WO2022104581A1 - Method for continuously synthesizing pseudoionone - Google Patents

Method for continuously synthesizing pseudoionone Download PDF

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WO2022104581A1
WO2022104581A1 PCT/CN2020/129698 CN2020129698W WO2022104581A1 WO 2022104581 A1 WO2022104581 A1 WO 2022104581A1 CN 2020129698 W CN2020129698 W CN 2020129698W WO 2022104581 A1 WO2022104581 A1 WO 2022104581A1
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acetone
pseudoionone
reactor
citral
reaction
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PCT/CN2020/129698
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French (fr)
Chinese (zh)
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魏高宁
戴剑坤
刘欣
汤镇伟
陈林锋
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厦门金达威维生素有限公司
厦门金达威集团股份有限公司
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Priority to CN202080002871.0A priority Critical patent/CN112638855B/en
Priority to PCT/CN2020/129698 priority patent/WO2022104581A1/en
Publication of WO2022104581A1 publication Critical patent/WO2022104581A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • 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

Definitions

  • the invention belongs to the field of preparation of pseudo-ionone, in particular to a continuous synthesis method of pseudo-ionone.
  • Pseudo-ionone chemical name 6,10-dimethyl-undecanotrien-2-one
  • scholars at home and abroad have been in continuous research on the improvement of its synthesis process.
  • pseudo-ionone There are two main synthetic process routes for pseudo-ionone: the first synthetic route is also the most commonly used industrial route, specifically Aldol condensation of citral and acetone under the condition of alkali catalyst to generate pseudo-ionone; the second synthetic route It is based on the reaction of dehydrolinalool with acetoacetate, diketene or isopropenyl ether to obtain dehydrolinalool acetoacetate, which is then rearranged by Claisen to obtain pseudoionone.
  • the first synthetic route is also the most commonly used industrial route, specifically Aldol condensation of citral and acetone under the condition of alkali catalyst to generate pseudo-ionone
  • the second synthetic route It is based on the reaction of dehydrolinalool with acetoacetate, diketene or isopropenyl ether to obtain dehydrolinalool acetoacetate, which is then rearranged by Claisen to obtain pseudoionone.
  • the side reaction of the second synthetic route is more, and the stability of dehydrolinalool, diketene and the intermediate acetoacetate dehydrolinalool ester is poor, especially the probability of polymerization under high temperature conditions increases, This will lead to more impurities in the final crude oil product, and it is more difficult to improve the yield by improving the process. Therefore, most of the research at this stage is to prepare pseudoionone by reacting citral and acetone under alkaline catalyst conditions.
  • CN108976108A discloses a method for preparing pseudoionone by utilizing self-made alkaline solid as a catalyst to catalyze the condensation reaction of citral and acetone. Cumbersome, high cost, large dosage, and the entire reaction time is too long.
  • US4874900 (1989) discloses the use of lithium hydroxide as a catalyst to catalyze the condensation of citral and acetone to prepare pseudoionone. This method needs to filter out excess catalyst when the reaction is completed, resulting in long reaction time, many side reactions and low yield. And solid waste is difficult to handle and other disadvantages.
  • CN103044223A discloses a method for continuously preparing pseudoionone by condensing citral and acetone with alkali metal hydroxide as a catalyst. Although the yield of the method is high, it needs to be carried out under higher pressure, and the equipment requirements are higher, and The reaction of citric acid is incomplete, and the reaction needs to be recovered again. Part of the acetone reaction generates diacetone alcohol, which will cause excessive consumption of acetone, and the process is relatively complicated.
  • the object of the present invention is to provide a method for continuously synthesizing pseudoionone that can improve yield and purity in order to overcome the defects of lower yield and lower purity when using the existing Aldol condensation method to synthesize pseudoionone.
  • the invention provides a kind of continuous synthesis method of pseudo-ionone, the method comprises:
  • the basic catalyst contains inorganic base and acetate
  • the tubular reactor sequentially includes along the flow direction Reaction section I, reaction section II and reaction section III, the reaction temperatures of the reaction section I, reaction section II and reaction section III gradually increase and are respectively 0 ⁇ 10 °C, 10 ⁇ 40 °C and 75 ⁇ 90 °C to obtain condensation reaction product;
  • the condensation reaction product is continuously introduced into the acetone recovery device to carry out acetone recovery, and the acetone recovery device is a multi-tank series device, and the temperature at which the condensation reaction product reclaims acetone in each kettle gradually rises to obtain a deacetone product;
  • step (1) the molar ratio of the citral to acetone is 1:(10-20).
  • step (1) the mass ratio of inorganic base to acetate in the basic catalyst is (1-10):1.
  • the inorganic base is selected from at least one of sodium hydroxide, potassium hydroxide, barium hydroxide, magnesium hydroxide and lithium hydroxide.
  • the acetate is sodium acetate and/or potassium acetate.
  • step (1) the inner diameter ⁇ of the tubular reactor is 1-5 mm, and the total length L is 1000-2000 mm.
  • reaction section I the reaction section II and the reaction section III each independently occupy 1/4-1/2 of the length of the tubular reactor.
  • step (1) the way of continuously introducing citral and acetone and basic catalyst into the tubular reactor is to mix citral and acetone as material A, and prepare the basic catalyst to a mass concentration of 0.1 ⁇
  • the 2% aqueous alkaline catalyst solution was used as feed B, and then feed A and feed B were continuously introduced into the tubular reactor.
  • step (1) the flow rate V of the material A citral-acetone is 1-20 mL/min, and the flow rate of the material B V of the basic catalyst is 0.3-6.5 mL/min.
  • the acetone recovery device is a three-tank series device or a four-tank series device, preferably a three-tank series device.
  • the three-reactor series device comprises a first reactor, a second reactor and a third reactor, the temperature of the first reactor is controlled at 85 ⁇ 87 °C, and the temperature of the second reactor is Controlled at 87 ⁇ 88 °C, the temperature of the third reactor is controlled at 88 ⁇ 90 °C.
  • step (2) the transmission mode of the condensation reaction product in the multi-tank series device is overflow.
  • the extraction agent used in the extraction and layering is selected from at least one of dichloromethane, petroleum ether, n-hexane, chloroform and monochlorobenzene.
  • the dilute acid is selected from at least one of acetic acid aqueous solution, hydrochloric acid aqueous solution, sulfuric acid aqueous solution and phosphoric acid aqueous solution.
  • step (3) the concentration of the dilute acid is 3-10 wt%.
  • the continuous synthesis method of pseudoionone provided by the present invention also includes recycling the recovered acetone and the aqueous layer obtained by extraction and layering as raw materials.
  • the Aldol condensation reaction is replaced by a traditional constant temperature reaction method by a stage temperature control method, which is very beneficial to the improvement of the pseudoionone conversion rate;
  • stage temperature control method which is very beneficial to the improvement of the pseudoionone conversion rate;
  • the acetone is recovered at high temperature and normal pressure by using the series reaction kettle after the reaction in the tubular reactor by adopting the stage temperature control method, by-products such as diacetone alcohol and mesityl oxide will not be produced, not only the recovery of unreacted acetone is realized, but also the recovery of unreacted acetone is realized.
  • the unreacted citral will continue to react in the series reaction kettle, so that the conversion rate of citral is close to complete.
  • the acetone can be gradually recovered after the Aldol condensation reaction is completed, the acetone in the system is gradually reduced, the organic matter layer and the alkaline water layer can finally be completely separated, and the recovery of the alkaline water layer is realized.
  • the present invention achieves high yield and high purity of pseudo-ionone and high conversion rate of raw material citral, and acetone and alkaline water layer are recovered and applied mechanically, reducing production cost.
  • adding acetate as a co-catalyst in the base catalyst is more conducive to the separation of the catalyst from the reaction product, and the base catalyst and acetone can be recycled and applied, which can perfectly solve the problem that the liquid base catalyst is difficult to separate from the reaction product and the catalyst Defects that cannot be reused.
  • the Aldol condensation reaction is mainly carried out in a tubular reactor, and is extended to a multi-tank series connection acetone recovery device, and the acetone is recovered in a manner that the temperature of each kettle is gradually increased, so that citral can be basically completely converted.
  • the tubular reactor includes reaction section I, reaction section II and reaction section III in sequence along the flow direction.
  • the reaction temperature of the reaction section I, the reaction section II and the reaction section III is gradually increased.
  • the reaction temperature of the reaction section I is 0 to 10°C, for example, it can be 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C , 10°C, etc.
  • the reaction temperature of the reaction section II is 10-40°C, for example, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, and the like.
  • the reaction temperature of the reaction section III is 75-90°C, for example, 75°C, 80°C, 85°C, 90°C, and the like.
  • the material of the tubular reactor is usually stainless steel, iron, copper, aluminum, etc., and its heat transfer effect is good. Therefore, the above reaction temperature can be controlled by the ambient temperature of the tubular reactor.
