阅读说明：本技术 一种香气可控的β-紫罗兰酮及其制备方法 (Fragrance-controllable beta-ionone and preparation method thereof ) 是由 林龙 冯磊 李金明 王豪 张涛 吕英东 黎源 于 2021-07-30 设计创作，主要内容包括：本发明提供一种香气可控的β-紫罗兰酮及其制备方法,通过控制杂醇物质的含量,使制备得到的β-紫罗兰酮产品香气指标满足市场需求且色值稳定。(The invention provides a fragrance-controllable beta-ionone and a preparation method thereof, which enables fragrance indexes of prepared beta-ionone products to meet market demands and have stable color values by controlling the content of fusel substances.)

1. The aroma-controllable beta-ionone is characterized by comprising the following fusel substances with the weight of less than or equal to 300 ppm:

preferably, the beta-ionone includes 270ppm or less of fusel materials.

2. The method for preparing beta-ionone with controllable aroma according to claim 1, characterized by comprising the steps of:

(1) continuously introducing the pseudo ionone solution material and the acid material into a reaction kettle, maintaining the residence time t1 for reaction, and continuously extracting the discharged material of the reaction kettle to enter a quenching kettle;

(2) continuously introducing water into the quenching kettle to quench the discharged material of the reaction kettle, and maintaining the residence time t2 for quenching reaction;

(3) continuously extracting the discharged material of the quenching kettle, and allowing the discharged material to enter a phase separator for phase separation to obtain an oil phase and a water phase;

(4) the oil phase is subjected to desolventizing and refining to obtain a product beta-ionone;

wherein the mass content of the fusel substances in the oil phase obtained in the step (3) is less than or equal to 120 ppm;

preferably, the content of fusel substances in the oil phase obtained in the step (3) is less than or equal to 100ppm by mass.

3. The preparation method according to claim 2, wherein the step (3) is that the oil phase I and the water phase are obtained by entering a phase separator I for a retention time t3, and then a neutralization and impurity removal agent is added into the oil phase I for a mixing time t 4; and (3) standing and phase splitting the mixed system to obtain an oil phase II and an impurity-removed phase, and maintaining the phase splitting time of the standing and phase splitting process to be t 5.

4. The preparation method according to claim 3, wherein the neutralization and impurity removal agent is one or more of monoethanolamine, diethanolamine, triethanolamine, mono-n-propanolamine, di-n-propanolamine, tri-n-propanolamine, mono-isopropanolamine, diisopropanolamine and triisopropanolamine.

5. The preparation method according to claim 2, wherein the residence time t1 is 1-10 min; the retention time t2 is 10-60 min; the residence time t3 is 10-120 min; the mixing time t4 in the deacidification and impurity removal process is 10-120 min; and the phase separation time t5 in the standing phase separation process is 10-120 min.

6. The preparation method according to claim 2, wherein the temperature of the system in the reaction kettle in the step (1) is maintained at 0-40 ℃; the system temperature in the quenching kettle in the step (2) is maintained at 5-50 ℃; in the step (3), the system temperature in the phase separator I is maintained at 5-50 ℃; the system temperature of the neutralization and impurity removal agent is maintained at 5-50 ℃; standing and phase splitting to obtain an oil phase II, and maintaining the system temperature at 5-50 ℃ in the impurity removal phase process.

7. The method according to claim 2, wherein the mass flow ratio of the acid in the acid material to the pseudoionone in the pseudoionone solution material is 10 to 1;

preferably, the mass flow ratio of the water introduced into the quenching kettle to the acid material introduced into the reaction kettle is 5-1;

preferably, the mass ratio of the oil phase I to the neutralization impurity removal agent is 7-100.

Technical Field

The invention belongs to the technical field of preparation of beta-ionone, and particularly relates to beta-ionone with controllable fragrance and a preparation method thereof.

Background

Beta-ionone [4- (2,6, 6-trimethyl-1-cyclohexenyl) -3-butene-2-one, beta-ionone ] is a famous and precious spice, has certain biological activity, shows stronger anticancer effect and particularly has obvious inhibition effect on tumor occurrence. In addition, the product is widely applied in industry, is a quite important medical intermediate, and is an important raw material for synthesizing vitamin A, E, beta-carotene, carotenoid, retinoic acid, phytol and the like.

