CN109704918B - Method for continuously catalytically preparing 2, 6-di-tert-butyl-4-methylcyclohexanol - Google Patents
Method for continuously catalytically preparing 2, 6-di-tert-butyl-4-methylcyclohexanol Download PDFInfo
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Abstract
The invention discloses a method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by continuous catalysis, wherein supported metal catalysts are respectively filled in two fixed bed reactors connected in series, preheated di-tert-butyl-4-methylphenol (BHT) liquid is continuously pumped into a fixed bed reactor I by a pump, and 2, 6-di-tert-butyl-4-methylcyclohexanone is obtained by continuous hydrogenation; and (2) simultaneously pumping the 2, 6-di-tert-butyl-4-methylcyclohexanone and the auxiliary agent into a reactor II respectively by using a pump, and continuously hydrogenating to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanol is more than 99.0%. The invention solves the problems of harsh reaction conditions, complex operation, environmental pollution, difficult industrial application and the like in the prior art.
Description
Technical Field
The invention belongs to a green process, and relates to a synthetic method of 2, 6-di-tert-butyl-4-methylcyclohexanol.
Background
2, 6-di-tert-butyl-4-methylcyclohexanol (English: 2,6-Bis-tert-butyl-4-methylcyclohexanol) is mainly used in the field of photography; can be used as a dispersant for color photography; can also be used as a solvent to be applied to the field of dyes; meanwhile, the compound can also be used as a medical intermediate and a pesticide intermediate. At present, a kettle type hydrogenation method is mainly adopted to prepare 2, 6-di-tert-butyl-4-methylcyclohexanol, di-tert-butyl-4-methylphenol (BHT) is taken as a raw material, and the 2, 6-di-tert-butyl-4-methylcyclohexanol is prepared through hydrogenation in the presence of a supported catalyst and a solvent, wherein the catalyst used in the preparation process is mainly a noble metal supported catalyst, and the supported metal mainly comprises Ni, Ru, Rh, Pd, Pt and the like. Under the process condition, the 2, 6-di-tert-butyl-4-methylcyclohexanone and the 2, 6-di-tert-butyl-4-methylcyclohexanol have higher selectivity; however, the process conditions are harsh, long-time reaction under high temperature and high pressure conditions is required, and hydrogenolysis is easily caused, which results in complex post-treatment.
EP0703210B describes the preparation of 2, 6-di-tert-butyl-4-methylcyclohexanol by a one-step process. Adding 0.5-200% of catalyst and a certain amount of di-tert-butyl-4-methylphenol in a mass ratio into an autoclave at the same time, and reacting at the reaction temperature of 50-300 ℃, the reaction time of 12h and the reaction pressure of 10-25 MPa to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol with the content of more than 95%.
EP0720981A1 relates to a process for the preparation of 2, 6-di-tert-butyl-4-methylcyclohexanol. Firstly, 100g of di-tert-butyl-4-methylphenol, 500ml of isopropanol and 10g of Raney nickel catalyst are added into an autoclave with the capacity of 1L, the reaction is carried out at the reaction temperature of 100 ℃, the reaction time of 9h and the reaction pressure of 1MPa, and after the reaction is finished, the 2, 6-di-tert-butyl-4-methylcyclohexanone is obtained through the filtration and separation of the catalyst and the reduced pressure distillation of the solvent; then adding 8.6g of lithium aluminum hydride and 200ml of tetrahydrofuran into a four-mouth bottle, slowly dripping the obtained 2, 6-di-tert-butyl-4-methylcyclohexanone under the condition of stirring at 0 ℃, slowly heating to room temperature after dripping is finished, maintaining the room temperature for reaction for 2 hours, adding 40ml of methanol for quenching after the reaction is finished, adding 600ml of ethyl acetate for extraction and concentration, separating and washing an organic phase, and removing the solvent by reduced pressure distillation to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol.
