阅读说明：本技术 植物油脂改性方法 (Vegetable oil and fat modification method ) 是由 彭欣欣 朱斌 夏长久 林民 罗一斌 舒兴田 于 2019-11-19 设计创作，主要内容包括：一种植物油脂改性方法,其特征在于在环氧化反应条件下,将植物油脂与有机过氧化物在一种钛硅复合氧化物和酮类溶剂存在下接触得到含环氧植物油脂的产物,其中,所述的钛硅复合氧化物为无定型结构,由纳米颗粒聚集而成,具有16-50nm范围的介孔,且介孔体积与总孔体积之比≥80％,介孔体积≥0.5cm～3/g。(A vegetable oil modification method is characterized in that under the condition of epoxidation reaction, vegetable oil and organic peroxide are contacted in the presence of a titanium-silicon composite oxide and a ketone solvent to obtain a product containing epoxy vegetable oil, wherein the titanium-silicon composite oxide is an amorphous structure and is formed by aggregating nano particles, has mesopores with the range of 16-50nm, the ratio of the volume of the mesopores to the total pore volume is more than or equal to 80 percent, and the volume of the mesopores is more than or equal to 0.5cm 3 /g。)

1. A vegetable oil modification method is characterized in that under the condition of epoxidation reaction, vegetable oil and organic peroxide are contacted in the presence of a titanium-silicon composite oxide and a ketone solvent to obtain a product containing epoxy vegetable oil, wherein the titanium-silicon composite oxide is an amorphous structure and is formed by aggregating nano particles, has mesopores with the range of 16-50nm, the ratio of the volume of the mesopores to the total pore volume is more than or equal to 80 percent, and the volume of the mesopores is more than or equal to 0.5cm³/g。

2. The method according to claim 1, wherein the titanium-silicon composite oxide contains silicon, titanium and oxygen, the silicon, titanium and oxygen account for more than 95% of the weight of the titanium-silicon composite oxide under the anhydrous drying condition, and the titanium accounts for not less than 0.1% of the weight of the titanium-silicon composite oxide in terms of titanium dioxide.

3. The process according to claim 1, wherein the titanium silicon composite oxide has a nanoparticle size of not more than 40nm, preferably not more than 30nm, more preferably not more than 20nm, and the nanoparticle size is more than 5nm, preferably more than 8 nm.

4. The method as claimed in claim 1, wherein the titanium-silicon composite oxide has a specific surface area of 200-550m²The ratio of the mesoporous volume to the total pore volume is preferably equal to or greater than 90%, more preferably equal to or greater than 93%, most preferably equal to or greater than 95%.

5. The method according to any one of claims 1 to 4, wherein the titanium silicon composite oxide has L acidity of 1450 ± 5cm in pyridine-infrared characterization^-1Has a first absorption peak at 1612 +/-5 cm^-1The titanium-silicon composite oxide has a second absorption peak, the intensity ratio of the first absorption peak to the second absorption peak is at least 1.5 and at most 6, and the titanium-silicon composite oxide has wide strong absorption within the range of 200-250nm and weak absorption above 300nm by the characterization of UV-Vis.

6. The process of claim 1, wherein the epoxidation reaction conditions are: the molar ratio of the vegetable oil to the organic peroxide is 1: (0.1-1), the reaction temperature is 80-160 ℃, and the weight ratio of the titanium-silicon composite oxide to the organic peroxide is (0.01-0.2): 1.

7. the method according to claim 1, wherein the vegetable oil or fat has a structure of R1CH ═ CHR2-R3, wherein R1 and R2 are each an alkyl group or an alkenyl group, R3 is a carboxyl group or an ester group, and the carbon number of the vegetable oil or fat is preferably 14 to 22.

8. The process according to claim 1, wherein the organic peroxide is at least one selected from the group consisting of t-butyl hydroperoxide, cyclohexyl hydroperoxide, ethylbenzene hydroperoxide and cumene hydroperoxide.

9. The method according to claim 1, wherein the ketone solvent has a carbon number of 3 to 10.

10. The method according to claim 9, wherein the ketone solvent is a cyclic ketone having 5 to 8 carbon atoms.

11. The process according to claim 1, wherein the molar ratio of the ketone solvent to the vegetable oil is (3-50): 1.

Technical Field

The invention relates to a vegetable oil modification method, and relates to the field of catalytic oxidation reactions.

Background

The molecules of the vegetable oil usually contain 3-4 double bonds, the chemical reaction activity is strong, and active functional groups such as hydroxyl, epoxy, double bonds, carboxyl and the like can be introduced through chemical reaction. The epoxy grease prepared by epoxidizing and modifying the plant grease can be widely applied to petrochemical products. For example, epoxy vegetable oils have been widely used as plasticizers and stabilizers for PVC because of their low cost, non-toxicity, heat resistance, and light resistance. The development of the vegetable oil and fat epoxidation technology has very important significance.

The traditional vegetable oil and fat epoxidation method is that carboxylic acid reacts with hydrogen peroxide to generate peroxy acid under the catalysis of acid, and the peroxy acid oxidizes double bonds in unsaturated fatty acid to generate epoxy vegetable oil and fat. CN104086513A reports a method for preparing epoxidized soybean oil by using high-concentration hydrogen peroxide reaction heat, which takes soybean oil with an iodine value of 120-135 g/100g as a raw material, high-concentration hydrogen peroxide with a mass concentration of 60-70% as an oxygen source and formic acid as a catalyst, and generates the epoxidized soybean oil by using the reaction heat without heating. The method has many disadvantages, such as low product selectivity, easy ring opening of epoxy bond to generate byproducts such as diol and hydroxy ester, dangerous treatment of high-concentration hydrogen peroxide and peroxy acid, equipment corrosiveness problem caused by acidic environment, etc.

