CN111871428A - Rhodium catalyst for preparing d, l-menthol and preparation method of d, l-menthol - Google Patents
Rhodium catalyst for preparing d, l-menthol and preparation method of d, l-menthol Download PDFInfo
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- CN111871428A CN111871428A CN202010711472.3A CN202010711472A CN111871428A CN 111871428 A CN111871428 A CN 111871428A CN 202010711472 A CN202010711472 A CN 202010711472A CN 111871428 A CN111871428 A CN 111871428A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a rhodium catalyst for preparing d, l-menthol and a preparation method of the d, l-menthol, wherein the rhodium catalyst is prepared by the following method: 1) adding rhodium salt, nickel salt and zinc salt into water to obtain mixed salt water solution; 2) soaking the carrier in a mixed saline solution, uniformly stirring, and performing reduced pressure distillation to remove water to obtain a powder; 3) reducing the powder in hydrogen atmosphere, washing and drying to obtain the rhodium catalyst. The preparation method of the d, l-menthol comprises the following steps: s1) adding a rhodium catalyst and thymol into a hydrogenation kettle, and replacing air with hydrogen; s2) heating and introducing hydrogen to carry out catalytic hydrogenation reaction, and then carrying out isomerization reaction. Compared with the prior art, the method utilizes the self-made rhodium catalyst to catalyze the hydrogenation of the thymol to obtain various isomers mainly comprising d, l-menthol, the conversion rate of the thymol can reach 99.9 percent, and the selectivity of the generated d, l-menthol is high and is 65.0-70.0 percent; the selectivity of d, l-isomenthol formation is low, 6.0-8.0%.
Description
Technical Field
The invention belongs to the technical field of preparation of d, l-menthol, and relates to gamma-Al for preparing d, l-menthol2O3A supported heterogeneous rhodium catalyst and a preparation method of d, l-menthol.
Background
The d, l-menthol is mainly used for synthesizing l-menthol, and the l-menthol is mainly used in the fields of medicines, food additives and spices. Due to the rapid growth of the global economy, the demand for menthol is also increasing. In 2007, the global annual production has increased from 6300 tons in 1992 to nearly 2 million tons, with synthetic menthol also increasing from 2200 tons in 1992 to 6300 tons. The natural menthol is extracted from plants, the yield is greatly influenced by seasons, planting areas and the like, so that the price fluctuation range is very large, and the yield of the natural menthol cannot meet the increasing industrial requirements. Synthetic menthol is produced in stable quantities and is relatively inexpensive, and chemically synthesized menthol is becoming increasingly important.
U.S. Pat. No. 2,2843636 discloses a process for isomerizing various isomers of menthol to d, l-menthol in an autoclave at 260 ℃ and 280 ℃ and at a pressure of 3.45 to 8.97MPa using copper chromite, cobalt and nickel as catalysts, the product obtained containing 60 to 64% d, l-menthol and 10 to 12% d, l-isomenthol, but in which process approximately 5% of non-reusable hydrocarbons are formed.
EP0563611 discloses a process for the reduction of thymol with hydrogen using a fixed bed catalyst comprising palladium, ruthenium or rhodium or a mixture of these elements as active component and an alkali metal hydroxide and/or sulphate as promoter supported on a support doped with a rare earth metal and manganese. The method is carried out at the temperature of 191 ℃ of 180 ℃ and the pressure of 270bar of 240 ℃ to obtain various isomers of the menthol. It contains 52.3-56.8% d, l-menthol and 25.4-32.6% d, l-neomenthol, the content of d, l-isomenthol is not specified.
US20020019573 discloses that using gamma-alumina supported ruthenium catalyst, isomerizing various isomers of menthol (with d, l-menthol content of 52.1-56.8% and d, l-isomenthol content of 12.0-12.6%) at 30-170 deg.C and 0.05-300bar pressure to obtain various isomers of menthol (with d, l-menthol content of 65.0-66.8% and d, l-isomenthol content of 8.2-10.3%).