US2505817 and US2574078 relate to a process for the preparation of 2, 6-di-tert-butyl-4-methylcyclohexanone. Adding 10-15% Raney's nickel catalyst (mass ratio) and a certain amount of di-tert-butyl-4-methylphenol into an autoclave, reacting at 160-250 ℃ for 1-2 h and 10-17 MPa to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone.
The method has some serious technical problems or defects in the prior art, such as harsh reaction conditions, complex operation, environmental pollution, difficult industrial application and the like.
Disclosure of Invention
The invention aims to solve the problems of harsh reaction conditions, complex operation, environmental pollution, difficult industrial application and the like in the prior art, thereby providing a method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by adopting supported metal catalysis.
The technical scheme provided by the invention comprises the following steps: the method for continuously catalytically preparing 2, 6-di-tert-butyl-4-methylcyclohexanol is characterized in that two fixed bed reactors connected in series are respectively filled with a supported metal catalyst, and after di-tert-butyl-4-methylphenol is preheated to be liquid, the liquid is firstly subjected to hydrogenation reduction through a reactor I to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone; and then, respectively pumping the obtained 2, 6-di-tert-butyl-4-methylcyclohexanone and an auxiliary agent into a reactor II simultaneously by using a pump, and carrying out hydrogenation reaction in a continuous feeding and discharging manner to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol.
Generally, the catalyst in the fixed bed reactor is Ru/Al 2 O 3 ,Rh/Al 2 O 3 ,Pd/C,Ni/SO 2 ,Pt/Al 2 O 3 Any one of them or a mixture thereof.
The auxiliary agent is a protic solvent.
The protic solvent is any one or mixture of water, ethanol, formic acid, acetic acid and ethylamine.
The volume flow ratio of the auxiliary agent to the 2, 6-di-tert-butyl-4-methylcyclohexanone is 1: 10-1: 4.
the reaction pressure of the fixed bed reactor I and the reactor II is 1 MPa-10 MPa.
The reaction temperature of the fixed bed reactor I and the reactor II is 100-200 ℃.
The feeding airspeed of the fixed bed reactor I is 0.5h -1 ~2h -1 The feeding space velocity of the reactor II is 0.25h -1 ~1h -1 。
The invention has the beneficial effects that:
(1) according to the invention, the fixed bed reactors are used in series, so that compared with an intermittent reaction, the complex operation is effectively reduced, the labor intensity is reduced, and the stable operation of the hydrogenation reaction is ensured;
(2) the invention uses the load type metal catalyst, has the advantages of low reaction temperature, low reaction pressure, short reaction time, high catalytic activity and the like, effectively inhibits the generation of byproducts, and is easy to separate from products after reaction;
(3) the invention uses the supported metal catalyst, belongs to the green environmental protection technology, and has no harm to the environment basically;
(4) in the invention, the supported metal catalyst is used for catalytic hydrogenation, the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanol is more than 99.0%.
Detailed Description
The following examples were carried out as follows.
(1) Preparation of supported catalyst
a: firstly, pretreating different types of activated carbon, silicon dioxide and alumina carriers by using nitric acid with the concentration of 20%, increasing oxygen-containing groups, and promoting the adsorption loading of noble metal active components;
b: preparing active metal precursors such as ruthenium trichloride, rhodium trichloride, palladium chloride, nickel nitrate, chloroplatinic acid and the like into aqueous solution, selecting any one of the aqueous solution and the aqueous solution to be uniformly mixed with a treated carrier, continuously stirring for a certain time, then aging for 6 hours, then reducing by using a reducing agent, washing, and carrying out suction filtration to obtain a supported metal catalyst, and drying in vacuum at 100 ℃ for later use.
(2) Filling the catalyst in the step (1) into a fixed bed reactor I and a reactor II respectively, continuously pumping the preheated di-tert-butyl-4-methylphenol liquid into the reactor I by a pump, controlling the reaction temperature to be 100-200 ℃, the reaction pressure to be 1-10 MPa and the feeding airspeed to be 0.5h -1 ~2h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone, and sending to a buffer tank; 2, 6-di-tert-butyl-4-methylcyclohexanone and an auxiliary agent are respectively pumped into a reactor II simultaneously according to a certain proportion, the reaction temperature is controlled to be 100-200 ℃, the reaction pressure is controlled to be 1-10 MPa, and the feeding airspeed is 0.25h -1 ~1h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol, and timing sampling, analyzing and detecting the reaction materials.