In order to solve the problems of the traditional acid catalysis method, various green catalysis methods are developed.

In a two-phase system, the tungstic heteropoly acid has good effect of catalyzing the reaction of the vegetable oil and the hydrogen peroxide. Kozhevnikov et al (Journal of Molecular Catalysis A: Chemical, 1998,134 (1-3): 223-₃[PO₄{WP(O₂)₂}₄]^3-When the method is used for the epoxidation reaction of oleic acid, the conversion rate of the oleic acid reaches 95 percent, the selectivity of an epoxy product reaches 89 percent, and the dihydroxy by-product is only 1.3 percent. He Muting et al (applied chemistry, 1998, 15:117-₅H₅)N(CH₂)₁₅-CH₃]₃PW₁₂O₄₀The oil is used for catalyzing the oxidation reaction of the plant oil, the retention rate of the epoxy value reaches 99%, the reaction time is 4.5h, and the epoxy value reaches 6.6.

The molybdenum-containing complex catalyst has the advantages of high reaction rate, high conversion rate and the like in the epoxidation reaction of vegetable oil and fat. Organic peroxide cumene hydroperoxide is taken as an oxidant, and the conversion rate of the epoxidation of the soybean oil catalyzed by molybdenum acetylacetonate can reach 60% (Applied Catalysis A: General 2010(384): 213-219). Nitrogen heterocyclic ring substituted molybdenum complex [ Mo₂O₆(2- (1-pentyl-3-pyrazolyl) pyridine)]_nFor the epoxidation of methyl oleate, after 10min, the conversion of methyl oleate reaches 30% and is completely converted into 9, 10-epoxy methyl stearate, while after 6h, the conversion of methyl oleate reaches 82%, the yield is 78%, and the selectivity is as high as 95% (Dalton Transactions 2014,43(16): 6059-6069).

But the heteropoly acid or the molybdenum-containing complex catalyst has the problems of difficult solid-carrying and easy loss.

The method for promoting the epoxidation of the epoxidized vegetable oil by using the organic peroxide as the oxygen carrier does not generate a large amount of waste water and waste residues, and has the advantages of cleanness, environmental protection and high efficiency. The titanium-containing heterogeneous catalyst has good catalytic action on double bond epoxidation, and corresponding research work is more in recent years.

CN104277013A discloses a method for catalyzing butylene and cumene hydroperoxide to react to generate butylene oxide by using titanium-containing mesoporous or macroporous silica catalytic materials Ti-HMS, Ti-MCM-41, Ti-TUD-1, Ti-SBA-15, Ti-KIT-1 or Ti-SiO2, however, the reaction needs to be carried out under certain temperature and pressure, the reaction conditions are relatively harsh, and the activity and the catalytic performance stability of the mesoporous or macroporous catalytic materials have certain problems.

CN105315239B discloses a method for preparing 3, 4-epoxy-1-butene by oxidizing 1, 3-butadiene with organic peroxide, which uses mesoporous or macroporous titanium-containing catalytic materials which are subjected to silanization treatment.

CN102295626A discloses a method for preparing 1, 2-epoxyhexane and alpha, alpha-dimethyl benzyl alcohol simultaneously by catalyzing cumene hydroperoxide and cyclohexene to react by using a mesoporous or macroporous material treated by organosilicon vapor, wherein the treatment method causes the increase of the cost of the catalyst and can obviously change the surface property of the catalyst.

Ti-. beta.and Ti-MCM-41 molecular sieves were prepared by Corma et al and used for the oxidation of methyl oleate with H2O2/TBHP (Chemical Communications (Cambridge)1997(8): 795-. For Ti- β, the substrate conversion was lower on both oxidants after 8h of reaction (45.3% and 49.3%); and for Ti-MCM-41, the substrate conversion rate can reach 64.6 percent when TBHP is used as an oxidant under the solvent-free condition.

CN107840347A discloses a method for preparing a titanium silicalite molecular sieve by using silane containing a benzene ring structure as a modified raw material, and the method is used for catalyzing an epoxidation reaction of methyl oleate and tert-butyl hydroperoxide, and there is still room for further improving the conversion rate of methyl oleate and the selectivity of an epoxidation product.

CN107840344A discloses a method for preparing a titanium silicalite molecular sieve by using silane containing long-chain alkylamine as a modified raw material, and the method is used for catalyzing epoxidation reaction of methyl oleate and tert-butyl hydroperoxide, and there is still room for further improving the conversion rate of methyl oleate and the selectivity of epoxidized products.

In conclusion, the traditional vegetable oil epoxidation method has the problems of low product selectivity, poor intrinsic safety, equipment corrosion and the like, the homogeneous catalyst has the problems of difficult catalyst recovery and the like, the titanium-containing heterogeneous catalytic material has a complex preparation process and high cost, the activity of the titanium-containing heterogeneous catalytic material for vegetable oil epoxidation is not high enough, and the product selectivity needs to be further improved.

