 10 drops / min, stir continuously for 3h, filter and wash until neutral, vacuum dry at 80 ℃ for 12h, then heat to 500 ℃ in hydrogen at 2℃ / min, the gas flow rate is 50mL / min, keep at the temperature for 3h and cool to room temperature to obtain Ir-Zr / C; (3) Weigh 0.06 g of magnesium nitrate hexahydrate and put it into 50 mL of deionized water and stir for 30 min; put the above Ir-Zr / C into the above solution, stir continuously for 2 h, and then add ammonia dropwise until pH=10. Filter and wash until neutral, dry under vacuum at 80 ℃ for 12 h, then raise the temperature to 400 ℃ at 5 ℃ / min under hydrogen atmosphere, keep the temperature constant for 2 h and then lower it to room temperature. The gas flow rate is 70 mL / min to obtain the trimetallic pre-oxidized carbon black supported catalyst.

2. A method for hydrogenating 2-hexanone to 2-hexanol, characterized in that: A trimetallic pre-oxidized carbon black supported catalyst was used. The preparation method of this trimetallic pre-oxidized carbon black supported catalyst includes the following steps: (1) Mix 100 mL of 15% hydrogen peroxide solution with 1 g of carbon black and heat. Stir continuously at 100 °C for 3 h. Then filter and wash until neutral and vacuum dry at 80 °C for 12 h. Calcine the dried carbon black at 200 °C for 3 h under an argon atmosphere with an argon flow rate of 20 mL / min and a heating rate of 5 °C / min. (2) Weigh 0.015g of chloroiridic acid, 0.02g of hydrated zirconium nitrate and 0.2g of CTAB, put them into 50mL of deionized water, stir for 20 min, adjust the pH to 10 with sodium hydroxide, add 0.6g of the above-treated carbon black and 3mL of hydrated hydrazine, the dropping rate of hydrated hydrazine is 10 drops / min, stir continuously for 3h, filter and wash until neutral, vacuum dry at 80 ℃ for 12h, then heat to 500 ℃ in hydrogen at 2℃ / min, the gas flow rate is 50mL / min, keep at the temperature for 3h and cool to room temperature to obtain Ir-Zr / C; (3) Weigh 0.06 g of magnesium nitrate hexahydrate and put it into 50 mL of deionized water and stir for 30 min; put the above Ir-Zr / C into the above solution, stir continuously for 2 h, and then add ammonia dropwise until pH=10. Filter and wash until neutral, dry under vacuum at 80 ℃ for 12 h, then raise the temperature to 400 ℃ at 5 ℃ / min under hydrogen atmosphere, keep the temperature constant for 2 h and then lower it to room temperature. The gas flow rate is 70 mL / min to obtain the trimetallic pre-oxidized carbon black supported catalyst.

3. The method as described in claim 2, characterized in that: The process employs an intermittent high-pressure autoclave liquid-phase hydrogenation process without the use of solvents.

4. The method as described in claim 3, characterized in that: In the intermittent high-pressure autoclave liquid-phase hydrogenation process, the hydrogen pressure is 0.5-5.5 MPa, the reaction temperature is 30-80℃, the catalyst feed rate / substrate is 0.001-0.01 g / mL, and the reaction time is 0.5-2 h.