CN108250044B - Preparation method and application of alkylcyclohexanol - Google Patents
Preparation method and application of alkylcyclohexanol Download PDFInfo
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Abstract
The invention belongs to the field of catalytic hydrogenation, and particularly relates to a method for producing alkyl cyclohexanol by catalytic hydrogenation of alkylphenol. The catalyst comprises 1% of Ru as an active component, 1-3% of one of manganese, cobalt and nickel as an auxiliary agent and one of zirconium oxide, titanium oxide, gamma-aluminum oxide and silicon oxide as a carrier.
Description
Technical Field
The invention belongs to the field of catalytic hydrogenation, and particularly relates to a method for preparing alkylcyclohexanol by catalytic hydrogenation of alkylphenol.
Background
Alkylphenol environmental hormones are widely present in living goods such as plastics, and under certain conditions, the alkylphenol environmental hormones may migrate into food, and along with various plastic products such as household garbage generated in life of people, the phenol environmental hormones may migrate from the plastic products into water and soil. The alkylphenol type environmental hormone has stable property, is difficult to degrade in the environment, has biological accumulation and amplification effects, and various countries have successively issued regulations to limit products containing the alkylphenol type environmental hormone. The alkyl cyclohexanol prepared by hydrogenating the alkylphenol can effectively reduce the harm to the environment and the influence on the human health.
Nonylphenol (NP) is an important fine chemical raw material and intermediate, and is a mixture of various isomers mainly composed of 4-nonylphenol. Nonyl phenol is an organic contaminant known as a "spermicide", and it has been found that low concentrations of nonyl phenol can have deleterious effects on the reproductive system of animals, which are exacerbated by biological enrichment. Nonyl phenol in the water body is difficult to degrade and has bioaccumulation, so that nonyl phenol can widely exist in the water environment. As nonyl phenol has excellent decontamination, wetting, dispersing and compatibilization emulsification performances and the like, the demand on nonyl phenol at home and abroad is still great, and researches find that the polyoxyethylene ether alcohol of nonyl cyclohexanol prepared from nonyl cyclohexanol obtained by further reacting nonyl phenol can be close to the performance of polyoxyethylene ether of nonyl phenol to the greatest extent. The nonyl cyclohexanol prepared by hydrogenating nonyl phenol has similar structure and performance to nonyl phenol, is an important intermediate for producing nonionic surfactant, and has the advantages of no environmental toxicity, no biological accumulation and biodegradability.
Chinese patent CN104151134A discloses a method for continuously preparing nonyl cyclohexanol by catalytic hydrogenation of nonyl phenol, which takes nonyl phenol and hydrogen as raw materials, takes metallic nickel and palladium as active components, and takes active carbon and TiO as well as active carbon2-SiO2And Al2O3As a carrier, preparing the hydrogenation catalystA catalyst is adopted, a fixed bed reactor is adopted, the temperature is 250 ℃, the reaction pressure is 6MPa, and the volume space velocity of the nonyl phenol solution is 0.1h-1And the hydrogen feeding amount is 40ml/min, gas-liquid-solid three-phase catalytic reaction is carried out, the conversion rate of nonyl phenol is 85.3%, and the selectivity is 97.7%. The conversion of the reaction was low and 2% by-product was still produced.
The catalyst is used for preparing propylcyclohexanol (ketone) by hydrogenation of propylphenol, and has a catalytic activity of 89.34% after reaction for 13-15 h under a hydrogen pressure of 1.5MPa and a temperature of 160-170 ℃. However, the amount of noble metal is large, the cost of the catalyst is high, the reaction time is long, and the conversion is incomplete.
Disclosure of Invention
The invention aims to provide a method for producing alkylcyclohexanol with small equipment investment, low hydrogen consumption and less side reaction, and the alkylcyclohexanol is used as an intermediate for producing surfactant alkylcyclohexanol polyoxyethylene ether instead of alkylphenol so as to reduce the pollution to the environment and the influence on the human health.
The preparation of the alkyl cyclohexanol adopts alkylphenol as raw material, adopts an intermittent kettle catalytic hydrogenation process under the action of ruthenium-based catalyst, and has the following temperature: 120-180 ℃, and the pressure is as follows: and (2) carrying out alkylphenol hydrogenation reaction under the pressure of 3-5 MPa to obtain alkylcyclohexanol, wherein the reaction time is as follows: 4-6 h, the catalyst dosage is as follows: 1 to 3 percent.
