CN108821941A - Method for preparing cyclopentanol or cyclopentanone by catalytic conversion of biomass - Google Patents

Abstract

The invention relates to a method for preparing cyclopentanol or cyclopentanone by catalytically converting biomass. Using Cu-containing catalyst, using deionized water as solvent, adding furfural or furfuryl alcohol into a high-pressure kettle, filling hydrogen, and reacting at a certain reaction temperature to obtain cyclopentanol or cyclopentanone. The catalyst is simple in preparation method, can catalyze furfural or furfuryl alcohol to prepare cyclopentanol or cyclopentanone through highly selective hydrogenation by controlling reaction conditions, is good in catalytic effect, easy to recover and reuse, and has good industrial application prospect.

Description

A kind of catalytic conversion biomass prepares the method for cyclopentanol or cyclopentanone

technical field

The invention relates to a method for catalytically converting biomass to prepare cyclopentanol or cyclopentanone.

Background technique

Cyclopentanol is an important fine chemical intermediate, which is widely used in the production of medicine, dyes and fragrances, and is also a solvent for drugs and fragrances. In industry, cyclopentanol is usually prepared by hydrogenation of cyclopentanone.

Cyclopentanone is a multifunctional fine chemical raw material. It can be used in the synthesis of drugs, pesticides, rubber chemicals, herbicides and fragrances. Cyclopentanone can easily dissolve various resins, so it is widely used as a solvent in the electronics industry. The traditional synthesis methods of cyclopentanone are pyrolysis of adipic acid and its derivatives and oxidation of cyclopentene. The reaction conditions are harsh and the process is cumbersome. Currently, cyclopentanone is in great demand, but still relies on fossil-based raw materials for its production.

As the world's fossil fuels decline, the need for alternative energy sources is growing rapidly. The production of chemicals from renewable biomass is of great significance for the sustainable development of the chemical industry in the future. Furfural is the acid-catalyzed dehydration product of xylose, a major component of hemicellulose. In industry, furfural is produced from pentosan-rich agricultural raw materials, such as straw, corncobs, oat husks, bagasse, etc. The catalytic hydrogenation of furfural is an important reaction, which can obtain furfuryl alcohol, tetrahydrofuran methanol, 2-methylfuran, 2-methyltetrahydrofuran, pentadiene, pentylene glycol, etc.

Furfural is the product of the acid-catalyzed dehydration of pentose sugars in water. The process of separating furfural from the aqueous solution formed increases the cost of its production. The use of furfural aqueous solution as a raw material for the preparation of chemicals and fuels will significantly reduce furfural production costs. Therefore, using deionized water as a solvent to catalyze the highly selective hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol or cyclopentanone has a good industrial application prospect.

Contents of the invention

The invention provides a method for catalytically converting biomass to prepare cyclopentanol or cyclopentanone. Catalyzing highly selective hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol or cyclopentanone by controlling reaction conditions. The catalytic effect is good, it is easy to recycle and reuse, and has a good industrial application prospect.

The technical scheme of the present invention is: a method for catalytically converting biomass to prepare cyclopentanol or cyclopentanone, which is characterized in that, using a Cu-containing catalyst, using deionized water as a solvent, adding furfural or furfuryl alcohol in an autoclave, fully Into hydrogen, react at a certain reaction temperature to obtain product cyclopentanol or cyclopentanone. Cool to room temperature after stopping heating, and detect the conversion rate of furfural or furfuryl alcohol and the selectivity of cyclopentanol or cyclopentanone.

Preferably, the above-mentioned Cu-containing catalyst is a compound of different molar ratios of Cu _x Mg _y Al ₂ , wherein x/y=0.07-0.25, (x+y)/2=3. The Cu-containing catalyst is prepared by a conventional method, that is, it is firstly prepared by co-precipitation, then calcined in an inert gas atmosphere, and finally reduced in a hydrogen atmosphere.

Preferably, the catalyst is used in an amount of 10%-30% of the mass of furfural or furfuryl alcohol. Preferably, the quality of deionized water is 1.6-20 times that of furfural or furfuryl alcohol.

Preferably, the amount of hydrogen used is 0.2MPa-4.0MPa. The preferred reaction temperature is 160-200°C; the reaction time is 3-21h.

Beneficial effect:

The preparation method of the catalyst provided by the invention is simple, and the highly selective hydrogenation of furfural or furfuryl alcohol is catalyzed to prepare cyclopentanol or cyclopentanone by controlling the reaction conditions. Using furfural aqueous solution as a raw material for preparing chemicals and fuels can significantly reduce furfural production costs. It has a good industrial application prospect.