Example 1
Adding 10ml of Ru/Al with the content of 5 percent into the fixed bed reactor I 2 O 3 The supported metal catalyst is added into a reactor II with 10ml of Ru/Al with the content of 5 percent 2 O 3 A supported metal catalyst is prepared by continuously pumping preheated di-tert-butyl-4-methylphenol liquid into a reactor I, controlling the temperature of the reactor I at 100 ℃, the reaction pressure at 2MPa and the feeding airspeed at 0.5h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone, and sending to a buffer tank; respectively pumping the 2, 6-di-tert-butyl-4-methylcyclohexanone and water into a reactor II at the same time, controlling the reactor temperature of the reactor II to be 200 ℃, the reaction pressure to be 6MPa and the feeding airspeed to be 0.5h -1 The air speed of the auxiliary agent feeding is 0.1h -1 And continuously hydrogenating to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol, and sampling, analyzing and detecting reaction materials, wherein the conversion rate of BHT is 100 percent, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 99.6 percent.
Example 2
Adding 10ml of Rh/Al with the content of 5 percent into a fixed bed reactor I 2 O 3 A load type metal catalyst, 10ml of Rh/Al with the content of 5 percent is added into a reactor II 2 O 3 The supported metal catalyst is prepared through pumping preheated di-tert-butyl-4-methyl phenol liquid into reactor I, controlling the temperature in reactor I to 120 deg.c and reactionThe reaction pressure is 2MPa, and the feeding airspeed is 1.0h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone, and sending to a buffer tank; respectively pumping 2, 6-di-tert-butyl-4-methylcyclohexanone and ethanol into a reactor II at the same time, controlling the reactor temperature of the reactor II to be 180 ℃, the reaction pressure to be 5MPa and the feeding airspeed to be 1.0h -1 The air speed of the auxiliary agent feeding is 0.1h -1 And continuously hydrogenating to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol, and sampling, analyzing and detecting reaction materials, wherein the conversion rate of BHT is 100 percent, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 99.4 percent.
Example 3
Adding 10ml of Ni/SO with the content of 5 percent into the fixed bed reactor I 2 The supported metal catalyst is added into a reactor II with 10ml of Ru/Al with the content of 5 percent 2 O 3 A supported metal catalyst is prepared by continuously pumping preheated di-tert-butyl-4-methylphenol liquid into a reactor I, controlling the temperature of the reactor I at 140 ℃, the reaction pressure at 3MPa and the feeding airspeed at 0.75h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone, and sending to a buffer tank; respectively pumping the 2, 6-di-tert-butyl-4-methylcyclohexanone and formic acid into a reactor II simultaneously, controlling the reactor temperature of the reactor II at 160 ℃, the reaction pressure at 4MPa and the feeding airspeed at 0.75h -1 The air speed of the auxiliary agent feeding is 0.1h -1 And continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol, and sampling, analyzing and detecting reaction materials, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanol is 99.1%.
Example 4
Adding 10ml of Pt/Al with the content of 5 percent into the fixed bed reactor I 2 O 3 The supported metal catalyst is added into a reactor II with 10ml of Pt/Al with the content of 5 percent 2 O 3 A supported metal catalyst is prepared by continuously pumping preheated di-tert-butyl-4-methylphenol liquid into a reactor I, controlling the temperature of the reactor I at 150 ℃, the reaction pressure at 4MPa and the feeding airspeed at 2.0h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone, and sending to a buffer tank; 2, 6-di-tert-butyl-4-methylcyclohexaneKetone and acetic acid are respectively pumped into a reactor II at the same time, the temperature of the reactor II is controlled to be 200 ℃, the reaction pressure is 4MPa, and the feeding airspeed is 1.5h -1 The space velocity of the auxiliary agent feeding is 0.15h -1 And continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol, and sampling, analyzing and detecting reaction materials, wherein the conversion rate of BHT is 100%, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanol is 99.3%.