  • the lengths of the reaction section I, the reaction section II and the reaction section III preferably each independently occupy 1/4 to 1/2 of the length of the tubular reactor.
  • the specification of the tubular reactor can be reasonably selected according to the actual situation.
  • the inner diameter ⁇ of the tubular reactor is 1-5 mm
  • the total length L is 1000-2000 mm.
  • the present invention has no particular limitation on the way of continuously introducing citral and acetone and basic catalyst into the tubular reactor.
  • Citral, acetone and basic catalyst can be introduced into the tubular reactor independently, or lemon Aldehyde and acetone are optionally premixed with the basic catalyst and then introduced into the tubular reactor.
  • the way of continuously introducing citral and acetone and the basic catalyst into the tubular reactor is to mix citral and acetone as material A, and prepare the basic catalyst to a mass concentration of 0.1-2 % aqueous solution of basic catalyst is used as feed B, and then feed A and feed B are continuously introduced into the tubular reactor.
  • the flow rate V of the material A citral-acetone is preferably 1-20 mL/min, and the flow rate V of the material B of the basic catalyst is preferably 0.3-6.5 mL/min.
  • the molar ratio of the citral to acetone is preferably 1:(10-20).
  • the Aldol condensation reaction is preferably carried out under normal pressure.
  • the basic catalyst contains inorganic base and acetate.
  • acetate is used as a co-catalyst, and inorganic base and acetate are used in combination, which can significantly improve the conversion rate of citral and the yield of pseudoionone.
  • the mass ratio of inorganic base to acetate in the basic catalyst is preferably (1-10):1.
  • Specific examples of the inorganic base include, but are not limited to, at least one of sodium hydroxide, potassium hydroxide, barium hydroxide, magnesium hydroxide and lithium hydroxide.
  • Specific examples of the acetate salt include, but are not limited to: sodium acetate and/or potassium acetate.
  • the basic catalyst is preferably used as a basic catalyst aqueous solution with a mass concentration of 0.1 to 2%.
  • the acetone recovery device is a multi-tank series device, at this time, not only can citral be further converted into pseudo-ionone, but also the efficient recovery of acetone can be realized by adopting the method that the temperature of each kettle is gradually increased.
  • the acetone recovery device can be a two-tank series device, a three-tank series device or a four-tank series device, preferably a three-tank series device or a four-tank series device, and most preferably a three-tank series device.
  • the three-tank series device comprises a first reactor, a second reactor and a third reactor, the temperature of the first reactor is controlled at 85-87°C, and the temperature of the second reactor is controlled at 85-87° C. At 87 ⁇ 88 °C, the temperature of the third reaction kettle is controlled at 88 ⁇ 90 °C.
  • the volume ratio of acetone and water is (92 ⁇ 96):(4 ⁇ 8), and the steaming amount preferably accounts for 60 ⁇ 85% of the total amount;
  • the volume ratio of acetone and water is (90 ⁇ 93): (7 ⁇ 10), and the steaming amount preferably accounts for 15 ⁇ 25% of the total amount;
  • the volume ratio of acetone and water is (85-90): (10-15), and the amount of distillation preferably accounts for 5-15% of the total.
  • the condensation reaction product is successively passed through each series reaction kettle of the acetone recovery device, and is preferably transported in an overflow mode in a multi-tank series device.
  • Acetone recovery is preferably carried out under normal pressure.
  • the recovered acetone can be recycled as a raw material.
  • the purpose of extracting and stratifying the deacetone product is to purify the pseudoionone and recover the basic catalyst.
  • Specific examples of the extractant used in the extraction and layering include, but are not limited to, at least one of dichloromethane, petroleum ether, n-hexane, chloroform and monochlorobenzene.
  • the oil layer obtained by the extraction and layering is a pseudo-ionone layer, and the oil layer is neutralized with dilute acid to obtain pseudo-ionone.
  • dilute acid examples include, but are not limited to, at least one of an aqueous acetic acid solution, an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, and an aqueous phosphoric acid solution.
  • concentration of the dilute acid is preferably 3 to 10 wt %.
  • the water layer obtained by the extraction and layering is an alkali-rich liquid layer, which can be recycled as a catalyst.
  • the mixed citral-acetone solution was introduced into the pipeline reactor (inner diameter ⁇ was 3mm, total length L was 1500mm, stainless steel (304) pipeline) according to the flow rate of 12mL/min, and the alkali solution was introduced into the pipeline reactor according to the flow rate of 4mL/min.
  • the pipeline reactor includes reaction section I, reaction section II and reaction section III of equal length in turn along the flow direction.
  • the external temperature of reaction section I is 5 °C
  • the external temperature of reaction section II is 15 °C
  • the external temperature of reaction section III is 85 °C. .
  • the reaction solution flowing out from the pipeline reactor enters into the triple reactor and carries out the recovery of unreacted acetone
  • the external temperature of the first reactor is 86 °C
  • the external temperature of the second reactor is 88 °C
  • the third reactor The external temperature is 90 °C
  • the amount of solvent recovered by the first reactor is 80% of the total recovery, and the volume ratio of acetone and water is 96:4
  • the amount of solvent recovered by the second reactor is 15% of the total recovery,
  • the volume ratio of acetone and water is 92:8
  • the amount of solvent recovered in the third reactor is 5% of the total recovery amount, and the volume ratio of acetone and water is 89:11.
  • the citral injection amount was 15.2g
  • the pseudoionone crude oil was 19.5g
  • the pseudoionone content was 92.5%
  • the citral conversion rate was 99.8%
  • the pseudoionone yield was 96.85%.
  • the volume of the water layer was 38.5 mL, and the alkali content was 1%.
  • step (1) the mol ratio of citral and acetone is adjusted to 1:10, and sodium acetate is replaced by potassium acetate, and the mass ratio of sodium hydroxide and potassium acetate is Adjusted to 5:1, the flow rate of the citral-acetone solution was adjusted to 10 mL/min, the flow rate of the alkali solution was adjusted to 1 mL/min, and the external temperatures of reaction section I, reaction section II and reaction section III were adjusted to 2 °C and 10 °C, respectively.
  • step (2) the amount of solvent recovered by the first reactor is 75% of the total recovery, the volume ratio of acetone and water is 96:4, and the amount of solvent recovered by the second reactor is 75% of the total recovery. 15%, the volume ratio of acetone and water is 92:8, the amount of solvent recovered in the third reactor is 10% of the total recovery amount, and the volume ratio of acetone and water is 85:15, and the remainder is the same as in Example 1.
  • the citral injection amount was 15.2g
  • the pseudoionone crude oil was 18.9g
  • the pseudoionone content was 91.2%
  • the citral conversion rate was 99.4%
  • the pseudoionone yield was 92.55%.
  • the total recovered acetone was 104 mL, the recovered solvent had an acetone content of 95.3%, and the recovered solvent had a water content of 4.7%.
  • the volume of the water layer was 38.3 mL, and the alkali content was 1%.
  • step (2) triple reaction still is replaced with quadruple reaction still, and the temperature of the first reaction still is controlled at 85 °C, and the amount of recovered solvent accounts for 50% of the total recovery, the volume ratio of acetone and water is 94:6; the temperature of the second reactor is controlled at 86 ° C, the amount of solvent recovered accounts for 35% of the total recovery, and the volume ratio of acetone and water is 92: 8; The temperature of the 3rd reactor is controlled at 87 °C, and the amount of solvent recovered accounts for 10% of the total recovery, and the volume ratio of acetone and water is 90:10; the temperature of the 4th reactor is controlled at 88 °C, and the recovered solvent The amount accounts for 5% of the total recovery amount, and the volume ratio of acetone and water is 89:11, and the rest is the same as in Example 1.
  • the pseudoionone crude oil was finally obtained 18.87g, the pseudoionone content was 91.9%, the citral conversion rate was 99.5%, and the pseudoionone yield was 93.11%.
  • the total recovered acetone was 108 mL, the recovered solvent had an acetone content of 92.6%, and the recovered solvent had a water content of 6.9%.
  • the volume of the water layer was 37.9 mL, and the alkali content was 1%.
  • Example 1 The sodium hydroxide-sodium acetate alkali solution in the step (1) of Example 1 is replaced with the alkaline water layer recovered by extraction and layering in Example 1, and the addition of the sodium hydroxide and sodium acetate that the mass ratio is 4:1 to The mass concentration of the alkaline water layer was made 1%, and the rest was the same as in Example 1.
  • the citral injection amount was 15.2g
  • the pseudoionone crude oil was 18.9g
  • the pseudoionone content was 91.7%
  • the citral conversion rate was 99.2%
  • the pseudoionone yield was 93.06%.
  • the total recovered acetone was 112 mL, the recovered solvent had an acetone content of 94.5%, and the recovered solvent had a water content of 4.9%.
  • the volume of the water layer was 37.7 mL, and the alkali content was 1%.
