CN107382670B - Preparation method of thymol - Google Patents
Preparation method of thymol Download PDFInfo
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- CN107382670B CN107382670B CN201710481004.XA CN201710481004A CN107382670B CN 107382670 B CN107382670 B CN 107382670B CN 201710481004 A CN201710481004 A CN 201710481004A CN 107382670 B CN107382670 B CN 107382670B
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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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
- B01J23/72—Copper
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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
- B01J37/03—Precipitation; Co-precipitation
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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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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Abstract
The invention discloses a method for preparing thymol, wherein m-cresol and isopropanol are used as reaction raw materials, and the preparation process comprises the following steps: uniformly stirring m-cresol and isopropanol, adding a catalyst into a mixture of the m-cresol and the isopropanol, and uniformly stirring again to obtain a reaction material; reacting the reaction materials for 5-15 min under microwave radiation with the power of 400-800W and at the reaction temperature of 150-200 ℃ to obtain a target product thymol; wherein the mass ratio of m-cresol to isopropanol is 1: 1-3; the using amount of the catalyst is 3-12% of the sum of the mass of m-cresol and isopropanol. The reaction temperature of the preparation method of thymol is greatly lower than the temperature of thymol prepared by the existing Friedel-crafts alkylation reaction; the reaction time is short and only needs 5-15 min.
Description
Technical Field
The invention is a divisional application of an invention patent application with the application number of 201510192742.3 and the application date of 2015, 4-22 and named as a method for preparing thymol.
Technical Field
The invention relates to a preparation method of thymol.
Background
Thymol (also called as thymol or thymol) has a chemical name of 5-methyl-2-isopropyl phenol, and is white crystal or colorless semitransparent crystal at normal temperature. Thymol is widely used as a common flavor, preservative, bactericide and antioxidant, and also as a primary raw material for the synthesis of many chemicals, such as menthol from thymol by hydrogenation.
Thymol is mainly derived from two sources: one is extracted from natural products (thyme oil, origanum oil, basil oil), and the other is obtained by artificial synthesis. Because of limited natural resources and high extraction cost and environmental pressure, artificial synthesis of thymol is mainly used at present.
The method for artificially synthesizing thymol mainly comprises the following steps: (1) uses oleum as catalyst to catalyze m-cresol and isopropanol to prepare thymol through sulfonation and alkylation. However, the strong fuming acid is too corrosive to sulfuric acid, and the process is not environment-friendly. (2) Decahydronaphthalene is used as a solvent, alpha-pinene is catalytically oxidized and then subjected to catalytic cracking to prepare thymol. The process has many reaction steps and low yield. (3) The thymol is prepared by catalytic dehydrogenation after ring closure is catalyzed by citronellol. The process has the advantages of multiple reaction steps, short service life of the catalytic dehydrogenation catalyst and less sources of the upper raw material citronellal. (4) The focus of the current research is mainly on the preparation of thymol by Friedel-crafts alkylation reaction using m-cresol and isopropanol as raw materials.
In the published literature and patents, the preparation of thymol by Friedel-crafts alkylation requires high temperature and long reaction time. For example: DE-OS 2528303 discloses a pressure of 48 to 50X 10 at 360 to 365 DEG C5The method is characterized in that m-cresol and propylene are utilized to prepare thymol under the condition of Pa, a catalyst used in the method is activated alumina, and the thymol is prepared by alkylation reaction in a liquid phase. The process needs to be carried out at high pressure and high temperature.
Chinese patent document CN 101402551A (application No. 200810219106.5) also discloses a method for preparing thymol, which comprises the step of reacting m-cresol and an isopropylation reagent serving as raw materials in a fixed bed reactor under normal pressure, wherein the reaction temperature is 200-300 ℃, the reaction time is 4-7 h, and inert gas is used as carrier gas. The preparation method needs to use a fixed bed reactor, the loading and replacement of the fixed bed catalyst are time-consuming and labor-consuming, an inert gas is also needed as a carrier, and the most important point is that the reaction still needs to be carried out at high temperature and the reaction time is long.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing thymol under the conditions of short reaction time, normal pressure and low temperature.
