A method for extracting perillaldehyde from perillaldehyde waste residue

Abstract

The present invention relates to the technical field of perillaldehyde extraction, and in particular to a method for extracting perillaldehyde from perillaldehyde waste residue. A method for extracting perillaldehyde from perillaldehyde waste residue comprises the following steps: step S1, heating the perillaldehyde waste residue, then adding a polar solvent to dissolve it, and then adding a non-polar solvent to extract it to obtain a reaction solution; step S2, standing the reaction solution obtained in step S1 for stratification to obtain an upper organic phase A1 and a lower organic phase B1. The method for extracting perillaldehyde from perillaldehyde waste residue can completely extract perillaldehyde and perillyl alcohol from the perillaldehyde waste residue, thereby improving the total yield of industrial production of perillaldehyde. The method is simple and convenient to operate, can be used in industrial production, and solves the technical problem that the perillaldehyde and perillyl alcohol of the heavy fractions generated in the existing perillyl alcohol oxidation method are difficult to be completely extracted, resulting in a low total yield of industrial production of perillaldehyde.

Description

Technical Field

[0001] The invention relates to the technical field of perillaldehyde extraction, in particular to a method for extracting perillaldehyde from perillaldehyde waste residue. Background Art

[0002] Perillaldehyde, scientific name [4-isopropenyl-1-cyclohexenyl] formaldehyde; also known as dihydrocuminaldehyde, is an optically active terpenoid compound with cherry, oil and cumin-like aromas. It exists in perilla oil, tung oil and bergamot oil. It is a characteristic aroma component of perilla oil and can be used to prepare floral daily chemical flavors such as jasmine and narcissus, as well as apple, citrus, spearmint and other edible flavors. Perillaldehyde is not only a spice substance, but also an important chemical intermediate. As an organic synthesis intermediate, perillaldehyde can be used to synthesize the sweetener perilla, which has the advantages of high sweetness, low calorific value and no toxic side effects. In addition, perillaldehyde can also be used to synthesize medicines and other drugs.

[0003] In the process of industrial production of perillyl aldehyde in my country, the perillyl alcohol oxidation method is mainly used, that is, perillyl alcohol is oxidized to perillyl aldehyde using an oxidant. The perillyl aldehyde obtained after the oxidation reaction is usually low in content and needs to be purified by a distillation method to obtain high-purity perillyl aldehyde. However, the distillation process will produce some heavy fractions, and due to its strong viscosity, it is difficult to completely distill out the perillyl alcohol and perillyl aldehyde that have not reacted completely, making it difficult to completely extract the perillyl aldehyde and perillyl alcohol in the perillyl aldehyde waste residue, and the total yield of the industrial production of perillyl aldehyde is low. Summary of the invention

[0004] In view of the problems raised by the background technology, the purpose of the present invention is to propose a method for extracting perillyl aldehyde from perillyl aldehyde waste residue, which can completely extract perillyl aldehyde and perillyl alcohol from the perillyl aldehyde waste residue, thereby improving the total yield of perillyl aldehyde industrial production. The method is simple and convenient to operate and can be used in industrial production. It solves the technical problem that the heavy fractions of perillyl aldehyde and perillyl alcohol produced in the existing perillyl alcohol oxidation method are difficult to completely extract, resulting in a low total yield of perillyl aldehyde industrial production.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] A method for extracting perillaldehyde from perillaldehyde waste residue comprises the following steps:

[0007] Step S1, heating the waste residue of perillaldehyde, then adding a polar solvent to dissolve it, and then adding a non-polar solvent to extract it to obtain a reaction solution;

[0008] Step S2, the reaction solution obtained in step S1 is allowed to stand for stratification to obtain an upper organic phase A1 and a lower organic phase B1; the lower organic phase B1 is extracted twice with a non-polar solvent to obtain an upper organic phase A2 and a lower organic phase B2; the upper organic phase A2 obtained by extraction is mixed with the upper organic phase A1 to obtain an upper organic phase mixed solution A;

[0009] Step S3, adding diatomaceous earth to the upper organic phase mixed solution A to remove impurities;

[0010] Step S4, concentrating the upper organic phase mixed solution A after impurities removal to recover the non-polar solvent to obtain a mixture of perillyl alcohol and perillyl aldehyde, adding a solvent and an oxidant to oxidize to obtain perillyl aldehyde.