  • Pseudo-ionone is prepared according to the method of embodiment 1, the difference is that in step (2), the triple reaction kettle is replaced with a single kettle device, and the temperature of the single kettle device is controlled at 90 °C and the holding time is controlled at 60min, The same as in Example 1.
  • the total recovered acetone was 109 mL, the recovered solvent had an acetone content of 94.3%, and the recovered solvent had a water content of 5.6%.
  • the volume of the water layer was 37.3 mL, and the alkali content was 1%.
  • Pseudo-ionone was prepared according to the method of Example 1, the difference was that the sodium hydroxide-sodium acetate alkali solution in step (1) was replaced with an aqueous sodium hydroxide solution with a mass concentration of 1% (that is, no sodium acetate was added) , the same as in Example 1.
  • the citral injection amount was 15.2g
  • the pseudoionone crude oil was 19.1g
  • the pseudoionone content was 85.6%
  • the citral conversion rate was 98.6%
  • the pseudoionone yield was 87.78%.
  • the total recovered acetone was 108 mL, the recovered solvent had an acetone content of 94.3%, and the recovered solvent had a water content of 4.7%.
  • the volume of the water layer was 38.5 mL, and the alkali content was 1%.
  • the pseudoionone was prepared according to the method of Example 1, except that the external temperature of the pipeline reactor was set to 5°C, and the rest was the same as that of Example 1.
  • the citral injection amount was 15.2g
  • the pseudoionone crude oil was 18.3g
  • the pseudoionone content was 85.4%
  • the citral conversion rate was 96.3%
  • the pseudoionone yield was 83.91%.
  • the volume of the water layer was 38.2 mL, and the alkali content was 1%.
  • the pseudoionone was prepared according to the method of Example 1, except that the external temperature of the pipeline reactor was set to 15° C., and the rest was the same as that of Example 1.
  • the total recovered acetone was 106 mL, the recovered solvent had an acetone content of 95.1%, and the recovered solvent had a water content of 4.5%.
  • the volume of the water layer was 38.5 mL, and the alkali content was 1%.
  • the pseudoionone was prepared according to the method of Example 1, except that the external temperature of the pipeline reactor was set to 85° C., and the rest was the same as that of Example 1.
  • the citral injection amount was 15.2g
  • the pseudoionone crude oil was 18.5g
  • the pseudoionone content was 88.6%
  • the citral conversion rate was 99.2%
  • the pseudoionone yield was 88.0%.
  • the total recovered acetone was 107 mL, the recovered solvent had an acetone content of 95.6%, and the recovered solvent had a water content of 4.6%.
  • the volume of the water layer was 39.1 mL, and the alkali content was 1%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention belongs to the field of the preparation of pseudoionone, and relates to a method for continuously synthesizing pseudoionone. The method comprises continuously introducing citral, acetone, and an alkaline catalyst containing an inorganic alkali and an acetate into a tubular reactor for an aldol condensation reaction, wherein the reaction temperature in the tubular reactor gradually increases; continuously introducing the condensation reaction product into an acetone recovery device with multiple kettles in series to recover acetone; subjecting the acetone-removed product to extraction and layering; and neutralizing an obtained oil layer with a dilute acid to obtain the pseudoionone. In the present invention, on the premise of the relatively high economy and environmental protection, a high yield and high purity of pseudoionone and a high conversion rate of the raw material citral are achieved, and the recycling and reuse of acetone and an alkaline aqueous layer are achieved, thereby reducing production costs.

Description

一种假性紫罗兰酮的连续合成方法A kind of continuous synthesis method of pseudo-ionone 技术领域technical field
本发明属于假性紫罗兰酮制备领域，具体涉及一种假性紫罗兰酮的连续合成方法。The invention belongs to the field of preparation of pseudo-ionone, in particular to a continuous synthesis method of pseudo-ionone.
背景技术Background technique
假性紫罗兰酮，化学名为6,10-二甲基-十一烷三烯-2-酮，是合成紫罗兰酮等香精香料、维生素A、维生素E和β-胡萝卜素等物质的重要中间体，在香精香料、医药、食品添加剂的合成化学中用途十分广泛。一直以来国内外学者对其合成工艺的改进研究在持续进行中。Pseudo-ionone, chemical name 6,10-dimethyl-undecanotrien-2-one, is an important intermediate for the synthesis of ionone and other flavors and fragrances, vitamin A, vitamin E and beta-carotene and other substances , It is widely used in the synthetic chemistry of flavors and fragrances, medicines and food additives. For a long time, scholars at home and abroad have been in continuous research on the improvement of its synthesis process.
假性紫罗兰酮的合成工艺路线主要有两条：第一条合成路线也是最常用的工业路线，具体为柠檬醛和丙酮在碱催化剂条件下进行Aldol缩合生成假性紫罗兰酮；第二条合成路线则是以脱氢芳樟醇与乙酰乙酸酯、双乙烯酮或异丙烯基乙醚反应得乙酰乙酸脱氢芳樟醇酯，再经Claisen重排制得假性紫罗兰酮。其中，第二条合成路线的副反应较多，而且脱氢芳樟醇、双乙烯酮及中间体乙酰乙酸脱氢芳樟醇酯的稳定性较差，尤其是在高温条件下发生聚合的几率增加，这样会导致最终粗油产品中杂质较多，通过改善工艺提高产率的难度较大。故现阶段研究比较多是以柠檬醛与丙酮在碱性催化剂条件下反应制备假性紫罗兰酮。There are two main synthetic process routes for pseudo-ionone: the first synthetic route is also the most commonly used industrial route, specifically Aldol condensation of citral and acetone under the condition of alkali catalyst to generate pseudo-ionone; the second synthetic route It is based on the reaction of dehydrolinalool with acetoacetate, diketene or isopropenyl ether to obtain dehydrolinalool acetoacetate, which is then rearranged by Claisen to obtain pseudoionone. Wherein, the side reaction of the second synthetic route is more, and the stability of dehydrolinalool, diketene and the intermediate acetoacetate dehydrolinalool ester is poor, especially the probability of polymerization under high temperature conditions increases, This will lead to more impurities in the final crude oil product, and it is more difficult to improve the yield by improving the process. Therefore, most of the research at this stage is to prepare pseudoionone by reacting citral and acetone under alkaline catalyst conditions.
CN108976108A公开了利用自制碱性固体作为催化剂催化柠檬醛与丙酮缩合反应制备假性紫罗兰酮的方法，虽然该方法取得了较高的收率及较低的丙酮自聚率，但是碱性催化剂制备过程繁琐、成本较高、用量大，且整个反应时间过长。US4874900(1989)公开了以氢氧化锂作为催化剂催化柠檬醛和丙酮缩合制备假性紫罗兰酮，该方法在反应完成时需要将过量的催化剂滤出，存在反应时间长、副反应多、收率低且固体废弃物难处理等缺点。CN103044223A公开了以碱金属氢氧化物作为催化剂缩合柠檬醛和丙酮的连续制备假性紫罗兰 酮的方法，虽然该方法收率较高，但是需要在较高压力下进行，对设备要求较高，且柠檬酸反应不完全，需要重新回收反应，部分丙酮反应生成双丙酮醇，会造成丙酮的过渡消耗，过程较为复杂。CN108976108A discloses a method for preparing pseudoionone by utilizing self-made alkaline solid as a catalyst to catalyze the condensation reaction of citral and acetone. Cumbersome, high cost, large dosage, and the entire reaction time is too long. US4874900 (1989) discloses the use of lithium hydroxide as a catalyst to catalyze the condensation of citral and acetone to prepare pseudoionone. This method needs to filter out excess catalyst when the reaction is completed, resulting in long reaction time, many side reactions and low yield. And solid waste is difficult to handle and other disadvantages. CN103044223A discloses a method for continuously preparing pseudoionone by condensing citral and acetone with alkali metal hydroxide as a catalyst. Although the yield of the method is high, it needs to be carried out under higher pressure, and the equipment requirements are higher, and The reaction of citric acid is incomplete, and the reaction needs to be recovered again. Part of the acetone reaction generates diacetone alcohol, which will cause excessive consumption of acetone, and the process is relatively complicated.
综上，如何在较为经济及绿色环保的条件下，实现高收率及高纯度的假性紫罗兰酮合成，已经成为当下制约假性紫罗兰酮应用的主要难题。To sum up, how to realize the synthesis of pseudo-ionone with high yield and high purity under relatively economical and environmentally friendly conditions has become the main problem restricting the application of pseudo-ionone at present.
发明内容SUMMARY OF THE INVENTION
本发明的目的是为了克服采用现有的Aldol缩合法合成假性紫罗兰酮时存在收率和纯度较低的缺陷，而提供一种能提高收率和纯度的连续合成假性紫罗兰酮的方法。The object of the present invention is to provide a method for continuously synthesizing pseudoionone that can improve yield and purity in order to overcome the defects of lower yield and lower purity when using the existing Aldol condensation method to synthesize pseudoionone.