The synthesis of beta-ionone is generally carried out by taking pseudo-ionone as raw material and carrying out cyclization reaction under the catalysis of acid. At present, the synthesis method of beta-ionone is industrialized, and sulfuric acid is used as an acid catalyst. Many studies have been made on the cyclization itself, such as chinese patent CN1508113, US patent US4565894 and chinese patent CN 106278853A. However, although the beta-ionone prepared by the prior art can reach a certain purity, the prepared beta-ionone has obvious fragrance, which is probably because the cyclization reaction process is accompanied by certain side reactions, and the side reactions or impurities generated by the reactions affect the fragrance of the beta-ionone product, so that the perfume beta-ionone product is unqualified. .

How to create the beta-ionone which can obtain qualified aroma and has stable color value and the preparation method thereof has very important significance.

Disclosure of Invention

The invention aims to provide the beta-ionone with controllable aroma and the preparation method thereof, and the beta-ionone prepared by the method can meet the requirement of product purity and can obtain the beta-ionone with stable aroma, aroma standard and stable color value.

In order to achieve the purpose, the invention provides the following technical scheme:

a controllable-aroma beta-ionone comprises less than or equal to 300ppm of the following fusel substances:

preferably, the beta-ionone includes 270ppm or less of fusel materials.

The invention provides a preparation method of beta-ionone with controllable fragrance, which comprises the following steps:

(1) continuously introducing the pseudo ionone solution material and the acid material into a reaction kettle, maintaining the residence time t1 for reaction, and continuously extracting the discharged material of the reaction kettle to enter a quenching kettle;

(2) continuously introducing water into the quenching kettle to quench the discharged material of the reaction kettle, and maintaining the residence time t2 for quenching reaction;

(3) continuously extracting the discharged material of the quenching kettle, and allowing the discharged material to enter a phase separator for phase separation to obtain an oil phase and a water phase;

(4) the oil phase is desolventized and refined to obtain the product beta-ionone.

Wherein the mass content of the fusel substances in the oil phase obtained in the step (3) is less than or equal to 120 ppm;

preferably, the content of fusel substances in the oil phase obtained in the step (3) is less than or equal to 100ppm by mass.

Through a great deal of research, the inventor of the application finds that the cyclization reaction of the pseudo-ionone solution under the acidic condition is accompanied by a great number of side reactions, wherein a part of the side reactions can generate the fusel substances described in the invention, and through a plurality of experiments, the existence of the fusel substances is a main reason influencing the aroma of the beta-ionone product of the perfume, and through controlling the content of the fusel substances in the beta-ionone, the aroma of the finally obtained beta-ionone product of the perfume meets the market requirement, and meanwhile, the color value of the prepared beta-ionone product is more stable.

Because the boiling point of the fusel substance is close to that of the beta-ionone, the fusel substance is difficult to separate by rectification, and the invention also preferably realizes the aim by controlling the mass content of the fusel substance in the oil phase to be less than or equal to 120 ppm.

In some preferred embodiments of the present invention, the step (3) is firstly performed by entering a phase separator I for maintaining the retention time t3 to obtain an oil phase I and a water phase, and then adding a neutralization and impurity removal agent into the oil phase I, and mixing for a mixing time t 4; and (3) standing and phase splitting the mixed system to obtain an oil phase II and an impurity-removed phase, and maintaining the phase splitting time of the standing and phase splitting process to be t 5.

In some preferred embodiments, the solute of the pseudo-ionone solution material is pseudo-ionone, and the solvent is one or more of dichloromethane, dichloroethane, n-heptane, benzene and toluene; the pseudo ionone concentration of the pseudo ionone solution material is 5 wt% -40 wt%, the acid is sulfuric acid, and the sulfuric acid concentration is 90 wt% -98 wt%.

In some preferred embodiments, the neutralization and impurity removal agent is one or more of monoethanolamine, diethanolamine, triethanolamine, mono-n-propanolamine, di-n-propanolamine, tri-n-propanolamine, mono-isopropanolamine, diisopropanolamine, triisopropanolamine.