DE19853562 discloses a process for the hydrogenation of thymol at low pressure using a fixed catalyst bed with palladium as the active component and an alkali metal hydroxide as promoter, supported on a support doped with a rare earth metal and manganese, to obtain a menthol isomer mixture comprising 64.4% d, l-menthol and 12.1% d, l-isomenthol at a pressure of 3 bar. Equimolar mixtures of d, l-neomenthol, d, l-isomenthol and d, l-neoisomenthol were isomerized at 70 ℃ under 1 kg hydrogen pressure to give a menthol isomer mixture of 65.3% d, l-menthol and 12.1% d, l-isomenthol.
US20060167322 discloses hydrogenating thymol to obtain isomers of menthol containing 57.6-60.6% d, l-menthol and 11.3-11.7% d, l-isomenthol by adding other metals (iron and/or chromium) as catalyst into Raney nickel at 165-185 deg.C under 5-25 bar; the same catalyst is used to isomerize menthol isomer mainly comprising d, l-neomenthol (81.9%) at 175 deg.C and 20bar to obtain menthol isomers (wherein the content of d, l-menthol is 56.8% and the content of d, l-isomenthol is 10.8%).
US20140066664 discloses the hydrogenation of thymol to d, l-neomenthol using metallic rhodium supported on a gamma-alumina carrier as catalyst and cyclohexane as solvent at 120 ℃ under 30bar followed by isomerization to obtain menthol isomers (d, l-menthol content 67-68% and d, l-isomenthol content 32-33%).
Wherein, thymol is hydrogenated to obtain four racemic menthol isomers of d, l-neomenthol (bp: 211.7 ℃), d, l-neoisomenthol (bp: 214.6 ℃), d, l-menthol (bp: 216.5 ℃) and d, l-isomenthol (bp: 218.6 ℃), and the structural formulas are respectively as follows:
in order to improve the yield of the d, l-menthol, the content of the d, l-menthol is required to be improved as much as possible and the content of the d, l-isomenthol is required to be reduced as much as possible in the synthesis process (the reduction of the content of the d, l-isomenthol is beneficial to rectification). In the prior art, the preparation is mainly carried out by adopting high temperature and high pressure or solvent and adopting a two-step reaction method. Among them, high temperature and high pressure generate some hydrocarbons which cannot be used for any longer, and the use of a solvent and a two-step process are disadvantageous in terms of production environmental protection and cost.
Disclosure of Invention
The invention aims to provide a rhodium catalyst for preparing d, l-menthol and a preparation method of the d, l-menthol, which improve the conversion rate of raw materials and the selectivity of the d, l-menthol and are suitable for industrial production.
The purpose of the invention can be realized by the following technical scheme:
a method of preparing a rhodium catalyst for use in the preparation of d, l-menthol, the method comprising the steps of:
1) adding rhodium salt, nickel salt and zinc salt into water to obtain mixed salt water solution;
2) soaking the carrier in a mixed saline solution, uniformly stirring, and performing reduced pressure distillation to remove water to obtain a powder;
3) reducing the powder in hydrogen atmosphere, washing and drying to obtain the rhodium catalyst (Rh-Ni-Zn/gamma-Al)2O3)。
Further, in step 1), the rhodium salt includes one or two of rhodium nitrate or rhodium chloride, the nickel salt includes one or more of nickel acetate, nickel nitrate or nickel chloride, and the zinc salt includes one or more of zinc acetate, zinc nitrate or zinc chloride.
Further, in the step 2), the carrier is gamma-Al2O3Said gamma-Al2O3BET specific surface area of 100-2The grain diameter is 30-50 nm. The rhodium catalyst takes nickel and zinc as auxiliary active components and gamma-Al2O3Is a carrier.
Further, in the step 3), the temperature is 250-300 ℃ and the time is 3-4h in the reduction process.