为了实现上述目的，本发明提供了一种假性紫罗兰酮的连续合成方法，该方法包括：In order to achieve the above object, the invention provides a kind of continuous synthesis method of pseudo-ionone, the method comprises:
(1)将柠檬醛和丙酮与碱性催化剂连续引入管式反应器中进行Aldol缩合反应，所述碱性催化剂中含有无机碱和醋酸盐，所述管式反应器沿着物流方向依次包括反应段Ⅰ、反应段Ⅱ和反应段Ⅲ，所述反应段Ⅰ、反应段Ⅱ和反应段Ⅲ的反应温度逐渐升高且分别为0～10℃、10～40℃和75～90℃，得到缩合反应产物；(1) Continuously introduce citral and acetone and a basic catalyst into a tubular reactor to carry out Aldol condensation reaction, the basic catalyst contains inorganic base and acetate, and the tubular reactor sequentially includes along the flow direction Reaction section I, reaction section II and reaction section III, the reaction temperatures of the reaction section I, reaction section II and reaction section III gradually increase and are respectively 0 ~ 10 ℃, 10 ~ 40 ℃ and 75 ~ 90 ℃ to obtain condensation reaction product;
(2)将缩合反应产物连续引入丙酮回收装置中进行丙酮回收，所述丙酮回收装置为多釜串联装置，且缩合反应产物在各釜中回收丙酮的温度逐渐升高，得到脱丙酮产物；(2) the condensation reaction product is continuously introduced into the acetone recovery device to carry out acetone recovery, and the acetone recovery device is a multi-tank series device, and the temperature at which the condensation reaction product reclaims acetone in each kettle gradually rises to obtain a deacetone product;
(3)将脱丙酮产物进行萃取分层，所得油层用稀酸进行中和，得到假性紫罗兰酮。(3) extracting and stratifying the deacetone product, and neutralizing the obtained oil layer with dilute acid to obtain pseudoionone.
进一步地，步骤(1)中，所述柠檬醛与丙酮的摩尔比为1:(10～20)。Further, in step (1), the molar ratio of the citral to acetone is 1:(10-20).
进一步地，步骤(1)中，所述碱性催化剂中无机碱与醋酸盐的质量比为(1～10):1。Further, in step (1), the mass ratio of inorganic base to acetate in the basic catalyst is (1-10):1.
进一步地，步骤(1)中，所述无机碱选自氢氧化钠、氢氧化钾、氢氧化钡、氢氧化镁和氢氧化锂中的至少一种。Further, in step (1), the inorganic base is selected from at least one of sodium hydroxide, potassium hydroxide, barium hydroxide, magnesium hydroxide and lithium hydroxide.
进一步地，步骤(1)中，所述醋酸盐为醋酸钠和/或醋酸钾。Further, in step (1), the acetate is sodium acetate and/or potassium acetate.
进一步地，步骤(1)中，所述管式反应器的内径φ为1～5mm，总长度L为1000～2000mm。Further, in step (1), the inner diameter φ of the tubular reactor is 1-5 mm, and the total length L is 1000-2000 mm.
进一步地，所述反应段Ⅰ、反应段Ⅱ和反应段Ⅲ的长度各自独立地占管式反应器长度的1/4～1/2。Further, the lengths of the reaction section I, the reaction section II and the reaction section III each independently occupy 1/4-1/2 of the length of the tubular reactor.
进一步地，步骤(1)中，将柠檬醛和丙酮与碱性催化剂连续引入管式反应器中的方式为将柠檬醛和丙酮混合后作为物料A，将碱性催化剂配制成质量浓度为0.1～2％的碱性催化剂水溶液后作为物料B，之后将物料A和物料B连续引入管式反应器中。Further, in step (1), the way of continuously introducing citral and acetone and basic catalyst into the tubular reactor is to mix citral and acetone as material A, and prepare the basic catalyst to a mass concentration of 0.1～ The 2% aqueous alkaline catalyst solution was used as feed B, and then feed A and feed B were continuously introduced into the tubular reactor.
进一步地，步骤(1)中，所述物料A的流速V 柠檬醛-丙酮为1～20mL/min，所述物料B的流速V 碱性催化剂为0.3～6.5mL/min。 Further, in step (1), the flow rate V of the material A citral-acetone is 1-20 mL/min, and the flow rate of the material B V of the basic catalyst is 0.3-6.5 mL/min.
进一步地，步骤(2)中，所述丙酮回收装置为三釜串联装置或四釜串联装置，优选为三釜串联装置。Further, in step (2), the acetone recovery device is a three-tank series device or a four-tank series device, preferably a three-tank series device.
进一步地，步骤(2)中，所述三釜串联装置包括第一反应釜、第二反应釜和第三反应釜，第一反应釜的温度控制在85～87℃，第二反应釜的温度控制在87～88℃，第三反应釜的温度控制在88～90℃。Further, in step (2), the three-reactor series device comprises a first reactor, a second reactor and a third reactor, the temperature of the first reactor is controlled at 85～87 ℃, and the temperature of the second reactor is Controlled at 87～88 ℃, the temperature of the third reactor is controlled at 88～90 ℃.
进一步地，步骤(2)中，所述缩合反应产物在多釜串联装置中的传输方式为溢流。Further, in step (2), the transmission mode of the condensation reaction product in the multi-tank series device is overflow.
进一步地，所述Aldol缩合反应和丙酮回收均在常压下进行。Further, both the Aldol condensation reaction and the acetone recovery are carried out under normal pressure.
进一步地，步骤(3)中，所述萃取分层所采用的萃取剂选自二氯甲烷、石油醚、正己烷、三氯甲烷和一氯代苯中的至少一种。Further, in step (3), the extraction agent used in the extraction and layering is selected from at least one of dichloromethane, petroleum ether, n-hexane, chloroform and monochlorobenzene.
进一步地，步骤(3)中，所述稀酸选自醋酸水溶液、盐酸水溶液、硫酸水溶液和磷酸水溶液中的至少一种。Further, in step (3), the dilute acid is selected from at least one of acetic acid aqueous solution, hydrochloric acid aqueous solution, sulfuric acid aqueous solution and phosphoric acid aqueous solution.
进一步地，步骤(3)中，所述稀酸的浓度为3～10wt％。Further, in step (3), the concentration of the dilute acid is 3-10 wt%.
进一步地，本发明提供的假性紫罗兰酮的连续合成方法还包括将回收的丙酮和萃取分层所得水层循环作为原料使用。Further, the continuous synthesis method of pseudoionone provided by the present invention also includes recycling the recovered acetone and the aqueous layer obtained by extraction and layering as raw materials.
本发明一方面通过往无机碱中添加醋酸盐作为助催化剂、同时将Aldol缩合反应由传统恒温反应方式采用阶段控温方式代替，非常有利于假性紫罗兰酮转化率的提高；另一方向，由于采用阶段控温方式在管式反应器中反应之后利 用串联反应釜进行高温常压回收丙酮，不会产生双丙酮醇及异丙叉丙酮等副产物，不仅实现了未反应丙酮的回收，而且未反应的柠檬醛在串联反应釜中会继续进行反应，使得柠檬醛的转化率接近完全。此外，由于在Aldol缩合反应完成后，丙酮能够得以逐步回收，体系中的丙酮逐渐减少，有机物层与碱水层最终能够得以完全分离，实现了碱水层的回收套用。总之，本发明在较为经济性、环保的前提下，实现了假性紫罗兰酮的高收率和高纯度及原料柠檬醛的高转化率，且丙酮及碱水层实现了回收套用，降低了生产成本。此外，在碱催化剂中增加醋酸盐作为助催化剂，更有利于催化剂从反应产物中分离出来，且碱性催化剂与丙酮可回收套用，能够完美地解决液体碱催化剂难以从反应产物中分离且催化剂不能重复利用的缺陷。In the present invention, on the one hand, by adding acetate to the inorganic base as a co-catalyst, and at the same time, the Aldol condensation reaction is replaced by a traditional constant temperature reaction method by a stage temperature control method, which is very beneficial to the improvement of the pseudoionone conversion rate; on the other hand, Because the acetone is recovered at high temperature and normal pressure by using the series reaction kettle after the reaction in the tubular reactor by adopting the stage temperature control method, by-products such as diacetone alcohol and mesityl oxide will not be produced, not only the recovery of unreacted acetone is realized, but also the recovery of unreacted acetone is realized. The unreacted citral will continue to react in the series reaction kettle, so that the conversion rate of citral is close to complete. In addition, since the acetone can be gradually recovered after the Aldol condensation reaction is completed, the acetone in the system is gradually reduced, the organic matter layer and the alkaline water layer can finally be completely separated, and the recovery of the alkaline water layer is realized. In a word, under the premise of being relatively economical and environmentally friendly, the present invention achieves high yield and high purity of pseudo-ionone and high conversion rate of raw material citral, and acetone and alkaline water layer are recovered and applied mechanically, reducing production cost. In addition, adding acetate as a co-catalyst in the base catalyst is more conducive to the separation of the catalyst from the reaction product, and the base catalyst and acetone can be recycled and applied, which can perfectly solve the problem that the liquid base catalyst is difficult to separate from the reaction product and the catalyst Defects that cannot be reused.