In some preferred embodiments, the residence time t1 is 1 to 10 min; the retention time t2 is 10-60 min; the residence time t3 is 10-120 min; the mixing time t4 in the deacidification and impurity removal process is 10-120 min; and the phase separation time t5 in the standing phase separation process is 10-120 min.

In some preferred embodiments, the temperature of the system in the reaction kettle in the step (1) is maintained at 0-40 ℃; the system temperature in the quenching kettle in the step (2) is maintained at 5-50 ℃; in the step (3), the system temperature in the phase separator I is maintained at 5-50 ℃; the system temperature of the neutralization and impurity removal agent is maintained at 5-50 ℃; standing and phase splitting to obtain an oil phase II, and maintaining the system temperature at 5-50 ℃ in the impurity removal phase process.

In some preferred embodiments, the mass flow ratio of the sulfuric acid in the sulfuric acid material to the pseudoionone in the pseudoionone solution material is 10-1.

In some preferred embodiments, the mass flow ratio of the water introduced into the quenching kettle to the sulfuric acid material introduced into the reaction kettle is 5-1.

In some preferred embodiments, the mass ratio of the oil phase I to the neutralization impurity removal agent is 7-100, that is, in the case of batch reaction, the mass ratio of the oil phase I to the neutralization impurity removal agent is 7-100, and in the case of continuous reaction, the mass flow ratio of the oil phase I to the neutralization impurity removal agent is 7-100.

In some preferred embodiments, the rectification reaction conditions are: the operating pressure is 100-200 Pa, the reflux ratio is 3-10, the rectifying tower is provided with 60-100 theoretical plates, and the temperature of the rectifying tower kettle is 120-170 ℃.

The technical scheme provided by the invention has the following beneficial effects:

in the cyclization reaction process for preparing the beta-ionone, some fusel substances which can influence the aroma are accompanied, and the existence of the fusel substances increases the burden and difficulty of the refining process of the beta-ionone product on the one hand and directly influences the aroma index of the perfume beta-ionone product on the other hand. According to the invention, the neutralizing and impurity removing agent is added into the oil phase I, so that the content of fusel substances in the beta-ionone is controlled to be less than or equal to 300ppm, the finally obtained beta-ionone can meet the requirement of product purity, the aroma index also meets the market demand, and the color value is stable.

Detailed Description

In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. The chemicals referred to in the examples are all commercially available.

Some of the raw materials used or possible to use in the examples are described below:

pseudoionone: Sigma-Aldrich Sigma Aldrich (Shanghai) trade, Inc.;

sulfuric acid, dichloromethane, dichloroethane, n-heptane, benzene, toluene: bailingwei Tech Co.

In the embodiment, the purity of the beta-ionone is analyzed through gas chromatography, an external standard curve is established by using a standard sample, the measured purity is the purity of a gas external standard method, and the purity of the fusel substances is calculated after the comparison and check of the gas phase peak area of the fusel substances and the beta-ionone.

The analysis method comprises the following steps:

gas chromatograph: SHIMADZU GC-2010Plus, chromatography column Agilent WAX (60m × 320 μm × 0.25 μm), injection port temperature: 280 ℃; the split ratio is 40: 1; carrier gas flow: 3 ml/min; temperature rising procedure: keeping the temperature at 50 ℃ for 5min, heating to 80 ℃ at 5 ℃/min, keeping the temperature for 0min, then heating to 280 ℃ at 25 ℃/min, and keeping the temperature for 2 min. Detector temperature: 280 ℃.

The aroma of the beta-ionone product is identified by Beijing Beida Zhengyuan science and technology Limited.

The residual acid content was determined by means of a Switzerland potentiometric titrator 905 Titrando.

The color value of the beta-ionone product is measured by a Hash LICO690 type colorimeter in Hazen unit.

