Aldehyde hydrogenation catalyst and preparation method thereof

Abstract

The invention discloses a hydroxypivalaldehyde hydrogenation catalyst which comprises the following components in percentage by mass: 40-55% of copper oxide, 3-10% of zinc oxide, 45-55% of aluminum oxide, 0.2-2% of nickel oxide and 0.1-1% of silicon dioxide. The invention also discloses a preparation method of the hydroxypivalaldehyde hydrogenation catalyst. The catalyst has the advantages of high activation speed, reduction time and usage amount of hydrogen, energy consumption reduction and cost saving.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalyst preparation, in particular to an aldehyde hydrogenation catalyst and a preparation method thereof, especially to a high-efficiency catalyst for selectively hydrogenating hydroxypivalaldehyde to prepare neopentyl glycol and a preparation method thereof, and the catalyst is a supported catalyst with copper oxide (CuO), zinc oxide (ZnO) and nickel oxide (NiO) as main active components. BACKGROUND

[0002] Hydrogenation of hydroxypivalaldehyde (HPA) to prepare neopentyl glycol (NPG) is an important reaction in the chemical industry, and neopentyl glycol is widely used in polyester, paint, medicine and other industries. Currently, Raney nickel or noble metal (such as Pd, Pt) catalysts are commonly used in industry, but there are the following problems: Raney nickel catalyst: easy to deactivate, low mechanical strength, and risk of nickel leaching pollution; noble metal catalyst: high cost, sensitive to reaction conditions, and low selectivity; existing copper-based catalyst: active component is easy to sinter, resulting in poor stability and high temperature and high pressure reaction.

[0003] Therefore, it is of great industrial value to develop a high-activity, high-selectivity and low-cost hydroxypivalaldehyde hydrogenation catalyst. SUMMARY

[0004] The present application provides a high-efficiency hydrogenation catalyst with copper oxide, zinc oxide and nickel oxide as main active components, which solves the problems of high cost, low selectivity and slow activation of existing catalysts.

[0005] The present application is realized by the following technical solutions: (1) The catalyst of the present application is composed of the following components (in mass percent): Copper oxide 40-55%, zinc oxide 3-10%, aluminum oxide 45-55%, nickel oxide 0.2-2%, and silicon dioxide 0.1-1%.

[0006] (2) The present application provides a preparation method of the hydroxypivalaldehyde hydrogenation catalyst, comprising the following steps: After dissolving the prepared copper salt, zinc, nickel nitrate or sulfate, add 15-25% alkali liquor of sodium hydroxide, sodium carbonate, sodium bicarbonate or ammonia water, and precipitate, wherein the volume ratio of nitrate solution to alkali liquor is 1:1.5-4, and the pH value after mixing is 8-10, at the same time, open the ultrasonic machine, set the ultrasonic power to 300W, and carry out ultrasonic precipitation, after the precipitation is completely, let the precipitation stand for 2-4h, and the precipitates of the three form complete crystal forms; The metal precipitate with complete crystal form is subjected to pressure filtration or suction filtration to obtain the metal precipitate, and after washing for 2-4 times; The filtered metal precipitate is added to alumina, silica powder with a particle size of 10-20 microns, and deionized water to form a uniform slurry, and the solid content of the slurry is 25-55%; The catalyst slurry is filtered and washed, and is pressure-filtered or suction-filtered 1-3 times with deionized water; the filter cake is collected and is dried at 110 DEG C, and the material is ball-milled after drying; After ball-milling, the material is sintered by SPS at a temperature of 480-530 DEG C for 10-60 min, and the sintered material is ground to be uniform, and is formed into a tablet with a size of 3.5-5.5 mm x 3.5-5.5 mm or is wetted with deionized water and is formed into a spherical disc to form a sphere with a size of 2.0-4.0 mm.

[0007] (3) The application provides application of the catalyst in catalyzing hydrogenation of hydroxy pivaldehyde.

