Acidic ionic liquid for preparing epoxidized soybean oil

Abstract

The invention is applicable to the technical field of epoxidized soybean oil preparation, and provides an acidic ionic liquid for preparing epoxidized soybean oil, the acidic ionic liquid comprises the following components: glacial acetic acid, sulfuric acid, an oxidant, a metal complex, a stabilizer, disulfonic acid imidazolium salt, 1-(3-sulfonic acid propyl)-3-methylimidazolium hydrogen sulfate and a solvent; the invention discloses a metal complex corrosion inhibitor which comprises the following components in percentage by mass: 22-39% of glacial acetic acid, 1-3% of sulfuric acid, 15-27% of an oxidant, 1.4-3.2% of a metal complex, 2-6% of a stabilizer, 1-3.5% of disulfonic acid imidazolium salt, 0.6-1.2% of 1-(3-sulfonic acid propyl)-3-methylimidazolium hydrogen sulfate and 15-60% of a solvent. Preferably, the solvent is one or more of ethanol, acetonitrile and carbon tetrachloride; the metal complex is one or more of cobalt chloride, titanium chloride and ferric chloride. The method shows excellent catalytic performance and reaction efficiency in the preparation of the epoxidized soybean oil, effectively improves the epoxy value of the epoxidized soybean oil, and has wide application prospects and important economic values.

Description

Technical Field

[0001] The present invention relates to the technical field of epoxidized soybean oil preparation, and specifically to an acidic ionic liquid for preparing epoxidized soybean oil. Background Technique

[0002] Epoxidized Soybean Oil (ESO) is a compound that converts the unsaturated double bonds in soybean oil into epoxy groups (-CH-O-) through an epoxidation reaction. It is a common plant-derived environmental protection additive and is widely used in plastics, rubbers, coatings, and other materials, mainly as a plasticizer, stabilizer, and softening agent.

[0003] The preparation method of epoxidized soybean oil mainly converts the unsaturated fatty acid double bonds in soybean oil into epoxy groups through an epoxidation reaction. Under the action of an acidic catalyst and an oxidant (such as hydrogen peroxide), the epoxidation reaction occurs. After the reaction, neutralization and purification are required to obtain high-quality epoxidized soybean oil.

[0004] The role of acidic ionic liquids in the preparation of epoxidized soybean oil is mainly reflected in aspects such as catalyzing the epoxidation reaction and improving the reaction efficiency. Acidic ionic liquids usually have strong acidity and can be used as catalysts in the epoxidation reaction to promote the reaction between hydrogen peroxide or other oxidants and the unsaturated double bonds in soybean oil. The acidic characteristics of acidic ionic liquids enable them to enhance the activity of hydrogen peroxide and promote the progress of the oxidation reaction, thereby increasing the conversion rate of epoxy groups; acidic ionic liquids can dissolve reactants (such as unsaturated fatty acids and hydrogen peroxide in soybean oil), improve the reaction efficiency, and avoid the phase separation problem between the solvent and the reactants.

[0005] By adjusting the composition, content, reaction conditions, etc. of the acidic ionic liquid, epoxidized soybean oil with a high epoxy content can be obtained. There is still a large room for improvement in the existing acidic ionic liquids used in the preparation of epoxidized soybean oil in terms of increasing the epoxy value of epoxidized soybean oil. In view of this, the present invention proposes an acidic ionic liquid for preparing epoxidized soybean oil. Summary of the Invention

[0006] The purpose of the present invention is to provide an acidic ionic liquid for preparing epoxidized soybean oil to solve the problems in the above background technique.

[0007] To achieve the above purpose, the present invention provides the following technical solution: An acidic ionic liquid for preparing epoxidized soybean oil, the components of the acidic ionic liquid include glacial acetic acid, sulfuric acid, oxidant, metal complex, stabilizer, bis-sulfonic acid imidazolium salt, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate, and solvent;

[0008] The mass percentage content of each component is as follows:

[0009] Glacial acetic acid 22 - 39%, sulfuric acid 1 - 3%, oxidant 15 - 27%, metal complex 1.4 - 3.2%, stabilizer 2 - 6%, disulfonic acid imidazole salt 1 - 3.5%, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate 0.6 - 1.2%, solvent 15 - 60%.

[0010] Preferably, the solvent is one or more of ethanol, acetonitrile, and carbon tetrachloride.

[0011] Preferably, the metal complex is one or more of cobalt chloride, titanium chloride, and iron chloride.

[0012] Preferably, the oxidant is one or more of hydrogen peroxide and benzoyl peroxide.

[0013] Preferably, the stabilizer is one or more of sodium dodecyl sulfate, sodium sulfite, and polyvinyl alcohol.

[0014] Preferably, the temperature of the acidic ionic liquid is 45 - 50 °C.

[0015] Preferably, the acidic ionic liquid further includes sodium chromate, and the mass percentage of sodium chromate is 0.4 - 0.9%.

[0016] Preferably, the mass fraction of sulfuric acid used in the acidic ionic liquid is 10 - 30%.

