Bimetallic carbon black supported catalyst and use thereof

Abstract

The application discloses a bimetal carbon black supported catalyst and application thereof, which takes pre-oxidized carbon black as a carrier, and a first metal element and a second metal element are loaded on the carrier, wherein the first metal element is selected from Rh, Re and Ag, and the second metal element is selected from V, Zn and Zr. The application is applied to catalytic hydrogenation of cycloheptanone to prepare cycloheptanol, and when the catalytic conversion of the cycloheptanone reaches 100%, the selectivity of the product cycloheptanol can reach 100%, so that the burden of separation and purification of the product is greatly reduced, and the production cost is lowered; the catalytic reaction process does not use a solvent, the operation temperature is low, the process is green and low in energy consumption; the catalyst presents high activity, the reaction time is relatively short, and the production efficiency can be improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of industrial catalysts, and particularly relates to a bimetallic carbon black supported catalyst and application thereof. BACKGROUND

[0002] Cycloheptanol, also known as suberinol, is an important chemical raw material, which can be used as an upstream material for fine organic synthesis and is an important intermediate for medicines and materials. Cycloheptanol can be prepared by hydrogenation of cycloheptanone, and no related patent for preparing cycloheptanol by hydrogenation of cycloheptanone has been found. There are some patent documents disclosing catalysts and processes for preparing alcohol compounds by hydrogenation of ketone compounds.

[0003] CN1152744C, CN1114490C and CN1347758A disclose a method for preparing sec-octanol by hydrogenation of sec-octanone, using a self-made catalyst system (containing copper catalyst and nickel catalyst) to achieve the method by adopting a fixed-bed liquid-phase hydrogenation process, and the reaction temperature is 100-250℃. The selectivity of sec-octanol is 96%-99.5%. CN1974514A discloses a method for preparing 2-octanol by hydrogenation reduction of 2-octanone, adding a hydrogenation catalyst with ferromagnetic property in a magnetically stabilized bed reactor, and reacting under the conditions of temperature 70-120℃, pressure 0.3-2.5 MPa, liquid volume space velocity 1-50 h-1, volume ratio of hydrogen to solution containing 2-octanone 2-100:1, and magnetic field intensity 10-50 kA / m, so that the yield of 2-octanol can reach 70%. Patent CN1083415C uses a CuO-ZnO mixture in the form of tablet pressing as a catalyst, and the conversion rate and selectivity of isopropyl alcohol prepared by gas-phase hydrogenation of acetone under the condition of reaction temperature 150-250℃ can reach 99%. The process for hydrogenation of acetone catalyzed by Ru / Al2O3 disclosed in Japanese patent Hei 2-279643 is harsh, and the reaction pressure is 9 MPa, which requires large investment in equipment. Japanese patent Hei-41038 and Soviet Union patent SU1118632A introduce a method for hydrogenation of acetone using a Cu-Cr catalyst, and Russian patent RU2047590 uses a catalyst containing NiO, CoO and Cr2O3, and the reaction temperature is 150-250℃. The reaction temperature of these patents is high, and the catalysts are not stable, which is not suitable for industrial production. uO components, but the conversion rate of these catalysts is not high, and the selectivity is poor, and the use of Cr2O3 as an additive will cause environmental pollution, which does not meet the requirements of green chemical industry. CN103030525A discloses a method for preparing isopropyl alcohol by liquid-phase hydrogenation of acetone, but the reaction temperature is relatively high, at 100-200℃, the conversion rate of acetone is more than 96%, and the selectivity of isopropyl alcohol is more than 95%. CN1962588 discloses a catalyst in which nickel and cobalt are supported on activated carbon for continuous reaction of gas-phase hydrogenation of acetone, the reaction temperature is at 100-150℃, the pressure is at 1.0-1.5 MPa, and relatively high conversion rate of acetone and selectivity of isopropyl alcohol can be obtained. CN103706365 discloses a catalyst in which nickel and copper are supported for hydrogenation of acetone in a gas phase at normal pressure, the reaction temperature is at 100-150℃, the selectivity of isopropyl alcohol is 100%, and the conversion rate of acetone is more than 85.5%. CN103706377A and CN103752327A disclose a catalyst in which Pt, Fe, Sn and Co are used as main components for liquid-phase hydrogenation of acetone to prepare isopropyl alcohol, the reaction temperature is at 100-150℃, and the reaction time is 4h. USP4,182,721 discloses a catalyst in which nickel is modified by molybdenum for catalytic hydrogenation of ketone compounds, although the reaction conditions are relatively mild (60℃, 2.1 MPa), but the selectivity of the product is poor. USP4,459,419 discloses a method for hydrogenation of organic ketones or aldehydes, a catalyst in which ruthenium is supported on molecular sieves is used, and the application of hydrogenation of furfuryl alcohol to prepare tetrahydrofurfuryl alcohol is listed, but the pressure required by the reaction system is relatively high, at 12.7 MPa.