Detailed ways

Implementation case 1:

Weigh 0.9664g of copper nitrate trihydrate, 14.3590g of magnesium nitrate hexahydrate, and 7.503g of aluminum nitrate nonahydrate into a round bottom flask, and dissolve them in 400ml of deionized water as a solvent, which is designated as solution A. Weigh 10.5990g of sodium carbonate, 13.3333g of sodium hydroxide in a round bottom flask, and dissolve it in 400ml of deionized water as a solvent, which is designated as solution B. The solution A was slowly added to the solution B under stirring at room temperature, and the drop was completed in 2 hours. The mixed solution was circulated at 110° C. for 12 hours. Filter and wash to pH 7 with distilled water. Then vacuum-dried at 80°C in a vacuum oven for 12 hours, and the obtained precatalyst was calcined in a tube furnace under a nitrogen atmosphere to a temperature of 300°C with a heating rate of 5°C/min, and kept at this temperature for 4h. Then it was calcined in a tube furnace under a hydrogen atmosphere to a temperature of 300 °C with a heating rate of 5 °C/min and kept at this temperature for 2 h. The catalyst Cu _0.4 Mg _5.6 Al ₂ was obtained after natural cooling to room temperature.

Implementation case 2:

Weigh 1.9328g of copper nitrate trihydrate, 13.3333g of magnesium nitrate hexahydrate, and 7.503g of aluminum nitrate nonahydrate in a round bottom flask, and dissolve them in 400ml of deionized water as a solvent, which is recorded as solution A. Weigh 10.5990g of sodium carbonate, 13.3333g of sodium hydroxide in a round bottom flask, and dissolve it in 400ml of deionized water as a solvent, which is designated as solution B. The solution A was slowly added to the solution B under stirring at room temperature, and the drop was completed in 2 hours. The mixed solution was circulated at 110° C. for 12 hours. Filter and wash to pH 7 with distilled water. Then vacuum-dried at 80°C in a vacuum oven for 12 hours, and the obtained precatalyst was calcined in a tube furnace under a nitrogen atmosphere to a temperature of 300°C with a heating rate of 5°C/min, and kept at this temperature for 4h. Then it was calcined in a tube furnace under a hydrogen atmosphere to a temperature of 300 °C with a heating rate of 5 °C/min and kept at this temperature for 2 h. The catalyst Cu _0.8 Mg _5.2 Al ₂ was obtained after natural cooling to room temperature.

Implementation case 3:

Weigh 2.8992g of copper nitrate trihydrate, 12.3077g of magnesium nitrate hexahydrate, and 7.503g of aluminum nitrate nonahydrate in a round bottom flask, and dissolve them in 400ml of deionized water as a solvent, which is recorded as solution A. Weigh 10.5990g of sodium carbonate, 13.3333g of sodium hydroxide in a round bottom flask, and dissolve it in 400ml of deionized water as a solvent, which is designated as solution B. The solution A was slowly added to the solution B under stirring at room temperature, and the drop was completed in 2 hours. The mixed solution was circulated at 110° C. for 12 hours. Filter and wash to pH 7 with distilled water. Then vacuum-dried at 80°C in a vacuum oven for 12 hours, and the obtained precatalyst was calcined in a tube furnace under a nitrogen atmosphere to a temperature of 300°C with a heating rate of 5°C/min, and kept at this temperature for 4h. Then it was calcined in a tube furnace under a hydrogen atmosphere to a temperature of 300 °C with a heating rate of 5 °C/min and kept at this temperature for 2 h. The catalyst Cu _1.2 Mg _4.8 Al ₂ was obtained after natural cooling to room temperature.

Example 4: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 4 in Table 1.

Example 5: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.8 Mg _5.2 Al ₂ , and the amount of catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 5 in Table 1.

Example 6: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _1.2 Mg _4.8 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 6 in Table 1.

Example 7: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reactor, add 0.1000g furfuryl alcohol, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of catalyst is 20.0mg, and seal the reactor. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 7 in Table 1.

Example 8: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 10.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 8 in Table 1.

Example 9: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 15.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 9 in Table 1.

Example 10: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 25.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 10 in Table 1.

Example 11: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 30.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 11 in Table 1.

Example 12: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 170°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 12 in Table 1.

Example 13: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 13 in Table 1.

Example 14: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 200°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 14 in Table 1.

Example 15: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 9 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 15 in Table 1.

Example 16: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 10 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 16 in Table 1.

Example 17: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C for a heating reaction for 11 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 17 in Table 1.

Example 18: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 13 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 18 in Table 1.

Example 19: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 1.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 19 in Table 1.

Example 20: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 1.5MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 20 in Table 1.

Example 21: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.5MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 12 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 21 in Table 1.

Example 22: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.2000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 40.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 2.5MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 13 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 22 in Table 1.

Example 23: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reaction kettle, add 0.5000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 100.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 3.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 18 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 23 in Table 1.

