Method for producing cyclohexanol

Abstract

The invention provides a method for producing cyclohexanol, which is characterized in that benzene is taken as an initial raw material, selective hydrogenation through benzene, addition esterification of cyclohexene, and hydrogenation of acetate and cyclohexyl acetate are carried out to produce cyclohexanol, and can co-produce cyclohexanol and ethanol. The method has the following characteristics that 1)the esterification reaction and the hydrogenation reaction have high selectivity, and the atom utilization rate is high; 2)the process is eco-friendly; and 3) when cyclohexanol is produced, ethanol is simultaneously co-produced.

Description

technical field

[0001] The invention relates to a method for producing cyclohexanol, in particular to a method for producing cyclohexanol and simultaneously co-producing ethanol and cyclohexane. Background technique

[0002] Both cyclohexanol and ethanol are important chemical raw materials and solvents. Cyclohexanol is mainly used to produce nylon 6, nylon 66 and other products; ethanol is not only a raw material for synthetic esters and other chemical products, but also widely used as a fuel additive for gasoline.

[0003] The method of industrially synthesizing ethanol is mainly the direct hydration method of ethylene, but in some countries rich in agricultural and sideline products, the fermentation method is still the main method of ethanol production. Due to the large population and insufficient arable land in our country, and the problem of "competing with the mouth for food" in the production of ethanol by fermentation, the fermentation method does not conform to th...

Examples

Embodiment 1

[0070] This example illustrates the method for the selective hydrogenation of benzene to cyclohexene.

[0071] Benzene and hydrogen are injected into the hydrogenation reactor filled with ruthenium particle catalyst at a molar ratio of 1:3, and the benzene hydrogenation reaction is carried out under the conditions of a reaction temperature of 135°C, a pressure of 4.5MPa, and a residence time of 15min. After the reaction product is separated from the hydrogen , Collect the liquid product and run continuously for 1000h. After the test, the collected liquid product was analyzed by gas chromatography, and its composition was: 53.3% benzene, 35.4% cyclohexene, and 11.3% cyclohexane.

Embodiment 2

[0073] 100mL of macroporous strongly acidic hydrogen-type ion exchange resin (synthesized in the laboratory according to the classic literature method, suspension copolymerization of styrene solution containing 15% divinylbenzene to make white balls, and then sulfonated with concentrated sulfuric acid, measured Its exchange capacity is 5.2mmolH + / g dry basis) into the middle of a stainless steel tube reactor with a jacket of φ32×4×1000mm, and a certain amount of quartz sand is filled at both ends. The raw materials of acetic acid and cyclohexene (53.3% benzene, 35.4% cyclohexene, and 11.3% cyclohexane) are pumped into the reactor by a metering pump at a certain flow rate for reaction, and heat is introduced into the external jacket of the reaction tube. Water is used to control the reaction temperature, and the reactor pressure is controlled through the reactor outlet back pressure valve. The outlet product of the reactor was sampled by an online sampling valve for online ch...

Embodiment 3

[0078] The test device, method and raw materials are the same as in Example 2, except that the catalyst is a phosphorus-modified Hβ molecular sieve catalyst (the Hβ molecular sieve with a silicon-aluminum ratio of 50 is modified with 85% phosphoric acid, and then kneaded with alumina to form , obtained by drying at 120°C and roasting at 500°C, with a phosphorus content of 2%). The reaction conditions and results are shown in Table 2. It can be seen from Table 2 that the reaction conversion rate of cyclohexene and acetic acid is greater than 80%, the selectivity of ester product is greater than 99%, and the catalyst activity and selectivity are stable after running for 480 hours.

[0079] Table 2 Hβ molecular sieve catalyst catalyzed acetic acid and cyclohexane / cyclohexene / phenyl esterification test data

[0080]

technical field

[0001] The invention relates to a method for producing cyclohexanol, in particular to a method for producing cyclohexanol and simultaneously co-producing ethanol and cyclohexane. Background technique

[0002] Both cyclohexanol and ethanol are important chemical raw materials and solvents. Cyclohexanol is mainly used to produce nylon 6, nylon 66 and other products; ethanol is not only a raw material for synthetic esters and other chemical products, but also widely used as a fuel additive for gasoline.

[0003] The method of industrially synthesizing ethanol is mainly the direct hydration method of ethylene, but in some countries rich in agricultural and sideline products, the fermentation method is still the main method of ethanol production. Due to the large population and insufficient arable land in our country, and the problem of "competing with the mouth for food" in the production of ethanol by fermentation, the fermentation method does not conform to th...

Examples

Embodiment 1

[0070] This example illustrates the method for the selective hydrogenation of benzene to cyclohexene.

[0071] Benzene and hydrogen are injected into the hydrogenation reactor filled with ruthenium particle catalyst at a molar ratio of 1:3, and the benzene hydrogenation reaction is carried out under the conditions of a reaction temperature of 135°C, a pressure of 4.5MPa, and a residence time of 15min. After the reaction product is separated from the hydrogen , Collect the liquid product and run continuously for 1000h. After the test, the collected liquid product was analyzed by gas chromatography, and its composition was: 53.3% benzene, 35.4% cyclohexene, and 11.3% cyclohexane.

Embodiment 2

[0073] 100mL of macroporous strongly acidic hydrogen-type ion exchange resin (synthesized in the laboratory according to the classic literature method, suspension copolymerization of styrene solution containing 15% divinylbenzene to make white balls, and then sulfonated with concentrated sulfuric acid, measured Its exchange capacity is 5.2mmolH + / g dry basis) into the middle of a stainless steel tube reactor with a jacket of φ32×4×1000mm, and a certain amount of quartz sand is filled at both ends. The raw materials of acetic acid and cyclohexene (53.3% benzene, 35.4% cyclohexene, and 11.3% cyclohexane) are pumped into the reactor by a metering pump at a certain flow rate for reaction, and heat is introduced into the external jacket of the reaction tube. Water is used to control the reaction temperature, and the reactor pressure is controlled through the reactor outlet back pressure valve. The outlet product of the reactor was sampled by an online sampling valve for online ch...

Embodiment 3

[0078] The test device, method and raw materials are the same as in Example 2, except that the catalyst is a phosphorus-modified Hβ molecular sieve catalyst (the Hβ molecular sieve with a silicon-aluminum ratio of 50 is modified with 85% phosphoric acid, and then kneaded with alumina to form , obtained by drying at 120°C and roasting at 500°C, with a phosphorus content of 2%). The reaction conditions and results are shown in Table 2. It can be seen from Table 2 that the reaction conversion rate of cyclohexene and acetic acid is greater than 80%, the selectivity of ester product is greater than 99%, and the catalyst activity and selectivity are stable after running for 480 hours.

[0079] Table 2 Hβ molecular sieve catalyst catalyzed acetic acid and cyclohexane / cyclohexene / phenyl esterification test data

[0080]

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