The technical scheme for realizing the aim of the invention is a preparation method of thymol, wherein m-cresol and isopropanol are used as reaction raw materials, and the preparation process is as follows: uniformly stirring m-cresol and isopropanol, adding a catalyst into a mixture of the m-cresol and the isopropanol, and uniformly stirring again to obtain a reaction material; reacting the reaction materials for 5-10 min under microwave radiation with the power of 400-800W and at the reaction temperature of 150-200 ℃ to obtain a target product thymol; wherein the mass ratio of m-cresol to isopropanol is 1: 1-3; the dosage of the catalyst is 1 to 30 percent of the sum of the mass of the m-cresol and the isopropanol.
The catalyst is an Al-Cu/HAP catalyst, HAP is hydroxyapatite, and aluminum atoms and copper atoms are loaded on the hydroxyapatite; the molar ratio of Al to Cu in the catalyst is 1: 0.001-3; the loading amount of Al-Cu in the catalyst is 1-50 wt%.
The preparation method of the Al-Cu/HAP comprises the following steps: dissolving Al salt and Cu salt in dilute hydrochloric acid to obtain a mixed solution; adding hydroxyapatite powder with the particle size of 100-200 meshes as a carrier into the mixed solution to obtain a mixture; and adding NaOH solution serving as a precipitator into the obtained mixture, uniformly stirring, filtering the materials, washing the obtained filter residue with deionized water, drying, and calcining to obtain the catalyst Al-Cu/HAP.
Wherein the Al salt is AlCl3、Al2(SO4)3、Al(NO3)3One or more than one of the above, the copper salt is CuCl2、CuSO4、Cu(NO3)2One or a mixture of more than one of them.
When the catalyst Al-Cu/HAP is prepared, the calcination temperature is 450-550 ℃, and the calcination time is 0.5-6 h.
The invention has the positive effects that: (1) the reaction temperature of the preparation method of thymol is 150-200 ℃, which is greatly lower than the temperature of thymol prepared by the existing Friedel-crafts alkylation reaction; the reaction time is short and only needs 5-10 min.
(2) The preparation method can be carried out at normal pressure and low temperature, the conversion rate of m-cresol is high, the selectivity of the reaction is high, and the side reaction is less; the production process is simple, the reaction energy consumption is low, the catalyst can be reused, and the method has good economic and social benefits.
Detailed Description
The reaction formula for synthesizing thymol of the invention is as follows:
in the above reaction formula, microwave is microwave. Al-Cu/HAP is used as a catalyst, and the preparation method of the Al-Cu/HAP comprises the following steps:
dissolving Al salt and Cu salt in dilute hydrochloric acid to obtain a mixed solution; adding Hydroxyapatite (HAP) powder with the particle size of 100-200 meshes as a carrier into the mixed solution to obtain a mixture; and adding NaOH solution serving as a precipitator into the obtained mixture, uniformly stirring, filtering the materials, washing the obtained filter residue with deionized water, drying, and calcining at 450-550 ℃ for 0.5-6 h to obtain the catalyst Al-Cu/HAP. Wherein the Al salt is AlCl3、Al2(SO4)3、Al(NO3)3One or more than one of the above, the copper salt is CuCl2、CuSO4、Cu(NO3)2One or a mixture of more than one of them; the molar ratio of Al to Cu in the catalyst is 1: 0.001-3; the loading amount (mass percentage) of Al-Cu in the catalyst is 1-50 wt%.
(example 1)
The thymol of this example was prepared as follows:
0.1 mol of m-cresol and 0.1 mol of isopropanol are added into a 50mL round-bottom flask, and after uniform stirring, 1g of Al-Cu/HAP catalyst is added into a mixture of the m-cresol and the isopropanol, and the mixture is stirred uniformly again to obtain a reaction material. The reaction mass is reacted for 5min under the microwave radiation with the power of 400W and the reaction temperature of 150 ℃ to obtain 7.38g of target product thymol. The conversion of the intermediate cresol was 50.36%, and the selectivity of the reaction was 97.57%.