In step 3), the reduced matter is washed completely with distilled water to remove CH3COO-、NO3 -、Cl-And after plasma, drying again and vacuum drying.
Furthermore, in the rhodium catalyst, the weight percentage of rhodium is 6-10%, the weight percentage of nickel is 0.3-1.0%, the weight percentage of zinc is 0.3-1.0%, and the balance is a carrier.
A rhodium catalyst for preparing d, l-menthol is prepared by the method.
A process for the preparation of d, l-menthol, the process comprising the steps of:
s1) adding the rhodium catalyst and thymol into a hydrogenation kettle, and replacing air with hydrogen;
s2) heating and introducing hydrogen to carry out catalytic hydrogenation reaction, and then carrying out isomerization reaction.
Further, in step S1), the mass ratio of the rhodium catalyst to the thymol is 1 (25-30), and the air is replaced by hydrogen for 1-3 times.
Further, in the step S2), in the process of catalytic hydrogenation, the reaction temperature is 80-100 ℃, the reaction pressure is 4.0-5.0MPa, and the reaction time is 10-12h, so that the product of gas phase analysis does not contain thymol.
Further, in step S2), the time of the isomerization reaction is 4-6h, so that the isomers are in equilibrium. Then filtering to obtain various isomer products mainly comprising d, l-menthol and recovered catalyst.
Compared with the prior art, the invention has the following characteristics:
1) catalyzing thymol to hydrogenate by using a self-made rhodium catalyst to obtain various isomers mainly containing d, l-menthol, wherein the conversion rate of thymol can reach 99.9%, and the selectivity of d, l-menthol is high and is 65.0-70.0%; the selectivity of d, l-isomenthol formation is low, 6.0-8.0%.
2) The rhodium catalyst has simple preparation process, mild conditions in the using process of the catalyst, good stability and repeated use, and is suitable for industrial production.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
into a 250ml round bottom flask, 15.35g of rhodium trichloride trihydrate, 1.21g of nickel dichloride hexahydrate and 0.63g of zinc chloride were charged, dissolved in 30ml of distilled water, and 93.4g of gamma-Al was added2O3(ii) a Fully stirring, distilling under reduced pressure to remove water to obtain powder; the powder is reduced in hydrogen at 250-300 ℃ for 3-4h, and then the reduced matter is washed by distilled water to completely remove Cl-And drying and vacuum drying to obtain the catalyst.
Example 2:
into a 250ml round bottom flask, 20.46g of rhodium trichloride trihydrate, 2.43g of nickel dichloride hexahydrate and 1.25g of zinc chloride were charged, dissolved in 35ml of distilled water, and 90.8g of γ -Al was added2O3(ii) a Fully stirring, distilling under reduced pressure to remove water to obtain powder; the powder is reduced in hydrogen at 250-300 ℃ for 3-4h, and then the reduced matter is washed by distilled water to completely remove Cl-And drying and vacuum drying to obtain the catalyst.
Example 3:
into a 250ml round bottom flask, 25.58g of rhodium trichloride trihydrate, 4.05g of nickel dichloride hexahydrate and 2.08g of zinc chloride were charged, dissolved in 40ml of distilled water, and 88g of gamma-Al was added2O3(ii) a Fully stirring, distilling under reduced pressure to remove water to obtain powder; the powder is reduced in hydrogen at 250-300 ℃ for 3-4h, and then the reduced matter is washed by distilled water to completely remove Cl-And drying and vacuum drying to obtain the catalyst.