[0011] To further illustrate, in step S1:

[0012] The polar solvent is any one or more of N,N-dimethylformamide and dimethyl sulfoxide;

[0013] The mass ratio of the perillaldehyde waste residue to the polar solvent is 1:(4-10).

[0014] To further illustrate, in step S1:

[0015] The non-polar solvent is any one or more of petroleum ether, cyclohexane and n-hexane;

[0016] The mass ratio of the perillaldehyde waste residue to the non-polar solvent is 1:(1-8).

[0017] To further illustrate, in step S1, the temperature of heating the waste residue of perillaldehyde and then adding a polar solvent for dissolution is 40°C to 70°C.

[0018] To further illustrate, in step S3, the mesh size of the diatomaceous earth is 20 to 100 meshes.

[0019] To further illustrate, in step S4:

[0020] The oxidant is any one or more of oxygen, manganese dioxide and hydrogen peroxide;

[0021] The reaction temperature for the oxidation is 40°C to 80°C.

[0022] To further illustrate, the reaction time for oxidation in step S4 is 2 to 8 hours.

[0023] To further illustrate, in step S4, the solvent added to the oxidant for oxidation is any one or more combinations of dichloromethane, ethyl acetate and 1,2-dichloroethane.

[0024] To further illustrate, in step S4:

[0025] The mass ratio of the mixture of perillyl alcohol and perillyl aldehyde to the solvent is 1:(5-20);

[0026] The molar ratio of the mixture of perillyl alcohol and perillyl aldehyde to the oxidant is 1:(0.5-4).

[0027] To further illustrate, the step S3 also includes: concentrating the lower organic phase B2 to recover the polar solvent.

[0028] Compared with the prior art, the embodiments of the present invention have the following beneficial effects:

[0029] The method comprises the following steps: heating and dissolving the waste residue, adding a non-polar solution to extract perillyl aldehyde and perillyl alcohol, adding diatomaceous earth to adsorb impurities, and finally oxidizing the perillyl alcohol to obtain perillyl aldehyde. Perillyl aldehyde is extracted from the perillyl aldehyde waste residue, and the perillyl alcohol and perillyl aldehyde in the waste residue are effectively recovered. The perillyl aldehyde and perillyl alcohol in the perillyl aldehyde waste residue can be completely extracted, thereby improving the total yield of the industrial production of perillyl aldehyde. The method is simple and convenient to operate and can be used in industrial production. DETAILED DESCRIPTION

[0030] A method for extracting perillaldehyde from perillaldehyde waste residue comprises the following steps:

[0031] Step S1, heating the waste residue of perillaldehyde, then adding a polar solvent to dissolve it, and then adding a non-polar solvent to extract it to obtain a reaction solution;

[0032] Step S2, the reaction solution obtained in step S1 is allowed to stand for stratification to obtain an upper organic phase A1 and a lower organic phase B1; the lower organic phase B1 is extracted twice with a non-polar solvent to obtain an upper organic phase A2 and a lower organic phase B2; the upper organic phase A2 obtained by extraction is mixed with the upper organic phase A1 to obtain an upper organic phase mixed solution A;

[0033] Step S3, adding diatomaceous earth to the upper organic phase mixed solution A to remove impurities;

[0034] Step S4, concentrating the upper organic phase mixed solution A after impurities removal to recover the non-polar solvent to obtain a mixture of perillyl alcohol and perillyl aldehyde, adding a solvent and an oxidant to oxidize to obtain perillyl aldehyde.

[0035] The perillaldehyde waste residue of the present invention is a heavy fraction obtained by distilling a perillaldehyde mother liquor obtained by epoxidation and oxidation of β-pinene as a raw material, wherein the content of perillaldehyde is 5-10% by mass ratio, and the content of perillyl alcohol is 5-8% by mass ratio.

[0036] The perillaldehyde waste residue has a high viscosity, so it is difficult to completely separate the desired materials by distillation; the heavy fraction after distillation often retains some perillaldehyde and perillyl alcohol. The inventor studied the process of heating and dissolving the waste residue, adding a non-polar solution to extract perillaldehyde and perillyl alcohol, adding diatomaceous earth to adsorb impurities, and finally oxidizing perillyl alcohol to obtain perillaldehyde, thereby achieving the purpose of the present invention of extracting perillaldehyde from perillaldehyde waste residue. The perillyl alcohol and perillaldehyde in the waste residue are effectively recovered.