[0004] In summary, the operation temperature of the hydrogenation process of ketone compounds disclosed in the prior art is relatively high, or the operation conditions require relatively high equipment, or the conversion rate and the selectivity of the product cannot simultaneously reach high standards. Therefore, if a heterogeneous catalyst which can react at a relatively low operation temperature, does not use solvent, and exhibits high activity and high selectivity of the product is developed, the burden of the separation and purification of the product can be reduced, the energy consumption can be reduced, and the production cost can be greatly reduced. Low energy consumption and high efficiency in production meet the production requirements of green chemical industry. SUMMARY

[0005] The present application aims to overcome the defects of the prior art, and provides a bimetallic carbon black supported catalyst.

[0006] Another object of the present application is to provide the application of the bimetallic carbon black supported catalyst.

[0007] The technical scheme of the present application is as follows:

[0008] A bimetallic carbon black supported catalyst characterized in that a first metal element and a second metal element are supported on carbon black as a carrier, wherein the first metal element is selected from Rh, Re and Ag, and the second metal element is selected from V, Zn and Zr;

[0009] The preparation process of the bimetallic carbon black supported catalyst comprises: first supporting the second metal element on the carbon black, and then supporting the first metal element on the activated carbon. The specific supporting method is: mixing and soaking a salt solution of a metal precursor with carbon black with stirring, adding a surfactant and adjusting the pH value of the salt solution of the metal precursor to 0.5-5.5 or 8-13, adding a chemical reducing agent for reduction, filtering and washing to neutral, and then vacuum drying at 75-85℃ for 10-12h; after supporting the second metal element and the first metal element in steps, annealing treatment is carried out in a hydrogen atmosphere.

[0010] In a preferred embodiment of the present application, the salt of the metal precursor is selected from nitrate, acetylacetone salt and chloride.

[0011] In a preferred embodiment of the present application, the surfactant is selected from polyvinylpyrrolidone and polyvinylpyrrolidone, and the chemical reducing agent is selected from hydrazine hydrate, formaldehyde solution and ascorbic acid.

[0012] In a preferred embodiment of the present application, the loading amount of the first metal element is 0.1-1.5wt.%, and the loading amount of the second metal element is 0.3-2.0wt.%.

[0013] The bimetallic carbon black supported catalyst is used in the preparation of cycloheptanol from cycloheptanone by hydrogenation.

[0014] In a preferred embodiment of the present application, a batch autoclave liquid phase hydrogenation process is used without using a solvent.

[0015] Further preferably, in the batch autoclave liquid phase hydrogenation process, the hydrogen pressure is 1-4.5MPa, the reaction temperature is 20-80℃, the catalyst dosage / substrate is 0.001-0.01g / mL, and the reaction time is 0.5-2h.

[0016] A method for preparing cycloheptanol from cycloheptanone by hydrogenation, which uses the bimetallic carbon black supported catalyst.

[0017] In a preferred embodiment of the present application, a batch autoclave liquid phase hydrogenation process is used without using a solvent.