具体实施方式Detailed ways
在本发明中，所述Aldol缩合反应主要在管式反应器中进行，并延续至多釜串联丙酮回收装置中，采用各釜温度逐渐升高的方式回收丙酮，能够使得柠檬醛基本完全转化。In the present invention, the Aldol condensation reaction is mainly carried out in a tubular reactor, and is extended to a multi-tank series connection acetone recovery device, and the acetone is recovered in a manner that the temperature of each kettle is gradually increased, so that citral can be basically completely converted.
在本发明中，所述管式反应器沿着物流方向依次包括反应段Ⅰ、反应段Ⅱ和反应段Ⅲ。所述反应段Ⅰ、反应段Ⅱ和反应段Ⅲ的反应温度逐渐升高。具体地，所述反应段Ⅰ的反应温度为0～10℃，例如，可以为0℃、1℃、2℃、3℃、4℃、5℃、6℃、7℃、8℃、9℃、10℃等。所述反应段Ⅱ的反应温度为10～40℃，例如，可以为10℃、15℃、20℃、25℃、30℃、35℃、40℃等。所述反应段Ⅲ的反应温度为75～90℃，例如，可以为75℃、80℃、85℃、90℃等。所述管式反应器的材质通常为不锈钢、铁、铜、铝等，其传热效果较好，因此，上述反应温度可以通过管式反应器的环境温度得以控制。此外，所述反应段Ⅰ、反应段Ⅱ和反应段Ⅲ的长度优选各自独立地占管式反应器长度的1/4～1/2。所述管式反应器的规格可以根据实际情况进行合理选择，在一种具体实施方式中，所述管式反应器的内径φ为1～5mm，总长度L为1000～2000mm。In the present invention, the tubular reactor includes reaction section I, reaction section II and reaction section III in sequence along the flow direction. The reaction temperature of the reaction section I, the reaction section II and the reaction section III is gradually increased. Specifically, the reaction temperature of the reaction section I is 0 to 10°C, for example, it can be 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C , 10℃, etc. The reaction temperature of the reaction section II is 10-40°C, for example, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, and the like. The reaction temperature of the reaction section III is 75-90°C, for example, 75°C, 80°C, 85°C, 90°C, and the like. The material of the tubular reactor is usually stainless steel, iron, copper, aluminum, etc., and its heat transfer effect is good. Therefore, the above reaction temperature can be controlled by the ambient temperature of the tubular reactor. In addition, the lengths of the reaction section I, the reaction section II and the reaction section III preferably each independently occupy 1/4 to 1/2 of the length of the tubular reactor. The specification of the tubular reactor can be reasonably selected according to the actual situation. In a specific embodiment, the inner diameter φ of the tubular reactor is 1-5 mm, and the total length L is 1000-2000 mm.
本发明对将柠檬醛和丙酮与碱性催化剂连续引入管式反应器中的方式没有特别的限定，可以将柠檬醛和丙酮与碱性催化剂各自独立地引入管式反应器 中，也可以将柠檬醛和丙酮与碱性催化剂按照任意方式预混之后再引入管式反应器中。在一种优选实施方式中，将柠檬醛和丙酮与碱性催化剂连续引入管式反应器中的方式为将柠檬醛和丙酮混合后作为物料A，将碱性催化剂配制成质量浓度为0.1～2％的碱性催化剂水溶液后作为物料B，之后将物料A和物料B连续引入管式反应器中。此时，所述物料A的流速V 柠檬醛-丙酮优选为1～20mL/min，所述物料B的流速V 碱性催化剂优选为0.3～6.5mL/min。所述柠檬醛与丙酮的摩尔比优选为1:(10～20)。另外，所述Aldol缩合反应优选在常压下进行。 The present invention has no particular limitation on the way of continuously introducing citral and acetone and basic catalyst into the tubular reactor. Citral, acetone and basic catalyst can be introduced into the tubular reactor independently, or lemon Aldehyde and acetone are optionally premixed with the basic catalyst and then introduced into the tubular reactor. In a preferred embodiment, the way of continuously introducing citral and acetone and the basic catalyst into the tubular reactor is to mix citral and acetone as material A, and prepare the basic catalyst to a mass concentration of 0.1-2 % aqueous solution of basic catalyst is used as feed B, and then feed A and feed B are continuously introduced into the tubular reactor. At this time, the flow rate V of the material A citral-acetone is preferably 1-20 mL/min, and the flow rate V of the material B of the basic catalyst is preferably 0.3-6.5 mL/min. The molar ratio of the citral to acetone is preferably 1:(10-20). In addition, the Aldol condensation reaction is preferably carried out under normal pressure.
在本发明中，所述碱性催化剂中含有无机碱和醋酸盐。其中，醋酸盐作为助催化剂，将无机碱和醋酸盐复配使用，能够显著提高柠檬醛的转化率以及假性紫罗兰酮的收率。其中，所述碱性催化剂中无机碱与醋酸盐的质量比优选为(1～10):1。所述无机碱的具体实例包括但不限于：氢氧化钠、氢氧化钾、氢氧化钡、氢氧化镁和氢氧化锂中的至少一种。所述醋酸盐的具体实例包括但不限于：醋酸钠和/或醋酸钾。此外，所述碱性催化剂优选制成质量浓度为0.1～2％的碱性催化剂水溶液使用。In the present invention, the basic catalyst contains inorganic base and acetate. Among them, acetate is used as a co-catalyst, and inorganic base and acetate are used in combination, which can significantly improve the conversion rate of citral and the yield of pseudoionone. Wherein, the mass ratio of inorganic base to acetate in the basic catalyst is preferably (1-10):1. Specific examples of the inorganic base include, but are not limited to, at least one of sodium hydroxide, potassium hydroxide, barium hydroxide, magnesium hydroxide and lithium hydroxide. Specific examples of the acetate salt include, but are not limited to: sodium acetate and/or potassium acetate. In addition, the basic catalyst is preferably used as a basic catalyst aqueous solution with a mass concentration of 0.1 to 2%.
在本发明中，所述丙酮回收装置为多釜串联装置，此时，不仅能够使得柠檬醛进一步转为假性紫罗兰酮，而且采用各釜温度逐渐升高的方式还能够实现丙酮的高效回收。所述丙酮回收装置可以为二釜串联装置、三釜串联装置或四釜串联装置，优选为三釜串联装置或四釜串联装置，最优选为三釜串联装置。在一种优选实施方式中，所述三釜串联装置包括第一反应釜、第二反应釜和第三反应釜，第一反应釜的温度控制在85～87℃，第二反应釜的温度控制在87～88℃，第三反应釜的温度控制在88～90℃。此时，所述第一反应釜蒸出的溶剂中，丙酮和水的体积比为(92～96):(4～8)，蒸出量优选占总量的60～85％；所述第二反应釜蒸出的溶剂中，丙酮和水的体积比为(90～93):(7～10)，蒸出量优选占总量的15～25％；所述第三反应釜蒸出的溶剂中，丙酮和水的体积比为(85～90):(10～15)，蒸出量优选占总量的5～15％。所述缩合反应产物依次通过丙酮回收装置的各个串联反应釜，且在多釜串联装置中优选采用溢流方式传输。丙酮回收优选在常压下进行。此外，回收的丙酮可以作为原料循环使用。In the present invention, the acetone recovery device is a multi-tank series device, at this time, not only can citral be further converted into pseudo-ionone, but also the efficient recovery of acetone can be realized by adopting the method that the temperature of each kettle is gradually increased. The acetone recovery device can be a two-tank series device, a three-tank series device or a four-tank series device, preferably a three-tank series device or a four-tank series device, and most preferably a three-tank series device. In a preferred embodiment, the three-tank series device comprises a first reactor, a second reactor and a third reactor, the temperature of the first reactor is controlled at 85-87°C, and the temperature of the second reactor is controlled at 85-87° C. At 87～88 ℃, the temperature of the third reaction kettle is controlled at 88～90 ℃. At this moment, in the solvent steamed from the first reaction kettle, the volume ratio of acetone and water is (92～96):(4～8), and the steaming amount preferably accounts for 60～85% of the total amount; In the solvent that two reaction stills steam, the volume ratio of acetone and water is (90～93): (7～10), and the steaming amount preferably accounts for 15～25% of the total amount; In the solvent, the volume ratio of acetone and water is (85-90): (10-15), and the amount of distillation preferably accounts for 5-15% of the total. The condensation reaction product is successively passed through each series reaction kettle of the acetone recovery device, and is preferably transported in an overflow mode in a multi-tank series device. Acetone recovery is preferably carried out under normal pressure. In addition, the recovered acetone can be recycled as a raw material.
