CN110327971B - Preparation method and application of acidic ionic liquid catalyst - Google Patents
Preparation method and application of acidic ionic liquid catalyst Download PDFInfo
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- CN110327971B CN110327971B CN201910553312.8A CN201910553312A CN110327971B CN 110327971 B CN110327971 B CN 110327971B CN 201910553312 A CN201910553312 A CN 201910553312A CN 110327971 B CN110327971 B CN 110327971B
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a preparation method of an acidic ionic liquid catalyst, which comprises the steps of synthesizing a bromine salt intermediate by using acetonitrile as a solvent and using N-methylimidazole and 1, 4-dibromobutane, washing the bromine salt intermediate by using acetone, drying the washing product, and reacting the dried product with silver oxide, deionized water and concentrated sulfuric acid to prepare the acidic ionic liquid catalyst bis- (3-methyl-1-imidazole) butylidene bisbisulfate; the acidic ionic liquid catalyst is applied to alpha-pinene esterification-saponification reaction to obtain alpha-terpineol with high selectivity; the method avoids the defects of difficult separation, long process consumption, low conversion rate and selectivity, equipment corrosion and the like of traditional catalysts such as sulfuric acid, acidic heteropoly acid, solid super acid, natural zeolite or natural zeolite modification, ion exchange resin and the like; and the ionic liquid as the catalyst has the advantages of greenness, environmental protection, easy separation of the product and the catalyst, high conversion rate and selectivity and the like.
Description
Technical Field
The invention relates to an acidic ionic liquid catalyst and application of the catalyst in catalyzing alpha-pinene two-step reaction to synthesize alpha-terpineol, belonging to the field of chemical industry.
Background
China has more raw material producing areas as one of the main producing countries of the alpha-pinene, the pinene resources in China are widely distributed and are concentrated in the south of China, mainly in the southwest, and the chemical components and the contents of the alpha-pinene in different producing areas are different. The alpha-pinene is a renewable essential oil, contains various terpenes, the main components of the alpha-pinene and the beta-pinene, and other minor components of the alpha-pinene comprise myrcene, limonene, camphene and the like, wherein the content of the alpha-pinene reaches over 90 percent. In foreign countries, especially developed countries, alpha-pinene is basically used as a chemical raw material for deep processing. In China, the alpha-pinene is mainly used for producing paint solvents, mineral oil, camphor, borneol, various spices and the like; the alpha-pinene can generate products such as terpineol, borneol and the like through different reactions; terpineol as an essence and flavor has a wide application range, is one of the most international flavors, has special fragrance, and is widely applied to daily chemical products.
At present, terpineol has two synthesis modes: one-step hydration method and two-step synthesis method, the one-step hydration method has the defects of low conversion rate and low yield. The research on the synthesis of terpineol by alpha-pinene mostly focuses on the selection of a catalyst and an esterification agent. The existing catalyst for generating alpha-terpineol by alpha-pinene hydration reaction has some defects, for example, common catalysts mainly comprise traditional sulfuric acid, acidic heteropoly acid, solid super acid, natural zeolite or natural zeolite modification, ion exchange resin, ionic liquid and the like, and common esterification agents are water, formic acid, acetic acid, glacial acetic acid, chloroacetic acid and the like. The traditional sulfuric acid catalyst has the defects of equipment corrosion, low conversion rate, low selectivity and the like; the acidic heteropoly acid catalyst has the disadvantages of slow reaction speed, long process consumption, low conversion rate, difficult separation and equipment corrosion; when the solid super acid is used for catalyzing the alpha-pinene hydration reaction, although a good catalytic effect is reflected, the problems that the synthesized solid acid has small specific surface area, is difficult to reuse, has small acid amount and the like exist; the zeolite catalyst and the ion exchange resin have the problem of low selectivity; ZrO (ZrO)2/SO4 2-The solid super acid has the catalytic effect that the conversion rate of alpha-pinene reaches 90 percent, and alpha-The terpineol selectivity is 64.9%; the ionic liquid B and chloroacetic acid form a composite catalytic system, the catalytic effect is that the conversion rate of alpha-pinene is 97%, the selectivity of terpineol is 47.1%, although the ionic liquid embodies good catalytic performance, the composite system formed by chloroacetic acid is not environment-friendly, and the chloroacetic acid belongs to dangerous goods and is not beneficial to industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of an acidic ionic liquid catalyst, and the method adopts a two-step method to synthesize ionic liquid bis- (3-methyl-1-imidazole) butylidene bisulphate (Im-HSO)4) The ionic liquid is directly used as a catalyst to catalyze the reaction, and a composite system is not required to be formed.
