A preparation device and method for β-ionone

Abstract

The present invention belongs to the field of fine chemical technology, and in particular to a kind of preparation device and method of β-ionone, the preparation device includes a mixing kettle, a mixing kettle outlet pipe, a strong acid storage tank, a catalyst-filled column and a washing kettle, wherein the catalyst-filled column, for filling a solid Lewis acid catalyst and carrying out a cyclization reaction, has a catalyst-filled column import and a catalyst-filled column export, and the catalyst-filled column import is communicated with the mixing kettle outlet pipe. The method uses the coordinated acid formed by Lewis acid and protic acid as a catalyst, assisted by chlorosulfonic acid to solve the adverse effects of protic acid containing water on the reaction. Reduced catalyst usage, reduced the number of catalysts entering wastewater, reduced the number of catalysts in wastewater, and reduced wastewater treatment costs.

Description

Technical Field

[0001] The present invention belongs to the technical field of fine chemicals, and in particular relates to a device and method for preparing beta-ionone. Background Art

[0002] β-ionone is a naturally occurring aromatic compound belonging to the terpenoid family, found widely in plants (such as violets, tomatoes, and carrots). Its chemical structure contains a conjugated double bond system, giving it a distinctive woody and fruity aroma. It is an important component of food flavorings and cosmetic fragrances, and is also used in the synthesis of vitamin A and carotenoids.

[0003] β-ionone is typically obtained by cyclizing pseudoionone in the presence of a strong acid catalyst, typically using sulfuric acid, fuming sulfuric acid, or perchloric acid. After the cyclization is complete, the reaction is terminated by quenching the reaction system with cold water. This preparation method suffers from the high use of acid catalysts, resulting in large amounts of wastewater and high wastewater treatment costs.

[0004] Chinese invention patent application publication number CN 113117753 A discloses a hydrophobic catalyst that catalyzes the reaction of pseudoionone with bisulfite to form an intermediate. The resulting intermediate then undergoes cyclization under the catalysis of an organic acid, which is then treated with a base to produce β-ionone. While this method can produce β-ionone in high yield, the complex catalyst preparation makes the indirect and complex preparation process uncompetitive.

[0005] Chinese invention patent application publication number CN 108329200 A discloses a method for preparing β-ionone using pseudoionone as a raw material. The pseudoionone undergoes a cyclization reaction catalyzed by sulfuric acid, followed by quenching. After quenching, nitric oxide gas is introduced into the reaction solution, followed by an isomerization reaction to obtain β-ionone. This preparation method suffers from the following issues: high sulfuric acid usage, a complex process, an unpleasant odor in the product, the formation of a gelatinous substance during washing, and a low product yield.

[0006] In summary, the existing technology generally has the following problems:

[0007] 1. The amount of wastewater is large, the treatment is difficult and the treatment cost is high;

[0008] 2. The prepared β-ionone has a burnt odor and needs to be deodorized. Summary of the Invention

[0009] In response to the above technical problems, the present invention aims to provide a device and method for preparing β-ionone with small amount of wastewater, low treatment difficulty, no odor and high yield.

[0010] The technical solutions of the present invention are as follows:

[0011] A device for preparing β-ionone, comprising:

[0012] A mixing kettle, used for mixing pseudoionone and protonic acid, wherein the mixing kettle has a material inlet and a material outlet;

[0013] a mixing kettle outlet pipe, connected to the material outlet of the mixing kettle;

[0014] A strong acid storage tank having a strong acid inlet and a strong acid outlet, wherein the strong acid outlet is connected to the mixing kettle outlet pipe through the storage tank outlet pipe;

[0015] A catalyst-filled column, for filling a solid Lewis acid catalyst and performing a cyclization reaction, having a catalyst-filled column inlet and a catalyst-filled column outlet, wherein the catalyst-filled column inlet is connected to the mixing kettle outlet pipe;

[0016] The washing kettle is used for receiving the cyclization liquid and performing post-processing, and has a water inlet and a cyclization liquid inlet. The cyclization liquid inlet is connected with the catalyst filling column outlet through a catalyst filling column outlet pipe.