[0018] Further preferably, in the intermittent autoclave liquid phase hydrogenation process, the hydrogen pressure is 1-4.5 MPa, the reaction temperature is 20-80℃, the catalyst feeding amount / substrate is 0.001-0.01 g / mL, and the reaction time is 0.5-2 h.

[0019] The beneficial effects of the present application are:

[0020] 1. The bimetallic carbon black supported catalyst of the present application is applied to the liquid phase hydrogenation process of cycloheptanone, and has a low operating temperature and low energy consumption. The operating pressure is moderate, and the equipment investment is not large.

[0021] 2. The catalytic reaction process of the present application does not use solvent, and the process is green. The catalyst has high activity, and the reaction time is short, which can improve the production efficiency.

[0022] 3. In the present application, the catalytic conversion of cycloheptanone is 100%, and the selectivity of the product cycloheptanol can reach 100%, which can greatly reduce the burden of product separation and purification and reduce the production cost.

[0023] 4. The preparation and production method of the bimetallic carbon black supported catalyst of the present application is relatively simple and easy to operate, and is suitable for mass production. DETAILED DESCRIPTION

[0024] The technical solutions of the present application are further described and explained below through specific embodiments.

[0025] Example 1

[0026] 0.02 g of zirconium nitrate hydrate was weighed into 50 mL of deionized water, 0.6 g of carbon black was added, stirred for 3 h, and then adjusted to pH=10 with ammonia water, 5 mL of anhydrous ethanol and 0.3 g of polyvinylpyrrolidone were added, and stirred for 1 h. Then 5 mL of hydrazine hydrate was added dropwise under ice water bath condition, and the dropping speed was 10 drops / min. After the dropping was completed, the stirring was continued for 2 h, and then filtered and washed to neutral, and vacuum dried at 80℃ for 12 h. Finally, it was heated to 400℃ at a rate of 5℃ / min in a hydrogen atmosphere, the gas flow was 80 mL / min, and the temperature was kept constant for 3 h, and then it was cooled to room temperature, to obtain Zr / C.

[0027] 0.012 g of silver nitrate was weighed into 50 mL of deionized water, and stirred for 30 min. The above Zr / C was added into the above solution, and adjusted to pH=10 with sodium hydroxide, and then stirred for 1 h. Then 3 mL of hydrazine hydrate was added dropwise under ice water bath condition, and the dropping speed was 10 drops / min. After stirring for 2 h, it was filtered and washed to neutral, and vacuum dried at 80℃ for 12 h. Finally, it was heated to 300℃ at a rate of 2℃ / min in a hydrogen atmosphere, the gas flow was 50 mL / min, and the temperature was kept constant for 3 h, and then it was cooled to room temperature, to obtain the bimetallic carbon black supported catalyst.

[0028] The bimetallic carbon black supported catalyst prepared in this example was used for the hydrogenation of cycloheptanone to cycloheptanol: the catalyst dosage / substrate was 0.01 g / mL, the reaction was carried out in a batch high-pressure reaction kettle, the reaction temperature was 80°C, the reaction time was 2 h, the hydrogen pressure was 4.5 MPa, and the stirring speed was 500 rpm. The conversion rate of cycloheptanone hydrogenation was 32.9%, and the selectivity of cycloheptanol reached 100%.

[0029] Example 2

[0030] 0.015 g of ammonium metavanadate was weighed into 50 mL of deionized water, 0.6 g of carbon black was added, and after stirring for 3 h, the pH was adjusted to 9 with sodium hydroxide, 5 mL of anhydrous ethanol and 0.3 g of polyvinylpyrrolidone were added, and after continuous stirring for 1 h, 10 mL of 35% aqueous formaldehyde solution was added dropwise at room temperature at a rate of 10 drops / min, and after continuous stirring for 3 h, it was filtered and washed to neutral, and vacuum dried at 80°C for 12 h. Finally, it was heated to 500°C at a rate of 5°C / min under a hydrogen atmosphere, the gas flow rate was 80 mL / min, and after holding at constant temperature for 3 h, it was cooled to room temperature, and the V / C was prepared.