The method specifically comprises the following steps:
(1) sequentially adding N-methylimidazole, 1, 4-dibromobutane and acetonitrile into a three-neck flask, heating and stirring in an oil bath, condensing and refluxing under the condition of nitrogen, collecting a lower-layer product after the reaction is finished, washing the lower-layer product for multiple times by using acetone, and concentrating and drying to obtain a white solid;
the molar ratio of the N-methylimidazole to the 1, 4-dibromobutane is (1-2) to (0.5-1);
the oil bath reaction temperature is 70-90 ℃, and the reaction time is 8-24 h;
(2) adding deionized water, concentrated sulfuric acid and silver oxide into the white solid, uniformly mixing, stirring at room temperature for reacting for 4-8 h, filtering, and concentrating the filtrate to obtain an acidic ionic liquid catalyst;
the molar ratio of the silver oxide to the concentrated sulfuric acid to the white solid is (0.5-1) to (1-2) to (0.5-1).
The invention also aims to provide the acidic ionic liquid catalyst prepared by the method.
The invention also aims to apply the acidic ionic liquid catalyst to the esterification-saponification synthesis of alpha-terpineol by alpha-pinene, specifically, according to the mass ratio of 5-9%, adding the ionic liquid catalyst and the alpha-pinene into a reactor, then adding acetic acid, wherein the molar ratio of the acetic acid to the alpha-pinene is 1-5: 1, and then heating and refluxing in an oil bath at 60-100 ℃ for 6-10 hours to obtain an esterification product; and (3) carrying out saponification reaction on the esterification product and a KOH alcohol solution, wherein the mass ratio of the esterification product to KOH is 0.6-0.7: 1, so as to prepare the alpha-terpineol.
The KOH alcoholic solution is an absolute ethyl alcohol solution with the KOH mass concentration of 20%.
The technical scheme of the invention has the following advantages:
(1) the invention adopts a two-step method to prepare the acidic ionic liquid catalyst bis- (3-methyl-1-imidazole) butylidene bisbisulfate (Im-HSO)4) Ion liquid Im-HSO4The ionic liquid can be directly used as a catalyst for esterification-saponification reaction, a composite system is not required to be formed, the side reaction products are few after the reaction, the selectivity is high, the ionic liquid can be recycled and reused, the pollution to the environment can be reduced, and the method is more economic and environment-friendly;
(2) the catalyst has acidity, contains a bisimidazole ring structure and hydrogen sulfate radicals in the catalyst, has hydrophilicity, is a high-efficiency catalyst for catalyzing homogeneous reaction, is easy to separate and recycle after reaction, has good stability, and is convenient to reuse, thereby prolonging the service life of the catalyst;
(3) the esterification-saponification reaction related by the invention is carried out at a lower temperature, so that the production cost can be effectively reduced, and the equipment requirement is reduced; the catalyst prepared by the invention is used for catalyzing alpha-pinene to prepare terpineol, the conversion rate of the alpha-pinene is 100%, and the selectivity of the alpha-terpineol in the product is up to 85.92%.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto.
Example 1: the preparation method and application of the esterification-saponification reaction catalyst are as follows:
(1) sequentially adding N-methylimidazole and 1, 4-dibromobutane into a three-neck flask according to the molar ratio of N-methylimidazole to 1, 4-dibromobutane being 2:1, measuring acetonitrile serving as a solvent, adding the acetonitrile into the three-neck flask, placing the three-neck flask into an oil bath, heating and stirring, wherein the reaction temperature of the oil bath is 80 ℃, the condensation reflux reaction time under the nitrogen condition is 24 hours, collecting a lower-layer product after the reaction is finished, washing the lower-layer product with acetone for 3 times, performing rotary evaporation at 80 ℃ after washing to obtain a white solid intermediate, and placing the white solid intermediate in a vacuum drying oven for later use;
(2) adding 30mL of deionized water, concentrated sulfuric acid and silver oxide into the white solid according to the molar ratio of the silver oxide to the concentrated sulfuric acid to the white solid intermediate of 1:2:1, uniformly mixing, stirring at room temperature for reacting for 8 hours, then vacuumizing, filtering, and performing rotary evaporation concentration at 80 ℃ to obtain an acidic ionic liquid catalyst;
(3) adding the obtained acidic ionic liquid catalyst and alpha-pinene into a flask according to the mass ratio of 8%, then adding acetic acid, wherein the molar ratio of the acetic acid to the alpha-pinene is 3:1, and then heating and refluxing in an oil bath at 90 ℃ for 8 hours to obtain an esterified product; performing saponification reaction on the esterification product and a KOH alcohol solution (20% by mass of an absolute ethyl alcohol solution) to obtain alpha-terpineol, wherein the mass ratio of the esterification product to KOH is 0.7: 1; the conversion of alpha-pinene is 100% and the selectivity of alpha-terpineol is 85.92%.