在本发明中，将脱丙酮产物进行萃取分层的目的是为了对假性紫罗兰酮进 行纯化并对碱性催化剂进行回收。所述萃取分层采用的萃取剂的具体实例包括但不限于：二氯甲烷、石油醚、正己烷、三氯甲烷和一氯代苯中的至少一种。所述萃取分层所得油层为假性紫罗兰酮层，该油层用稀酸进行中和便得到假性紫罗兰酮。其中，所述稀酸的具体实例包括但不限于：醋酸水溶液、盐酸水溶液、硫酸水溶液和磷酸水溶液中的至少一种。所述稀酸的浓度优选为3～10wt％。所述萃取分层所得水层为富碱液层，可以作为催化剂循环使用。In the present invention, the purpose of extracting and stratifying the deacetone product is to purify the pseudoionone and recover the basic catalyst. Specific examples of the extractant used in the extraction and layering include, but are not limited to, at least one of dichloromethane, petroleum ether, n-hexane, chloroform and monochlorobenzene. The oil layer obtained by the extraction and layering is a pseudo-ionone layer, and the oil layer is neutralized with dilute acid to obtain pseudo-ionone. Wherein, specific examples of the dilute acid include, but are not limited to, at least one of an aqueous acetic acid solution, an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, and an aqueous phosphoric acid solution. The concentration of the dilute acid is preferably 3 to 10 wt %. The water layer obtained by the extraction and layering is an alkali-rich liquid layer, which can be recycled as a catalyst.
以下将通过实施例对本发明进行详细描述。所述实施例的示例旨在用于解释本发明，而不能理解为对本发明的限制。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。The present invention will be described in detail below by means of examples. The examples of the embodiments are intended to explain the present invention and should not be construed to limit the present invention. If no specific technology or condition is indicated in the examples, the technology or condition described in the literature in the field or the product specification is used. The reagents or instruments used without the manufacturer's indication are conventional products that can be obtained from the market.
实施例1Example 1
(1)将柠檬醛(质量含量为97％)与丙酮以1:15的摩尔比连续混匀，将质量比为4:1的氢氧化钠和醋酸钠溶于水中配制成质量浓度为1％的碱溶液。将混匀的柠檬醛-丙酮溶液按照12mL/min的流速、碱溶液按照4mL/min的流速引入管道反应器(内径φ为3mm，总长度L为1500mm，不锈钢(304)管道)中，所述管道反应器沿着物流方向依次包括长度相等的反应段Ⅰ、反应段Ⅱ和反应段Ⅲ，反应段Ⅰ外温为5℃，反应段Ⅱ外温为15℃，反应段Ⅲ外温为85℃。(1) Continuously mix citral (mass content of 97%) and acetone at a molar ratio of 1:15, dissolve sodium hydroxide and sodium acetate with a mass ratio of 4:1 in water to prepare a mass concentration of 1% alkaline solution. The mixed citral-acetone solution was introduced into the pipeline reactor (inner diameter φ was 3mm, total length L was 1500mm, stainless steel (304) pipeline) according to the flow rate of 12mL/min, and the alkali solution was introduced into the pipeline reactor according to the flow rate of 4mL/min. The pipeline reactor includes reaction section I, reaction section II and reaction section III of equal length in turn along the flow direction. The external temperature of reaction section I is 5 °C, the external temperature of reaction section II is 15 °C, and the external temperature of reaction section III is 85 °C. .
(2)从管道反应器流出的反应液进入到三联反应釜中进行未反应丙酮的回收，第一反应釜的外温为86℃，第二反应釜的外温为88℃，第三反应釜的外温为90℃；第一反应釜回收的溶剂量为总回收量的80％，丙酮和水的体积比为96:4；第二反应釜回收的溶剂量为总回收量的15％，丙酮和水的体积比为92:8；第三反应釜回收的溶剂量为总回收量的5％，丙酮和水的体积比为89:11。(2) the reaction solution flowing out from the pipeline reactor enters into the triple reactor and carries out the recovery of unreacted acetone, the external temperature of the first reactor is 86 ℃, the external temperature of the second reactor is 88 ℃, the third reactor The external temperature is 90 ℃; The amount of solvent recovered by the first reactor is 80% of the total recovery, and the volume ratio of acetone and water is 96:4; The amount of solvent recovered by the second reactor is 15% of the total recovery, The volume ratio of acetone and water is 92:8; the amount of solvent recovered in the third reactor is 5% of the total recovery amount, and the volume ratio of acetone and water is 89:11.
(3)从三联反应釜流出的脱丙酮产物进入萃取装置中，加入二氯甲烷萃取剂进行萃取分层，所得假性紫罗兰酮粗油用质量浓度为5％的醋酸水溶液中和至pH值为7左右。(3) the deacetone product flowing out from the triple reaction kettle enters the extraction device, and the dichloromethane extractant is added to carry out the extraction layering, and the obtained pseudoionone crude oil is neutralized to a pH value of 5% with an aqueous acetic acid solution with a mass concentration of 5%. 7 or so.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油19.5g，假性紫罗兰酮含量92.5％，柠檬醛转化率99.8％，假性紫罗兰酮收率96.85％。When the citral injection amount was 15.2g, the pseudoionone crude oil was 19.5g, the pseudoionone content was 92.5%, the citral conversion rate was 99.8%, and the pseudoionone yield was 96.85%.
总回收丙酮110mL，回收溶剂丙酮含量95.1％，回收溶剂含水量4.8％。A total of 110 mL of acetone was recovered, the acetone content of the recovered solvent was 95.1%, and the water content of the recovered solvent was 4.8%.
萃取分层后水层体积38.5mL，碱含量1％。After extraction and separation, the volume of the water layer was 38.5 mL, and the alkali content was 1%.
实施例2Example 2
按照实施例1的方法制备假性紫罗兰酮，不同的是，步骤(1)中柠檬醛与丙酮的摩尔比调整为1:10，醋酸钠替换为醋酸钾，氢氧化钠和醋酸钾的质量比调整为5:1，柠檬醛-丙酮溶液的流速调整为10mL/min，碱溶液的流速调整为1mL/min，反应段Ⅰ、反应段Ⅱ和反应段Ⅲ的外温分别调整为2℃、10℃、75℃；步骤(2)中，第一反应釜回收的溶剂量为总回收量的75％，丙酮和水的体积比96:4，第二反应釜回收的溶剂量为总回收量的15％，丙酮和水的体积比92:8，第三反应釜回收的溶剂量为总回收量的10％，丙酮和水的体积比85:15，余同实施例1。Prepare pseudoionone according to the method of embodiment 1, the difference is that in step (1), the mol ratio of citral and acetone is adjusted to 1:10, and sodium acetate is replaced by potassium acetate, and the mass ratio of sodium hydroxide and potassium acetate is Adjusted to 5:1, the flow rate of the citral-acetone solution was adjusted to 10 mL/min, the flow rate of the alkali solution was adjusted to 1 mL/min, and the external temperatures of reaction section I, reaction section II and reaction section III were adjusted to 2 °C and 10 °C, respectively. ℃, 75 ℃; In step (2), the amount of solvent recovered by the first reactor is 75% of the total recovery, the volume ratio of acetone and water is 96:4, and the amount of solvent recovered by the second reactor is 75% of the total recovery. 15%, the volume ratio of acetone and water is 92:8, the amount of solvent recovered in the third reactor is 10% of the total recovery amount, and the volume ratio of acetone and water is 85:15, and the remainder is the same as in Example 1.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油18.9g，假性紫罗兰酮含量91.2％，柠檬醛转化率为99.4％，假性紫罗兰酮收率92.55％。When the citral injection amount was 15.2g, the pseudoionone crude oil was 18.9g, the pseudoionone content was 91.2%, the citral conversion rate was 99.4%, and the pseudoionone yield was 92.55%.
总回收丙酮104mL，回收溶剂丙酮含量95.3％，回收溶剂含水量4.7％。The total recovered acetone was 104 mL, the recovered solvent had an acetone content of 95.3%, and the recovered solvent had a water content of 4.7%.
萃取分层后水层体积38.3mL，碱含量1％。After extraction and separation, the volume of the water layer was 38.3 mL, and the alkali content was 1%.