[0031] 0.012 g of silver nitrate was weighed into 50 mL of deionized water and stirred for 30 min. The above V / C was added to the above solution, the pH was adjusted to 10 with sodium hydroxide, and after continuous stirring for 1 h, 3 mL of hydrazine hydrate was added dropwise under an ice water bath at a rate of 10 drops / min, and after stirring for 2 h, it was filtered and washed to neutral, and vacuum dried at 80°C for 12 h. Finally, it was heated to 200°C at a rate of 2°C / min under a hydrogen atmosphere, the gas flow rate was 50 mL / min, and after holding at constant temperature for 3 h, it was cooled to room temperature, and the bimetallic carbon black supported catalyst was prepared.

[0032] The bimetallic carbon black supported catalyst prepared in this example was used for the hydrogenation of cycloheptanone to cycloheptanol: the catalyst dosage / substrate was 0.01 g / mL, the reaction was carried out in a batch high-pressure reaction kettle, the reaction temperature was 80°C, the reaction time was 2 h, the hydrogen pressure was 4.5 MPa, and the stirring speed was 500 rpm. The conversion rate of cycloheptanone hydrogenation was 32.9%, and the selectivity of cycloheptanol reached 100%.

[0033] Example 3

[0034] Take 0.03 g of zinc nitrate hexahydrate, put into 50 mL of deionized water, add 0.6 g of carbon black, stir for 3 h, then adjust pH to 10 with sodium hydroxide, add 5 mL of absolute ethanol and 0.3 g of polyvinylpyrrolidone, continue stirring for 1 h, then add 5 mL of hydrazine hydrate dropwise under ice water bath conditions, the dropwise addition rate of hydrazine hydrate is 10 drops / min, continue stirring for 2 h, then filter and wash to neutral, vacuum dry at 80°C for 12 h. Finally, heat to 400°C at a rate of 5°C / min under hydrogen atmosphere, the gas flow rate is 80 mL / min, keep constant temperature for 3 h, then reduce to room temperature, to obtain Zn / C.

[0035] Take 0.015 g of rhodium chloride hydrate, dissolve in 50 mL of deionized water. Put the above Zn / C into the above solution, adjust pH to 10 with sodium hydroxide, add 10 mL of 5 mol / L ascorbic acid aqueous solution, continue stirring for 3 h, then dry quickly with infrared lamp, then vacuum dry at 80°C for 12 h. Finally, heat to 200°C at a rate of 2°C / min under hydrogen atmosphere, the gas flow rate is 50 mL / min, keep constant temperature for 3 h, then reduce to room temperature, to obtain the bimetallic carbon black supported catalyst.

[0036] The bimetallic carbon black supported catalyst prepared in this example is used for the hydrogenation of cycloheptanone to cycloheptanol: the catalyst dosage is 0.01 g / mL, the reaction is carried out in a batch high-pressure reaction kettle, the reaction temperature is 40°C, the reaction time is 1.5 h, the hydrogen pressure is 4.5 MPa, and the stirring rate is 500 rpm. The conversion rate of cycloheptanone hydrogenation is 79.6%, and the selectivity of cycloheptanol reaches 100%.

[0037] Example 4

[0038] Take 0.015 g of ammonium metavanadate, put into 50 mL of deionized water, add 0.6 g of carbon black, stir for 3 h, then adjust pH to 8 with sodium hydroxide, add 5 mL of absolute ethanol and 0.3 g of polyvinylpyrrolidone, continue stirring for 1 h, then add 10 mL of 35% formaldehyde aqueous solution dropwise at room temperature, the dropwise addition rate is 10 drops / min, continue stirring for 3 h, then filter and wash to neutral, vacuum dry at 80°C for 12 h. Finally, heat to 500°C at a rate of 5°C / min under hydrogen atmosphere, the gas flow rate is 80 mL / min, keep constant temperature for 3 h, then reduce to room temperature, to obtain V / C.