[0017] In the present invention, pseudoionone is first uniformly mixed with a protic acid in a mixing kettle; then, a strong acid from a strong acid storage tank is slowly added to the mixture; the mixture of pseudoionone, protic acid, and strong acid then enters a catalyst-packed column for a cyclization reaction; finally, the cyclized liquid, after the cyclization reaction in the catalyst-packed column, enters a washing kettle for washing to obtain β-ionone. Unlike the preparation devices of the prior art, the present invention improves the prior art liquid-liquid phase preparation process to a liquid-solid phase preparation process, thereby reducing the amount of catalyst entering the wastewater, reducing the amount of wastewater to be treated, and reducing the cost of wastewater treatment. The use of a new catalytic system also achieves the goal of improving the quality and yield of β-ionone.

[0018] To further improve the preparation effect of the preparation device of the present invention, preferably, a delivery pump for transporting the material in the mixing kettle to the catalyst-packed column inlet is further provided on the mixing kettle outlet pipe and downstream of the connection between the strong acid outlet pipe and the mixing kettle outlet pipe. Simply relying on the static pressure of the liquid column cannot meet the use requirements of all working conditions. By providing a delivery pump, the installation of the device of the present invention is not limited by space, and the material flow entering the catalyst-packed column can be flexibly adjusted. By controlling the flow entering the catalyst-packed column, the residence time of the pseudoionone in the catalyst-packed column is controlled, and ultimately the conversion rate of the cyclization reaction is controlled. The inventors determined through a large number of comparative experiments that the optimal operating condition is a pseudoionone conversion rate of 99.6%. When the conversion rate is greater than 99.6%, it indicates that the β-ionone obtained after the reaction is completed has increased cascade side reactions. When the conversion rate is less than 99.6%, it is necessary to reduce the material flow entering the catalyst-packed column and extend the residence time.

[0019] Preferably, the catalyst packed column comprises a vertically arranged cylindrical body, a first end cap and a second end cap for sealing both ends of the cylindrical body, a plurality of tubes arranged in the body, and a first tube sheet and a second tube sheet sleeved on both ends of the tubes and fixing the tubes to the cylindrical body;

[0020] A filter plate is provided at the outlet of each tube array, and the interior of the tube array forms a catalyst filling cavity;

[0021] The catalyst filling column inlet and the catalyst filling column outlet are respectively arranged on the first head and the second head;

[0022] The first end cap's internal cavity forms the distribution space before the material enters the catalyst-filled chamber. After buffering within the first end cap's cavity, the material is evenly distributed and enters the various tube arrays. The second end cap's internal cavity forms the mixing space before the material leaves the catalyst-filled chamber. After buffering and mixing in the second end cap, the material leaves the catalyst-filled column. The first end cap's internal cavity, the second end cap's internal cavity, and the catalyst-filled chamber within the tube array together form the tube-side cavity.

[0023] The outer surface of the tubes, the inner surface of the cylindrical shell, the first tube sheet and the second tube sheet form a cooling medium cavity. A cooling medium inlet and a cooling medium outlet communicating with the cooling medium cavity are provided on the surface of the cylindrical shell.

[0024] The first and / or second end caps are selected from a spherical, elliptical, conical, and butterfly-shaped caps. Spherical caps have high pressure resistance but occupy a large space; conical caps have low pressure resistance but facilitate material distribution and collection; and elliptical caps are relatively more suitable for use in the field of fine chemical technology. The upper outer surface of the cylinder is provided with a cooling medium outlet connected to the cooling medium cavity, forming a passage for the cooling medium to leave the cooling medium cavity; the lower outer surface of the cylinder is provided with a cooling medium inlet connected to the cooling medium cavity, forming a passage for the cooling medium to enter the cooling medium cavity. The cooling medium cavity constitutes the shell-side cavity. A circular baffle can also be provided in the shell-side cavity to improve the cooling effect. The structure of the entire catalyst-packed column is similar to that of a single-pass shell-and-tube heat exchanger in the field of heat transfer technology, except that a filter plate is provided at the bottom of the tubes of the single-pass heat exchanger to isolate the catalyst within the tubes.