Example 4:
in a 250ml autoclave, 6.5g of catalyst (from example 1) and 180.0g of thymol were added and replaced twice with hydrogen; stirring and heating, introducing hydrogen, controlling the internal pressure at 4.0-5.0MPa and the internal temperature at 80-100 ℃, carrying out gas phase analysis, detecting that no thymol exists in the reaction mixture for 10-11h, and continuing to carry out isomerization reaction for 5-6 h; after the reaction is finished, cooling, filtering and recovering the catalyst for the next reaction. 187.2g of crude product were collected and analyzed for composition as follows:
example 5:
in a 250ml autoclave, 6.5g of catalyst (from example 2) and 180.0g of thymol were added and replaced twice with hydrogen; stirring and heating, introducing hydrogen, controlling the internal pressure at 4.0-5.0MPa and the internal temperature at 80-100 ℃, carrying out gas phase analysis, detecting that no thymol exists in the reaction mixture for 9-10h, and continuing to carry out isomerization reaction for 4-5 h; after the reaction is finished, cooling, filtering and recovering the catalyst for the next reaction. 187.2g of crude product were collected and analyzed for composition as follows:
example 6:
in a 250ml autoclave, 6.5g of catalyst (from example 3) and 180.0g of thymol were added and replaced twice with hydrogen; stirring and heating, introducing hydrogen, controlling the internal pressure at 4.0-5.0MPa and the internal temperature at 80-100 ℃, carrying out gas phase analysis, detecting that no thymol exists in the reaction mixture for 8-9h, and continuing to carry out isomerization reaction for 4-5 h; after the reaction is finished, cooling, filtering and recovering the catalyst for the next reaction. 187.2g of crude product were collected and analyzed for composition as follows:
example 7:
in a 250ml autoclave, 6.0g of catalyst (from example 2) and 180.0g of thymol were added and replaced twice with hydrogen; stirring and heating, introducing hydrogen, controlling the internal pressure at 4.0-5.0MPa and the internal temperature at 80-100 ℃, carrying out gas phase analysis, detecting that no thymol exists in the reaction mixture for 8-9h, and continuing to carry out isomerization reaction for 4-5 h; after the reaction is finished, cooling, filtering and recovering the catalyst for the next reaction. 187.2g of crude product were collected and analyzed for composition as follows:
example 8:
in a 250ml autoclave, 7.2g of catalyst (from example 2) and 180.0g of thymol were added and replaced twice with hydrogen; stirring and heating, introducing hydrogen, controlling the internal pressure at 4.0-5.0MPa and the internal temperature at 80-100 ℃, carrying out gas phase analysis, detecting that no thymol exists in the reaction mixture for 8-9h, and continuing to carry out isomerization reaction for 4-5 h; after the reaction is finished, cooling, filtering and recovering the catalyst for the next reaction. 187.2g of crude product were collected and analyzed for composition as follows:
example 9:
6.5g of catalyst (from example 2, used repeatedly for 15 times) and 180.0g of thymol were placed in a 250ml autoclave and replaced twice with hydrogen; stirring and heating, introducing hydrogen, controlling the internal pressure at 4.0-5.0MPa and the internal temperature at 80-100 ℃, carrying out gas phase analysis, detecting that no thymol exists in the reaction mixture for 11-12h, and continuing to carry out isomerization reaction for 5-6 h; after the reaction is finished, cooling, filtering and recovering the catalyst for the next reaction. 187.2g of crude product were collected and analyzed for composition as follows:
example 10:
a method of preparing a rhodium catalyst for use in the preparation of d, l-menthol, the method comprising the steps of:
1) adding rhodium salt, nickel salt and zinc salt into water to obtain mixed salt water solution;
2) soaking the carrier in a mixed saline solution, uniformly stirring, and performing reduced pressure distillation to remove water to obtain a powder;
3) reducing the powder in hydrogen atmosphere, washing and drying to obtain the rhodium catalyst.
In the step 1), the rhodium salt is rhodium nitrate, the nickel salt is nickel acetate, and the zinc salt is zinc acetate.
In the step 2), the carrier is gamma-Al2O3，γ-Al2O3BET specific surface area of 100-2The grain diameter is 30-50 nm.
In the step 3), the temperature is 250 ℃ and the time is 4h in the reduction process.
In the rhodium catalyst, the weight percentage of rhodium is 10%, the weight percentage of nickel is 0.3%, the weight percentage of zinc is 1.0%, and the rest is carrier.