[0008] The application has the following beneficial effects: By integrating multiple metal elements, the copper-based catalyst is obtained by adding the relatively active nickel element to hydroxy pivaldehyde hydrogenation catalyst, and the catalyst has good catalytic activity, the catalyst activation speed is faster than that of the previous catalyst in the case of short reduction time, and the conversion rate of hydroxy pivaldehyde and the selectivity of neopentyl glycol are close to 100% in a short time after activation. In use, the system temperature and pressure are stable, the product yield is stable, and the catalyst has a long service life. The catalyst has a fast activation speed, reduces the hydrogen reduction time and usage, reduces energy consumption, and saves costs. BRIEF DESCRIPTION OF DRAWINGS

[0009] The drawings accompanying the specification of the application form a part of the application and serve to further understand the application. The schematic embodiments of the application and the description thereof are used to explain the application, and do not constitute an improper limitation on the application.

[0010] Figure 1 It is a preparation process flow chart of the copper-zinc-aluminum catalyst of each embodiment of the application. DETAILED DESCRIPTION

[0011] In order for the personnel in the technical field to better understand the application scheme, and to make the above-mentioned purposes, characteristics and advantages of the application more obvious and easy to understand, the application is further described in detail below with reference to the embodiments In the following embodiments, the copper salt is an inorganic salt of copper, the zinc salt is an inorganic salt of zinc, and the nickel salt is an inorganic salt of nickel.

[0012] In the following embodiments, the precipitant for precipitating the copper salt, the zinc salt and the nickel salt is one or two of sodium hydroxide, sodium carbonate, sodium bicarbonate or ammonia.

[0013] Embodiment 1 Catalyst composition (in mass fraction): copper oxide 40%, zinc oxide 4%, aluminum oxide 54.5%, nickel oxide 1%, silicon dioxide 0.5%.

[0014] According to the mass fraction of the catalyst oxide converted into the mass of nitrate, the calculated nitrate was weighed and dissolved in deionized water while stirring. The ratio of metal salt to deionized water was 1:100. The precipitate was prepared by dissolving sodium carbonate in deionized water, and the ratio of sodium carbonate to deionized water was 1:4. The volume ratio of the nitrate solution to the alkali solution was 1:2 while stirring.

[0015] The dissolved copper nitrate, zinc nitrate solution, and nickel nitrate solution were added to the sodium carbonate solution, and the pH value of the mixture was 9. At the same time, the ultrasonic machine was turned on, and the ultrasonic power was set to 300W. The copper, zinc, and nickel were ultrasonically precipitated.

[0016] The precipitate was allowed to stand and crystallize, and the three kinds of precipitates formed complete crystal forms. The metal precipitates with complete crystal forms were allowed to stand for 4h, and then pressure filtration or suction filtration was performed to obtain the metal precipitates. The filtered metal precipitates, aluminum oxide, silicon dioxide powder with a particle size of 10-20 microns, and deionized water were mixed to form a uniform slurry, and the solid content of the slurry was 40%. The catalyst slurry was filtered and washed, and deionized water was used for pressure filtration or suction filtration twice. The filter cake was collected and dried at 110°C. After drying, the material was uniformly ball milled. After ball milling, SPS sintering was performed at a temperature of 480°C for 30min. The sintered material was ground uniformly, and was formed into a disc with a diameter of 4.0mm and a height of 4.0mm or was wetted with deionized water and formed into a spherical disc with a diameter of 2.0-4.0mm.

[0017] A fixed bed hydrogenation evaluation reactor was used to test the catalyst life. The catalyst was ground to 20-40 mesh, and the catalyst was added to the reactor. The reactor temperature was set to 260°C, and reduction was performed using a mixture of hydrogen and nitrogen for 8h. After completion, hydrogenation reaction was performed. The reaction conditions were set as follows: reaction temperature 140°C, reaction pressure 4.2MPa, hydroxyisopentyl aldehyde concentration 10%, and feed rate 0.13mL / min. The performance test results were as follows: hydroxyisopentyl aldehyde conversion rate 95%, and neopentyl glycol selectivity 94%.

[0018] Example 2 Catalyst composition (in mass fraction): copper oxide 40%, zinc oxide 4%, aluminum oxide 55%, nickel oxide 1%, silicon dioxide 0.5%.