Disclosure of Invention

In order to solve the problems in the prior art, the inventor finds that the amorphous titanium-silicon composite oxide with rich mesopores is stable in structure and can efficiently catalyze the vegetable oil epoxidation reaction by taking organic peroxide as an oxidant through a large number of experiments. Based on this, the present invention was made.

A vegetable oil modifying method is characterized in that under the condition of epoxidation reaction, vegetable oil is contacted with organic peroxide in the presence of a titanium-silicon composite oxide and a ketone solvent to obtain the epoxy-containing vegetable oilThe product of the grease, wherein the titanium-silicon composite oxide is of an amorphous structure, is formed by aggregating nano particles, has mesopores in the range of 16-50nm, the ratio of the volume of the mesopores to the total pore volume is more than or equal to 80 percent, and the volume of the mesopores is more than or equal to 0.5cm³/g。

According to the method, the titanium-silicon composite oxide contains silicon element, titanium element and oxygen element, wherein the silicon element, the titanium element and the oxygen element account for more than 95% of the weight of the titanium-silicon composite oxide under the anhydrous drying condition, and the mass percentage of the titanium element is not less than 0.1% in terms of titanium dioxide.

The method according to the present invention, wherein the titanium silicon composite oxide has a nanoparticle size of not more than 40nm, preferably not more than 30nm, more preferably not more than 20nm, and the nanoparticle size is more than 5nm, preferably more than 8 nm.

The method according to the invention, wherein the specific surface area of the titanium-silicon composite oxide is 200-550m²The ratio of the mesoporous volume to the total pore volume is preferably equal to or greater than 90%, more preferably equal to or greater than 93%, most preferably equal to or greater than 95%.

The method of the invention, wherein the titanium-silicon composite oxide has L acidity, and the titanium-silicon composite oxide is 1450 +/-5 cm in pyridine-infrared characterization^-1Has a first absorption peak at 1612 +/-5 cm^-1The titanium-silicon composite oxide has a second absorption peak, the intensity ratio of the first absorption peak to the second absorption peak is at least 1.5 and at most 6, and the titanium-silicon composite oxide has a wide strong absorption within the range of 200-250nm and a weak absorption above 300nm according to the UV-Vis characterization.

The process according to the invention, wherein the epoxidation reaction conditions are: the molar ratio of the vegetable oil to the organic peroxide is 1: (0.1-1), the reaction temperature is 80-160 ℃, and the weight ratio of the titanium-silicon composite oxide to the organic peroxide is (0.01-0.2): 1.

the method of the invention, wherein the vegetable fat has the structure of R1CH ═ CHR2-R3, wherein R1 and R2 are alkyl or alkenyl respectively, R3 is carboxyl or ester group, and the carbon number of the vegetable fat is preferably 14-22.

The method according to the present invention, wherein the organic peroxide is preferably at least one of t-butyl hydroperoxide, cyclohexyl hydroperoxide, ethylbenzene hydroperoxide and cumene hydroperoxide.

The method according to the present invention, wherein the ketone solvent is a cyclic ketone having 3 to 10 carbon atoms, preferably 5 to 8 carbon atoms.

The method of the invention has the following steps that the molar ratio of the ketone solvent to the vegetable oil is (3-50): 1.

the vegetable oil modification method provided by the invention is a method for preparing epoxy alkane by carrying out epoxidation reaction on vegetable oil and organic peroxide, amorphous titanium-silicon composite oxide rich in mesopores is used as a catalyst, and contact reaction is carried out in the presence of a ketone solvent.

Drawings

FIG. 1 is an XRD spectrum of a titanium-silicon composite oxide prepared in preparation example 1 of a titanium-silicon composite oxide.

FIG. 2 is a pore distribution diagram of the titanium-silicon composite oxide prepared in preparation example 1 of titanium-silicon composite oxide.

FIG. 3 is a UV-Vis spectrum of the titanium silicon composite oxide prepared in preparation example 1.

Fig. 4 is an SEM image of the titanium-silicon composite oxide prepared in preparation example 1 of the titanium-silicon composite oxide.

Detailed Description

A vegetable oil modification method is characterized in that under the condition of epoxidation reaction, vegetable oil and organic peroxide are contacted in the presence of a titanium-silicon composite oxide and a ketone solvent to obtain a product containing epoxy vegetable oil, wherein the titanium-silicon composite oxide is an amorphous structure and is formed by aggregating nano particles, has mesopores with the range of 16-50nm, the ratio of the volume of the mesopores to the total pore volume is more than or equal to 80 percent, and the volume of the mesopores is more than or equal to 0.5cm³/g。

In the method of the present invention, the amorphous structure of the titanium-silicon composite oxide is analyzed by XRD, electron diffraction, or the like, and among them, measurement by XRD is preferable. The titanium-silicon composite oxide contains silicon, titanium and oxygen, wherein the silicon, the titanium and the oxygen account for more than 95 percent of the weight of the titanium-silicon composite oxide under the anhydrous drying condition. Titanium is the main catalytic active center of the titanium-silicon composite oxide, and the mass percentage of the titanium element calculated by titanium dioxide is not less than 0.1%, preferably not less than 1%, more preferably not less than 2%, most preferably not less than 4%, and preferably not more than 15%.