The preparation method of the Al-Cu/HAP catalyst comprises the following steps: 0.1 mol of Al (NO)3)3•••9H2O、0.01 mol CuSO4•5H2Dissolving O in 100mL of 0.05 mol/L dilute hydrochloric acid to obtain a mixed solution; adding 5 g of Hydroxyapatite (HAP) as a carrier into the mixed solution to obtain a solid-liquid mixture; and adding 400mL of 1mol/L NaOH solution into the obtained solid-liquid mixture, uniformly stirring, filtering the materials, washing the obtained filter residue with deionized water, drying, and calcining at 500 ℃ for 2 hours to obtain the catalyst Al-Cu/HAP.
(example 2)
The thymol of this example was prepared as follows:
0.1 mol of m-cresol and 0.3 mol of isopropanol are added into a 50mL round-bottom flask, and after uniform stirring, 1g of Al-Cu/HAP catalyst is added into a mixture of the m-cresol and the isopropanol, and the mixture is stirred uniformly again to obtain a reaction material. The reaction mass is reacted for 5min under the microwave radiation with the power of 400W and the reaction temperature of 150 ℃ to obtain 13.34g of target product thymol. The conversion of the intermediate cresol was 91.48%, and the selectivity of the reaction was 97.12%.
The catalyst used in this example was the same as in example 1.
(example 3)
The thymol of this example was prepared by the same method as in example 1 except that: the reaction mass is reacted for 10min under the microwave radiation with the power of 400W and the reaction temperature of 150 ℃ to obtain 9.51g of target product thymol. The conversion of the intermediate cresol was 65.34%, and the selectivity of the reaction was 96.98%.
(example 4)
The thymol of this example was prepared by the same method as in example 1 except that: the reaction mass is reacted for 5min under the microwave radiation with the power of 600W and the reaction temperature of 150 ℃ to obtain 10.90g of target product thymol. The conversion of the intermediate cresol was 75.16%, and the selectivity of the reaction was 96.57%.
(example 5)
The thymol of this example was prepared by the same method as in example 1 except that: the addition amount of the Al-Cu/HAP catalyst is 2 g; 8.51g of target product thymol is obtained after the reaction is finished. The conversion of the intermediate cresol was 57.19%, and the selectivity of the reaction was 98.98%.
(example 6)
The thymol of this example was prepared as follows:
0.1 mol of m-cresol and 0.3 mol of isopropanol are added into a 50mL round-bottom flask, and after uniform stirring, 2g of Al-Cu/HAP catalyst is added into the mixture of the m-cresol and the isopropanol, and the mixture is stirred uniformly again to obtain a reaction material. The reaction mass is reacted for 5min under the microwave radiation with the power of 600W and the reaction temperature of 180 ℃ to obtain 14.30g of target product thymol. The conversion of the intermediate cresol was 98.34%, and the selectivity of the reaction was 96.82%.
(example 7)
The procedure for the preparation of thymol in this example was otherwise the same as in example 1 except that the Al-Cu/HAP catalyst used was prepared as follows: 0.05mol of Al2(SO4)3•16H2O、0.01mol CuCl2•2H2Dissolving O in 100mL of 0.05 mol/L dilute hydrochloric acid to obtain a mixed solution; adding 5 g of Hydroxyapatite (HAP) as a carrier into the mixed solution to obtain a solid-liquid mixture; adding 400mL of 1mol/L NaOH solution into the obtained solid-liquid mixture, stirring uniformly, filtering the materials, washing the obtained filter residue with deionized water, and dryingAfter drying, the catalyst Al-Cu/HAP is obtained after calcining for 2 h at 500 ℃.
7.21g of thymol is obtained after the reaction is finished; the conversion of m-cresol was 49.53%, and the selectivity of the reaction was 96.85%.