[0019] According to the mass fraction of catalyst oxide, the calculated nitrate is weighed and dissolved in deionized water, and the mixture is stirred while adding. The ratio of metal salt to deionized water is 1:100. The precipitate is prepared by dissolving sodium carbonate in deionized water, and the ratio of sodium carbonate to deionized water is 1:4. The volume ratio of nitrate solution to alkali solution is 1:2 while stirring.

[0020] The dissolved copper nitrate, zinc nitrate solution and nickel nitrate solution are added to the sodium carbonate solution, and the pH value of the mixture is 7. At the same time, the ultrasonic machine is turned on, and the ultrasonic power is set to 300W. The copper, zinc and nickel are ultrasonically precipitated.

[0021] The precipitate is allowed to stand and crystallize, and the three kinds of precipitates form complete crystal forms. The metal precipitate with complete crystal form is obtained by pressure filtration or suction filtration after standing for 2h; The filtered metal precipitate is added to alumina, silica powder with a particle size of 10-20 microns and deionized water to form a uniform slurry. The solid content of the slurry is 40%; The catalyst slurry is filtered and washed with deionized water. The filter cake is collected and dried at 110°C. After drying, the material is uniformly ball milled; After ball milling, the material is sintered by SPS method at a temperature of 500°C for 15min. The sintered material is ground uniformly and formed into a sheet with a size of 4.0mm x 4.0mm. Or after wetting with deionized water, the material is formed into a spherical disc and a sphere with a size of 2.0-4.0mm.

[0022] The catalyst life is tested by using a fixed bed hydrogenation evaluation reactor. The catalyst is ground to 20-40 mesh, and the catalyst is added to the reactor. The reactor temperature is set to 260°C, and the mixture of hydrogen and nitrogen is used to reduce for 8h. After completion, the hydrogenation reaction is carried out. The reaction conditions are set as follows: reaction temperature 140°C, reaction pressure 4.2MPa, hydroxy pentafulfuraldehyde concentration 10%, and feed rate 0.13mL / min. The performance test results are as follows: hydroxy pentafulfuraldehyde conversion rate 94%, and neopentyl glycol selectivity 93%.

[0023] Example 3 The catalyst composition (in mass fraction) is as follows: copper oxide 45%, zinc oxide 6%, aluminum oxide 47%, nickel oxide 1%, and silicon dioxide 1%.

[0024] According to the mass fraction of catalyst oxide, the calculated nitrate is weighed and dissolved in deionized water, and the mixture is stirred while adding. The ratio of metal salt to deionized water is 1:100. The precipitate is prepared by dissolving sodium carbonate in deionized water, and the ratio of sodium carbonate to deionized water is 1:4. The volume ratio of nitrate solution to alkali solution is 1:2 while stirring.

[0025] The dissolved copper nitrate, zinc nitrate solution, nickel nitrate solution is added into the sodium carbonate solution, the pH value of the mixture is 9, and the ultrasonic machine is opened at the same time, the ultrasonic power is set to 300 W, and the copper, zinc and nickel ultrasonic precipitation is carried out.

[0026] The precipitate is allowed to stand and crystallize, the precipitates of the three kinds are formed into complete crystal forms, and the metal precipitates formed into complete crystal forms are subjected to pressure filtration or suction filtration to obtain the metal precipitates. The filtered metal precipitates are added into alumina, silica powder with a particle size of 10-20 microns and deionized water to form a uniform slurry, and the solid content of the slurry is 40%. The catalyst slurry is filtered and washed, and is subjected to pressure filtration or suction filtration twice with deionized water; the filter cake is collected and is subjected to drying at 110°C, and the material is uniformly ball milled after drying. After ball milling, the material is sintered by SPS method at a temperature of 480°C for 30 min, the sintered material is uniformly ground, and is formed into a sheet with a size of 4.0 mm x 4.0 mm or is wetted with deionized water to form a spherical disc and a sphere with a size of 2.0-4.0 mm.