The titanium-silicon composite oxide is formed by aggregating nano particles, wherein the particle size of the nano particles is more than 5nm, preferably more than 8nm, and not more than 40nm, preferably not more than 30nm, and more preferably not more than 20 nm.

The specific surface area of the titanium-silicon composite oxide is 200-550m²Per g, preferably 240-400m²Per g, more preferably 260-330m²(ii) in terms of/g. The volume of the mesoporous is more than or equal to 0.5cm³In g, preferably ≥ 0.8cm³G, more preferably 1.0 cm or more³G, most preferably 1.1cm or more³/g。

The titanium-silicon composite oxide has mesopores with the range of 16-50nm, further has mesopores with the range of 24-48nm, and further has mesopores with the range of 30-42nm, and the titanium-silicon composite oxide has a very small amount of microporous structures, mainly mesopores, and the ratio of the mesopore volume (2-50nm, measured by a BET method) to the total pore volume is more than or equal to 80%, preferably more than or equal to 90%, more preferably more than or equal to 93%, and most preferably more than or equal to 95%.

The titanium-silicon composite oxide has L acidity, and in pyridine-infrared characterization, the titanium-silicon composite oxide is 1450 +/-5 cm^-1Has a first absorption peak at 1612 +/-5 cm^-1Has a second absorption peak, the ratio of the intensity of the first absorption peak to the intensity of the second absorption peak being at least 1.5 and at most 6, preferably 2 to 5, more preferably 2.5 to 4.

The titanium-silicon composite oxide has wide strong absorption within the range of 200-250nm and weak absorption above 300nm by the characterization of UV-Vis. The strong absorption at 200-250nm indicates that the titanium is mainly present in the four-coordinate state (high catalytic activity), while the weak absorption above 300nm indicates that the anatase titanium species (low catalytic activity) is low in content.

In the method of the invention, the titanium-silicon composite oxide can be prepared by the following method:

the optional preparation method I comprises the following steps:

(1) mixing optional silicon source, titanium source, alkali source and water, and treating at 5-90 deg.C for 0.5-24 hr to obtain SiO₂:TiO₂The alkali source comprises 1: (0.001-0.2): (0.05-0.2): (10-100) the first product;

(2) according to TiO aspect₂Halogen ion (according to X)^-X is halogen) in a molar ratio of 1: (0.5-3) adding a halogen ion compound to obtain a second product;

(3) treating the second product at the temperature of 100-150 ℃ for 1-72h to obtain gel;

(4) recovering the solid product to obtain the titanium-silicon composite oxide;

in the first preparation method, the silicon source in step (1) has no special requirement, and silicon content of more than 80%, 90%, 95%, 99% calculated on dry basis of silicon dioxide of the silicon source can be used as the silicon source, preferably the silicon source is at least one of tetraalkoxysilicon, white carbon black, silica gel, silica sol, more preferably contains tetraalkoxysilicon, and most preferably contains at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate.

In the first preparation method, there is no particular requirement for a titanium source, and a common titanium source known to those skilled in the art can be used as the titanium source of the present invention, and preferably, the titanium source is at least one selected from the group consisting of tetraalkoxytitanium, titanium tetrachloride, titanium trichloride, titanium sulfate, and titanium nitrate, more preferably, at least one selected from the group consisting of tetraalkoxytitanium and titanium tetrachloride, and most preferably, at least one selected from the group consisting of tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.

In the first preparation method, the alkali is not particularly required, preferably, the alkali source is at least one selected from the group consisting of aliphatic amines, aliphatic alcamines, quaternary ammonium bases, and inorganic alkali compounds, the aliphatic amines and the aliphatic alcamines are preferably at least one having less than 10 carbon atoms, the inorganic alkali is preferably at least one selected from the group consisting of group I and/or group II hydroxide compounds and ammonia water, more preferably at least one selected from the group consisting of C1-C5 aliphatic amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, sodium hydroxide, and ammonia water, and most preferably, the alkali is tetraethylammonium hydroxide. .

The first preparation method has no special requirement on water, and can be deionized water, distilled water, secondary distilled water, industrial water and domestic water, and the conductivity of the water can be 3000 microsiemens/cm, 1000 microsiemens/cm, 500 microsiemens/cm, 100 microsiemens/cm, 10 microsiemens/cm and 5 microsiemens/cm.

The preparation method I has no special requirements on the charging sequence, the mixing mode, the mixing atmosphere and the mixing equipment of the raw materials in the step (1), and can mix the raw materials in a reaction kettle according to the charging proportion and treat the raw materials at normal pressure in the air atmosphere from the viewpoint of simple and convenient operation. The treatment is preferably carried out at 20-60 ℃ for 4-18h, more preferably at 30-50 ℃ for 6-12 h. The composition of the first product after the treatment in the step (1) is preferably SiO2: TiO2: alkali source: water: 1: (0.01-0.17): (0.07-0.17): (25-90), more preferably SiO2: TiO2: alkali source: water ═ 1: (0.03-0.14): (0.09-0.15): (35-80), SiO2: TiO2: alkali source: water 1: (0.05-0.12): (0.10-0.14): (45-70), most preferred are SiO2: TiO2: alkali source: water ═ 1: (0.07-0.10): (0.12-0.13): (50-65).