Example 2: the preparation method and application of the esterification-saponification reaction catalyst are as follows:
(1) sequentially adding N-methylimidazole and 1, 4-dibromobutane into a three-neck flask according to the molar ratio of the N-methylimidazole to the 1, 4-dibromobutane of 1.6:0.9, measuring acetonitrile as a solvent, adding the acetonitrile into the three-neck flask, placing the three-neck flask into an oil bath, heating and stirring, wherein the reaction temperature of the oil bath is 90 ℃, the condensation reflux reaction time under the nitrogen condition is 16h, collecting a lower-layer product after the reaction is finished, washing the lower-layer product for 3 times by using acetone, carrying out rotary evaporation at 80 ℃ after washing to obtain a white solid intermediate, and placing the white solid intermediate in a vacuum drying oven for later use;
(2) adding 30mL of deionized water, concentrated sulfuric acid and silver oxide into the white solid according to the molar ratio of the silver oxide to the concentrated sulfuric acid to the white solid intermediate of 0.5:1.2:0.6, uniformly mixing, stirring at room temperature for reacting for 6h, then vacuumizing, filtering, and performing rotary evaporation concentration at 80 ℃ to obtain the acidic ionic liquid catalyst;
(3) adding the obtained acidic ionic liquid catalyst and alpha-pinene into a flask according to the mass ratio of 9%, then adding acetic acid, wherein the molar ratio of the acetic acid to the alpha-pinene is 5:1, and then heating and refluxing in an oil bath at the temperature of 80 ℃ for 6 hours to obtain an esterified product; performing saponification reaction on the esterification product and a KOH alcohol solution (20% by mass of an absolute ethyl alcohol solution) to obtain alpha-terpineol, wherein the mass ratio of the esterification product to KOH is 0.7: 1; the conversion of alpha-pinene was 90.18% and the selectivity of alpha-terpineol was 70.04%.
Example 3: the preparation method and application of the esterification-saponification reaction catalyst are as follows:
(1) sequentially adding N-methylimidazole and 1, 4-dibromobutane into a three-neck flask according to the molar ratio of the N-methylimidazole to the 1, 4-dibromobutane of 1.8:0.5, measuring acetonitrile as a solvent, adding the acetonitrile into the three-neck flask, placing the three-neck flask into an oil bath, heating and stirring, wherein the reaction temperature of the oil bath is 70 ℃, the condensation reflux reaction time under the nitrogen condition is 20 hours, collecting a lower-layer product after the reaction is finished, washing the lower-layer product for 3 times by using acetone, carrying out rotary evaporation at 80 ℃ after washing to obtain a white solid intermediate, and placing the white solid intermediate in a vacuum drying oven for later use;
(2) adding 30mL of deionized water, concentrated sulfuric acid and silver oxide into the white solid according to the molar ratio of the silver oxide to the concentrated sulfuric acid to the white solid intermediate of 0.8:1.4:0.7, uniformly mixing, stirring at room temperature for reacting for 4 hours, then vacuumizing, filtering, and performing rotary evaporation concentration at 80 ℃ to obtain the acidic ionic liquid catalyst;
(3) adding the obtained acidic ionic liquid catalyst and alpha-pinene into a flask according to the mass ratio of 7%, then adding acetic acid, wherein the molar ratio of the acetic acid to the alpha-pinene is 1:1, and then heating and refluxing in an oil bath at 65 ℃ for 10 hours to obtain an esterified product; performing saponification reaction on the esterification product and a KOH alcoholic solution (20% absolute ethyl alcohol solution by mass concentration) to obtain alpha-terpineol, wherein the mass ratio of the esterification product to KOH is 0.65: 1; the conversion of alpha-pinene was 93.77% and the selectivity of alpha-terpineol was 66.13%.