实施例3Example 3
按照实施例1的方法制备假性紫罗兰酮，不同的是，步骤(2)中，将三联反应釜替换为四联反应釜，且第一反应釜的温度控制在85℃，回收的溶剂量占总回收量的50％，丙酮和水的体积比为94:6；第二反应釜的温度控制在86℃，回收的溶剂量占总回收量的35％，丙酮和水的体积比为92:8；第三反应釜的温度控制在87℃，回收的溶剂量占总回收量的10％，丙酮和水的体积比为90:10；第四反应釜的温度控制在88℃，回收的溶剂量占总回收量的5％，丙酮和水的体积比为89:11，余同实施例1。Prepare pseudoionone according to the method of embodiment 1, the difference is that in step (2), triple reaction still is replaced with quadruple reaction still, and the temperature of the first reaction still is controlled at 85 ℃, and the amount of recovered solvent accounts for 50% of the total recovery, the volume ratio of acetone and water is 94:6; the temperature of the second reactor is controlled at 86 ° C, the amount of solvent recovered accounts for 35% of the total recovery, and the volume ratio of acetone and water is 92: 8; The temperature of the 3rd reactor is controlled at 87 ℃, and the amount of solvent recovered accounts for 10% of the total recovery, and the volume ratio of acetone and water is 90:10; the temperature of the 4th reactor is controlled at 88 ℃, and the recovered solvent The amount accounts for 5% of the total recovery amount, and the volume ratio of acetone and water is 89:11, and the rest is the same as in Example 1.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油18.87g，假性紫 罗兰酮含量91.9％，柠檬醛转化率99.5％，假性紫罗兰酮收率93.11％。When the citral injection amount was 15.2g, the pseudoionone crude oil was finally obtained 18.87g, the pseudoionone content was 91.9%, the citral conversion rate was 99.5%, and the pseudoionone yield was 93.11%.
总回收丙酮108mL，回收溶剂丙酮含量92.6％，回收溶剂含水量6.9％。The total recovered acetone was 108 mL, the recovered solvent had an acetone content of 92.6%, and the recovered solvent had a water content of 6.9%.
萃取分层后水层体积37.9mL，碱含量1％。After extraction and separation, the volume of the water layer was 37.9 mL, and the alkali content was 1%.
实施例4Example 4
将实施例1步骤(1)中的氢氧化钠-醋酸钠碱溶液替换为实施例1中萃取分层回收的碱水层，并补加质量比为4:1的氢氧化钠和醋酸钠以使得碱水层的质量浓度为1％，余同实施例1。The sodium hydroxide-sodium acetate alkali solution in the step (1) of Example 1 is replaced with the alkaline water layer recovered by extraction and layering in Example 1, and the addition of the sodium hydroxide and sodium acetate that the mass ratio is 4:1 to The mass concentration of the alkaline water layer was made 1%, and the rest was the same as in Example 1.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油18.9g，假性紫罗兰酮含量91.7％，柠檬醛转化率99.2％，假性紫罗兰酮收率93.06％。When the citral injection amount was 15.2g, the pseudoionone crude oil was 18.9g, the pseudoionone content was 91.7%, the citral conversion rate was 99.2%, and the pseudoionone yield was 93.06%.
总回收丙酮112mL，回收溶剂丙酮含量94.5％，回收溶剂含水量4.9％。The total recovered acetone was 112 mL, the recovered solvent had an acetone content of 94.5%, and the recovered solvent had a water content of 4.9%.
萃取分层后水层体积37.7mL，碱含量1％。After extraction and separation, the volume of the water layer was 37.7 mL, and the alkali content was 1%.
将萃取分层后的碱水层再次进行循环套用，每次套用之前经过检测标定后，将碱量增加到所需的量(质量浓度为1％)，余同实施例1，结果见表1。The alkaline water layer after the extraction and layering is recirculated and applied again, and after the detection and calibration before each application, the amount of alkali is increased to the required amount (mass concentration is 1%), and the remainder is the same as in Example 1, and the results are shown in Table 1 .
表1Table 1
套用次数number of applications 22 33 44 55
假性紫罗兰酮含量Pseudo-ionone content 92.1％92.1% 91.5％91.5% 91.2％91.2% 92.0％92.0%
假性紫罗兰酮收率Pseudo-ionone yield 93.1％93.1% 92.6％92.6% 92.2％92.2% 93.0％93.0%
从表1的结果可以看出，碱水层经过检测标定后，将碱量增加到所需的量用于催化反应，试验效果良好。由此可见，本发明可实现碱性催化剂的回收套用，减少环境污染。It can be seen from the results in Table 1 that after the alkali water layer is detected and calibrated, the amount of alkali is increased to the required amount for catalytic reaction, and the test effect is good. It can be seen that the present invention can realize the recovery and application of the basic catalyst and reduce environmental pollution.
对比例1Comparative Example 1
按照实施例1的方法制备假性紫罗兰酮，不同的是，步骤(2)中，将三联反应釜替换为单釜装置，并将单釜装置的温度控制在90℃且保温时间控制在60min，余同实施例1。Pseudo-ionone is prepared according to the method of embodiment 1, the difference is that in step (2), the triple reaction kettle is replaced with a single kettle device, and the temperature of the single kettle device is controlled at 90 ℃ and the holding time is controlled at 60min, The same as in Example 1.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油18.1g，假性紫罗兰酮含量85.3％，柠檬醛转化率99.2％，假性紫罗兰酮收率82.9％。When the citral injection amount was 15.2g, the pseudoionone crude oil was finally obtained 18.1g, the pseudoionone content was 85.3%, the citral conversion rate was 99.2%, and the pseudoionone yield was 82.9%.
总回收丙酮109mL，回收溶剂丙酮含量94.3％，回收溶剂含水量5.6％。The total recovered acetone was 109 mL, the recovered solvent had an acetone content of 94.3%, and the recovered solvent had a water content of 5.6%.
萃取分层后水层体积37.3mL，碱含量1％。After extraction and separation, the volume of the water layer was 37.3 mL, and the alkali content was 1%.
对比例2Comparative Example 2
按照实施例1的方法制备假性紫罗兰酮，不同的是，将步骤(1)中的氢氧化钠-醋酸钠碱溶液替换为质量浓度为1％的氢氧化钠水溶液(即未添加醋酸钠)，余同实施例1。Pseudo-ionone was prepared according to the method of Example 1, the difference was that the sodium hydroxide-sodium acetate alkali solution in step (1) was replaced with an aqueous sodium hydroxide solution with a mass concentration of 1% (that is, no sodium acetate was added) , the same as in Example 1.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油19.1g，假性紫罗兰酮含量85.6％，柠檬醛转化率98.6％，假性紫罗兰酮收率87.78％。When the citral injection amount was 15.2g, the pseudoionone crude oil was 19.1g, the pseudoionone content was 85.6%, the citral conversion rate was 98.6%, and the pseudoionone yield was 87.78%.
总回收丙酮108mL，回收溶剂丙酮含量94.3％，回收溶剂含水量4.7％。The total recovered acetone was 108 mL, the recovered solvent had an acetone content of 94.3%, and the recovered solvent had a water content of 4.7%.
萃取分层后水层体积38.5mL，碱含量1％。After extraction and separation, the volume of the water layer was 38.5 mL, and the alkali content was 1%.
对比例3Comparative Example 3
按照实施例1的方法制备假性紫罗兰酮，不同的是，管道反应器的外温均设置为5℃，余同实施例1。The pseudoionone was prepared according to the method of Example 1, except that the external temperature of the pipeline reactor was set to 5°C, and the rest was the same as that of Example 1.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油18.3g，假性紫罗兰酮含量85.4％，柠檬醛转化率96.3％，假性紫罗兰酮收率83.91％。When the citral injection amount was 15.2g, the pseudoionone crude oil was 18.3g, the pseudoionone content was 85.4%, the citral conversion rate was 96.3%, and the pseudoionone yield was 83.91%.
总回收丙酮110mL，回收溶剂丙酮含量94.6％，回收溶剂含水量4.7％。A total of 110 mL of acetone was recovered, the acetone content of the recovered solvent was 94.6%, and the water content of the recovered solvent was 4.7%.
萃取分层后水层体积38.2mL，碱含量1％。After extraction and separation, the volume of the water layer was 38.2 mL, and the alkali content was 1%.
对比例4Comparative Example 4
按照实施例1的方法制备假性紫罗兰酮，不同的是，管道反应器的外温均设置为15℃，余同实施例1。The pseudoionone was prepared according to the method of Example 1, except that the external temperature of the pipeline reactor was set to 15° C., and the rest was the same as that of Example 1.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油18.7g，假性紫罗兰酮含量86.8％，柠檬醛转化率97.5％，假性紫罗兰酮收率87.15％。When the injection amount of citral was 15.2g, the pseudoionone crude oil was 18.7g, the pseudoionone content was 86.8%, the citral conversion rate was 97.5%, and the pseudoionone yield was 87.15%.
总回收丙酮106mL，回收溶剂丙酮含量95.1％，回收溶剂含水量4.5％。The total recovered acetone was 106 mL, the recovered solvent had an acetone content of 95.1%, and the recovered solvent had a water content of 4.5%.
萃取分层后水层体积38.5mL，碱含量1％。After extraction and separation, the volume of the water layer was 38.5 mL, and the alkali content was 1%.