[0037] The method for extracting perillyl aldehyde from perillyl aldehyde waste residue of the present invention can completely extract perillyl aldehyde and perillyl alcohol from the perillyl aldehyde waste residue, thereby improving the total yield of industrial production of perillyl aldehyde. The method is simple and convenient to operate and can be used in industrial production.

[0038] To further illustrate, in step S1:

[0039] The polar solvent is any one or more of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO);

[0040] The mass ratio of the perillaldehyde waste residue to the polar solvent is 1:(4-10).

[0041] Preferably, in step S1, the polar solvent is N,N-dimethylformamide (DMF).

[0042] Preferably, in step S1, the mass ratio of the perillaldehyde waste residue to the polar solvent is 1:5.

[0043] To further illustrate, in step S1:

[0044] The non-polar solvent is any one or more of petroleum ether, cyclohexane and n-hexane;

[0045] The mass ratio of the perillaldehyde waste residue to the non-polar solvent is 1:(1-8).

[0046] Preferably, in step S1, the non-polar solvent is cyclohexane.

[0047] Preferably, in step S1, the mass ratio of the perillaldehyde waste residue to the non-polar solvent is 1:3.

[0048] To further illustrate, in step S1, the temperature of heating the waste residue of perillaldehyde and then adding a polar solvent for dissolution is 40°C to 70°C.

[0049] Preferably, in step S1, the temperature for heating the perillaldehyde waste residue and then adding a polar solvent for dissolution is 50°C.

[0050] To further illustrate, in step S3, the mesh size of the diatomaceous earth is 20 to 100 meshes.

[0051] Preferably, in step S3, the mesh size of the diatomaceous earth is 40 meshes.

[0052] Specifically, in step S3, the mass ratio of the diatomaceous earth to the perillaldehyde waste residue is (0.1-0.2):1.

[0053] To further illustrate, in step S4:

[0054] The oxidant is any one or more of oxygen, manganese dioxide and hydrogen peroxide;

[0055] The reaction temperature for the oxidation is 40°C to 80°C.

[0056] Preferably, in step S4, the oxidant is manganese dioxide, and the oxidation reaction temperature is 80°C.

[0057] To further illustrate, the reaction time for oxidation in step S4 is 2 to 8 hours.

[0058] Preferably, the reaction time for oxidation in step S4 is 4 hours.

[0059] To further illustrate, in step S4, the solvent added to the oxidant for oxidation is any one or more combinations of dichloromethane, ethyl acetate and 1,2-dichloroethane.

[0060] Preferably, in step S4, the solvent added to the solvent and oxidant for oxidation is 1,2-dichloroethane.

[0061] To further illustrate, in step S4:

[0062] The mass ratio of the mixture of perillyl alcohol and perillyl aldehyde to the solvent is 1:(5-20);

[0063] The molar ratio of the mixture of perillyl alcohol and perillyl aldehyde to the oxidant is 1:(0.5-4).

[0064] Preferably, in step S4: the mass ratio of the mixture of perillyl alcohol and perillaldehyde to the solvent is 1:10; and the molar ratio of the mixture of perillyl alcohol and perillaldehyde to the oxidant is 1:1.

[0065] To further illustrate, the step S3 also includes: concentrating the lower organic phase B2 to recover the polar solvent.

[0066] In order to facilitate the understanding of the present invention, the present invention is described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0067] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0068] The specific preparation method of the perillaldehyde waste residue in the following embodiment is as follows: using β-pinene as a raw material, adding peracetic acid to carry out an epoxidation reaction to obtain epoxy pinane; dissolving epoxy pinane in N,N-dimethylformamide (DMF), adding a catalyst, carrying out an isomerization reaction, and recovering the solvent after the reaction to obtain perillyl alcohol; dissolving perillyl alcohol in dichloroethane, adding an oxidant to carry out a reaction, and recovering the solvent after the reaction to obtain a crude perillaldehyde product, and distilling and purifying the crude perillaldehyde product to obtain a heavy fraction as the perillaldehyde waste residue.