[0025] In order to further improve the preparation efficiency of the preparation device, preferably, the inlet of the mixing kettle includes a pseudoionone inlet for inputting pseudoionone and a protonic acid inlet for inputting protonic acid. The upper part of the mixing kettle can also be provided with a sight glass hole, a sight light hole and a spare inlet. The outlet of the mixing kettle includes an outlet for allowing the material to leave the mixing kettle, and an emptying port can also be provided as needed. The mixing kettle has a jacket, and the jacket has a refrigerant inlet for passing a cooling medium into the jacket, and a refrigerant outlet for allowing the refrigerant to leave the jacket. The main function of the jacket is to control the temperature of the material in the mixing kettle. In actual application, the material in the mixing kettle can be cooled by the jacket first, and the subsequent cyclization reaction can be carried out after reaching the required temperature.

[0026] The present invention also provides a method for preparing β-ionone using the above-mentioned preparation device, comprising:

[0027] The pseudoionone and the protonic acid are uniformly mixed in the mixing kettle and then introduced into the outlet pipe of the mixing kettle. At the same time, the strong acid in the strong acid storage tank is introduced into the outlet pipe of the mixing kettle. The mixed material in the outlet pipe of the mixing kettle then enters the catalyst-filled column for cyclization reaction. The cyclization liquid obtained after the reaction enters the washing kettle and is washed to obtain β-ionone. The catalyst-filled column is pre-filled with a solid Lewis acid catalyst.

[0028] While studying the cyclization reaction of pseudoionone, the inventors discovered that the acidity of the strong acid used as a catalyst has a significant impact on the selectivity of the cyclization reaction. The stronger the acid, the lower the cyclization reaction temperature can be, resulting in higher selectivity. Sulfuric acid, the most commonly used in the prior art, has a strong dehydrating property, resulting in a distinct burnt odor in the prepared β-ionone. A black colloidal suspension of unknown structure also forms during the washing process. To address this issue, the present invention utilizes a complex acid of a proton acid and a Lewis acid to catalyze the cyclization reaction of pseudoionone. The specific reaction equation for forming the complex acid is as follows:

[0029]

[0030] Due to the strong electrophilicity of Lewis acids, the acidity of complex acids is greater than that of simple proton acids.

[0031] In the preparation method described herein, pseudoionone and protic acid are uniformly mixed beforehand, and then a strong acid, chlorosulfonic acid, is added to the mixed materials. The strong acid serves to consume water from the protic acid, preventing it from causing catalyst loss in the catalyst column. Furthermore, the reaction between the strong acid and water forms protic acid and sulfuric acid, which promote the catalytic activity of the protic acid and the complexing acid.

[0032] Since the cyclization reaction is a highly exothermic reaction, preferably, the preparation method further comprises adding the pseudoionone and protonic acid into the mixing kettle for cooling, and then conveying the materials in the mixing kettle to the catalyst-filled column for reaction;

[0033] Alternatively, or alternatively, the production method further comprises cooling the pseudo-ionone mixed solution in a catalyst-filled column.

[0034] Precooling the pseudoionone and protic acid in the mixing vessel can reduce the cooling load of the subsequent cyclization reaction in the catalyst-packed column and improve the accuracy of temperature control in the catalyst-packed column. The cyclization reaction is highly exothermic, requiring a good heat exchange system to keep the reaction temperature within a reasonable range.

[0035] The catalytic system of the present invention includes a protonic acid, a strong acid, and a Lewis acid. The main active agent is the complex acid formed by the Lewis acid and the protonic acid, and the secondary agent is the sulfuric acid formed by the decomposition of the strong acid and the water in the protonic acid. This catalytic system can reduce the amount of catalyst used and reduce the difficulty of subsequent wastewater treatment. Preferably, the molar ratio of the protonic acid to the pseudoionone in the mixing kettle is controlled to be 0.01-0.05:1; and the protonic acid is selected from one of hydrochloric acid and hydrobromic acid. The actual catalytic system of the present invention is a two-way catalytic system, which reduces the amount of protonic acid catalyst through mutual cooperation.

[0036] Further preferably, the molar ratio of water in the protonic acid to chlorosulfonic acid is controlled to be 2.5-5.0:1. At this ratio, the chlorosulfonic acid can substantially completely absorb the water in the protonic acid, thereby preventing the loss of Lewis acid caused by water entering the catalyst-packed column and the increased cost caused by adding too much chlorosulfonic acid. Furthermore, the process has optimal selectivity. Using the above ratio, even if the water in the protonic acid is not completely consumed, the Lewis acid in the catalyst-packed column will not be lost. At this point, only a small amount of sulfuric acid formed by the hydrolysis of chlorosulfonic acid and a very small amount of protonic acid enter the wastewater. The inorganic acid content in the wastewater is low, making it easier to process. A large amount of Lewis acid remains in the catalyst-packed column, allowing the next batch of catalytic reactions to proceed.