The conversion rate of the alkylphenol can reach 100% at most, the selectivity can reach 99.9%, the product purity is high, the consumption of noble metal in the catalyst is low, the hydrogen consumption is low, the cost is low, the reaction condition is mild, and the reaction time is short.
The ruthenium-based catalyst comprises the following components in percentage by mass: 1 percent of active component ruthenium, 2 percent of auxiliary agent and the balance of carrier. Wherein, the auxiliary agent of the catalyst is one of manganese, cobalt and nickel, preferably cobalt; the carrier is one of zirconia, titania, gamma-alumina or silica.
The preparation method of the ruthenium-based catalyst specifically comprises the following steps:
(1) weighing a calculated amount of carrier, and adding the carrier into an ammonium dihydrogen phosphate solution for pretreatment to obtain a phosphorus modified precursor; wherein the mass concentration of the ammonium dihydrogen phosphate solution is 1-5%.
(2) Preparing soluble salt of an auxiliary agent into a soluble salt solution of the auxiliary agent by using deionized water, adding a calculated amount of the phosphorus modified precursor obtained in the step (1), uniformly stirring, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4 hours, aging for 24 hours, performing suction filtration, drying at 110 ℃, roasting in a muffle furnace for 5 hours, and grinding and sieving to obtain a modified carrier; wherein, soluble salt of the auxiliary agent is prepared into solution by 30g of water, and the roasting temperature is 300-600 ℃.
(3) Weighing ruthenium trichloride in a calculated amount to prepare a ruthenium trichloride solution, adding the carrier modified in the step (2), uniformly stirring, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, roasting for 5h in a muffle furnace, grinding and sieving to obtain a catalyst precursor; wherein, ruthenium trichloride is prepared into a solution by using 30g of water, and the roasting temperature is 300-600 ℃.
(4) And (4) putting the catalyst precursor obtained in the step (4) into a tubular furnace for normal-pressure hydrogen reduction at the temperature of 100-600 ℃ for 3-6 hours to obtain the ruthenium-based catalyst.
The ruthenium-based catalyst is suitable for hydrogenation catalytic reaction of other benzene rings such as nonyl phenol, octyl phenol, dodecyl phenol, bisphenol A, isophthalonitrile and the like.
The auxiliary agent in the catalyst promotes the reduction of active component ruthenium oxide, enhances the capability of the catalyst for absorbing hydrogen, increases the specific surface area of active metal and the dispersion degree of the metal, further improves the catalytic hydrogenation effect of the catalyst on alkylphenol, improves the dispersion degree of an active phase on the surface of a carrier by phosphorus modification, inhibits the generation of inactive species, and changes the distribution of acid sites on the surface of the catalyst.
The invention also provides the application of the alkylcyclohexanol prepared by the method, which is characterized in that: the prepared alkylcyclohexanol is used for preparing alkylcyclohexanol polyoxyethylene ether.
Has the advantages that:
the high-activity catalyst used in the invention has the advantages that the active component and the auxiliary agent have synergistic effect, the activation energy of the reaction can be reduced, the reaction condition is reduced, and the side reaction is reduced.
The hydrogenation process has the advantages of short reaction time, small equipment investment, low hydrogen consumption and high yield of reaction target products, and the alkyl cyclohexanol is used as an intermediate for producing the surfactant alkyl cyclohexanol polyoxyethylene ether instead of alkylphenol, so that the pollution to the environment and the influence on the human health can be reduced.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1
Weighing 5g of silicon oxide, soaking and modifying the silicon oxide by using 3 percent ammonium dihydrogen phosphate solution for 8h, drying the silicon oxide at 110 ℃, roasting the silicon oxide at 400 ℃ to obtain a phosphorus modified carrier, and weighing 0.7866g of Mn (NO)3)2·4H2Dissolving O in 30g of distilled water, ultrasonically dissolving, adding 5g of phosphorus modified carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, filtering, drying at 110 ℃, grinding, roasting for 5h at 300 ℃, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of distilled water, ultrasonically dissolving, adding the carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, filtering, drying at 110 ℃, grinding, roasting for 5h at 300 ℃, washing to remove Cl, and removing Cl-Then, the mixture is reduced by hydrogen under normal pressure at the temperature of 300 ℃ for 5 hours. The content of Ru was 1% and the content of Mn was 2%.