[0069] Example 1

[0070] A method for extracting perillaldehyde from perillaldehyde waste residue comprises the following steps:

[0071] Step S1, heating 100 kg of perillyl aldehyde waste residue (perillyl alcohol mass content of 5%, perillyl aldehyde mass content of 8%) to 50° C., then adding 500 kg of polar solvent (N,N-dimethylformamide) to dissolve, and then adding 300 kg of non-polar solvent (cyclohexane) to extract (vigorously stir for 30 min) to obtain a reaction solution;

[0072] Step S2, the reaction solution obtained in step S1 is allowed to stand for stratification to obtain an upper organic phase A1 and a lower organic phase B1; the lower organic phase B1 is extracted twice with 100 kg of a non-polar solvent (cyclohexane) to obtain an upper organic phase A2 and a lower organic phase B2; the upper organic phase A2 obtained by extraction is mixed with the upper organic phase A1 to obtain an upper organic phase mixed solution A;

[0073] Step S3, adding 10 kg of diatomaceous earth (diatomaceous earth has a mesh size of 40 meshes) to the upper organic phase mixed solution A to remove impurities;

[0074] Step S4, heating the upper organic phase mixed solution A after impurities removal to 50° C., stirring for 30 min, filtering and concentrating, recovering the non-polar solvent to obtain 25 kg of a mixture of perillyl alcohol and perillyl aldehyde (the mass content of perillyl alcohol is about 20%, and the mass content of perillyl aldehyde is about 32%), adding 125 kg of a solvent (1,2-dichloroethane) to dissolve the 25 kg mixture of perillyl alcohol and perillyl aldehyde, adding 14.5 kg of an oxidant (manganese dioxide) for oxidation, heating to 80° C. and reflux for 4 h, filtering after the reaction is completed, and concentrating to obtain 27.5 kg of perillyl aldehyde (the material content is 43.5%).

[0075] Example 2

[0076] A method for extracting perillaldehyde from perillaldehyde waste residue comprises the following steps:

[0077] Step S1, heating 100 kg of perillyl aldehyde waste residue (perillyl alcohol mass content of 5%, perillyl aldehyde mass content of 8%) to 50° C., then adding 400 kg of polar solvent (N,N-dimethylformamide) to dissolve, and then adding 300 kg of non-polar solvent (cyclohexane) to extract (vigorously stir for 30 min) to obtain a reaction solution;

[0078] Step S2, the reaction solution obtained in step S1 is allowed to stand for stratification to obtain an upper organic phase A1 and a lower organic phase B1; the lower organic phase B1 is extracted twice with 100 kg of a non-polar solvent (cyclohexane) to obtain an upper organic phase A2 and a lower organic phase B2; the upper organic phase A2 obtained by extraction is mixed with the upper organic phase A1 to obtain an upper organic phase mixed solution A;

[0079] Step S3, adding 20 kg of diatomaceous earth (diatomaceous earth has a mesh size of 40 meshes) to the upper organic phase mixed solution A to remove impurities;

[0080] Step S4, heating the upper organic phase mixed solution A after impurity removal to 50° C., stirring for 30 min, filtering and concentrating, recovering the non-polar solvent, and obtaining a mixture of 21.2 kg of perillyl alcohol and perillyl aldehyde (perillyl alcohol mass content is about 20%, perillyl aldehyde mass content is about 32%), adding 106 kg of solvent (1,2-dichloroethane) to the 21.2 kg mixture of perillyl alcohol and perillyl aldehyde to dissolve, adding 12.3 kg of oxidant (manganese dioxide) to oxidize, heating to 80° C. and reflux for 4 h, filtering after the reaction is completed, and concentrating to obtain 25.4 kg of perillyl aldehyde (substance content is 40.1%).