[0037] Unlike existing technologies, the present invention utilizes a fixed-bed liquid-solid phase catalytic cyclization reaction apparatus to perform the cyclization reaction of pseudoionone to β-ionone. Preferably, the mass ratio of the catalyst to the pseudoionone is controlled to be 0.2-0.5:1, and the catalyst is selected from zinc chloride or zinc bromide corresponding to the protic acid anion. Although the catalyst column is loaded with a Lewis acid catalyst, the primary catalyst is the complexing acid formed by the combination of the Lewis acid and the protic acid. The molar weight of the Lewis acid is much greater than that of the protic acid. This is done, firstly, to maximize the ionization of the protic acid and form the complexing acid, thereby avoiding the addition side reaction of the Lewis acid alone to the pseudoionone. Secondly, the greater the amount of Lewis acid loaded into the catalyst column, the more evenly the pseudoionone is distributed throughout the tubes.

[0038] To reduce the addition reaction of the proton acid with pseudoionone or β-ionone and improve the selectivity of the cyclization reaction, it is preferred that the mixing process and / or the cyclization reaction process be carried out under preset temperature conditions, wherein the preset temperature is 10-30°C. The low temperature reaction can reduce the number of side reactions of the proton acid with pseudoionone or β-ionone, and can also reduce the number of cyclization side reactions. Under the action of the super-strong complexing acid, the lower cyclization reaction temperature is more conducive to the formation of β-ionone, reducing the amount of α-ionone and γ-ionone formed, and reducing the difficulty of separation.

[0039] Compared with the prior art, the present invention has the following advantages:

[0040] (1) The device and preparation method of the present invention require less catalyst feed, less catalyst is introduced into the wastewater, and the wastewater treatment is less difficult;

[0041] (2) The device and preparation method of the present invention have high selectivity and high yield of β-ionone. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is a schematic diagram of the preparation device of the present invention.

[0043] Among them: Mark 1-mixing kettle; Mark 11-pseudoionone inlet; Mark 12-protonic acid inlet; Mark 13-refrigerant inlet; Mark 14-material outlet; Mark 141-mixing kettle outlet pipe; Mark 2-strong acid storage tank; Mark 21-strong acid inlet; Mark 22-strong acid outlet; Mark 221-storage tank outlet pipe; Mark 3-delivery pump; Mark 4-catalyst filling column; Mark 41-cylindrical barrel; Mark 42-tube; Mark 43-first tube sheet; Mark 44-second tube sheet; Mark 45-filter plate; Mark 46-catalyst filling column inlet; Mark 47-catalyst filling column outlet; Mark 471-catalyst filling column outlet pipe; Mark 48-cooling medium inlet; Mark 5-washing kettle; Mark 51-water inlet; Mark 52-cyclization liquid inlet; Mark 53-washing kettle outlet. DETAILED DESCRIPTION

[0044] Figure 1 Schematic diagram of the preparation device of the present invention, the preparation device comprises: a mixing kettle 1, a strong acid storage tank 2, a catalyst filling column 4 and a washing kettle 5.

[0045] The mixing kettle 1 is used to mix pseudoionone and protonic acid. The mixing kettle 1 has a material inlet and a material outlet 14 . The material outlet 14 is connected to the mixing kettle outlet pipe 141 . The material inlet includes a pseudoionone inlet 11 and a protonic acid inlet 12 .

[0046] The strong acid storage tank 2 has a strong acid inlet 21 and a strong acid outlet 22, and the strong acid outlet 22 is connected to the storage tank outlet pipe 221;

[0047] The catalyst-packed column 4 comprises a vertically arranged cylindrical body 41 and a tube array 42 arranged in the cylindrical body 41; the upper outer wall of the tube array 42 is connected to the upper inner wall of the cylindrical body 41 through a first tube sheet 43, and the lower outer wall of the tube array 42 is connected to the lower inner wall of the cylindrical body 41 through a second tube sheet 44; a filter plate 45 is provided at the bottom of the tube array 42, and the interior of the tube array 42 constitutes a catalyst-packed cavity; the outer surface of the tube array 42, the inner surface of the cylindrical body 41, the lower surface of the first tube sheet 43, and the upper surface of the second tube sheet 44 together constitute a cooling medium cavity; the upper portion of the catalyst-packed column 4 comprises a catalyst-packed column inlet 46, and the lower portion of the catalyst-packed column 4 comprises a catalyst-packed column outlet 47 communicating with the catalyst-packed cavity, and the catalyst-packed column outlet 47 is communicated with a catalyst-packed column outlet pipe 471;