[0039] Take 0.012 g of ammonium perrhenate into 50 mL of deionized water, stir for 30 min. Put the above V / C into the above solution, adjust pH = 10 with sodium hydroxide, continue to stir for 1 h, then add 3 mL of hydrazine hydrate dropwise under ice water bath condition, the dropwise speed is 10 drops / min, continue to stir for 2 h, then filter and wash to neutral, vacuum dry at 80℃ for 12 h. Finally, in the hydrogen atmosphere, the temperature is raised to 300℃ at the rate of 2℃ / min, the gas flow is 50 mL / min, constant temperature for 3 h, then reduced to room temperature, the bimetallic carbon black supported catalyst is prepared.

[0040] The bimetallic carbon black supported catalyst prepared in this example is used for the hydrogenation of cycloheptanone to cycloheptanol: the catalyst dosage / substrate is 0.01 g / mL, the reaction is carried out in a batch high-pressure reaction kettle, the reaction temperature is 40℃, the reaction time is 1.5 h, the hydrogen pressure is 4.5 MPa, and the stirring speed is 500 rpm. The conversion rate of cycloheptanone hydrogenation is 100%, and the selectivity of cycloheptanol reaches 99.2%.

[0041] Example 5

[0042] Take 0.025 g of zinc nitrate hexahydrate into 50 mL of deionized water, add 0.6 g of carbon black, stir for 3 h, then adjust pH = 10 with sodium hydroxide, add 5 mL of anhydrous ethanol and 0.3 g of polyvinylpyrrolidone, continue to stir for 1 h, then add 5 mL of hydrazine hydrate dropwise under ice water bath condition, the dropwise speed is 10 drops / min. Continue to stir for 3 h, then filter and wash to neutral, vacuum dry at 80℃ for 12 h. Finally, in the hydrogen atmosphere, the temperature is raised to 500℃ at the rate of 5℃ / min, the gas flow is 80 mL / min, constant temperature for 3 h, then reduced to room temperature, the Zn / C is prepared.

[0043] Take 0.012 g of ammonium perrhenate into 50 mL of deionized water, stir for 30 min. Put the above Zn / C into the above solution, adjust pH = 10 with sodium hydroxide, continue to stir for 1 h, then add 3 mL of hydrazine hydrate dropwise under ice water bath condition, the dropwise speed is 10 drops / min. Continue to stir for 3 h, then filter and wash to neutral, vacuum dry at 80℃ for 12 h. Finally, in the hydrogen atmosphere, the temperature is raised to 300℃ at the rate of 2℃ / min, the gas flow is 50 mL / min, constant temperature for 3 h, then reduced to room temperature, the bimetallic carbon black supported catalyst is prepared.

[0044] The bimetallic carbon black supported catalyst prepared in this example is used for the hydrogenation of cycloheptanone to cycloheptanol: the catalyst dosage / substrate is 0.01 g / mL, the reaction is carried out in a batch high-pressure reaction kettle, the reaction temperature is 40℃, the reaction time is 1.5 h, the hydrogen pressure is 4.5 MPa, and the stirring speed is 500 rpm. The conversion rate of cycloheptanone hydrogenation is 100%, and the selectivity of cycloheptanol reaches 100%.

[0045] Example 6

[0046] 0.015 g of ammonium metavanadate was weighed and put into 50 mL of deionized water, 0.6 g of carbon black was added, and after stirring for 3 h, the pH was adjusted to 10 with sodium hydroxide, 5 mL of anhydrous ethanol and 0.1 g of polyvinylpyrrolidone were added, and after continuous stirring for 1 h, 10 mL of a 35% aqueous formaldehyde solution was added dropwise at room temperature at a rate of 10 drops / min. After continuous stirring for 3 h, the mixture was filtered and washed to neutral, and vacuum dried at 80°C for 12 h. Finally, the V / C was prepared by heating to 500°C at a rate of 5°C / min under a hydrogen atmosphere, with a gas flow rate of 80 mL / min, and holding the temperature for 3 h before cooling to room temperature.

