Synthesis method of 3, 3, 5-trimethyl cyclohexanol

Abstract

The invention relates to a synthesis method of 3, 3, 5-trimethyl cyclohexanol, which comprises the following steps: adopting a fixed bed reactor, and carrying out deep hydrogenation reduction by using a Zn-promoted Ni-Mo non-supported catalyst under the conditions that the reaction temperature is 140-180 DEG C, the reaction pressure is 1.5-3.0 Mpa, the liquid phase volume space velocity is 0.5-2.5 h <-1 > and the hydrogen-oil volume ratio is 240: 1-720: 1 to obtain the 3, 3, 5-trimethyl cyclohexanol. Under the action of the catalyst, the raw material conversion rate reaches 100%, the selectivity of the product 3, 3, 5-trimethyl cyclohexanol is greater than 99.70%, the cis-trans ratio reaches 6.7, and efficient and continuous production of 3, 3, 5-trimethyl cyclohexanol is realized. The catalyst is simple to prepare, easy to operate, short in period, low in cost, environment-friendly and suitable for large-scale production and application.

Description

technical field

[0001] The invention belongs to the technical field of fine chemical synthesis, in particular to a method for synthesizing 3,3,5-trimethylcyclohexanol. Background technique

[0002] 3,3,5-trimethylcyclohexanol, i.e. isophorol, is mainly obtained by deep hydrogenation of 1,1,3-trimethylcyclohexenone (alias: isophorone), which can be combined with carboxylic acid. Esterification to synthesize isophorol esters for the treatment of vascular diseases. In addition, isophorol can also be ammoniated to synthesize 3,3,5-trimethylcyclohexylamine, used as emulsifier, antistatic agent, latex coagulant, petroleum product additive, corrosion inhibitor, fungicide, insecticide Synthesis of agents, etc. At the same time, the synthesis of many new fragrances, plasticizers, lubricants, dicyanogens, diamines or alcohol intermediates is also inseparable from the role of isophorol. Therefore, isophorol is a fine chemical product or pharmaceutical intermediate with great applica...

Examples

Embodiment approach 1

[0035] In a 10ml fixed bed reactor, the deep hydrogenation of isophorone to 3,3,5-trimethylcyclohexanol was carried out using a Zn-promoted Ni-Mo unsupported catalyst. The reaction temperature was 140 °C and the reaction pressure was 1.5 MPa. , the raw material liquid phase space velocity is 0.5h -1 , under the condition of hydrogen oil volume ratio of 240, through gas chromatography analysis, the conversion rate of raw material isophorone is 99.46%, the average selectivity of 3,3,5-trimethylcyclohexanol is 99.78%, and the ratio of cis-trans isophorol is 99.78%. 5.8.

[0036] The used Zn-promoted Ni-Mo unsupported catalyst preparation steps:

[0037] (1) At 30°C, add 0.5 g of ethanolamine to 60 ml of deionized water, and stir evenly.

[0038] (2) Continue to add 15.0g basic nickel carbonate, 10.8g ammonium heptamolybdate and 1.6g zinc nitrate into the above solution, and stir for 1h.

[0039] (3) Pour the above mixture into the reaction kettle, crystallize at 150°C for 6h, co...

Embodiment approach 2

[0044] In a 10ml fixed bed reactor, the deep hydrogenation of isophorone to 3,3,5-trimethylcyclohexanol was carried out using a Zn-promoted Ni-Mo unsupported catalyst, the reaction temperature was 160 °C, and the reaction pressure was 2.0 MPa , the raw material liquid phase volume space velocity is 1.5h -1 , under the condition of hydrogen oil volume ratio of 240, through gas chromatography analysis, the conversion rate of raw material isophorone is 99.52%, the average selectivity of 3,3,5-trimethylcyclohexanol is 99.09%, and the ratio of cis-trans isophorol is 99.09%. 6.1.

[0045] The used Zn-promoted Ni-Mo unsupported catalyst preparation steps:

[0046] (1) Add 1.5 g of ethanolamine to 60 ml of deionized water under the condition of 45°C, and stir evenly.

[0047] (2) Continue to add 33.6 g of nickel acetate, 7.9 g of ammonium heptamolybdate, and 2.4 g of zinc nitrate into the above solution, and stir for 1.0 h.

[0048] (3) Pour the above mixture into the reaction kett...

Embodiment approach 3

[0053] In a 10ml fixed bed reactor, the deep hydrogenation of isophorone to 3,3,5-trimethylcyclohexanol was carried out using a zinc-promoted Ni-Mo unsupported catalyst. The reaction temperature was 160 °C and the reaction pressure was 2.0 MPa. , the raw material liquid phase space velocity is 1.5h -1 , under the condition of hydrogen oil volume ratio of 480, through gas chromatography analysis, the conversion rate of raw material isophorone is 99.81%, the average selectivity of 3,3,5-trimethylcyclohexanol is 99.54%, and the ratio of cis-trans isophorol is 99.54%. 6.3.