[0027] A fixed bed hydrogenation evaluation reactor is used to test the catalyst life. The catalyst is ground to a size of 20-40 mesh, and the catalyst is added into the reactor, the reactor temperature is set to 260°C, and the catalyst is reduced for 8 hours with a mixture of hydrogen and nitrogen, and then hydrogenation reaction is carried out. The reaction conditions are set as follows: reaction temperature 140°C, reaction pressure 4.2 MPa, hydroxy penta-l-al concentration 10%, and feed rate 0.13 mL / min. The performance test results are as follows: hydroxy penta-l-al conversion rate 96%, and neopentyl glycol selectivity 94%.

[0028] Comparative Example 1 The catalyst composition (by mass fraction) is as follows: copper oxide 41%, zinc oxide 4%, and alumina 55%. The mass of the nitrate salt is calculated according to the mass fraction of the catalyst oxide, the calculated nitrate salt is weighed and dissolved in deionized water while stirring, and the ratio of the metal salt to deionized water is 1:100. The precipitate solution is prepared, sodium carbonate is dissolved in deionized water, the ratio of sodium carbonate to deionized water is 1:4, and the volume ratio of the nitrate salt solution to the alkali solution is 1:2 while stirring.

[0029] The dissolved copper nitrate, zinc nitrate solution is added into the sodium carbonate solution, the pH value of the mixture is 9, and the ultrasonic machine is opened at the same time, the ultrasonic power is set to 300 W, and the copper, zinc and nickel ultrasonic precipitation is carried out.

[0030] The precipitate is allowed to stand and crystallize, the precipitates of the three kinds are formed into complete crystal forms, and the metal precipitates formed into complete crystal forms are subjected to pressure filtration or suction filtration to obtain the metal precipitates. The filtered metal precipitate is added to alumina and deionized water to form a uniform slurry, and the solid content of the slurry is 40%; the catalyst slurry is filtered and washed, and is pressure filtered or suction filtered twice with deionized water; the filter cake is collected and dried at 110°C, and after drying, the material is evenly spread in an evaporating dish, and is calcined at 500°C in a muffle furnace for 9 hours; the calcined material is uniformly ground, and is formed into tablets with a size of 4.0 mm x 4.0 mm or is wetted with deionized water and then formed into a ball pan to form balls with a size of 2.0-4.0 mm.

[0031] A fixed bed hydrogenation evaluation reactor is used to test the catalyst life. The catalyst is ground to 20-40 mesh, and the catalyst is added to the reactor, the reactor temperature is set to 260°C, and reduction is performed for 8 hours using a mixture of hydrogen and nitrogen, and after completion, hydrogenation reaction is performed. The reaction conditions are set as follows: reaction temperature 140°C, reaction pressure 4.2 MPa, hydroxy pivaldehyde concentration 10%, and feed rate 0.13 mL / min. The performance test results are as follows: hydroxy pivaldehyde conversion rate 85%, and neopentyl glycol selectivity 82%.

[0032] Comparative Example 2 The catalyst composition (by mass fraction) is as follows: copper oxide 45%, zinc oxide 6%, and alumina 48%. The mass of the nitrate salt corresponding to the mass fraction of the catalyst oxides is calculated, and the calculated nitrate salt is dissolved in deionized water while stirring. The ratio of the metal salt to deionized water is 1:100. The precipitate solution is prepared, and sodium carbonate is dissolved in deionized water, and the ratio of sodium carbonate to deionized water is 1:4. The volume ratio of the nitrate salt solution to the alkali solution is 1:2 while stirring.

[0033] The dissolved copper nitrate and zinc nitrate solutions are added to the sodium carbonate solution, and the pH value of the mixture is 9. An ultrasonic machine is turned on, and the ultrasonic power is set to 300 W to perform copper and zinc ultrasonic precipitation.