Example 5
Adding 10ml of Pd/C supported metal catalyst with the content of 5 percent into a fixed bed reactor I, and adding 10ml of Rh/Al with the content of 5 percent into a reactor II 2 O 3 A supported metal catalyst is prepared by continuously pumping preheated di-tert-butyl-4-methylphenol liquid into a reactor I, controlling the temperature of the reactor I at 160 ℃, the reaction pressure at 2MPa and the feeding airspeed at 1.5h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone, and sending to a buffer tank; respectively pumping the 2, 6-di-tert-butyl-4-methylcyclohexanone and ethylamine into a reactor II simultaneously, controlling the reactor temperature of the reactor II to be 180 ℃, the reaction pressure to be 5MPa and the feeding airspeed to be 1.0h -1 The air speed of the auxiliary agent feeding is 0.2h -1 And continuously hydrogenating to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol, and sampling, analyzing and detecting reaction materials, wherein the conversion rate of BHT is 100 percent, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 99.5 percent.
Example 6
Adding 10ml of Ni/SO with the content of 5 percent into the fixed bed reactor I 2 The supported metal catalyst is added into a reactor II with 10ml of Ni/SO with the content of 5 percent 2 A supported metal catalyst is prepared by continuously pumping preheated di-tert-butyl-4-methylphenol liquid into a reactor I, controlling the temperature of the reactor I at 140 ℃, the reaction pressure at 3MPa and the feeding airspeed at 1.0h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone, and sending to a buffer tank; respectively pumping 2, 6-di-tert-butyl-4-methylcyclohexanone and ethylamine into a reactor II, controlling the temperature of the reactor II to be 190 ℃, the reaction pressure to be 4MPa and the feeding airspeed to be 1.0h -1 The air speed of the auxiliary agent feeding is 0.1h -1 Continuous hydrogenation ofObtaining the 2, 6-di-tert-butyl-4-methylcyclohexanol, and sampling, analyzing and detecting reaction materials, wherein the conversion rate of BHT is 100 percent, and the selectivity of 2, 6-di-tert-butyl-4-methylcyclohexanol is 99.0 percent.
Example 7
Adding 10ml of Ru/Al with the content of 5 percent into a fixed bed reactor I 2 O 3 The supported metal catalyst is added into a reactor II with 10ml of Ru/Al with the content of 5 percent 2 O 3 A supported metal catalyst is prepared by continuously pumping preheated di-tert-butyl-4-methylphenol liquid into a reactor I, controlling the temperature of the reactor I at 150 ℃, the reaction pressure at 2MPa and the feeding airspeed at 1.0h -1 Continuously hydrogenating to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone, and sending to a buffer tank; respectively pumping the 2, 6-di-tert-butyl-4-methylcyclohexanone and ethylamine into a reactor II simultaneously, controlling the reactor temperature of the reactor II to be 200 ℃, the reaction pressure to be 6MPa and the feeding airspeed to be 0.75h -1 The air speed of the auxiliary agent feeding is 0.1h -1 And continuously hydrogenating to obtain the 2, 6-di-tert-butyl-4-methylcyclohexanol, and sampling, analyzing and detecting reaction materials, wherein the conversion rate of BHT is 100 percent, and the selectivity of the 2, 6-di-tert-butyl-4-methylcyclohexanol is 99.4 percent.
Claims (4)
1. A method for preparing 2, 6-di-tert-butyl-4-methylcyclohexanol by continuous catalysis is characterized in that two fixed bed reactors connected in series are respectively filled with a supported metal catalyst, and after di-tert-butyl-4-methylphenol is preheated to be liquid, the liquid passes through a reactor I and is subjected to hydrogenation reduction to obtain 2, 6-di-tert-butyl-4-methylcyclohexanone; then, the obtained 2, 6-di-tert-butyl-4-methylcyclohexanone and an auxiliary agent are simultaneously and respectively pumped into a reactor II, and hydrogenation reaction is carried out in a continuous feeding and discharging mode to obtain 2, 6-di-tert-butyl-4-methylcyclohexanol; the auxiliary agent is a protic solvent, and the protic solvent is any one or a mixture of ethanol, formic acid, acetic acid and ethylamine; the volume flow ratio of the auxiliary agent to the 2, 6-di-tert-butyl-4-methylcyclohexanone is 1: 10-1: 4; the catalyst in the fixed bed reactor is Ni/SiO 2 ,Pt/Al 2 O 3 Any one of them or a mixture thereof.