[0054] The used Zn-promoted Ni-Mo unsupported catalyst preparation steps:

[0055] (1) Add 1.9 g of ethanolamine to 60 ml of deionized water under the condition of 60°C, and stir evenly.

[0056] (2) Continue to add 26.2g of nickel nitrate, 14.1g of ammonium tetramolybdate and 3.2g of zinc nitrate into the above solution, and stir for 1h.

[0057] (3) Pour the above mixture into the reaction kettle, crystal...

technical field

[0001] The invention belongs to the technical field of fine chemical synthesis, in particular to a method for synthesizing 3,3,5-trimethylcyclohexanol. Background technique

[0002] 3,3,5-trimethylcyclohexanol, i.e. isophorol, is mainly obtained by deep hydrogenation of 1,1,3-trimethylcyclohexenone (alias: isophorone), which can be combined with carboxylic acid. Esterification to synthesize isophorol esters for the treatment of vascular diseases. In addition, isophorol can also be ammoniated to synthesize 3,3,5-trimethylcyclohexylamine, used as emulsifier, antistatic agent, latex coagulant, petroleum product additive, corrosion inhibitor, fungicide, insecticide Synthesis of agents, etc. At the same time, the synthesis of many new fragrances, plasticizers, lubricants, dicyanogens, diamines or alcohol intermediates is also inseparable from the role of isophorol. Therefore, isophorol is a fine chemical product or pharmaceutical intermediate with great applica...

Examples

Embodiment approach 1

[0035] In a 10ml fixed bed reactor, the deep hydrogenation of isophorone to 3,3,5-trimethylcyclohexanol was carried out using a Zn-promoted Ni-Mo unsupported catalyst. The reaction temperature was 140 °C and the reaction pressure was 1.5 MPa. , the raw material liquid phase space velocity is 0.5h -1 , under the condition of hydrogen oil volume ratio of 240, through gas chromatography analysis, the conversion rate of raw material isophorone is 99.46%, the average selectivity of 3,3,5-trimethylcyclohexanol is 99.78%, and the ratio of cis-trans isophorol is 99.78%. 5.8.

[0036] The used Zn-promoted Ni-Mo unsupported catalyst preparation steps:

[0037] (1) At 30°C, add 0.5 g of ethanolamine to 60 ml of deionized water, and stir evenly.

[0038] (2) Continue to add 15.0g basic nickel carbonate, 10.8g ammonium heptamolybdate and 1.6g zinc nitrate into the above solution, and stir for 1h.

[0039] (3) Pour the above mixture into the reaction kettle, crystallize at 150°C for 6h, co...

Embodiment approach 2

[0044] In a 10ml fixed bed reactor, the deep hydrogenation of isophorone to 3,3,5-trimethylcyclohexanol was carried out using a Zn-promoted Ni-Mo unsupported catalyst, the reaction temperature was 160 °C, and the reaction pressure was 2.0 MPa , the raw material liquid phase volume space velocity is 1.5h -1 , under the condition of hydrogen oil volume ratio of 240, through gas chromatography analysis, the conversion rate of raw material isophorone is 99.52%, the average selectivity of 3,3,5-trimethylcyclohexanol is 99.09%, and the ratio of cis-trans isophorol is 99.09%. 6.1.

[0045] The used Zn-promoted Ni-Mo unsupported catalyst preparation steps:

[0046] (1) Add 1.5 g of ethanolamine to 60 ml of deionized water under the condition of 45°C, and stir evenly.

[0047] (2) Continue to add 33.6 g of nickel acetate, 7.9 g of ammonium heptamolybdate, and 2.4 g of zinc nitrate into the above solution, and stir for 1.0 h.

[0048] (3) Pour the above mixture into the reaction kett...

Embodiment approach 3

[0053] In a 10ml fixed bed reactor, the deep hydrogenation of isophorone to 3,3,5-trimethylcyclohexanol was carried out using a zinc-promoted Ni-Mo unsupported catalyst. The reaction temperature was 160 °C and the reaction pressure was 2.0 MPa. , the raw material liquid phase space velocity is 1.5h -1 , under the condition of hydrogen oil volume ratio of 480, through gas chromatography analysis, the conversion rate of raw material isophorone is 99.81%, the average selectivity of 3,3,5-trimethylcyclohexanol is 99.54%, and the ratio of cis-trans isophorol is 99.54%. 6.3.

[0054] The used Zn-promoted Ni-Mo unsupported catalyst preparation steps:

[0055] (1) Add 1.9 g of ethanolamine to 60 ml of deionized water under the condition of 60°C, and stir evenly.

[0056] (2) Continue to add 26.2g of nickel nitrate, 14.1g of ammonium tetramolybdate and 3.2g of zinc nitrate into the above solution, and stir for 1h.

[0057] (3) Pour the above mixture into the reaction kettle, crystal...

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