[0034] The precipitate is allowed to stand and crystallize, and the precipitate forms a complete crystal form. The metal precipitate with a complete crystal form is pressure filtered or suction filtered to obtain a metal precipitate. The filtered metal precipitate is added to alumina and deionized water to form a uniform slurry, and the solid content of the slurry is 40%; the catalyst slurry is filtered and washed, and is pressure filtered or suction filtered twice with deionized water; the filter cake is collected and dried at 110°C, and after drying, the material is evenly spread in an evaporating dish, and 10-20 micron silicon powder is added, and is calcined at 500°C in a muffle furnace for 9 hours; the calcined material is uniformly ground, and is formed into tablets with a size of 4.0 mm x 4.0 mm or is wetted with deionized water and then formed into a ball pan to form balls with a size of 2.0-4.0 mm.

[0035] The catalyst life was tested by using a fixed bed hydrogenation evaluation reactor. The catalyst was ground to 20-40 mesh, and the catalyst was added to the reactor, the reactor temperature was set to 260°C, and the reduction was completed by using a mixture of hydrogen and nitrogen for 8 hours, and then the hydrogenation reaction was carried out. The reaction conditions were set as follows: reaction temperature 140°C, reaction pressure 4.2 MPa, hydroxy pivaldehyde concentration 10%, and feed rate 0.13 mL / min. The performance test results: hydroxy pivaldehyde conversion rate 83%, and neopentyl glycol selectivity 79%.

[0036] Comparative Example 3 The catalyst composition (by mass fraction): copper oxide 45%, zinc oxide 6%, aluminum oxide 47%, nickel oxide 1%, and silicon dioxide 1%.

[0037] The calculated nitrate salt was weighed and dissolved in deionized water while stirring, and the ratio of metal salt to deionized water was 1:100. The precipitate solution was prepared, and sodium carbonate was dissolved in deionized water, and the ratio of sodium carbonate to deionized water was 1:4, and the volume ratio of nitrate salt solution to alkali solution was 1:2 while stirring.

[0038] The dissolved copper nitrate, zinc nitrate solution, and nickel nitrate solution were added to the sodium carbonate solution, and the pH value of the mixture was 9, and the ultrasonic machine was turned on, and the ultrasonic power was set to 300 W, and the copper, zinc, and nickel were ultrasonically precipitated.

[0039] The precipitate was allowed to crystallize, and the three precipitates formed complete crystal forms, and the metal precipitates with complete crystal forms were pressure filtered or suction filtered to obtain the metal precipitates; The filtered metal precipitates were added to aluminum oxide, silicon dioxide powder with a particle size of 10-20 microns, and deionized water to form a uniform slurry, and the solid content of the slurry was 40%; The catalyst slurry was filtered and washed, and was pressure filtered or suction filtered twice with deionized water; the filter cake was collected and dried at 110°C, and after drying, the material was placed flat in an evaporating dish, and was calcined at 500°C in a muffle furnace for 9 hours, and the sintered material was ground uniformly, and was pressed into a tablet with a size of 4.0 mm x 4.0 mm, or was wetted with deionized water and then was formed into a ball disk to form a ball with a size of 2.0-4.0 mm.

[0040] The catalyst life was tested by using a fixed bed hydrogenation evaluation reactor. The catalyst was ground to 20-40 mesh, and the catalyst was added to the reactor, the reactor temperature was set to 260°C, and the reduction was completed by using a mixture of hydrogen and nitrogen for 8 hours, and then the hydrogenation reaction was carried out. The reaction conditions were set as follows: reaction temperature 140°C, reaction pressure 4.2 MPa, hydroxy pivaldehyde concentration 10%, and feed rate 0.13 mL / min. The performance test results: hydroxy pivaldehyde conversion rate 91%, and neopentyl glycol selectivity 92%.

[0041] Comparative Example 4 The catalyst composition (by mass fraction): copper oxide 45%, zinc oxide 6%, aluminum oxide 48%, and silicon dioxide 1%.

[0042] According to the mass fraction of catalyst oxides, the mass of nitrate salt was converted, and the calculated nitrate salt was dissolved in deionized water while stirring. The ratio of metal salt to deionized water was 1:100. The precipitate solution was prepared, and sodium carbonate was dissolved in deionized water. The ratio of sodium carbonate to deionized water was 1:4, and the volume ratio of nitrate salt solution to alkali solution was 1:2 while stirring.