[0048] A washing tank 5 having a water inlet 51, a cyclization liquid inlet 52 and a washing tank outlet 53;

[0049] The mixing kettle outlet pipe 141 is connected to the catalyst filling column inlet 46 ; the catalyst filling column outlet pipe 471 is connected to the washing kettle cyclization liquid inlet 52 ; and the storage tank outlet pipe 221 is connected to the mixing kettle outlet pipe 141 .

[0050] A delivery pump 3 for delivering the material in the mixing kettle 1 to the catalyst filling column inlet 46 is further provided on the mixing kettle outlet pipe 141 and downstream of the connection between the storage tank outlet pipe 221 and the mixing kettle outlet pipe 141 .

[0051] The catalyst-filled column 4 has a first head at the upper part, and the catalyst-filled column 4 has a second head at the lower part; the catalyst-filled column inlet 46 is provided on the first head and is connected to the internal cavity of the first head; the catalyst-filled column outlet 47 is provided on the second head and is connected to the internal cavity of the second head; the first head, and / or the second head are selected from one of a spherical head, an elliptical head, a conical head, and a butterfly head; the upper outer surface of the cylindrical body 41 is provided with a cooling medium outlet connected to the cooling medium cavity, and the cooling medium outlet constitutes a channel for the cooling medium to leave the cooling medium cavity; the lower outer surface of the cylindrical body 41 is provided with a cooling medium inlet 48 connected to the cooling medium cavity, and the cooling medium inlet 48 constitutes a channel for the cooling medium to enter the cooling medium cavity.

[0052] The mixing kettle 1 has a jacket, and the jacket has a refrigerant inlet 13 for introducing a cooling medium into the jacket, and a refrigerant outlet for allowing the refrigerant to leave the jacket.

[0053] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1

[0054] 2.04 kg of anhydrous zinc bromide was evenly added to each tube of the catalyst packed column, with a total of 100.0 kg of anhydrous zinc bromide added. The total number of tubes was 49, arranged in an equilateral triangle, and the inner diameter of the tubes was 50 mm.

[0055] Add 4.0 kg of chlorosulfonic acid into the strong acid storage tank.

[0056] Add 350.0 kg (99.3 wt%) of pseudoionone to the mixing kettle and start stirring. Cool the contents to 15°C with low-temperature water in the jacket and set aside. When the kettle temperature reaches 15°C, add 5.2 kg (65.4 wt%) of hydrobromic acid to the mixing kettle and mix thoroughly.

[0057] Add 300kg of tap water to the washing kettle in advance and start stirring. Add low-temperature water to the jacket of the washing kettle and reduce the water temperature in the washing kettle to 15℃. Set aside.

[0058] Start the delivery pump and set the delivery pump flow rate to 250 kg / h. Simultaneously, open the strong acid storage tank outlet valve and control the chlorosulfonic acid flow rate to 4.0 kg / h. After the chlorosulfonic acid is mixed with the mixture of pseudoionone and hydrobromic acid from the mixing kettle, the mixture is pumped into the catalyst column for a cyclization reaction. By adjusting the flow rate of low-temperature water entering the shell of the catalyst column, the temperature of the cyclization liquid at the catalyst column outlet is controlled at 15°C. When the mixed liquid in the mixing kettle is fully fed, quickly add 80 kg of n-hexane to the mixing kettle to wash the mixing kettle. The n-hexane is delivered to the catalyst column via the delivery pump to wash the catalyst. The washed n-hexane and cyclization liquid are combined in the washing kettle.