[0017] The present invention has at least the following beneficial effects:

[0018] An acidic ionic liquid for preparing epoxidized soybean oil provided by the present invention exhibits excellent catalytic performance and reaction efficiency in the preparation of epoxidized soybean oil, effectively improving the epoxy value of epoxidized soybean oil, and has broad application prospects and important economic value. Detailed Embodiments

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0020] Example 1

[0021] This example provides an acidic ionic liquid for preparing epoxidized soybean oil, which includes the following components:

[0022] Glacial acetic acid, sulfuric acid, oxidant, metal complex, stabilizer, disulfonic acid imidazole salt, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate, solvent;

[0023] The mass percentage content of each component is as follows:

[0024] Glacial acetic acid 22%, sulfuric acid 1%, oxidant 15%, metal complex 1.4%, stabilizer 2%, disulfonic acid imidazole salt 1%, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate 0.6%, solvent 57%.

[0025] Among them, the solvent is ethanol; the metal complex is cobalt chloride; the oxidant is hydrogen peroxide; the stabilizer is sodium dodecyl sulfate.

[0026] Among them, the temperature of the acidic ionic liquid is 45 °C; the mass fraction of sulfuric acid used in the acidic ionic liquid is 10%.

[0027] Example 2

[0028] This example provides an acidic ionic liquid for preparing epoxidized soybean oil, which comprises the following components:

[0029] Glacial acetic acid, sulfuric acid, oxidant, metal complex, stabilizer, disulfonic acid imidazole salt, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate, solvent;

[0030] The mass percentage content of each component is as follows:

[0031] Glacial acetic acid 27%, sulfuric acid 2%, oxidant 18%, metal complex 2%, stabilizer 5%, disulfonic acid imidazole salt 2.9%, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate 1%, solvent 42.1%.

[0032] Among them, the solvent is acetonitrile; the metal complex is titanium chloride; the oxidant is benzoyl peroxide; the stabilizer is sodium sulfite.

[0033] Among them, the temperature of the acidic ionic liquid is 47 °C; the mass fraction of sulfuric acid used in the acidic ionic liquid is 20%.

[0034] Example 3

[0035] This example provides an acidic ionic liquid for preparing epoxidized soybean oil, which comprises the following components:

[0036] Glacial acetic acid, sulfuric acid, oxidant, metal complex, stabilizer, disulfonic acid imidazole salt, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate, solvent;

[0037] The mass percentage content of each component is as follows:

[0038] Glacial acetic acid 39%, sulfuric acid 3%, oxidant 27%, metal complex 3.2%, stabilizer 6%, disulfonic acid imidazole salt 3.5%, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate 1.2%, solvent 17.1%.

[0039] Among them, the solvent is carbon tetrachloride; the metal complex is ferric chloride; the oxidant is hydrogen peroxide; the stabilizer is polyvinyl alcohol.

[0040] Among them, the temperature of the acidic ionic liquid is 50 °C; the mass fraction of sulfuric acid used in the acidic ionic liquid is 30%.

[0041] Example 4

[0042] This example provides an acidic ionic liquid for preparing epoxidized soybean oil, which includes the following components:

[0043] Glacial acetic acid, sulfuric acid, oxidant, metal complex, stabilizer, disulfonic acid imidazole salt, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate, solvent, sodium chromate;

[0044] The mass percentage content of each component is as follows:

[0045] Glacial acetic acid 22%, sulfuric acid 1%, oxidant 15%, metal complex 1.4%, stabilizer 2%, disulfonic acid imidazole salt 1%, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate 0.6%, solvent 56.6%, sodium chromate 0.4%.

[0046] Among them, the solvent is ethanol; the metal complex is cobalt chloride; the oxidant is hydrogen peroxide; the stabilizer is sodium dodecyl sulfate.

[0047] Among them, the temperature of the acidic ionic liquid is 45 °C; the mass fraction of sulfuric acid used in the acidic ionic liquid is 10%.

[0048] Example 5

[0049] This example provides an acidic ionic liquid for preparing epoxidized soybean oil, which includes the following components:

[0050] Glacial acetic acid, sulfuric acid, oxidant, metal complex, stabilizer, disulfonic acid imidazole salt, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate, solvent, sodium chromate;

[0051] The mass percentage content of each component is as follows:

[0052] Glacial acetic acid 27%, sulfuric acid 2%, oxidant 18%, metal complex 2%, stabilizer 5%, disulfonic acid imidazole salt 2.9%, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate 1%, solvent 41.3%, sodium chromate 0.8%.

[0053] Among them, the solvent is acetonitrile; the metal complex is titanium chloride; the oxidant is benzoyl peroxide; the stabilizer is sodium sulfite.

[0054] Among them, the temperature of the acidic ionic liquid is 47 °C; the mass fraction of sulfuric acid used in the acidic ionic liquid is 20%.