A process for the preparation of d, l-menthol, the process comprising the steps of:
s1) adding the rhodium catalyst and thymol into a hydrogenation kettle, and replacing air with hydrogen;
s2) heating and introducing hydrogen to carry out catalytic hydrogenation reaction, and then carrying out isomerization reaction.
In step S1), the mass ratio of the rhodium catalyst to thymol was 1:25, and air was replaced with hydrogen gas 3 times.
In the step S2), in the catalytic hydrogenation reaction process, the reaction temperature is 80 ℃, the reaction pressure is 5.0MPa, and the reaction time is 10 h. The isomerization reaction time was 6 h.
Example 11:
a method of preparing a rhodium catalyst for use in the preparation of d, l-menthol, the method comprising the steps of:
1) adding rhodium salt, nickel salt and zinc salt into water to obtain mixed salt water solution;
2) soaking the carrier in a mixed saline solution, uniformly stirring, and performing reduced pressure distillation to remove water to obtain a powder;
3) reducing the powder in hydrogen atmosphere, washing and drying to obtain the rhodium catalyst.
In the step 1), the rhodium salt is rhodium chloride, the nickel salt is nickel nitrate, and the zinc salt is zinc nitrate.
In the step 2), the carrier is gamma-Al2O3，γ-Al2O3BET specific surface area of 100-2The grain diameter is 30-50 nm.
In the step 3), the temperature is 300 ℃ and the time is 3h in the reduction process.
In the rhodium catalyst, the weight percentage of rhodium is 6%, the weight percentage of nickel is 1.0%, the weight percentage of zinc is 0.3%, and the rest is carrier.
A process for the preparation of d, l-menthol, the process comprising the steps of:
s1) adding the rhodium catalyst and thymol into a hydrogenation kettle, and replacing air with hydrogen;
s2) heating and introducing hydrogen to carry out catalytic hydrogenation reaction, and then carrying out isomerization reaction.
In step S1), the mass ratio of the rhodium catalyst to thymol was 1:30, and air was replaced with hydrogen gas 1 time.
In the step S2), in the catalytic hydrogenation reaction process, the reaction temperature is 100 ℃, the reaction pressure is 4.0MPa, and the reaction time is 12 h. The isomerization reaction time was 4 h.
Example 12:
a method of preparing a rhodium catalyst for use in the preparation of d, l-menthol, the method comprising the steps of:
1) adding rhodium salt, nickel salt and zinc salt into water to obtain mixed salt water solution;
2) soaking the carrier in a mixed saline solution, uniformly stirring, and performing reduced pressure distillation to remove water to obtain a powder;
3) reducing the powder in hydrogen atmosphere, washing and drying to obtain the rhodium catalyst.
In the step 1), the rhodium salt is rhodium chloride, the nickel salt is nickel chloride, and the zinc salt is zinc chloride.
In the step 2), the carrier is gamma-Al2O3，γ-Al2O3BET specific surface area of 100-2The grain diameter is 30-50 nm.
In the step 3), the temperature is 270 ℃ and the time is 3.5h in the reduction process.
In the rhodium catalyst, the weight percentage of rhodium is 8%, the weight percentage of nickel is 0.7%, the weight percentage of zinc is 0.5%, and the rest is carrier.
A process for the preparation of d, l-menthol, the process comprising the steps of:
s1) adding the rhodium catalyst and thymol into a hydrogenation kettle, and replacing air with hydrogen;
s2) heating and introducing hydrogen to carry out catalytic hydrogenation reaction, and then carrying out isomerization reaction.
In step S1), the mass ratio of the rhodium catalyst to thymol was 1:28, and air was replaced with hydrogen gas for 2 times.