对比例5Comparative Example 5
按照实施例1的方法制备假性紫罗兰酮，不同的是，管道反应器的外温均设置为85℃，余同实施例1。The pseudoionone was prepared according to the method of Example 1, except that the external temperature of the pipeline reactor was set to 85° C., and the rest was the same as that of Example 1.
当柠檬醛进样量为15.2g时，最终所得假性紫罗兰酮粗油18.5g，假性紫罗兰酮含量88.6％，柠檬醛转化率99.2％，假性紫罗兰酮收率88.0％。When the citral injection amount was 15.2g, the pseudoionone crude oil was 18.5g, the pseudoionone content was 88.6%, the citral conversion rate was 99.2%, and the pseudoionone yield was 88.0%.
总回收丙酮107mL，回收溶剂丙酮含量95.6％，回收溶剂含水量4.6％。The total recovered acetone was 107 mL, the recovered solvent had an acetone content of 95.6%, and the recovered solvent had a water content of 4.6%.
萃取分层后水层体积39.1mL，碱含量1％。After extraction and separation, the volume of the water layer was 39.1 mL, and the alkali content was 1%.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在不脱离本发明的原理和宗旨的情况下在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and those of ordinary skill in the art will not depart from the principles and spirit of the present invention Variations, modifications, substitutions, and alterations to the above-described embodiments are possible within the scope of the present invention without departing from the scope of the present invention.

Claims (10)

  1. 一种假性紫罗兰酮的连续合成方法，其特征在于，该方法包括：A kind of continuous synthesis method of pseudo-ionone, it is characterised in that the method comprises:
    (1)将柠檬醛和丙酮与碱性催化剂连续引入管式反应器中进行Aldol缩合反应，所述碱性催化剂中含有无机碱和醋酸盐，所述管式反应器沿着物流方向依次包括反应段Ⅰ、反应段Ⅱ和反应段Ⅲ，所述反应段Ⅰ、反应段Ⅱ和反应段Ⅲ的反应温度逐渐升高且分别为0～10℃、10～40℃和75～90℃，得到缩合反应产物；(1) Continuously introduce citral and acetone and a basic catalyst into a tubular reactor to carry out Aldol condensation reaction, the basic catalyst contains inorganic base and acetate, and the tubular reactor sequentially includes along the flow direction Reaction section I, reaction section II and reaction section III, the reaction temperatures of the reaction section I, reaction section II and reaction section III gradually increase and are respectively 0 ~ 10 ℃, 10 ~ 40 ℃ and 75 ~ 90 ℃ to obtain condensation reaction product;
    (2)将缩合反应产物连续引入丙酮回收装置中进行丙酮回收，所述丙酮回收装置为多釜串联装置，且缩合反应产物在各釜中回收丙酮的温度逐渐升高，得到脱丙酮产物；(2) the condensation reaction product is continuously introduced into the acetone recovery device to carry out acetone recovery, and the acetone recovery device is a multi-tank series device, and the temperature at which the condensation reaction product reclaims acetone in each kettle gradually rises to obtain a deacetone product;
    (3)将脱丙酮产物进行萃取分层，所得油层用稀酸进行中和，得到假性紫罗兰酮。(3) extracting and stratifying the deacetone product, and neutralizing the obtained oil layer with dilute acid to obtain pseudoionone.
  2. 根据权利要求1所述的假性紫罗兰酮的连续合成方法，其特征在于，步骤(1)中，所述柠檬醛与丙酮的摩尔比为1:(10～20)。The continuous synthesis method of pseudoionone according to claim 1, wherein, in step (1), the molar ratio of citral and acetone is 1:(10～20).
  3. 根据权利要求1所述的假性紫罗兰酮的连续合成方法，其特征在于，步骤(1)中，所述碱性催化剂中无机碱与醋酸盐的质量比为(1～10):1；优选地，所述无机碱选自氢氧化钠、氢氧化钾、氢氧化钡、氢氧化镁和氢氧化锂中的至少一种；优选地，所述醋酸盐为醋酸钠和/或醋酸钾。The continuous synthesis method of pseudoionone according to claim 1, is characterized in that, in step (1), the mass ratio of inorganic base and acetate in described basic catalyst is (1～10): 1; Preferably, the inorganic base is selected from at least one of sodium hydroxide, potassium hydroxide, barium hydroxide, magnesium hydroxide and lithium hydroxide; preferably, the acetate salt is sodium acetate and/or potassium acetate .
  4. 根据权利要求1所述的假性紫罗兰酮的连续合成方法，其特征在于，步骤(1)中，所述管式反应器的内径φ为1～5mm，总长度L为1000～2000mm；所述反应段Ⅰ、反应段Ⅱ和反应段Ⅲ的长度各自独立地占管式反应器长度的1/4～1/2。The continuous method for synthesizing pseudoionone according to claim 1, wherein in step (1), the inner diameter φ of the tubular reactor is 1-5 mm, and the total length L is 1000-2000 mm; the The lengths of reaction section I, reaction section II and reaction section III each independently occupy 1/4 to 1/2 of the length of the tubular reactor.
  5. 根据权利要求4所述的假性紫罗兰酮的连续合成方法，其特征在于，步骤(1)中，将柠檬醛和丙酮与碱性催化剂连续引入管式反应器中的方式为将柠檬醛和丙酮混合后作为物料A，将碱性催化剂配制成质量浓度为0.1～2％的碱性催化剂水溶液后作为物料B，之后将物料A和物料B连续引入管式反应器中；优选地，所述物料A的流速V 柠檬醛-丙酮为1～20mL/min，所述物料B的流速V 碱性催化剂为0.3～6.5mL/min。 The continuous synthesis method of pseudoionone according to claim 4, is characterized in that, in step (1), the mode that citral and acetone and basic catalyst are continuously introduced into tubular reactor is to mix citral and acetone After mixing, it is used as material A, and the basic catalyst is prepared into a basic catalyst aqueous solution with a mass concentration of 0.1 to 2% as material B, and then material A and material B are continuously introduced into the tubular reactor; preferably, the material The flow rate V of A citral-acetone is 1-20 mL/min, and the flow rate V of the material B is 0.3-6.5 mL/min of the basic catalyst .
  6. 根据权利要求1～5中任意一项所述的假性紫罗兰酮的连续合成方法，其特征在于，步骤(2)中，所述丙酮回收装置为三釜串联装置或四釜串联装置；优选地，所述三釜串联装置包括第一反应釜、第二反应釜和第三反应釜，第一反应釜的温度控制在85～87℃，第二反应釜的温度控制在87～88℃，第三反应釜的温度控制在88～90℃；优选地，所述缩合反应产物在多釜串联装置中的传输方式为溢流。The continuous method for synthesizing pseudoionone according to any one of claims 1 to 5, characterized in that, in step (2), the acetone recovery device is a three-tank series device or a four-tank series device; preferably, The three-reactor series device comprises a first reactor, a second reactor and a third reactor, the temperature of the first reactor is controlled at 85-87°C, the temperature of the second reactor is controlled at 87-88°C, The temperature of the reaction kettle is controlled at 88-90°C; preferably, the conveying mode of the condensation reaction product in the multi-tank series device is overflow.
  7. 根据权利要求1～5中任意一项所述的假性紫罗兰酮的连续合成方法，其特征在于，所述Aldol缩合反应和丙酮回收均在常压下进行。The continuous method for synthesizing pseudoionone according to any one of claims 1 to 5, wherein the Aldol condensation reaction and the acetone recovery are both carried out under normal pressure.
  8. 根据权利要求1～5中任意一项所述的假性紫罗兰酮的连续合成方法，其特征在于，步骤(3)中，所述萃取分层所采用的萃取剂选自二氯甲烷、石油醚、正己烷、三氯甲烷和一氯代苯中的至少一种。The continuous synthesis method of pseudoionone according to any one of claims 1 to 5, characterized in that, in step (3), the extraction agent used in the extraction and layering is selected from methylene chloride, petroleum ether , at least one of n-hexane, chloroform and monochlorobenzene.
  9. 根据权利要求1～5中任意一项所述的假性紫罗兰酮的连续合成方法，其特征在于，步骤(3)中，所述稀酸选自醋酸水溶液、盐酸水溶液、硫酸水溶液和磷酸水溶液中的至少一种；所述稀酸的浓度为3～10wt％。The continuous synthesis method of pseudoionone according to any one of claims 1 to 5, wherein in step (3), the dilute acid is selected from aqueous acetic acid, aqueous hydrochloric acid, aqueous sulfuric acid and aqueous phosphoric acid At least one of the dilute acids; the concentration of the dilute acid is 3-10 wt%.
  10. 根据权利要求1～5中任意一项所述的假性紫罗兰酮的连续合成方法，其特征在于，该方法还包括将回收的丙酮和萃取分层所得水层循环作为原料使用。The continuous method for synthesizing pseudoionone according to any one of claims 1 to 5, wherein the method further comprises recycling the recovered acetone and the aqueous layer obtained by extraction and layering as raw materials.
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