[0043] The dissolved copper nitrate, zinc nitrate solution, and nickel nitrate solution were added to the sodium carbonate solution, and the pH value of the mixture was 9. At the same time, the ultrasonic machine was turned on, and the ultrasonic power was set to 300 W. The copper, zinc, and nickel were ultrasonically precipitated.

[0044] The precipitate was allowed to stand and crystallize, and the three precipitates formed complete crystal forms. The metal precipitates with complete crystal forms were allowed to stand for 4 h, and then pressure filtration or suction filtration was performed to obtain the metal precipitates. The filtered metal precipitates were added to aluminum oxide and deionized water to form a uniform slurry, and the solid content of the slurry was 40%. The catalyst slurry was filtered and washed, and deionized water was used for pressure filtration or suction filtration for 2 times. The filter cake was collected and dried at 110°C. After drying, the material was uniformly ball milled. After ball milling, SPS sintering was performed at a temperature of 480°C for 30 min. The sintered material was ground uniformly, and was formed into a tablet with a size of 4.0 mm x 4.0 mm or was wetted with deionized water and formed into a spherical disc with a size of 2.0-4.0 mm.

[0045] The catalyst life was tested by using a fixed bed hydrogenation evaluation reactor. The catalyst was ground to 20-40 mesh, and the catalyst was added into the reactor. The reactor temperature was set to 260°C, and the hydrogenation reaction was carried out after reduction for 8 hours by using a mixture of hydrogen and nitrogen. The reaction conditions were set as follows: reaction temperature 140°C, reaction pressure 4.2 MPa, hydroxy pivaldehyde concentration 10%, and feed rate 0.13 mL / min. The performance test results were as follows: hydroxy pivaldehyde conversion rate 89%, and neopentyl glycol selectivity 90%.

[0046] The catalysts obtained from Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 were respectively analyzed and tested, and the results are shown in the following table.

Claims

1. A hydroxypivaldehyde hydrogenation catalyst characterized by, Copper oxide 40-55%, zinc oxide 3-10%, aluminum oxide 45-55%, nickel oxide 0.2-2%, silicon dioxide 0.1-1% by mass. The method comprises the following steps:

2. A process for preparing the hydroxypivaldehyde hydrogenation catalyst according to claim 1, characterized in that (1) dissolving the prepared copper salt, zinc, nickel nitrate or sulfate, adding sodium hydroxide, sodium carbonate, sodium bicarbonate or ammonia water to precipitate, ultrasonic, static, and form a complete crystal form; (2) the metal precipitate with complete crystal form is subjected to pressure filtration or suction filtration to obtain a metal precipitate, which is washed; (3) the filtered metal precipitate is added to aluminum oxide, silicon dioxide powder and deionized water to form a uniform slurry, and the solid content of the slurry is 25-55%; (4) the catalyst slurry is filtered and washed, and is subjected to pressure filtration or suction filtration 1-3 times with deionized water; the filter cake is collected and dried at 110°C, and the material is uniformly ball milled after drying; (5) SPS sintering after ball milling, the sintered material is uniformly ground to obtain a catalyst. In step (1), the volume ratio of the nitrate solution to the lye is 1:1.5-4.

3. The method of making a hydroxypivaldehyde hydrogenation catalyst according to claim 2, wherein, In step (1), the mixed pH value is 8-10, and the ultrasonic power is 300W.

4. The method of making a hydroxypivaldehyde hydrogenation catalyst according to claim 2, wherein, In step (1), the particle size of the silicon dioxide is 10-20 microns.

5. The method of making a hydroxypivaldehyde hydrogenation catalyst according to claim 2, wherein, SPS sintering, temperature is 480-530°C, time is 10-60min.

6. The method of making a hydroxypivaldehyde hydrogenation catalyst according to claim 2, wherein, 7. The use of a catalyst prepared by the preparation method of any one of claims 2-6 in catalyzing the hydrogenation of hydroxyisovaleraldehyde. ​

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