Example 1

5 wt% pseudoionone solution is prepared, and the solvent is benzene. The prepared pseudo ionone solution and 90 wt% sulfuric acid are respectively and continuously introduced into the reaction kettle at 19kg/min and 1.06kg/min, the liquid holdup of the reaction kettle is maintained at 20kg, the balance of the materials entering and leaving the reaction kettle is adjusted, the reaction residence time is ensured to be 1min, and the temperature in the reaction kettle is adjusted to be 40 ℃. Discharging from the reaction kettle (20.06kg/min) and water (1.06kg/min) are continuously introduced into the quenching kettle, the liquid holdup of the quenching kettle is maintained at 1266.67kg, the balance of materials in and out of the quenching kettle is adjusted, the residence time of the quenching reaction is ensured for 60min, and the temperature in the quenching kettle is adjusted to 50 ℃. Discharging from the quenching kettle (21.11kg/min), continuously introducing into the phase separator I, maintaining the liquid holdup of 2533.33kg, adjusting the balance of the materials in and out of the phase separator I, ensuring the phase separation time to be 120min, and adjusting the temperature in the phase separator I to be 50 ℃. The oil phase I from the phase separator I is sampled and analyzed by gas chromatography to obtain the beta-ionone with the yield of 85.61 percent by calculation, and the residual acid content is 1.7823 percent by a potentiometric titrator.

Mixing 25kg of the obtained oil phase I with 3.59kg of triisopropanolamine serving as a neutralization impurity removal agent, fully stirring at 50 ℃ for 120min, and then standing at 50 ℃ for phase separation for 120min to obtain an oil phase II and an impurity removal phase. The total content of fusel substances in the oil phase II is 14 ppm. Removing the solvent from the oil phase II to obtain a crude product of the beta-ionone, carrying out reduced pressure rectification on the crude product to collect 98-100 ℃/133Pa fraction (80 theoretical plates, batch rectification tower, reflux ratio 5) to obtain a product of the beta-ionone with the purity of 98.16 percent, wherein the total content of fusel substances is 294ppm, and the color value is 84Hazen (the color value is unchanged after being stored for one month in dark and oxygen-isolated conditions at 25 ℃). Product evaluation fragrance result: the product is qualified, and the fragrance of the violet flower and the sweet fragrance are obvious.

Example 2

Preparing a 40 wt% pseudo-ionone solution, wherein a solvent is dichloromethane. The prepared pseudo ionone solution and 98 wt% sulfuric acid are respectively and continuously introduced into the reaction kettle at 1.5kg/min and 6.12kg/min, the liquid holdup of the reaction kettle is maintained at 76.2kg, the balance of the materials entering and leaving the reaction kettle is adjusted, the reaction residence time is ensured for 10min, and the temperature in the reaction kettle is adjusted to be 0 ℃. Discharging from the reaction kettle (7.62kg/min) and water (30.61kg/min) are continuously introduced into the quenching kettle, the liquid holdup of the quenching kettle is maintained at 382.35kg, the balance of materials in and out of the quenching kettle is adjusted, the residence time of the quenching reaction is ensured for 10min, and the temperature in the quenching kettle is adjusted to be 5 ℃. Discharging from the quenching kettle (38.23kg/min), continuously introducing into the phase separator I, maintaining the liquid holdup of 382.35kg, adjusting the balance of the materials in and out of the phase separator I, ensuring the phase separation time to be 10min, and adjusting the temperature in the phase separator I to be 5 ℃. The oil phase I from the phase separator I is sampled and analyzed by gas chromatography to obtain the beta-ionone with the yield of 85.68 percent by calculation, and the residual acid content is 0.4866 percent by a potentiometric titrator.

Mixing 25kg of the obtained oil phase I with 0.25kg of neutralizing and impurity removing agent isopropanolamine, stirring at 5 ℃ for 10min, and standing at 5 ℃ for phase separation for 10min to obtain an oil phase II and an impurity removing phase. The total content of fusel substances in the oil phase II is 118 ppm. Removing the solvent from the oil phase II to obtain a crude product of the beta-ionone, carrying out reduced pressure rectification on the crude product to collect 98-100 ℃/133Pa fraction (80 theoretical plates, batch rectification tower, reflux ratio 5) to obtain a product of the beta-ionone with the purity of 98.18 percent, wherein the total content of fusel substances is 299ppm, and the color value is 88Hazen (the color value is unchanged after being stored for one month in dark and oxygen-isolated conditions at 25 ℃). Product evaluation fragrance result: the product is qualified, and the fragrance of the violet flower and the sweet fragrance are obvious.