[0059] Start the washing kettle and stir, extract for 10 minutes, then turn off the stirring and let it stand for 30 minutes. After standing, separate the lower layer of water. In this way, add 120kg of tap water to wash the cyclized liquid, and the washing is complete. Then use 120kg of 5wt% sodium bicarbonate aqueous solution to wash the cyclized liquid. After washing, transfer the washing liquid to the recovery kettle to recover n-hexane, and then remove the heavy components under high vacuum conditions. Finally, β-ionone is obtained: 343.3kg, α-ionone content: 0.33wt%, β-ionone content: 98.7wt%, γ-ionone content: 0.05wt%, β-ionone yield: 97.5%. Example 2

[0060] The process apparatus and process parameters of Example 2 were essentially the same as those of Example 1, except that 2.3 kg of hydrobromic acid (content: 65.4 wt %) was added to the mixing kettle for mixing. The resulting mixture contained 343.2 kg of β-ionone, with an α-ionone content of 0.62 wt %, a β-ionone content of 98.2 wt %, and a γ-ionone content of 0.1 wt %, yielding a β-ionone yield of 97.0%. Example 3

[0061] The process apparatus and process parameters of Example 3 were essentially the same as those of Example 1, except that 11.2 kg of hydrobromic acid (content: 65.4 wt%) was added to the mixing kettle for mixing, and 5.1 kg of chlorosulfonic acid was added to the strong acid storage tank for reaction. The resulting product was 343.2 kg of β-ionone, with an α-ionone content of 0.12 wt%, a β-ionone content of 99.2 wt%, and a γ-ionone content of 0.03 wt%, for a β-ionone yield of 98.0%. Example 4

[0062] The process apparatus and process parameters of Example 4 were substantially the same as those of Example 1, except that 2.4 kg of chlorosulfonic acid was added to the strong acid storage tank for the reaction. Finally, 343.4 kg of β-ionone was obtained, with an α-ionone content of 0.42 wt %, a β-ionone content of 98.4 wt %, a γ-ionone content of 0.07 wt %, and a β-ionone yield of 97.2%. Example 5

[0063] The process apparatus and process parameters of Example 5 were substantially the same as those of Example 1, except that 4.7 kg of chlorosulfonic acid was added to the strong acid storage tank for the reaction. Finally, 343.1 kg of β-ionone was obtained, with an α-ionone content of 0.13 wt %, a β-ionone content of 99.1 wt %, a γ-ionone content of 0.02 wt %, and a β-ionone yield of 97.8%. Example 6

[0064] The process apparatus and process parameters of Example 6 are basically the same as those of Example 1, except that the mixing temperature and the cyclization reaction temperature are both controlled at 10° C. 343.8 kg of β-ionone are finally obtained, with an α-ionone content of 0.21 wt %, a β-ionone content of 98.2 wt %, a γ-ionone content of 0.04 wt %, and a β-ionone yield of 97.1%. Example 7

[0065] The process apparatus and process parameters of Example 7 are basically the same as those of Example 1, except that the mixing temperature and the cyclization reaction temperature are both controlled at 30° C. 340.2 kg of β-ionone are finally obtained, with an α-ionone content of 0.71 wt %, a β-ionone content of 98.1 wt %, a γ-ionone content of 0.12 wt %, and a β-ionone yield of 96.0%.

[0066] Comparative Example 1

[0067] Add 100.0 kg of anhydrous zinc bromide, 5.2 kg of hydrobromic acid (65.4 wt%), 80 kg of n-hexane, and 4.0 kg of chlorosulfonic acid to a washing kettle and start stirring. Cool the contents to 15°C in the jacketed low-temperature water tank. Slowly add 350.0 kg of pseudoionone (99.3 wt%) to the washing kettle, ensuring that the addition is complete within 1.0 hour. Once the pseudoionone is complete, add 300 kg of tap water to the washing kettle. After 10 minutes of extraction, turn off stirring and allow the mixture to stand for 30 minutes. After the stand is complete, remove the lower water layer. Wash the cyclized liquid with 120 kg of tap water to complete the washing process. Then, wash the cyclized liquid with 120 kg of a 5 wt% aqueous sodium bicarbonate solution. After washing, transfer the washing liquid to a recovery kettle to recover the n-hexane, and then remove the heavy components under high vacuum. Finally, 331.5 kg of β-ionone was obtained, with an α-ionone content of 0.28 wt%, a β-ionone content of 98.9 wt%, a γ-ionone content of 0.04 wt%, and a β-ionone yield of 94.3%.