Example 2
Weighing 5g of titanium oxide, soaking and modifying the titanium oxide by using 5% ammonium dihydrogen phosphate solution for 8h, drying the titanium oxide at 110 ℃, roasting the titanium oxide at 400 ℃ to obtain a phosphorus modified carrier, and weighing 0.2478g of Ni (NO)3)2·6H2Dissolving O in 30g of distilled water, dissolving by ultrasonic, adding 5g of phosphorus modified carrier into the solution, dripping ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, filtering, drying at 110 ℃, grinding, roasting for 5h at 400 ℃, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of ruthenium trichloride, and steamingDissolving in distilled water by ultrasonic wave, adding carrier into the solution, adding ammonia water at 30 deg.C, adjusting pH to 10, stirring for 4 hr, aging for 24 hr, filtering, oven drying at 110 deg.C, grinding, calcining at 400 deg.C for 5 hr, washing with water to remove Cl-Then, the mixture is reduced by hydrogen under normal pressure at the temperature of 600 ℃ for 6 hours. The content of Ru was 1% and the content of Ni was 2%.
Example 3
Weighing 5g of gamma-alumina, soaking and modifying the gamma-alumina by using 3 percent ammonium dihydrogen phosphate solution for 8 hours, drying the gamma-alumina at 110 ℃, roasting the gamma-alumina at 400 ℃ to obtain a phosphorus modified carrier, and weighing 0.4939g of Co (NO)3)2·6H2Dissolving O in 30g of distilled water, ultrasonically dissolving, adding 5g of phosphorus modified carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting for 5h at 500 ℃, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of distilled water, ultrasonically dissolving, adding the carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting for 5h at 500 ℃, washing to remove Cl, and removing Cl-Then, the mixture is reduced by hydrogen under normal pressure at 500 ℃ for 3 hours. The content of Ru is 1% and the content of Co is 2%.
Example 4
5g of gamma-alumina were weighed, without modification, 0.4939g of Co (NO) were weighed3)2·6H2Dissolving O in 30g of distilled water, ultrasonically dissolving, adding 5g of carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting at 500 ℃ for 5h, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of distilled water, ultrasonically dissolving, adding the carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting at 500 ℃ for 5h, washing with water to remove Cl, and drying at 500 DEG C-Then, the mixture is reduced by hydrogen under normal pressure at 500 ℃ for 3 hours. The content of Ru is 1% and the content of Co is 2%.
Example 5
Weighing 5g of gamma-alumina, soaking and modifying the gamma-alumina by using 3 percent ammonium dihydrogen phosphate solution for 8 hours, drying the gamma-alumina at 110 ℃, roasting the gamma-alumina at 400 ℃ to obtain a phosphorus modified carrier, and weighing 0.7234g of Fe (NO)3)3·9H2Dissolving O in 30g of distilled water, ultrasonically dissolving, adding 5g of phosphorus modified carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting at 600 ℃ for 5h, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of distilled water, ultrasonically dissolving, adding the carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting at 600 ℃ for 5h, washing with water to remove Cl-Then, the mixture is reduced by hydrogen under normal pressure at 500 ℃ for 3 hours. The content of Ru is 1% and the content of Fe is 2%.
Example 6
Weighing 5g of zirconium oxide, soaking and modifying the zirconium oxide by using 1% ammonium dihydrogen phosphate solution for 8h, drying the zirconium oxide at 110 ℃, roasting the zirconium oxide at 400 ℃ to obtain a phosphorus modified carrier, and weighing 0.191g of Cu (NO)3)2·3H2Dissolving O in 30g of distilled water, ultrasonically dissolving, adding a phosphorus modified carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting at 300 ℃ for 5h, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of distilled water, ultrasonically dissolving, adding the carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting at 400 ℃ for 5h, washing with water to remove Cl, and drying at 400 DEG C-Then, the mixture is reduced by hydrogen under normal pressure at the temperature of 100 ℃ for 4 hours. The Ru content was 1% and the Cu content was 2%.
Example 7
Weighing 5g of gamma-alumina, soaking and modifying the gamma-alumina by using 3 percent ammonium dihydrogen phosphate solution for 8 hours, drying the gamma-alumina at 110 ℃, roasting the gamma-alumina at 400 ℃ to obtain a phosphorus modified carrier, weighing 0.1351g of ruthenium trichloride, dissolving the ruthenium trichloride in 30g of distilled water, adding the phosphorus modified carrier into the solution after ultrasonic dissolution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring the solution for 4 hours, aging the solution for 24 hours, filtering the solution, drying the solution at 110 ℃, grinding the solution, roasting the solution for 5 hours at 500 ℃, and washing the solution to remove Cl-Then, hydrogen is reduced under normal pressure at 500 ℃ for 3 hours, and the content of Ru is 1%.