Example 3

Preparing 25 wt% pseudoionone solution with dichloroethane as solvent. The prepared pseudo ionone solution and 94 wt% sulfuric acid are respectively and continuously introduced into the reaction kettle at 2.44kg/min and 3.24kg/min, the liquid holdup of the reaction kettle is maintained at 28.4kg, the balance of the materials entering and leaving the reaction kettle is adjusted, the reaction residence time is ensured for 5min, and the temperature in the reaction kettle is adjusted to be 20 ℃. Discharging from the reaction kettle (5.68kg/min) and water (9.73kg/min) are continuously introduced into the quenching kettle, the liquid holdup of the quenching kettle is maintained at 539.66kg, the balance of materials in and out of the quenching kettle is adjusted, the residence time of the quenching reaction is ensured for 30min, and the temperature in the quenching kettle is adjusted to 35 ℃. Discharging from the quenching kettle (15.42kg/min) and continuously introducing into the phase separator I, maintaining the liquid holdup of the phase separator I of 925.12kg, adjusting the balance of the materials in and out of the phase separator I, ensuring the phase separation time to be 60min, and adjusting the temperature in the phase separator I to be 30 ℃. Sampling an oil phase I from the phase separator I, calculating to obtain the beta-ionone with the yield of 85.83% after gas chromatography analysis, and measuring the residual acid content of 0.8021% by a potentiometric titrator.

Mixing 25kg of the obtained oil phase I with 0.92kg of neutralizing impurity removal agent triethanolamine, stirring at 30 deg.C for 60min, and standing at 30 deg.C for phase separation for 60min to obtain oil phase II and impurity removal phase. The total content of fusel substances in the oil phase II is 62 ppm. Removing the solvent from the oil phase II to obtain a crude product of the beta-ionone, carrying out reduced pressure rectification on the crude product to collect 98-100 ℃/133Pa fraction (80 theoretical plates, batch rectification tower, reflux ratio 5) to obtain a product of the beta-ionone with the purity of 98.21 percent, wherein the total content of fusel substances is 253ppm, and the color value is 73Hazen (the color value is unchanged after being stored for one month in dark and oxygen-isolated conditions at 25 ℃). Product evaluation fragrance result: the product is qualified, and the fragrance of the violet flower and the sweet fragrance are obvious.

Example 4

Preparing 20 wt% pseudoionone solution with n-heptane as solvent. The prepared pseudo ionone solution and 92 wt% sulfuric acid are respectively and continuously introduced into the reaction kettle at 5kg/min and 3.26kg/min, the liquid holdup of the reaction kettle is maintained at 24.8kg, the balance of the materials entering and leaving the reaction kettle is adjusted, the reaction residence time is ensured to be 3min, and the temperature in the reaction kettle is adjusted to be 30 ℃. Discharging from the reaction kettle (8.26kg/min) and water (6.52kg/min) are continuously introduced into the quenching kettle, the liquid holdup of the quenching kettle is maintained at 665.22kg, the balance of materials in and out of the quenching kettle is adjusted, the residence time of the quenching reaction is ensured to be 45min, and the temperature in the quenching kettle is adjusted to be 40 ℃. The discharge (14.78kg/min) of the quenching kettle is continuously fed into the phase separator I, the liquid holdup of the phase separator I is maintained at 1330.43kg, the balance of the materials fed in and out of the phase separator I is adjusted, the phase separation time is ensured for 90min, and the temperature in the phase separator I is adjusted to be 40 ℃. Sampling an oil phase I from the phase separator I, calculating to obtain the beta-ionone with the yield of 86.06% after gas chromatography analysis, and measuring the residual acid content of 1.0445% by a potentiometric titrator.