2. The method of claim 1, wherein the reaction pressure in the fixed bed reactor I and the reactor II is 1MPa to 10 MPa.
3. The method according to claim 1, wherein the reaction temperature of the fixed bed reactor I and the reactor II is 100 ℃ to 200 ℃.
4. The method of claim 1, wherein the fixed bed reactor I has a feed space velocity of 0.5h -1 ~2h -1 The space velocity of the feed to the reactor II was 0.25h -1 ~1h -1 。
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CN112174777A (en) * | 2020-11-06 | 2021-01-05 | 本源精化环保科技有限公司 | Preparation method of 2,2' -di (4-hydroxycyclohexyl) propane |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4551564A (en) * | 1983-10-22 | 1985-11-05 | Chemische Werke Huels, Ag | Process for the production of 2- and 4-tert-butylcyclohexanols with high proportions of cis-isomers by catalytic-hydrogenation of the corresponding tert-butylphenols |
EP0703210A1 (en) * | 1994-09-20 | 1996-03-27 | Fuji Photo Film Co., Ltd. | Process for producing 2,6-di-tert-alkylcyclohexanol |
EP0720981A1 (en) * | 1995-01-05 | 1996-07-10 | Fuji Photo Film Co., Ltd. | Cyclohexyloxycarbonylacetohydrazides and method for producing 1H-1,2,4-triazoles using the hydrazides |
CN1847206A (en) * | 2006-05-10 | 2006-10-18 | 浙江工业大学 | Synthesis process of cyclohexanone and cyclohexanol |
CN104428276A (en) * | 2012-06-28 | 2015-03-18 | 帝斯曼知识产权资产管理有限公司 | Process for the production of a mixture comprising cyclohexanone and cyclohexanol from 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 |
CN106831330A (en) * | 2017-01-17 | 2017-06-13 | 江苏理工学院 | A kind of method that orthoresol catalytic hydrogenation prepares 2 methyl cyclohexanols |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP4581078B2 (en) * | 2003-04-18 | 2010-11-17 | 独立行政法人産業技術総合研究所 | Method for hydrogenating phenols |
-
2017
- 2017-10-25 CN CN201711005506.1A patent/CN109704918B/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4551564A (en) * | 1983-10-22 | 1985-11-05 | Chemische Werke Huels, Ag | Process for the production of 2- and 4-tert-butylcyclohexanols with high proportions of cis-isomers by catalytic-hydrogenation of the corresponding tert-butylphenols |
EP0703210A1 (en) * | 1994-09-20 | 1996-03-27 | Fuji Photo Film Co., Ltd. | Process for producing 2,6-di-tert-alkylcyclohexanol |
EP0720981A1 (en) * | 1995-01-05 | 1996-07-10 | Fuji Photo Film Co., Ltd. | Cyclohexyloxycarbonylacetohydrazides and method for producing 1H-1,2,4-triazoles using the hydrazides |
CN1847206A (en) * | 2006-05-10 | 2006-10-18 | 浙江工业大学 | Synthesis process of cyclohexanone and cyclohexanol |
CN104428276A (en) * | 2012-06-28 | 2015-03-18 | 帝斯曼知识产权资产管理有限公司 | Process for the production of a mixture comprising cyclohexanone and cyclohexanol from 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 |
CN106831330A (en) * | 2017-01-17 | 2017-06-13 | 江苏理工学院 | A kind of method that orthoresol catalytic hydrogenation prepares 2 methyl cyclohexanols |
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