The above embodiments and application examples are illustrative of specific embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art can make various changes and modifications to obtain equivalent technical solutions without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should be included in the scope of the present invention.
Claims (1)
1. The preparation method of thymol adopts m-cresol and isopropanol as reaction raw materials and is characterized in that the preparation process comprises the following steps: uniformly stirring m-cresol and isopropanol, adding a catalyst into a mixture of the m-cresol and the isopropanol, and uniformly stirring again to obtain a reaction material; reacting the reaction materials for 5-10 min under microwave radiation with the power of 400-800W and at the reaction temperature of 150-200 ℃ to obtain a target product thymol; wherein the mass ratio of m-cresol to isopropanol is 1: 1-3; the dosage of the catalyst is 1 to 30 percent of the sum of the mass of m-cresol and isopropanol;
the catalyst is an Al-Cu/HAP catalyst, HAP is hydroxyapatite, and aluminum atoms and copper atoms are loaded on the hydroxyapatite; the molar ratio of Al to Cu in the catalyst is 1: 0.001-3; the loading amount of Al-Cu in the catalyst is 1-50 wt%;
the preparation method of the Al-Cu/HAP comprises the following steps: dissolving Al salt and Cu salt in dilute hydrochloric acid to obtain a mixed solution; adding hydroxyapatite powder with the particle size of 100-200 meshes as a carrier into the mixed solution to obtain a mixture; adding NaOH solution serving as a precipitator into the obtained mixture, uniformly stirring, filtering the materials, washing the obtained filter residue with deionized water, drying, and calcining at 450-550 ℃ for 0.5-6 h to obtain a catalyst Al-Cu/HAP;
wherein the Al salt is AlCl3、Al2(SO4)3、Al(NO3)3One or more than one of the above, the copper salt is CuCl2、CuSO4、Cu(NO3)2One or a mixture of more than one of them.
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| CN201510192742.3A CN104744219B (en) | 2015-04-22 | 2015-04-22 | The preparation method of thymol |
| CN201710481004.XA CN107382670B (en) | 2015-04-22 | 2015-04-22 | Preparation method of thymol |
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| CN105693471B (en) * | 2016-01-21 | 2019-01-15 | 上海延安药业（湖北）有限公司 | The preparation method of thymol |
| CN108911951B (en) * | 2018-08-15 | 2021-05-14 | 漳州水仙药业股份有限公司 | Thymol and preparation method and pharmaceutical composition thereof |
| CN112939739A (en) * | 2021-01-11 | 2021-06-11 | 吴樟强 | Acid catalysis preparation method of thymol |
| CN114849769B (en) * | 2022-04-25 | 2023-06-13 | 安徽海华科技集团有限公司 | Catalyst for synthesizing thymol and preparation method and application thereof |
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| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
| CN103772154A (en) * | 2014-01-21 | 2014-05-07 | 湘潭大学 | Method for catalyzed synthesis of bisphenol F by using modified hydroxyapatite |
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| CN101402551A (en) * | 2008-11-14 | 2009-04-08 | 广东省石油化工研究院 | Method of preparing thymol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103480401A (en) * | 2013-09-30 | 2014-01-01 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
| CN103772154A (en) * | 2014-01-21 | 2014-05-07 | 湘潭大学 | Method for catalyzed synthesis of bisphenol F by using modified hydroxyapatite |
Non-Patent Citations (1)
| Title |
|---|
| "Microwave-Assisted Process Intensification of Synthesis of Thymol Using Carbonized Sulfonic Acidic Resin(CSA) Catalyst";Asraf A. Ali et al.,;《Ind. Eng. Chem. Res.》;20110416;第50卷;第6543-6555页 * |
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| CN107398290A (en) | 2017-11-28 |
| CN104744219A (en) | 2015-07-01 |
| CN107398290B (en) | 2020-01-10 |
| CN104744219B (en) | 2017-07-11 |
| CN107382670A (en) | 2017-11-24 |
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