[0047] 0.015 g of rhodium chloride hydrate was weighed and dissolved in 50 mL of deionized water. The above V / C was put into the above solution, the pH was adjusted to 10 with sodium hydroxide, 10 mL of a 5 mol / L aqueous ascorbic acid solution was added, and after stirring at room temperature for 12 h, the mixture was quickly dried using an infrared lamp and vacuum dried at 80°C for 12 h. Finally, the bimetallic carbon black supported catalyst was prepared by heating to 400°C at a rate of 2°C / min under a hydrogen atmosphere, with a gas flow rate of 50 mL / min, and holding the temperature for 3 h before cooling to room temperature.

[0048] The bimetallic carbon black supported catalyst prepared in this example was used to prepare cycloheptanol by hydrogenation of cycloheptanone: the catalyst dosage was 0.01 g / mL, the reaction was carried out in a batch high-pressure reactor, the reaction temperature was 40°C, the reaction time was 2 h, the hydrogen pressure was 4.5 MPa, and the stirring rate was 500 rpm. The conversion rate of cycloheptanone hydrogenation was 90.6%, and the selectivity of cycloheptanol was 99.5%.

[0049] The above only describes preferred embodiments of the present application and therefore cannot limit the scope of the present application, i.e., equivalent changes and modifications made in accordance with the scope and content of the present patent should still fall within the scope of the present application.

Claims

1. Use of a bimetallic carbon black supported catalyst for the hydrogenation of cycloheptanone to cycloheptanol, characterized in that: The bimetallic carbon black supported catalyst takes carbon black as a carrier, and a first metal element and a second metal element are loaded on the carbon black, wherein the first metal element is Re, and the second metal element is Zn; the loading amount of the first metal element is 0.1-1.5 wt.%, and the loading amount of the second metal element is 0.3-2.0 wt.%. The preparation of the bimetallic carbon black supported catalyst includes: first loading the second metal element on the carbon black, and then loading the first metal element on the carbon black, and the specific loading method is: mixing and soaking a salt solution of a metal precursor with carbon black with stirring, adding a surfactant and adjusting the pH value of the salt solution of the metal precursor to 0.5-5.5 or 8-13, adding a chemical reducing agent for reduction, filtering and washing to neutral, and then vacuum drying at 75-85 ℃ for 10-12 h; after loading the second metal element and the first metal element in steps, annealing and calcination treatment under a hydrogen atmosphere are performed; The salt of the metal precursor is selected from nitrate, acetylacetone salt and chloride; the surfactant is selected from polyvinylpyrrolidone and polyvinylpyrrolidone, and the chemical reducing agent is selected from hydrazine hydrate, formaldehyde solution and ascorbic acid.

2. Use according to claim 1, characterized in that: The intermittent autoclave liquid phase hydrogenation process is used, and no solvent is used.

3. Use according to claim 2, wherein: In the intermittent autoclave liquid phase hydrogenation process, the hydrogen pressure is 1-4.5 MPa, the reaction temperature is 20-80 ℃, the catalyst feeding amount / substrate is 0.001-0.01 g / mL, and the reaction time is 0.5-2 h.

4. A process for the hydrogenation of cycloheptanone to cycloheptanol, characterized in that: The bimetallic carbon black supported catalyst used in the application of claim 1 is used.

5. The method of claim 4, wherein: The intermittent autoclave liquid phase hydrogenation process is used, and no solvent is used.

6. The method of claim 5, wherein: In the intermittent autoclave liquid phase hydrogenation process, the hydrogen pressure is 1-4.5 MPa, the reaction temperature is 20-80 ℃, the catalyst feeding amount / substrate is 0.001-0.01 g / mL, and the reaction time is 0.5-2 h.