[0081] Example 3

[0082] A method for extracting perillaldehyde from perillaldehyde waste residue comprises the following steps:

[0083] Step S1, heating 100 kg of perillyl aldehyde waste residue (perillyl alcohol mass content of 8%, perillyl aldehyde mass content of 13%) to 50° C., then adding 500 kg of polar solvent (N,N-dimethylformamide) to dissolve, and then adding 300 kg of non-polar solvent (cyclohexane) to extract (vigorously stir for 30 min) to obtain a reaction solution;

[0084] Step S2, the reaction solution obtained in step S1 is allowed to stand for stratification to obtain an upper organic phase A1 and a lower organic phase B1; the lower organic phase B1 is extracted twice with 100 kg of a non-polar solvent (cyclohexane) to obtain an upper organic phase A2 and a lower organic phase B2; the upper organic phase A2 obtained by extraction is mixed with the upper organic phase A1 to obtain an upper organic phase mixed solution A;

[0085] Step S3, adding 10 kg of diatomaceous earth (diatomaceous earth has a mesh size of 40 meshes) to the upper organic phase mixed solution A to remove impurities;

[0086] Step S4, heating the upper organic phase mixed solution A after impurity removal to 60° C., stirring for 30 min, filtering and concentrating, recovering the non-polar solvent, and obtaining 32.4 kg of a mixture of perillyl alcohol and perillyl aldehyde (the mass content of perillyl alcohol is about 24.7%, and the mass content of perillyl aldehyde is about 40.1%), adding 162 kg of a solvent (1,2-dichloroethane) to the 32.4 kg mixture of perillyl alcohol and perillyl aldehyde to dissolve, adding 18.8 kg of an oxidant (manganese dioxide) to oxidize, heating to 80° C. and reflux for 4 h, filtering after the reaction is completed, and concentrating to obtain 38.9 kg of perillyl aldehyde (the material content is 50.0%).

[0087] Example 4

[0088] A method for extracting perillaldehyde from perillaldehyde waste residue comprises the following steps:

[0089] Step S1, heating 100 kg of perillyl aldehyde waste residue (perillyl alcohol mass content of 5%, perillyl aldehyde mass content of 8%) to 50° C., then adding 500 kg of polar solvent (N,N-dimethylformamide) to dissolve, and then adding 100 kg of non-polar solvent (cyclohexane) to extract (vigorously stir for 30 min) to obtain a reaction solution;

[0090] Step S2, the reaction solution obtained in step S1 is allowed to stand for stratification to obtain an upper organic phase A1 and a lower organic phase B1; 50 kg of a non-polar solvent (cyclohexane) is added to the lower organic phase B1 for extraction twice to obtain an upper organic phase A2 and a lower organic phase B2; the upper organic phase A2 obtained by extraction is mixed with the upper organic phase A1 to obtain an upper organic phase mixed solution A;

[0091] Step S3, adding 10 kg of diatomaceous earth (diatomaceous earth has a mesh size of 40 meshes) to the upper organic phase mixed solution A to remove impurities;

[0092] Step S4, heating the upper organic phase mixed solution A after impurities removal to 50° C., stirring for 30 min, filtering and concentrating, recovering the non-polar solvent to obtain 25 kg of a mixture of perillyl alcohol and perillyl aldehyde (the mass content of perillyl alcohol is about 20%, and the mass content of perillyl aldehyde is about 32%), adding 125 kg of a solvent (1,2-dichloroethane) to dissolve the 25 kg mixture of perillyl alcohol and perillyl aldehyde, adding 14.5 kg of an oxidant (manganese dioxide) for oxidation, heating to 80° C. and reflux for 4 h, filtering after the reaction is completed, and concentrating to obtain 27.5 kg of perillyl aldehyde (the material content is 43.5%).

[0093] Example 5

[0094] A method for extracting perillaldehyde from perillaldehyde waste residue comprises the following steps:

[0095] Step S1, heating 100 kg of perillyl aldehyde waste residue (perillyl alcohol mass content of 4%, perillyl aldehyde mass content of 8%) to 70° C., then adding 500 kg of polar solvent (N,N-dimethylformamide) to dissolve, and then adding 300 kg of non-polar solvent (cyclohexane) to extract (vigorously stir for 30 min) to obtain a reaction solution;

[0096] Step S2, the reaction solution obtained in step S1 is allowed to stand for stratification to obtain an upper organic phase A1 and a lower organic phase B1; the lower organic phase B1 is extracted twice with 100 kg of a non-polar solvent (cyclohexane) to obtain an upper organic phase A2 and a lower organic phase B2; the upper organic phase A2 obtained by extraction is mixed with the upper organic phase A1 to obtain an upper organic phase mixed solution A;