In the first preparation method, the halide ion compound in step (2) is a salt containing a halide ion, preferably, a salt, an ammonium salt, and a quaternary ammonium salt of a group I element are included, more preferably, at least one of a sodium salt, a potassium salt, an ammonium salt, and a quaternary ammonium salt, and most preferably, the salt is at least one of a sodium salt and a quaternary ammonium salt; the halogen ions comprise fluorine, chlorine, bromine and iodine, and preferably, the halogen ions are chloride ions; more preferably, the halogen ion compound is at least one selected from the group consisting of sodium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and cetyltrimethylammonium chloride, and most preferably tetraethylammonium chloride. The halogen ions are preferably added in an amount of TiO2 halogen ions (in terms of X)^-In terms of X is halogenElement) molar ratio of 1: (0.8-2.5), more preferably 1: (1.2-2.2), and more preferably 1: (1.5-2.0), most preferably 1: (1.7-1.9).

According to the first preparation method, the product after being processed in the steps (1) and (2) is still liquid, and the product after being processed in the step (3) is gelatinous solid; the treatment conditions in the step (3) are preferably treatment at 110-140 ℃ for 12-48h, more preferably treatment at 120-135 ℃ for 18-36h, and further preferably treatment at 125-130 ℃ for 24-30 h.

The first preparation method, the step (4) of recovering the solid product, comprises the steps of carrying out first drying and first roasting on the gel product obtained in the step (3). The first drying is preferably carried out at 60 to 130 ℃, more preferably 80 to 110 ℃, more preferably 90 to 100 ℃, for a treatment time of preferably 1 to 24 hours, preferably 6 to 18 hours, more preferably 8 to 12 hours, in air or inert gas, and may be carried out in a suitable drying oven or by spray drying. The first calcination is to treat the product at a temperature above 350 ℃, and the calcination of the invention generally comprises treating at a temperature of 400-700 ℃, preferably 450-600 ℃, under a suitable atmosphere (such as air, lean air, oxygen, nitrogen) for 1-10h, preferably 3-8h, more preferably 4-6 h.

The preparation method comprises the first step of recovering the solid product, and the second step of treating the product after the first roasting under a liquid phase condition, at least partially separating the solid product, and performing second drying and second roasting to obtain the titanium-silicon composite oxide material.

In the first preparation method, the liquid phase condition is an ammonium salt-containing solution with a concentration of 0.1-5mol/L, preferably 0.5-3mol/L, more preferably 1-2mol/L, the ammonium salt is ammonium chloride, ammonium nitrate or ammonium carbonate, preferably ammonium nitrate, the pH of the solution is 1-5, preferably 2-3, the pH of the solution is measured by a pH meter, and the weight ratio of the first calcined product to the ammonium salt-containing solution is 1: (10-50), preferably 1: (20-40), more preferably 1: (25-30) the treatment temperature is 40-90 ℃, preferably 60-85 ℃, more preferably 70-80 ℃, and the treatment time is 1-18h, preferably 3-14h, more preferably 5-10h, most preferably 6-8 h.

In the first preparation method, the method for separating the solid product can be centrifugation, filtration, nanofiltration, membrane separation and the like, and the invention has no special requirements.

In the first preparation method, the second drying is preferably carried out at 60-130 ℃, more preferably 80-110 ℃, more preferably 90-100 ℃ under the condition of air or inert gas, the treatment time is preferably 1-24h, preferably 6-18h, more preferably 8-12h, and the treatment can be completed in a suitable drying oven or can be completed by spray drying. The second calcination is to treat the product at a temperature above 350 ℃, and the calcination of the invention generally comprises treating at a temperature of 400-700 ℃, preferably 450-600 ℃, under a suitable atmosphere (such as air, lean air, oxygen, nitrogen) for 1-10h, preferably 3-8h, more preferably 4-6 h.

The optional preparation method II comprises the following steps:

(1) and (2) mixing an optional silicon source (calculated according to SiO 2), a titanium source (calculated according to TiO 2), an alkali source and water according to a molar ratio of SiO2 to TiO2 to the alkali source (1): (0.001-0.2): (0.05-0.2), and treating for 0.5-24h at 5-60 ℃ to obtain a product A with the composition;

(2) neutralizing the product A (calculated by SiO 2) with acid to neutralize alkali, mixing with polyquaternium and water, and treating at 60-90 ℃ for 0.5-12h to obtain the product A and the polyquaternium with the weight ratio of 1: (0.001-0.1), product A: the water molar ratio is 1: (10-100) the product B, wherein water is water contained in the product B;

(3) treating the product B at the temperature of 100-150 ℃ for 2-168h to obtain a gel product C;

(4) at least partially recovering the solid product obtained in the step (3) to obtain the titanium-silicon composite oxide.

In the second preparation method, no special requirement is imposed on the silicon source, and the silicon source with a silicon content of more than 80%, 90%, 95% and 99% calculated on the dry basis of silicon dioxide of the silicon source can be used as the silicon source, preferably the silicon source is at least one of tetraalkoxysilicon, white carbon black, silica gel and silica sol, more preferably the silicon source contains tetraalkoxysilicon, and most preferably at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.

In the second preparation method, there is no particular requirement for a titanium source, and a common titanium source known to those skilled in the art can be used as the titanium source of the present invention, and preferably, the titanium source is at least one selected from the group consisting of titanium tetraalkoxide, titanium tetrachloride, titanium trichloride, titanium sulfate, and titanium nitrate, more preferably, at least one selected from the group consisting of titanium tetraalkoxide, titanium tetrachloride, and most preferably, at least one selected from the group consisting of tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.

