CN116803500A - Catalyst for cyclohexyl acetate catalytic hydrogenation and preparation method and application thereof - Google Patents

Catalyst for cyclohexyl acetate catalytic hydrogenation and preparation method and application thereof Download PDF

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CN116803500A
CN116803500A CN202310515578.XA CN202310515578A CN116803500A CN 116803500 A CN116803500 A CN 116803500A CN 202310515578 A CN202310515578 A CN 202310515578A CN 116803500 A CN116803500 A CN 116803500A
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catalyst
cyclohexyl acetate
copper
temperature
soluble
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朱志荣
李晓红
贾文志
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Zhejiang Huanhua Technology Co ltd
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Zhejiang Huanhua Technology Co ltd
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Abstract

The invention relates to the field of chemical raw material processing, in particular to a catalyst for cyclohexyl acetate catalytic hydrogenation, a preparation method and application thereof. The catalyst takes copper as an active component and zirconium oxide as a carrier. The base catalyst is prepared by adopting a coprecipitation method, a sol-gel method or an impregnation method, is used for preparing cyclohexanol and ethanol by catalytic hydrogenation of cyclohexyl acetate under mild reaction conditions, and has the advantages of good low-temperature reaction activity, high product selectivity, good stability and the like. The catalyst is used for hydrogenation reaction of cyclohexyl acetate, and the defects of high temperature and high pressure in the traditional process are overcome.