Example 8
25g of nonyl phenol is used as a raw material, and a batch kettle catalytic hydrogenation process is adopted under the action of 0.5g of the catalyst in the embodiment 1, the reaction is carried out for 6 hours at the temperature of 150 ℃, the pressure of 4MPa, the conversion rate of alkyl phenol is 76.8 percent, and the selectivity is 94.5 percent.
Example 9
25g of nonyl phenol is used as a raw material, and a batch kettle catalytic hydrogenation process is adopted under the action of 0.5g of the catalyst in the embodiment 2, the reaction is carried out for 6 hours at the temperature of 150 ℃, the pressure of 4MPa, the conversion rate of alkyl phenol is 78.6 percent, and the selectivity is 85.9 percent.
Example 10
25g of nonyl phenol is used as a raw material, and a batch kettle catalytic hydrogenation process is adopted under the action of 0.5g of the catalyst in the embodiment 3, the reaction is carried out for 6 hours at the temperature of 150 ℃ and the pressure of 4MPa, the alkylphenol conversion rate is 100 percent, and the selectivity is 99.9 percent.
Example 11
25g of nonyl phenol is used as a raw material, and a batch kettle catalytic hydrogenation process is adopted under the action of 0.5g of the catalyst in the embodiment 4, the reaction is carried out for 6 hours at the temperature of 150 ℃ and the pressure of 4MPa, the conversion rate of alkyl phenol is 89.9 percent, and the selectivity is 98.5 percent.
Example 12
25g of nonyl phenol is used as a raw material, and a batch kettle catalytic hydrogenation process is adopted under the action of 0.5g of the catalyst in the embodiment 5, the reaction is carried out for 6 hours at the temperature of 150 ℃ and the pressure of 4MPa, the conversion rate of alkyl phenol is 35.5%, and the selectivity is 44.5%.
Example 13
25g of nonyl phenol is used as a raw material, and a batch kettle catalytic hydrogenation process is adopted under the action of 0.5g of the catalyst in the embodiment 6, the reaction is carried out for 6 hours at the temperature of 150 ℃, the pressure of 4MPa, the conversion rate of alkyl phenol is 29.6 percent, and the selectivity is 39.9 percent.
Example 14
25g of nonyl phenol is used as a raw material, and a batch kettle catalytic hydrogenation process is adopted under the action of 0.5g of the catalyst in the embodiment 7, the reaction is carried out for 6 hours at the temperature of 150 ℃, the pressure of 4MPa, the conversion rate of alkyl phenol is 27.9 percent, and the selectivity is 38.5 percent.
From a comparison of examples 8, 9 and 10 it can be seen that: cobalt is selected as an auxiliary agent, so that the catalytic effect is best; from a comparison of examples 10 and 11 it can be seen that: the conversion rate and selectivity of alkylphenol are greatly reduced without a phosphorus modified catalyst; from a comparison of examples 10 and 12, 13, it can be seen that: the effect of selecting other auxiliary agents on the catalyst is not improved; from the comparison of examples 10 and 14 it can be seen that: the presence of the auxiliary agent has a good promoting effect on the catalytic effect of the catalyst.
Example 15
25g of nonyl phenol is used as a raw material, a batch kettle catalytic hydrogenation process is adopted under the action of 0.25g of the catalyst in the embodiment 3, the reaction is carried out for 3 hours at the temperature of 120 ℃ and the pressure of 3MPa, the alkylphenol conversion rate is 82.1 percent, and the selectivity is 98.9 percent.
Example 16
25g of nonyl phenol is used as a raw material, a batch kettle catalytic hydrogenation process is adopted under the action of 0.75g of the catalyst in the embodiment 3, the reaction is carried out for 6 hours at the temperature of 180 ℃ and the pressure of 5MPa, the alkylphenol conversion rate is 99.9 percent, and the selectivity is 90.2 percent.