Example 24: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanol

In the reactor, add 1.2500g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of catalyst is 250.0mg, and seal the reactor. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 4.0MPa hydrogen. Place it in a heating mantle at 190°C and heat it for 21 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanol by gas chromatography. selective. The reaction results are shown in Example 24 in Table 1.

Example 25: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 25 in Table 2.

Example 26: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.8 Mg _5.2 Al ₂ , and the amount of catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 26 in Table 2.

Example 27: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _1.2 Mg _4.8 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 27 in Table 2.

Example 28: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reactor, add 0.1000g furfuryl alcohol, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of catalyst is 20.0mg, and seal the reactor. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C for a heating reaction for 4 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 28 in Table 2.

Example 29: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 10.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 29 in Table 2.

Example 30: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 15.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 30 in Table 2.

Example 31: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 25.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 31 in Table 2.

Example 32: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 30.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 32 in Table 2.

Example 33: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 160°C for a heating reaction for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and place it at room temperature to lower the temperature to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 33 in Table 2.

Example 34: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 170°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 34 in Table 2.

Example 35: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 190°C for a heating reaction for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and place it at room temperature to lower the temperature to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 35 in Table 2.

Example 36: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C for a heating reaction for 3 hours. After the reaction is over, take out the reaction kettle from the heating mantle and place it at room temperature to lower the temperature to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 36 in Table 2.

Example 37: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C for a heating reaction for 4 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 37 in Table 2.

Example 38: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 6 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 38 in Table 2.

Example 39: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.2MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 7 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 39 in Table 2.

Example 40: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.4MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 40 in Table 2.

Example 41: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.6MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 41 in Table 2.

Example 42: Catalytic hydrogenation of furfural or furfuryl alcohol to prepare cyclopentanone

In the reaction kettle, add 0.1000g furfural, 2.0000g deionized water and catalyst Cu _0.4 Mg _5.6 Al ₂ , and the amount of the catalyst is 20.0mg, and seal the reaction kettle. Replace the air in the reactor with hydrogen, and after replacing it 3 times, fill it with 0.8MPa hydrogen. Place it in a heating mantle at 180°C and heat it for 5 hours. After the reaction is over, take out the reaction kettle from the heating mantle and let it cool down to room temperature, extract with ethyl acetate, and detect the conversion rate of furfural and cyclopentanone by gas chromatography. selective. The reaction results are shown in Example 42 in Table 2.

Table 1:

Implementation case Furfural conversion rate Cyclopentanol selectivity 4 100% 98% 5 100% 97% 6 99% 85% 7 100% 98% 8 93% 98% 9 98% 98% 10 100% 98% 11 100% 98% 12 100% 75% 13 100% 94% 14 100% 98% 15 100% 83% 16 100% 90% 17 100% 96% 18 100% 98% 19 100% 73% 20 100% 81% twenty one 100% 98% twenty two 100% 98% twenty three 100% 97% twenty four 100% 93%

Table 2:

The catalyst in Example 4 was filtered and washed with acetone, dried and reused. The process flow is consistent with the implementation case 4, and the recovery and use of the catalyst are as follows:

Recycling times Furfural conversion rate Cyclopentanol selectivity 1 100% 98% 2 99% 98% 3 99% 97% 4 100% 98% 5 100% 97% 6 99% 98%

The catalyst in Example 25 was filtered and washed with acetone, dried and reused. The process flow is consistent with the implementation case 25, and the recovery and use of the catalyst is as follows:

Recycling times Furfural conversion rate Cyclopentanone selectivity 1 100% 98% 2 99% 98% 3 100% 98% 4 98% 98% 5 98% 97% 6 99% 98%

Claims (7)

1. a kind of catalytic conversion biomass prepares the method for cyclopentanol or cyclopentanone, it is characterized in that, use contains Cu catalyst, make solvent with deionized water, add furfural or furfuryl alcohol in autoclave, charge into hydrogen, at certain Reaction at the reaction temperature to obtain product cyclopentanol or cyclopentanone. 2. The method according to claim 1, characterized in that the Cu-containing catalyst is a Cu _x Mg _y Al ₂ compound, wherein x/y=0.07-0.25, (x+y)/2=3. 3. The method according to claim 1, characterized in that the consumption of the catalyst is 10%-30% of furfural or furfuryl alcohol quality. 4. The method according to claim 1, characterized in that the quality of deionized water is 1.6-20 times of furfural or furfuryl alcohol quality. 5. The method according to claim 1, characterized in that the amount of hydrogen is 0.2MPa-4.0MPa. 6. The method according to claim 1, characterized in that the reaction temperature is 160-200°C. 7. The method according to claim 1, characterized in that the reaction time is 3-21h.