In the second preparation method, no special requirement is required for the alkali required for preparing the titanium-silicon composite oxide, and the amount of the alkali only needs to meet the requirement that at least the silicon source and the titanium source are partially hydrolyzed. Preferably, the alkali source is at least one selected from the group consisting of aliphatic amines, aliphatic alcohol amines, quaternary ammonium bases and inorganic alkali compounds, the aliphatic amines and the aliphatic alcohol amines are preferably at least one with the carbon number less than 10, and the inorganic alkali is preferably at least one of hydroxide radical compounds of main group I and/or main group II and ammonia water; preferably an inorganic base, further preferably at least one of sodium hydroxide and potassium hydroxide, most preferably the base is sodium hydroxide.

In the second preparation method, no special requirement is required for the acid, and the proton neutralization base can be directly or indirectly generated in the solution. Preferably, the acid comprises an organic acid and an inorganic acid, the organic acid is a carboxyl-containing compound with the carbon number of C1-C20, and the inorganic acid comprises hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, sulfuric acid, carbonic acid, monohydrogen sulfate and dihydrogen phosphate. Preferably, the acid is an inorganic acid, more preferably hydrochloric acid, nitric acid, phosphoric acid, dihydrogen phosphate, and most preferably hydrochloric acid.

In the second preparation method, the reaction of neutralizing the alkali by the acid is the reaction of neutralizing hydrogen protons and hydroxide ions to generate water, and the neutralization process is carried out so as to achieve the pH value of the product A to be 3-11, preferably 5-9, and more preferably 6-8. The pH value is preferably measured by a precision pH meter.

In the second preparation method, the polyquaternary ammonium salt is a polymer with a polymerization degree of 10-100000, preferably 100-50000, more preferably 500-10000, and most preferably 1000-5000, wherein the polymerization degree refers to the average polymerization degree, i.e. the average value of the number of repeating units contained in the macromolecular chain of the polymer. The polyquaternium is preferably at least one of the following polyquaterniums:

polyquaternium-2, CAS No.: 68555-36-2, quaternization of poly [ bis (2-chloroethyl) ether-alt-1, 3-bis [3- (dimethylamino) propyl ] urea ], structural formula is

Polyquaternium-6, CAS No.: 26062-79-3, poly dimethyl diallyl ammonium chloride with structural formula

Polyquaternium-7, CAS No.: 26590-05-6, copolymer of dimethyl diallyl ammonium chloride and acrylamide with structural formula

Polyquaternium-10, CAS No.: 68610-92-4, chlorinated-2-hydroxy-3- (trimethylamino) propyl polyethylene oxide cellulose ether with structural formula

Polyquaternium-11, CAS No.: 53633-54-8 cationic polymer of Vinyl Pyrrolidone (VP)/N, N dimethylamino ethyl methacrylate (DMAEMA) with structural formula

Polyquaternium-22, CAS No.: 53694-17-0, dimethyl diallyl ammonium chloride-acrylic acid copolymer with structural formula

Polyquaternium-32, CAS No.: 35429-19-7, N, N, N-trimethyl-2- (2-methyl-1-oxo-2-propenyl oxy) ethyl ammonium chloride-acrylamide copolymer with structural formula

Polyquaternium-37, CAS No.: 26161-33-1, N, N, N-trimethyl-2- [ (2-methyl-1-oxo-2-propenyl) oxy ] ethanamine hydrochloride homopolymer with structural formula

Polyquaternium-39, CAS No.: 25136-75-8, dimethyl diallyl ammonium chloride-acrylamide-acrylic acid copolymer with structural formula

Polyquaternium-44, CAS No.: 150599-70-5, N-vinyl pyrrolidone and quaternized vinyl imidazole copolymer with structural formula

Polyquaternium-47, CAS No.: 197969-51-0, N, N, N-trimethyl-3- [ (2-methyl-1-oxo-2-propenyl) amino ] -1-propanaminium chloride was polymerized with methyl 2-acrylate and 2-acrylic acid by polymerizing the following monomers

Polyquaternium-51, CAS No.: 125275-25-4, methacryloyloxyethyl phosphorylcholine-n-butyl methacrylate, by polymerization of the following monomers

According to the common knowledge in the field, the template agent for synthesizing the molecular sieve or related materials is usually organic amine or a compound containing quaternary ammonium ions, and the inventor finds that the titanium-silicon composite oxide which is amorphous, rich in mesopores with larger size, rich in active titanium species and high in catalytic performance is favorable to be synthesized when the polyquaternium does not exert the structure guiding effect under the neutral condition or the condition close to the neutral condition, particularly the polyquaternium-2, the polyquaternium-47 and the polyquaternium-51 have the optimal effect, and the polyquaternium-51 is most preferred. Therefore, among the above-mentioned polyquaterniums, at least one of polyquaternium-2, polyquaternium-47 and polyquaternium-51 is preferable, and polyquaternium-51 is most preferably contained.

The second preparation method has no special requirement on the water used in the step (1), and can be deionized water, distilled water, secondary distilled water, industrial water and domestic water, and the conductivity of the water can be 3000 microsiemens/cm, 1000 microsiemens/cm, 500 microsiemens/cm, 100 microsiemens/cm, 10 microsiemens/cm and 5 microsiemens/cm.