From examples 15 and 16 it can be seen that: the higher the condition for hydrogenating the alkylphenol is, the better, and when the condition is too high, the alcoholic hydroxyl group of the produced alkylcyclohexanol is easily removed by hydrogenation dehydration, and the selectivity is reduced; when the conditions are too low, the reaction conversion is not high.
Comparative example 1
Weighing 5g of gamma-alumina, adding 0.15g of triphenylphosphine into 30g of water to prepare a solution, impregnating the carrier for modification for 8h, drying at 110 ℃, roasting at 400 ℃ to obtain a phosphorus modified carrier, and weighing 0.4939g of Co (NO)3)2·6H2Dissolving O in 30g of distilled water, ultrasonically dissolving, adding 5g of phosphorus modified carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting for 5h at 500 ℃, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of distilled water, ultrasonically dissolving, adding the carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting for 5h at 500 ℃, washing to remove Cl, and removing Cl-Then, the mixture is reduced by hydrogen under normal pressure at 500 ℃ for 3 hours. The content of Ru is 1% and the content of Co is 2%.
Taking 25g of nonyl phenol as a raw material, weighing 0.5g of the catalyst, reacting for 6 hours at the temperature of 150 ℃ and the pressure of 4MPa, wherein the conversion rate is 73.9 percent, and the selectivity is 94.4 percent.
Comparative example 2
Weighing 5g of gamma-alumina, adding 0.15g of pyrophosphoric acid into 30g of water to prepare a solution, impregnating the carrier for modification for 8 hours, drying at 110 ℃, roasting at 400 ℃ to obtain a phosphorus modified carrier, and weighing 0.4939g of Co (NO)3)2·6H2Dissolving O in 30g of distilled water, ultrasonically dissolving, adding 5g of phosphorus modified carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting for 5h at 500 ℃, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of distilled water, ultrasonically dissolving, adding the carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting for 5h at 500 ℃, washing to remove Cl, and removing Cl-Then, the mixture is reduced by hydrogen under normal pressure at 500 ℃ for 3 hours. The content of Ru is 1% and the content of Co is 2%.
Taking 25g of nonyl phenol as a raw material, weighing 0.5g of the catalyst, reacting for 6 hours at the temperature of 150 ℃ and the pressure of 4MPa, wherein the conversion rate is 68.5 percent, and the selectivity is 94.6 percent.
Comparative example 3
25g of nonyl phenol is taken as a raw material, and Ni/TiO with the Ni content of 20 percent is weighed2-SiO20.5g, reaction for 6h at 150 ℃ and 4MPa, conversion of 68.5% and selectivity of 94.6%.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (2)
1. A method for preparing alkylcyclohexanol is characterized in that: the preparation method comprises the following steps: the method comprises the following steps of taking alkylphenol as a raw material, and carrying out hydrogenation reaction on the alkylphenol by adopting a batch still catalytic hydrogenation process under the action of a ruthenium-based catalyst to obtain alkylcyclohexanol, wherein the ruthenium-based catalyst comprises the following components in percentage by mass: 1% of active component ruthenium, 2% of auxiliary agent and the balance of carrier;
the catalytic hydrogenation pressure is 3-4 MPa;
the dosage of the catalyst is 2-3%
The preparation process of the ruthenium-based catalyst is as follows:
weighing 5g of gamma-alumina, soaking and modifying the gamma-alumina by using 3 percent ammonium dihydrogen phosphate solution for 8 hours, drying the gamma-alumina at 110 ℃, roasting the gamma-alumina at 400 ℃ to obtain a phosphorus modified carrier, and weighing 0.4939g of Co (NO)3)2·6H2Dissolving O in 30g of distilled water, ultrasonically dissolving, adding 5g of phosphorus modified carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting for 5h at 500 ℃, weighing 0.1351g of ruthenium trichloride, dissolving in 30g of distilled water, ultrasonically dissolving, adding the carrier into the solution, dropwise adding ammonia water at 30 ℃, adjusting the pH to 10, stirring for 4h, aging for 24h, performing suction filtration, drying at 110 ℃, grinding, roasting for 5h at 500 ℃, washing to remove Cl, and removing Cl-Then hydrogen is reduced under normal pressure at 500 ℃ for 3 hours, wherein the content of Ru is 1 percent and the content of Co is 2 percent;
the prepared ruthenium-based catalyst is used for catalytic hydrogenation of nonyl phenol, octyl phenol and dodecyl phenol.