Mixing 25kg of the obtained oil phase I with 0.98kg of neutralizing impurity removal agent diethanolamine, fully stirring for 90min at 40 ℃, and then standing for phase separation for 90min at 40 ℃ to obtain an oil phase II and an impurity removal phase. The total content of fusel substances in the oil phase II is 58 ppm. Removing the solvent from the oil phase II to obtain a crude product of the beta-ionone, carrying out reduced pressure rectification on the crude product to collect 98-100 ℃/133Pa fraction (80 theoretical plates, batch rectification tower, reflux ratio 5) to obtain a product of the beta-ionone with the purity of 98.27 percent, wherein the total content of fusel substances is 295ppm, and the color value is 85Hazen (the color value is unchanged after being stored for one month in dark and oxygen-isolated conditions at 25 ℃). Product evaluation fragrance result: the product is qualified, and the fragrance of the violet flower and the sweet fragrance are obvious.

Example 5

Preparing 30 wt% pseudoionone solution with toluene as solvent. The prepared pseudo ionone solution and 96 wt% sulfuric acid are respectively and continuously introduced into the reaction kettle at 2.4kg/min and 5.25kg/min, the liquid holdup of the reaction kettle is maintained at 61.2kg, the balance of the materials entering and leaving the reaction kettle is adjusted, the reaction residence time is ensured for 8min, and the temperature in the reaction kettle is adjusted to 10 ℃. Discharging materials (7.65kg/min) from the reaction kettle and water (21kg/min) are continuously introduced into the quenching kettle, the liquid holdup of the quenching kettle is maintained at 573kg, the balance of the materials in and out of the quenching kettle is adjusted, the residence time of the quenching reaction is ensured for 20min, and the temperature in the quenching kettle is adjusted to be 15 ℃. The discharge of the quenching kettle (28.65kg/min) is continuously fed into the phase separator I, the liquid holdup of the phase separator I is maintained to be 859.50kg, the balance of the materials fed into and discharged from the phase separator I is adjusted, the phase separation time is ensured to be 30min, and the temperature in the phase separator I is adjusted to be 15 ℃. Sampling an oil phase I from the phase separator I, calculating to obtain the beta-ionone with the yield of 85.79% after gas chromatography analysis, and measuring the residual acid content of 0.6045% by a potentiometric titrator.

Mixing 25kg of the obtained oil phase I with 0.38kg of monoethanolamine as a neutralization impurity removal agent, fully stirring for 30min at 15 ℃, and then standing for phase separation for 30min at 15 ℃ to obtain an oil phase II and an impurity removal phase. The total content of fusel substances in the oil phase II is 79 ppm. Removing the solvent from the oil phase II to obtain a crude product of the beta-ionone, carrying out reduced pressure rectification on the crude product to collect 98-100 ℃/133Pa fraction (80 theoretical plates, batch rectifying tower, reflux ratio 5) to obtain a product of the beta-ionone with the purity of 98.08 percent, wherein the total content of fusel substances is 267ppm, and the color value is 77Hazen (the color value is unchanged after being stored for one month in dark and oxygen-isolated conditions at 25 ℃). Product evaluation fragrance result: the product is qualified, and the fragrance of the violet flower and the sweet fragrance are obvious.

Comparative example 1

25kg of oil phase I obtained in example 1 is mixed with 0.21kg of neutralizing and impurity removing agent isopropanolamine, the mixture is fully stirred for 10min at the temperature of 5 ℃, and then the mixture is kept stand and phase separated for 10min at the temperature of 5 ℃ to obtain oil phase II and an impurity removing phase. The total content of fusel substances in the oil phase II is 163 ppm. Removing the solvent from the oil phase II to obtain a crude product of the beta-ionone, carrying out reduced pressure rectification on the crude product to collect 98-100 ℃/133Pa fraction (80 theoretical plates, batch rectifying tower, reflux ratio 5) to obtain a product of the beta-ionone with the purity of 98.05 percent, wherein the total content of fusel substances is 415ppm, and the color value 243Hazen (the color value is changed into 591Hazen after being stored for one month in dark and oxygen-isolated conditions at 25 ℃). Product evaluation fragrance result: the product is unqualified, the flower fragrance is weak, and the sweet fragrance is poor.