The second preparation method has no special requirements on the raw material feeding sequence, the mixing mode, the mixing atmosphere and the mixing equipment in each step of the operation steps, and can mix the raw materials in a reaction kettle according to the feeding proportion and treat the raw materials at normal pressure in the air atmosphere from the viewpoint of simple and convenient operation.

In the second preparation method, the composition of the product A in the step (1) is 1: (0.001-0.2): (0.05-0.2), preferably 1: (0.02-0.17): (0.055-0.17), more preferably 1: (0.05-0.15): (0.06 to 0.13), further preferably SiO2: TiO2: alkali source (molar ratio) ═ 1: (0.07-0.12): (0.065-0.10); the composition of the product B is preferably that the weight ratio of the product A to the polyquaternium is 1: (0.005-0.08), more preferably 1: (0.01-0.06), further preferably 1: (0.02-0.04), product a: the water molar ratio is 1: (25-90), more preferably 1: (40-80), and more preferably 1: (50-70).

In the second preparation method, the product after the treatment in the steps (1) and (2) is still liquid, and the product after the treatment in the step (3) is a gel-like solid product.

In the second preparation method, the treatment conditions in the step (1) are preferably treatment at 20-50 ℃ for 2-18h, and further preferably treatment at 30-40 ℃ for 6-12 h; the treatment condition of the step (2) is preferably treatment at 65-85 ℃ for 1-8h, more preferably treatment at 70-80 ℃ for 3-6 h; the treatment conditions in the step (3) are preferably treatment at 110-140 ℃ for 24-120h, and more preferably treatment at 125-135 ℃ for 36-72 h.

And (2) in the second preparation method, the step (4) of recovering the solid product comprises the steps of carrying out first drying and first roasting on the gelatinous solid product obtained in the step (3). The first drying is preferably carried out at 60 to 130 ℃, more preferably 80 to 110 ℃, still more preferably 90 to 100 ℃ under air or inert gas conditions for a treatment time of preferably 1 to 24 hours, still more preferably 6 to 18 hours, still more preferably 8 to 12 hours, and may be carried out in a suitable drying oven or may be carried out by spray drying. The first calcination is to treat the product at a temperature above 350 ℃, and the calcination of the invention generally comprises treating at a temperature of 400-700 ℃, preferably 450-600 ℃, under a suitable atmosphere (such as air, lean air, oxygen, nitrogen) for 1-10h, preferably 3-8h, more preferably 4-6 h.

In the second preparation method, preferably, the first roasted product is subjected to liquid phase treatment under the condition of water, then at least part of the solid product is separated, and the titanium-silicon composite oxide material is obtained after second drying and second roasting. Wherein, the liquid phase treatment is carried out under the condition of ammonium salt-containing solution with the concentration of 0.1-5mol/L, preferably 0.5-3mol/L, and more preferably 1-2 mol/L; the ammonium salt is ammonium chloride, ammonium nitrate, ammonium carbonate, preferably ammonium chloride, the pH value of the solution is 1-5, preferably 3-4, the pH value of the solution is measured by a precision pH meter, and the weight ratio of the product after the first roasting to the ammonium salt-containing solution is 1: (10-50), preferably 1: (20-40), more preferably 1: (25-30) the treatment temperature is 40-90 ℃, preferably 60-85 ℃, more preferably 70-80 ℃, and the treatment time is 1-18h, preferably 3-14h, more preferably 6-10 h.

In the second preparation method, the solid product can be separated by centrifugation, filtration, nanofiltration, membrane separation and the like, and the method has no special requirements.

In the second preparation method, the second drying is preferably performed at 60 to 130 ℃, more preferably 80 to 110 ℃, and even more preferably 90 to 100 ℃ under the condition of air or inert gas, the treatment time is preferably 1 to 24 hours, more preferably 6 to 18 hours, and even more preferably 8 to 12 hours, and the second drying can be completed in a suitable drying oven or can be completed by spray drying. The second calcination is to treat the product at a temperature above 350 ℃, and the calcination of the invention generally comprises treating at a temperature of 400-700 ℃, preferably 450-600 ℃, under a suitable atmosphere (such as air, lean air, oxygen, nitrogen) for 1-10h, preferably 3-8h, more preferably 4-6 h.

The molar ratio of the vegetable oil or fat to the organic peroxide in the method of the present invention is not limited, and may be, for example, 1: (0.01 to 100) in view of sufficiently utilizing the organic peroxide, the molar ratio of the vegetable oil or fat to the organic peroxide is preferably 1: (0.01-1), in order to reduce the energy consumed by the separation of unreacted products while maintaining the conversion rate of the vegetable fat and oil, it is preferable that the molar ratio of the vegetable fat and oil to the organic peroxide is 1: (0.1-1), more preferably 1: (0.6-1), more preferably 1: (0.8-1); the reaction temperature is 80-160 ℃, preferably 100-140 ℃, and more preferably 120-130 ℃; the invention has no special requirement on the reaction pressure, the reaction can be carried out under the condition of normal pressure or pressure, for example, the reaction pressure can be 0.1-5Mpa, and the invention is preferably carried out under the normal pressure from the viewpoint of reducing the operation cost; the weight ratio of the catalyst to the organic peroxide is (0.01-0.2): 1. preferably (0.05-0.18): 1. more preferably (0.08-0.15): 1; the contact time is at least 10min, preferably 20-90 min.