2. A process for the preparation of alkylcyclohexanols as claimed in claim 1, wherein: the catalytic hydrogenation process conditions are as follows: the temperature is 120-180 ℃, and the reaction time is 4-6 h.
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| CN110743546B (en) * | 2019-10-31 | 2022-11-18 | 西安凯立新材料股份有限公司 | Catalyst for continuously preparing cis-p-tert-butylcyclohexanol, preparation method and application thereof |
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| CN114272924A (en) * | 2021-11-22 | 2022-04-05 | 泰兴市凌飞化学科技有限公司 | Method for recycling waste resin |
| CN116273051A (en) * | 2023-03-21 | 2023-06-23 | 榆林学院 | Gamma-Al 2 O 3 Supported ruthenium-nickel catalyst and application thereof in phenol hydrogenation reaction |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07112948A (en) * | 1993-10-15 | 1995-05-02 | New Japan Chem Co Ltd | Production of mixture of 4-alkylcyclohexanol isomers |
| WO1999011594A1 (en) * | 1997-09-03 | 1999-03-11 | Rayburn Randy L | Alkyl cyclohexanol alkoxylates and method for making same |
| JP2000072699A (en) * | 1998-09-01 | 2000-03-07 | Mitsui Chemicals Inc | Production of highly pure alkylcyclohexanol |
| CN103435449A (en) * | 2013-08-05 | 2013-12-11 | 江苏康恒化工有限公司 | Method for preparing p-nonyl cyclohexanol with hydrogenating p-nonyl phenol |
| CN104151134A (en) * | 2014-07-16 | 2014-11-19 | 常州大学 | Method for continuously preparing nonyl cyclohexanol through catalytic hydrogenation of nonyl phenol |
| CN104628525A (en) * | 2013-11-13 | 2015-05-20 | 湖南长岭石化科技开发有限公司 | Preparation method of o-methylcyclohexanol |
| CN105170143A (en) * | 2015-09-29 | 2015-12-23 | 浙江工业大学 | Preparation method and application of ruthenium-carbon catalyst |
| CN106866365A (en) * | 2017-03-30 | 2017-06-20 | 荣成市科盛化工有限公司 | A kind of continuous preparation method of hydrogenated bisphenol A |
-
2018
- 2018-01-19 CN CN201810052782.1A patent/CN108250044B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07112948A (en) * | 1993-10-15 | 1995-05-02 | New Japan Chem Co Ltd | Production of mixture of 4-alkylcyclohexanol isomers |
| WO1999011594A1 (en) * | 1997-09-03 | 1999-03-11 | Rayburn Randy L | Alkyl cyclohexanol alkoxylates and method for making same |
| JP2000072699A (en) * | 1998-09-01 | 2000-03-07 | Mitsui Chemicals Inc | Production of highly pure alkylcyclohexanol |
| CN103435449A (en) * | 2013-08-05 | 2013-12-11 | 江苏康恒化工有限公司 | Method for preparing p-nonyl cyclohexanol with hydrogenating p-nonyl phenol |
| CN104628525A (en) * | 2013-11-13 | 2015-05-20 | 湖南长岭石化科技开发有限公司 | Preparation method of o-methylcyclohexanol |
| CN104151134A (en) * | 2014-07-16 | 2014-11-19 | 常州大学 | Method for continuously preparing nonyl cyclohexanol through catalytic hydrogenation of nonyl phenol |
| CN105170143A (en) * | 2015-09-29 | 2015-12-23 | 浙江工业大学 | Preparation method and application of ruthenium-carbon catalyst |
| CN106866365A (en) * | 2017-03-30 | 2017-06-20 | 荣成市科盛化工有限公司 | A kind of continuous preparation method of hydrogenated bisphenol A |
Non-Patent Citations (4)
| Title |
|---|
| MOFs衍生纳米材料的制备及其催化苯酚选择性加氢研究;李爱琴;《中国优秀硕士学位论文全文数据库》;20170430;第B014-469页 * |
| 氧化铝和磷改性对非负载型催化剂结构和加氢脱硫性能的影响;曾鹤;《CNKI中国知网》;20160831;第951-959页 * |
| 烷基苯酚加氢制烷基环己醇的Pd/C催化剂的制备;贺红军等;《烟台大学学报(自然科学与工程版)》;20030725(第03期);第185-189页 * |
| 酚类化合物催化加氢的研究进展;李贵贤等;《化学研究》;20161130(第06期);第786-790页 * |
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