[0068] Comparative Example 2

[0069] The process apparatus and process parameters of Comparative Example 2 were basically the same as those of Example 1, except that chlorosulfonic acid was not added for the reaction. The final yield was 333.1 kg of β-ionone, with an α-ionone content of 0.55 wt %, a β-ionone content of 98.0 wt %, a γ-ionone content of 0.13 wt %, and a β-ionone yield of 93.9%.

Claims

1. A device for preparing β-ionone, characterized in that: include: A mixing kettle for mixing pseudoionone and protonic acid, the mixing kettle having a material inlet and a material outlet, wherein the protonic acid is selected from hydrochloric acid or hydrobromic acid; a mixing kettle outlet pipe, connected to the material outlet of the mixing kettle; A strong acid storage tank having a strong acid inlet and a strong acid outlet, wherein the strong acid outlet is connected to the mixing kettle outlet pipe through the storage tank outlet pipe, and the strong acid used is chlorosulfonic acid; a catalyst-filled column, for filling a solid Lewis acid catalyst and performing a cyclization reaction, having a catalyst-filled column inlet and a catalyst-filled column outlet, wherein the catalyst-filled column inlet is connected to the outlet pipe of the mixing kettle, and the solid Lewis acid catalyst is selected from zinc chloride or zinc bromide corresponding to the protonic acid anion; The washing kettle is used for receiving the cyclization liquid and performing post-processing, and has a water inlet and a cyclization liquid inlet. The cyclization liquid inlet is connected with the catalyst filling column outlet through a catalyst filling column outlet pipe.

2. The preparation device according to claim 1, characterized in that A delivery pump for delivering the material in the mixing kettle to the inlet of the catalyst filling column is further provided on the mixing kettle outlet pipe at the downstream of the connection between the storage tank outlet pipe and the mixing kettle outlet pipe.

3. The preparation device according to claim 1, characterized in that The catalyst packed column comprises a vertically arranged cylindrical body, a first end cap and a second end cap for sealing both ends of the cylindrical body, a plurality of tubes arranged in the body, and a first tube sheet and a second tube sheet sleeved on both ends of the tubes and fixing the tubes on the cylindrical body. A filter plate is provided at the outlet of each tube array, and the interior of the tube array forms a catalyst filling cavity; The catalyst filling column inlet and the catalyst filling column outlet are respectively arranged on the first head and the second head; The outer surface of the tubes, the inner surface of the cylindrical shell, the first tube sheet and the second tube sheet form a cooling medium cavity. A cooling medium inlet and a cooling medium outlet communicating with the cooling medium cavity are provided on the surface of the cylindrical shell.

4. The preparation device according to claim 1, characterized in that The mixing kettle has a jacket, and the jacket has a refrigerant inlet for introducing a cooling medium into the jacket, and a refrigerant outlet for allowing the refrigerant to leave the jacket.

5. A method for preparing β-ionone using the preparation device according to any one of claims 1 to 4, characterized in that: include: The pseudoionone and the protonic acid are uniformly mixed in the mixing kettle and then introduced into the outlet pipe of the mixing kettle. Meanwhile, the strong acid in the strong acid storage tank is introduced into the outlet pipe of the mixing kettle. The mixed material in the outlet pipe of the mixing kettle then enters the catalyst-packed column for cyclization reaction. The cyclization liquid obtained after the reaction enters the washing kettle and is washed to obtain β-ionone. The catalyst-filled column is pre-filled with a solid Lewis acid catalyst.

6. The method according to claim 5, characterized in that The pseudoionone and protonic acid are mixed in the mixing kettle and cooled simultaneously; and / or, cooling is performed while the cyclization reaction is carried out in the catalyst-packed column.

7. The method according to claim 5, characterized in that The molar ratio of the protonic acid to the pseudoionone is 0.01-0.05:

1.

8. The method according to claim 7, characterized in that The concentration of the hydrochloric acid is ≤40wt%, and the concentration of the hydrobromic acid is ≤70wt%; The molar ratio of water in the protonic acid to the chlorosulfonic acid is 2.5-5.0:

1.

9. The method according to claim 7, characterized in that The mass ratio of the solid Lewis acid catalyst to the pseudoionone is 0.2-0.5:

1.

10. The method according to any one of claims 5 to 9, characterized in that The mixing process and the cyclization reaction process are carried out under a preset temperature condition, which is 10-30°C.

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