[0097] Step S3, adding 10 kg of diatomaceous earth (diatomaceous earth has a mesh size of 40 meshes) to the upper organic phase mixed solution A to remove impurities;

[0098] Step S4, heating the upper organic phase mixed solution A after impurity removal to 70° C., stirring for 30 min, filtering and concentrating, recovering the non-polar solvent, and obtaining a mixture of 24.1 kg of perillyl alcohol and perillyl aldehyde (perillyl alcohol mass content is about 19%, perillyl aldehyde mass content is about 30.2%), adding 125 kg of solvent (1,2-dichloroethane) to the 24.1 kg mixture of perillyl alcohol and perillyl aldehyde to dissolve, adding 14.5 kg of oxidant (manganese dioxide) to oxidize, heating to 80° C. and reflux for 4 h, filtering after the reaction is completed, and concentrating to obtain 24.5 kg of perillyl aldehyde (substance content is 40%).

[0099] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for extracting perillaldehyde from perillaldehyde waste residue, characterized in that: The following steps are involved: Step S1, heating the waste residue of perillaldehyde, then adding a polar solvent to dissolve it, and then adding a non-polar solvent to extract it to obtain a reaction solution; Step S2, the reaction solution obtained in step S1 is allowed to stand for stratification to obtain an upper organic phase A1 and a lower organic phase B1; the lower organic phase B1 is extracted twice with a non-polar solvent to obtain an upper organic phase A2 and a lower organic phase B2; the upper organic phase A2 obtained by extraction is mixed with the upper organic phase A1 to obtain an upper organic phase mixed solution A; Step S3, adding diatomaceous earth to the upper organic phase mixed solution A to remove impurities; Step S4, concentrating the upper organic phase mixed solution A after impurities removal to recover the non-polar solvent to obtain a mixture of perillyl alcohol and perillaldehyde, adding a solvent and an oxidant to oxidize to obtain perillaldehyde.

2. The method for extracting perillaldehyde from perillaldehyde waste residue according to claim 1, characterized in that: In step S1: The polar solvent is any one or more of N,N-dimethylformamide and dimethyl sulfoxide; The mass ratio of the perillaldehyde waste residue to the polar solvent is 1:(4-10).

3. The method for extracting perillaldehyde from perillaldehyde waste residue according to claim 1, characterized in that: In step S1: The non-polar solvent is any one or more of petroleum ether, cyclohexane and n-hexane; The mass ratio of the perillaldehyde waste residue to the non-polar solvent is 1:(1-8).

4. The method for extracting perillaldehyde from perillaldehyde waste residue according to claim 1, characterized in that: In the step S1, the perillaldehyde waste residue is heated, and then a polar solvent is added to dissolve it at a temperature of 40°C to 70°C.

5. The method for extracting perillaldehyde from perillaldehyde waste residue according to claim 1, characterized in that: In the step S3, the mesh size of the diatomaceous earth is 20 to 100 meshes.

6. The method for extracting perillaldehyde from perillaldehyde waste residue according to claim 1, characterized in that: In step S4: The oxidant is any one or more of oxygen, manganese dioxide and hydrogen peroxide; The reaction temperature for the oxidation is 40°C to 80°C.

7. The method for extracting perillaldehyde from perillaldehyde waste residue according to claim 6, characterized in that: The reaction time for oxidation in step S4 is 2 to 8 hours.

8. The method for extracting perillaldehyde from perillaldehyde waste residue according to claim 1, characterized in that: In the step S4, the solvent added with the solvent and the oxidant for oxidation is any one or more combinations of dichloromethane, ethyl acetate and 1,2-dichloroethane.

9. The method for extracting perillaldehyde from perillaldehyde waste residue according to claim 1, characterized in that: In step S4: The mass ratio of the mixture of perillyl alcohol and perillyl aldehyde to the solvent is 1:(5-20); The molar ratio of the mixture of perillyl alcohol and perillyl aldehyde to the oxidant is 1:(0.5-4).

10. The method for extracting perillyl aldehyde from perillyl aldehyde waste residue according to claim 1, characterized in that: The step S3 further comprises: concentrating the lower organic phase B2 to recover the polar solvent.