Example 4: the preparation method and application of the esterification-saponification reaction catalyst are as follows:
(1) sequentially adding N-methylimidazole and 1, 4-dibromobutane into a three-neck flask according to the molar ratio of the N-methylimidazole to the 1, 4-dibromobutane being 1:0.7, measuring acetonitrile serving as a solvent, adding the acetonitrile into the three-neck flask, placing the three-neck flask into an oil bath, heating and stirring, wherein the oil bath reaction temperature is 80 ℃, the condensation reflux reaction time under the nitrogen condition is 8 hours, collecting a lower-layer product after the reaction is finished, washing the lower-layer product for 3 times by using acetone, performing rotary evaporation at 80 ℃ after washing to obtain a white solid intermediate, and placing the white solid intermediate in a vacuum drying oven for later use;
(2) adding 30mL of deionized water, concentrated sulfuric acid and silver oxide into the white solid according to the molar ratio of the silver oxide to the concentrated sulfuric acid to the white solid intermediate of 0.9:1.6:1, uniformly mixing, stirring at room temperature for reaction for 7 hours, then vacuumizing, filtering, and performing rotary evaporation concentration at 80 ℃ to obtain an acidic ionic liquid catalyst;
(3) adding the obtained acidic ionic liquid catalyst and alpha-pinene into a flask according to the mass ratio of 6%, then adding acetic acid, wherein the molar ratio of the acetic acid to the alpha-pinene is 3:1, and then heating and refluxing in an oil bath at 100 ℃ for 9 hours to obtain an esterified product; performing saponification reaction on the esterification product and a KOH alcohol solution (20% by mass of an absolute ethyl alcohol solution) to obtain alpha-terpineol, wherein the mass ratio of the esterification product to KOH is 0.6: 1; the conversion of alpha-pinene was 91.23%, and the selectivity of alpha-terpineol was 61.01%.
Claims (5)
1. An application of acidic ionic liquid catalyst in alpha-pinene esterification-saponification synthesis of alpha-terpineol is characterized in that: adding an acidic ionic liquid catalyst and alpha-pinene into a reactor according to the mass ratio of 5-9%, adding acetic acid, wherein the molar ratio of the acetic acid to the alpha-pinene is 1-5: 1, and then performing oil bath heating reflux reaction at 60-100 ℃ for 6-10 hours to obtain an esterified product; performing saponification reaction on the esterification product and a KOH alcohol solution, wherein the mass ratio of the esterification product to KOH is 0.6-0.7: 1, and preparing alpha-terpineol;
the preparation method of the acidic ionic liquid catalyst comprises the following steps:
(1) sequentially adding N-methylimidazole, 1, 4-dibromobutane and acetonitrile into a three-neck flask, heating and stirring in an oil bath, condensing and refluxing under the condition of nitrogen, collecting a lower-layer product after the reaction is finished, washing the lower-layer product with acetone, and concentrating and drying to obtain a white solid;
(2) and adding deionized water, concentrated sulfuric acid and silver oxide into the white solid, uniformly mixing, stirring at room temperature for reacting for 4-8 h, filtering, and concentrating the filtrate to obtain the acidic ionic liquid catalyst.
2. Use according to claim 1, characterized in that: the molar ratio of N-methylimidazole to 1, 4-dibromobutane is (1-2) to (0.5-1).
3. Use according to claim 1, characterized in that: the oil bath reaction temperature in the step (1) is 70-90 ℃, and the reaction time is 8-24 h.
4. Use according to claim 1, characterized in that: the molar ratio of the silver oxide to the concentrated sulfuric acid to the white solid is (0.5-1) to (1-2) to (0.5-1).
5. Use according to claim 1, characterized in that: the KOH alcoholic solution is an absolute ethyl alcohol solution with the KOH mass concentration of 20 percent.
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CN102924254B (en) * | 2012-10-30 | 2015-03-11 | 浙江新和成股份有限公司 | Method for preparing ionone by using super-strong acid or super-strong-acid-based ionic liquid as catalyst |
CN105016970A (en) * | 2015-06-27 | 2015-11-04 | 青岛科技大学 | Method of catalyzing alpha-pinene hydration reaction with amino acid functionalized heteropoly ionic liquid |
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CN105016970A (en) * | 2015-06-27 | 2015-11-04 | 青岛科技大学 | Method of catalyzing alpha-pinene hydration reaction with amino acid functionalized heteropoly ionic liquid |
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酸性离子液体催化α-蒎烯反应的研究;季开慧;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20090615(第6期);第2.2.2.4节及第3.3.2节 * |
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