Description

Catalyst for cyclohexyl acetate catalytic hydrogenation and preparation method and application thereof
Technical Field
The invention relates to the field of preparation and application of chemical catalytic materials, in particular to a catalyst for catalytic hydrogenation of cyclohexyl acetate, and a preparation method and application thereof.
Background
Cyclohexanol is an industrial raw material with wide application, and is mainly used for preparing cyclohexanone. Cyclohexanone is an important chemical raw material and is a main intermediate for manufacturing nylon, caprolactam and adipic acid. In addition, cyclohexanol is a high boiling point solvent with wide application, and can be used as a solvent for paint, varnish and coating, so that the fluidity and smoothness can be improved, and the coating film can be prevented from being frosted; a stabilizer for the water-soluble latex; raw materials for pesticides and herbicides; petroleum processing aids; a rubber additive; raw materials of pharmaceuticals, cosmetics (disinfecting soap, dry lotion) and dyes; also used as leather degreasing agent, fur washing agent, metal washing agent and polishing agent; textile aids (fibre finishes), etc. In 1906, beta Ji Yefu produced cyclohexanol by hydrogenation of phenol, and was first commercialized by bardenaniline soda ash in germany. In the 60 s, cyclohexane oxidation gradually replaced phenol hydrogenation due to the cost of raw materials, but cyclohexane oxidation is relatively complex and various oxidation byproducts are produced.
Ethanol is another downstream product of cyclohexyl acetate, has wide application field, and can be used as industrial raw materials, disinfection products, beverage products, organic raw materials, automobile raw materials and the like. Particularly, the ethanol gasoline is used as a novel clean fuel, PM2.5 and CO in automobile exhaust can be effectively reduced by combusting the ethanol gasoline, and the ethanol gasoline is used as one representative of renewable liquid fuels, can supplement fossil fuel resources, reduce the external dependence of the petroleum resources, and reduce the emission of greenhouse gases and pollutants, and is widely paid attention to all countries in the world in recent years, so the demand of ethanol is continuously increased. At present, the method for producing ethanol in China is mainly a grain fermentation method, but the route for producing ethanol by the grain fermentation method is greatly influenced by the price of grains and has low economic benefit. There is a need for further energy efficient and environmentally friendly processes for producing ethanol.
At present, china becomes the first country of acetic acid production, the surplus of domestic acetic acid market is normal for a long time, the chemical industry is counted online, and the domestic productivity shows a year-by-year increasing trend. The market risk of single acetic acid products can be reduced by continuously developing downstream fine chemical products and prolonging the industrial chain; in recent years, the technology for preparing ethanol by hydrogenating acetic acid and acetic ester has become a research hot spot. Because a noble metal catalyst is needed for preparing ethanol by directly hydrogenating acetic acid, the catalyst cost is high; meanwhile, acetic acid has high corrosion resistance, and the process has high requirements on equipment materials, and equipment investment in industrial production is high, so that the economy of the acetic acid is to be verified. The industrial esterification technology of acetic acid in China is quite mature, cyclohexyl acetate is taken as a raw material, and the cyclohexyl acetate is directly subjected to catalytic hydrogenation reaction by using a copper-based catalyst, so that cyclohexanol and ethanol can be co-produced, and the catalyst cost is low. Meanwhile, as the raw materials and products have weaker candidiasis, carbon steel materials can be adopted, the investment is greatly reduced, and the production cost is obviously reduced.
Therefore, development of downstream products of cyclohexyl acetate can expand the outlet of acetic acid products, solve the problem of excess acetic acid productivity, provide a new supporting point for development of acetic acid industry and seek a new outlet for mass production of cyclohexanol and ethanol.
Disclosure of Invention
The invention aims to solve the problems in the background technology and provides a catalyst for catalyzing and hydrogenating cyclohexyl acetate, a preparation method and application thereof, wherein the catalyst has the advantages of high product selectivity, good low-temperature activity, low price, simple preparation process, easy operation, suitability for large-scale industrial production and the like.
The technical aim of the invention is realized by the following technical scheme: catalyst for hydrogenation reaction of cyclohexyl acetate, wherein the catalyst is Cu x Zr 10-x Wherein x is the molar quantity of Cu, and the value range is 1-5. The preparation method of the catalyst for cyclohexyl acetate hydrogenation is characterized in that a certain amount of soluble copper salt and soluble zirconium salt are weighed according to the proportion of the molar ratio of Cu/Zr of x (10-x) and dissolved in 50-100 mL of deionized water, and the mixture is fully stirred until the soluble copper salt and the soluble zirconium salt are completely dissolved; adding a proper amount of citric acid into the beaker under a stirring state, fully stirring until the citric acid is completely dissolved, continuously stirring for 6-10 hours at room temperature, transferring the beaker into a water bath kettle, continuously stirring until the mixture is sol gel, stopping heating and stirring, and drying the beaker for 12-h; finally, calcining the obtained solid powder to obtain the catalyst precursor.
Preferably, the soluble salt of copper is copper nitrate, copper sulfate, copper acetate, or the like; the soluble precursor of the zirconium element is nitrate, sulfate or metal chloride.
Preferably, the molar ratio of the citric acid to the metal ions is 1:1-3:1.
Preferably, the water bath temperature is set to 80-100 ℃; the drying temperature is 110-180 ℃ and the drying time is 12-16 h; the roasting temperature of the solid powder is 400-600 ℃, the heating rate is 3-10 ℃/min, and the roasting time is 2-8 h.
The application of the catalyst for hydrogenating the cyclohexyl acetate is characterized in that the CuxZr10-x catalyst is reduced in normal pressure hydrogen at the temperature of 250-500 ℃ for 3-4 hours (the hydrogen flow is 20-60 mL/min), then the reduced catalyst is transferred into a high-pressure reaction kettle, cyclohexyl acetate and a solvent are added, the cyclohexyl acetate accounts for 5-20 wt.% of the solvent, the copper-based catalyst is 10-30 wt.% of the cyclohexyl acetate, hydrogen with the purity of 1.0-4.0 MPa (99.9%) is filled, then the temperature is raised to 200-280 ℃, the reaction time is 1-5 h, the high-pressure kettle is cooled, and then the liquid part is filtered and analyzed by gas chromatography.