[0055] Example 6

[0056] This example provides an acidic ionic liquid for preparing epoxidized soybean oil, which comprises the following components:

[0057] Glacial acetic acid, sulfuric acid, oxidant, metal complex, stabilizer, disulfonic acid imidazole salt, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate, solvent, sodium chromate;

[0058] The mass percentage content of each component is as follows:

[0059] Glacial acetic acid 39%, sulfuric acid 3%, oxidant 27%, metal complex 3.2%, stabilizer 6%, disulfonic acid imidazole salt 3.5%, 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate 1.2%, solvent 16.2%, sodium chromate 0.9%.

[0060] Among them, the solvent is carbon tetrachloride; the metal complex is ferric chloride; the oxidant is hydrogen peroxide; the stabilizer is polyvinyl alcohol.

[0061] Among them, the temperature of the acidic ionic liquid is 50 °C; the mass fraction of sulfuric acid used in the acidic ionic liquid is 30%.

[0062] In the present invention, glacial acetic acid serves as the main acidic component, which not only provides the acidic environment required for the reaction but also participates in the catalytic process of the epoxidation reaction; sulfuric acid enhances the acidity of the system and contributes to the decomposition of hydrogen peroxide and the progress of the epoxidation reaction; the oxidant is the key to the epoxidation reaction, which oxidizes the unsaturated double bonds in soybean oil to epoxy groups; the metal complex serves as a co-catalyst, which can stabilize the reaction intermediates and improve the selectivity and efficiency of the reaction; the stabilizer is used to prevent possible side reactions during the reaction and ensure the stability of the product; disulfonic acid imidazole salt and 1-(3-sulfopropyl)-3-methylimidazolium hydrogen sulfate, as components of the ionic liquid, not only provide good solubility but also promote the contact and reaction between reactants; the addition of sodium chromate further improves the catalytic performance of the acidic ionic liquid and promotes the progress of the epoxidation reaction.

[0063] The acidic ionic liquid prepared by the present invention exhibits excellent catalytic performance and reaction efficiency in the preparation of epoxidized soybean oil, effectively improving the epoxy value of epoxidized soybean oil.

[0064] The epoxy value tests were carried out on the above Examples 1-6, and the results are as follows:

[0065] Test Items Epoxy Value Example 1 7.04％ Example 2 7.11％ Example 3 7.16％ Example 4 7.07％ Example 5 7.13％ Example 6 7.21％

[0066] The results of Examples 1 to 6 show that the epoxy value of the epoxy soybean oil prepared with the acidic ionic liquid of the present invention has reached a relatively high level.

[0067] In summary, the acidic ionic liquid provided by the present invention has high catalytic activity and selectivity, and can effectively improve the epoxy value of epoxy soybean oil. The acidic ionic liquid in the present invention not only optimizes the conditions of the epoxidation reaction, but also enhances the stability and quality of the product. Therefore, the present invention has broad application prospects and important economic value in the field of preparing epoxy soybean oil.

[0068] The foregoing shows and describes the basic principles, main features and advantages of the present invention. For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic features of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, it is intended to embrace all changes falling within the meaning and scope of the equivalent elements of the claims in the present invention.

[0069] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An acidic ionic liquid for preparing epoxidized soybean oil, characterized in that: The components of the acidic ionic liquid include glacial acetic acid, sulfuric acid, an oxidant, a metal complex, a stabilizer, a disulfonic acid imidazole salt, 1-(3-sulfonic acid propyl)-3-methylimidazole hydrogen sulfate, and a solvent; The mass percentage content of each component is as follows: Glacial acetic acid 22-39%, sulfuric acid 1-3%, oxidant 15-27%, metal complex 1.4-3.2%, stabilizer 2-6%, bissulfonic acid imidazole salt 1-3.5%, 1-(3-sulfonic acid propyl)-3-methylimidazole hydrogen sulfate 0.6-1.2%, solvent 15-60%.

2. The acidic ionic liquid for preparing epoxidized soybean oil according to claim 1, characterized in that: The solvent is one or more of ethanol, acetonitrile and carbon tetrachloride.

3. The acidic ionic liquid for preparing epoxidized soybean oil according to claim 1, characterized in that: The metal complex is one or more of cobalt chloride, titanium chloride and ferric chloride.

4. The acidic ionic liquid for preparing epoxidized soybean oil according to claim 1, characterized in that: The oxidant is one or more of hydrogen peroxide and benzoyl peroxide.

5. The acidic ionic liquid for preparing epoxidized soybean oil according to claim 1, characterized in that: The stabilizer is one or more of sodium lauryl sulfate, sodium sulfite and polyvinyl alcohol.

6. The acidic ionic liquid for preparing epoxidized soybean oil according to claim 1, characterized in that: The temperature of the acidic ionic liquid is 45-50°C.

7. The acidic ionic liquid for preparing epoxidized soybean oil according to claim 1, characterized in that: The acidic ionic liquid also includes sodium chromate, and the mass percentage of the sodium chromate is 0.4-0.9%.

8. The acidic ionic liquid for preparing epoxidized soybean oil according to claim 1, characterized in that: The mass fraction of sulfuric acid used in the acidic ionic liquid is 10-30%.