In the step S2), in the catalytic hydrogenation reaction process, the reaction temperature is 90 ℃, the reaction pressure is 4.5MPa, and the reaction time is 11 h. The isomerization reaction time was 5 hours.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method of preparing a rhodium catalyst for use in the preparation of d, l-menthol, the method comprising the steps of:
1) adding rhodium salt, nickel salt and zinc salt into water to obtain mixed salt water solution;
2) soaking the carrier in a mixed saline solution, uniformly stirring, and performing reduced pressure distillation to remove water to obtain a powder;
3) reducing the powder in hydrogen atmosphere, washing and drying to obtain the rhodium catalyst.
2. The method of claim 1, wherein in step 1), the rhodium salt comprises one or both of rhodium nitrate and rhodium chloride, the nickel salt comprises one or more of nickel acetate, nickel nitrate and nickel chloride, and the zinc salt comprises one or more of zinc acetate, zinc nitrate and zinc chloride.
3. The method for preparing a rhodium catalyst for preparing d, l-menthol according to claim 1, wherein the carrier in step 2) is γ -Al2O3Said gamma-Al2O3BET specific surface area of 100-2The grain diameter is 30-50 nm.
4. The method as claimed in claim 1, wherein the temperature of the reduction step in step 3) is 250-300 ℃ and the time is 3-4 h.
5. The method for preparing the rhodium catalyst for preparing the d, l-menthol as claimed in claim 1, wherein the rhodium catalyst comprises 6-10 wt% of rhodium, 0.3-1.0 wt% of nickel, 0.3-1.0 wt% of zinc and the balance of carrier.
6. A rhodium catalyst for the preparation of d, l-menthol, characterized in that it is prepared by a process according to any one of claims 1 to 5.
7. A method for preparing d, l-menthol, comprising the steps of:
s1) adding the rhodium catalyst of claim 6 and thymol to a hydrogenation kettle and displacing air with hydrogen;
s2) heating and introducing hydrogen to carry out catalytic hydrogenation reaction, and then carrying out isomerization reaction.
8. The method for preparing d, l-menthol according to claim 7, wherein in step S1), the mass ratio of the rhodium catalyst to the thymol is 1 (25-30), and air is replaced with hydrogen gas 1-3 times.
9. The method for preparing d, l-menthol as claimed in claim 7, wherein in step S2), the reaction temperature is 80-100 ℃, the reaction pressure is 4.0-5.0MPa, and the reaction time is 10-12h during the catalytic hydrogenation reaction.
10. The method for preparing d, l-menthol as claimed in claim 7, wherein the isomerization reaction time in step S2) is 4-6 h.
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| US4138443A (en) * | 1976-06-22 | 1979-02-06 | Societe Francaise Des Produits Pour Catalyse "Procatalyse" | Hydrodealkylation of alkylaromatic hydrocarbons |
| US5300706A (en) * | 1992-03-17 | 1994-04-05 | Bayer Aktiengesellschaft | Process for the preparation of d,1-menthol |
| CN1323775A (en) * | 2000-05-12 | 2001-11-28 | 拜尔公司 | Method for prepn. of D,L-menthol |
| US20020051742A1 (en) * | 2000-09-08 | 2002-05-02 | Masatoshi Hotta | Catalyst for decomposing nitrous oxide, process for producing the same and method for decomposing nitrous oxide |
| US20140066664A1 (en) * | 2012-08-31 | 2014-03-06 | Lanxess Deutschland Gmbh | Process for the preparation of menthol |
| CN107952473A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Preparing isopropyl alcohol by acetone hydrogenation catalyst |
| CN107952468A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Preparing isopropyl alcohol by acetone hydrogenation catalyst and method |
| CN110743540A (en) * | 2019-11-06 | 2020-02-04 | 中国天辰工程有限公司 | Catalyst for preparing cyclododecene through selective hydrogenation and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112844389A (en) * | 2021-02-03 | 2021-05-28 | 合肥工业大学 | Preparation method of cobalt-nickel alloy catalyst for synthesizing d, l-menthol, prepared catalyst and application thereof |
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| CN111871428B (en) | 2023-04-28 |
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