In conclusion, the catalyst provided by the invention has better low-temperature activity and product selectivity in the hydrogenation reaction of the ester compound. Under the optimized condition, the conversion rate of the cyclohexyl acetate reaches 100%, and the selectivity of the ethanol and the cyclohexanol is over 95%.
Description of the embodiments
The following specific examples are intended to be illustrative of the invention and are not intended to be limiting, as modifications of the invention will be apparent to those skilled in the art upon reading the specification without inventive contribution thereto, and are intended to be protected by the patent law within the scope of the appended claims.
Example 1
At room temperature, a certain amount of Cu (NO) is weighed according to the proportion of Cu/Zr mol ratio of 3/7 3 ) 2 ·3H 2 O and ZrO (NO) 3 ) 2 ·xH 2 O was dissolved in 100 mL deionized water and stirred well to complete dissolution. Then adding a proper amount of citric acid into the beaker under stirring, wherein the citric acid and metal ions are in moleThe molar ratio was 1/1, stirring was sufficient until the citric acid was completely dissolved, stirring was continued at room temperature for 2 h, then the beaker was transferred to a 80 ℃ water bath with continued stirring until the mixture had a sol gel form, heating and stirring was stopped, and finally the beaker was placed in a 180 ℃ oven and dried overnight. Finally, the obtained solid powder is heated to 450 ℃ in a muffle furnace at a heating rate of 10 ℃ per min to be roasted to 6 h to prepare a catalyst precursor, which is marked as Cu 3 Zr 7 -SG. The catalyst and its composition are shown in Table 1
Catalyst reduction and cyclohexyl acetate hydrogenation: placing 50 mg calcined catalyst precursor into a special quartz tube, pre-reducing at 350deg.C under hydrogen atmosphere for 2 h, and controlling hydrogen flow to 30 mL ×min -1 . After cooling to room temperature, the reduced catalyst was immediately transferred to an autoclave containing 5 ml of 1, 4-dioxane and 5 mmol of cyclohexyl acetate. Filling 3 MPa hydrogen pressure, putting the high-pressure reaction kettle into a programmed heating sleeve with preset reaction temperature, and heating to 250 o And C, stirring is started, and the stirring speed is 800 revolutions per minute. After the reaction is finished, cooling the mixture to room temperature, taking supernatant for gas chromatography analysis, and calculating the cyclohexyl acetate conversion rate and the selectivity of various products by adopting a correction factor normalization method, wherein the specific results are shown in Table 1.
Example 2
As in example 1, the difference was that the Cu/Zr molar ratio was 2/8. The conditions for catalyst reduction and cyclohexyl acetate hydrogenation are the same as in example 1, and the reaction results are shown in Table 1.
Example 3
As in example 1, the difference was that the Cu/Zr molar ratio was 4/6. The conditions for catalyst reduction and cyclohexyl acetate hydrogenation are the same as in example 1, and the reaction results are shown in Table 1.
Example 4
As in example 1, the difference was that the Cu/Zr molar ratio was 5/5. The conditions for catalyst reduction and cyclohexyl acetate hydrogenation are the same as in example 1, and the reaction results are shown in Table 1.
Example 5
As in example 1, except that the catalyst precursor calcination temperature was 350 o C. Catalyst reduction and acetic acidThe hydrogenation conditions of cyclohexyl ester are the same as in example 1, and the reaction results are shown in Table 1.
Example 6
As in example 1, except that the catalyst precursor calcination temperature was 550 o C. The conditions for catalyst reduction and cyclohexyl acetate hydrogenation are the same as in example 1, and the reaction results are shown in Table 1.
Example 7
As in example 1, except that the catalyst precursor calcination temperature was 650 o C. The conditions for catalyst reduction and cyclohexyl acetate hydrogenation are the same as in example 1, and the reaction results are shown in Table 1.
Example 8
As in example 1, except that the hydrogenation reaction temperature of cyclohexyl acetate was 230 o C. The reaction results are shown in Table 1.
Example 9
As in example 1, except that the hydrogenation reaction temperature of cyclohexyl acetate was 240 o And C, the reaction results are shown in Table 1.
Example 10
As in example 1, except that the hydrogenation reaction temperature of cyclohexyl acetate was 260 o And C, the reaction results are shown in Table 1.
Example 11
The procedure of example 1 is repeated except that the hydrogen pressure during the hydrogenation of cyclohexyl acetate is 1 MPa, and the reaction results are shown in Table 1.
Example 12
The procedure of example 1 is repeated except that the pressure of hydrogen in the hydrogenation of cyclohexyl acetate is 2 MPa, and the reaction results are shown in Table 1.
Examples
The procedure of example 1 is repeated except that the pressure of hydrogen in the hydrogenation of cyclohexyl acetate is 4 MPa, and the reaction results are shown in Table 1.
Comparative example 1
The procedure is as in example 1, except that the catalyst is prepared by coprecipitation. At room temperature, a certain amount of Cu (NO) is weighed according to the proportion of Cu/Zr mol ratio of 3/7 3 ) 2 ·3H 2 O and ZrO (NO) 3 ) 2 ·xH 2 O was dissolved in 50 mL deionized water and stirred well to complete dissolution. The mixed solution is then subjected toWas added to a round bottom flask containing 50 mL deionized water and kept at constant temperature in a 50 ℃ water bath, and stirred well at that temperature for 15 min. Slowly and dropwise adding 1 mol/L Na under stirring 2 CO 3 The solution was placed in the above round bottom flask to give a titration endpoint pH of around 10, ensuring complete precipitation of the metal salt. Then, the mixture was aged 6 h under stirring at a constant temperature of 50 ℃. Subsequently, after the above mixed solution was cooled to room temperature, it was filtered, washed with a large amount of deionized water to neutrality, dried overnight in a 180 ℃ oven, and finally calcined in a muffle furnace at a temperature rising rate of 10 ℃ per minute to 450 ℃ for 6 h to obtain a catalyst precursor, labeled Cu 3 Zr 7 -CP. The conditions for catalyst reduction and cyclohexyl acetate hydrogenation are the same as in example 1, and the reaction results are shown in Table 1.
Comparative example 2
As in example 1, cu was prepared by dipping 3 Zr 7 t-IM catalyst (t is the ZrO employed 2 The powder crystalline phase is tetragonal phase), the specific preparation process is as follows: weighing Cu (NO) 3 ) 2 ·3H 2 O is dissolved in a small amount of deionized water and stirred well until it is completely dissolved. Subsequently self-made ZrO 2 Adding the metal salt solution into the powder, carrying out ultrasonic treatment for half an hour, stirring at room temperature for 6 h, drying in a 180 ℃ oven overnight, heating to 450 ℃ in a tube furnace at a heating rate of 10 ℃ per minute, and calcining for 6 h to obtain a catalyst precursor, which is marked as Cu 3 Zr 7 -t-IM. The catalyst is marked as Cu 3 Zr 7 -IM. The conditions for catalyst reduction and cyclohexyl acetate hydrogenation are the same as in example 1, and the reaction results are shown in Table 1.

Claims (6)

1. A catalyst for hydrogenating cyclohexyl acetate is characterized in that the catalyst is Cu x Zr 10-x Wherein x is the molar quantity of Cu, and the value range is 1-5.
2. Preparation method of catalyst for cyclohexyl acetate hydrogenation, wherein Cu is as follows x Zr 10-x The copper-based catalyst is prepared by adopting a sol-gel method, and is characterized in that soluble copper salt and soluble zirconium salt are weighed according to the proportion of (10-x) of Cu/Zr molar ratio and dissolved in 50-100 mL of deionized water, and fully stirred until the soluble copper salt and the soluble zirconium salt are completely dissolved; then adding citric acid into the beaker under the stirring state, fully stirring until the citric acid is completely dissolved, continuously stirring for 6-10 hours at room temperature, transferring reactants in the beaker into a water bath kettle, continuously stirring until the mixture is sol gel, stopping heating and stirring, and finally drying the beaker for 12-h; finally, calcining the obtained solid powder to obtain the catalyst precursor.
3. The method for preparing the catalyst for hydrogenating cyclohexyl acetate according to claim 2, wherein the soluble salt of copper is copper nitrate, copper sulfate, copper acetate and the like; the soluble precursor of the zirconium element is nitrate, sulfate or metal chloride.
4. The method for preparing the catalyst for hydrogenating cyclohexyl acetate according to claim 2, wherein the molar ratio of the citric acid to the metal ions is 1:1-3:1.
5. The method for preparing a catalyst for cyclohexyl acetate hydrogenation according to claim 2, wherein the water bath temperature is set to 80-100 ℃; the drying temperature is 110-180 ℃ and the drying time is 12-16 hours; the roasting temperature of the solid powder is 400-600 ℃, the heating rate is 3-10 ℃/min, and the roasting time is 2-8 h.
6. The application of the catalyst for hydrogenating the cyclohexyl acetate is characterized in that Cu is used for hydrogenating the cyclohexyl acetate x Zr 10-x The catalyst is reduced for 3 to 4 hours at the temperature of 250 to 500 ℃ in normal pressure hydrogen (hydrogen flow rate)Transferring the reduced catalyst into a high-pressure reaction kettle, adding cyclohexyl acetate and a solvent, wherein the cyclohexyl acetate accounts for 5-20wt% of the solvent, the copper-based catalyst accounts for 10-30wt% of the cyclohexyl acetate, hydrogen with the purity of 99.9% at 1.0-4.0 MPa is filled into the cyclohexyl acetate, and then the temperature is raised to 200-280 ℃ for 1-5 h; after the reaction, the autoclave was cooled and then opened, and the liquid portion was filtered and analyzed by gas chromatography.
CN202310515578.XA 2023-05-09 2023-05-09 Catalyst for cyclohexyl acetate catalytic hydrogenation and preparation method and application thereof Pending CN116803500A (en)

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