In the method of the invention, the vegetable fat has the following structure: r1CH ═ CHR2-R3, wherein R1 and R2 are each alkyl or alkenyl, the alkyl contains no other substituent or hydroxyl or carbonyl, the alkenyl contains 1 to 5 double bonds, R3 is carboxyl or ester group, the ester group includes methanol ester, ethanol ester, propanol ester, ethylene glycol ester, glycerol ester and the like, the carbon number of the vegetable fat is not limited, and may be, for example, C6 to C35, preferably 14 to 22. The vegetable oil and fat of the present invention includes, but is not limited to, oleic acid ((Z) -9-octadecenoic acid), linoleic acid (cis-9, 12-octadecenoic acid), linolenic acid (all cis-9, 12, 15-octadecenoic acid), arachidonic acid, DHA (22-carbon 6-enoic acid), EPA (20-carbon 5-enoic acid), ricinoleic acid (cis-9-octadecenoic acid), and ester compounds thereof, such as methanol ester, ethanol ester, propylene ester, and glycerol ester.

In the method of the present invention, the organic peroxide is not particularly selected, and may be, for example, at least one of t-butyl hydroperoxide, cyclohexyl hydroperoxide, ethylbenzene hydroperoxide, isopropyl hydroperoxide, cumene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, t-butyl peroxypivalate, t-amyl hydroperoxide and di-t-butyl peroxide, and preferably at least one of t-butyl hydroperoxide, cyclohexyl hydroperoxide, ethylbenzene hydroperoxide and cumene hydroperoxide.

The process of the present invention is carried out in the presence of a ketone solvent, which is preferably a cyclic ketone having 3 to 10 carbon atoms, more preferably 5 to 8 carbon atoms. The molar ratio of the ketone solvent to the vegetable oil is (3-50): 1. preferably (5-30): 1. further preferably (8-20): 1. more preferably (10-15): 1.

according to the method, the titanium-silicon composite oxide can be used in the form of raw powder, can also be used after being formed, and can be mixed with other oxidation catalysts for use; the titanium-silicon composite oxide can be used in various reactors such as a kettle reactor, a slurry bed reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a micro-channel reactor and the like; the reaction raw materials and the catalyst can be fed at one time, intermittently or continuously, and the invention is not limited.

It will be understood by those skilled in the art that the separation of the product from the catalyst can be achieved in various ways, for example, when the original powdery titanium silicalite molecular sieve is used as the catalyst, the separation of the product and the recovery and reuse of the catalyst can be achieved by settling, filtering, centrifuging, evaporating, membrane separation, or the like, or the catalyst can be molded and then loaded into a fixed bed reactor, and the catalyst is recovered after the reaction is finished, and various methods for separating and recovering the catalyst are often referred to in the prior art and will not be described herein again.

The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

In each of the following examples and comparative examples, the material structure was determined by XRD analysis; the chemical composition was determined by XRF analysis; the pore volume and pore distribution were determined according to the method described in RIPP 151-90 in "analytical methods for petrochemical industry" compiled by Yangchi et al (published by scientific Press in 1990, 9 months, first edition); the appearance analysis adopts an SEM method to observe the particle size and appearance; the acid analysis is carried out by adopting a pyridine infrared spectrum method; the state of the titanium species was analyzed by UV-Vis spectroscopy

The raw materials used are analytically pure reagents, unless otherwise specified.

The reaction product is analyzed by gas chromatography, and the analysis result is quantified by an external standard method. Wherein, the chromatographic analysis conditions are as follows: agilent-6890 type chromatograph, HP-5 capillary chromatographic column, sample amount of 0.5 μ L, and sample inlet temperature of 280 deg.C. The column temperature was maintained at 100 ℃ for 2min, then ramped up to 250 ℃ at a rate of 15 ℃/min and maintained for 10 min. FID detector, detector temperature 300 ℃.

In each of the examples and comparative examples:

the percent conversion of vegetable oil or fat (%) (the number of moles of vegetable oil or fat in the starting material-the number of moles of vegetable oil or fat in the product)/the number of moles of vegetable oil or fat in the starting material X100%

Conversion ratio (%) of organic peroxide (number of moles of organic peroxide in raw material-number of moles of organic peroxide in product)/number of moles of organic peroxide in raw material X100%

Selectivity (%) of epoxidized product (mole number of epoxidized product produced in product/(mole number of vegetable oil and fat in raw material-mole number of vegetable oil and fat in product) × 100%

Preparation examples 1 to 8 illustrate the preparation process and physicochemical characteristic parameters of the titanium-silicon composite oxide used in the method of the present invention.

Preparation example 1

(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetraethylammonium hydroxide and water, and treating at 30 ℃ for 12 hours to obtain a mixture with a molar composition of SiO2, TiO2, tetraethylammonium hydroxide and water of 1: 0.1: 0.12: 60;

(2) according to the molar ratio of TiO2 to chloride ion of 1: 1.8 adding tetraethyl ammonium chloride to obtain a second product;

(3) treating the second product at 130 ℃ for 24h to obtain gel;

(4) and (3) drying the gel obtained in the step (3) at 100 ℃ for 10h, roasting at 550 ℃ for 4h, recovering a first roasted product, treating at 80 ℃ for 8h according to the weight ratio of the first roasted product to ammonium nitrate solution with the pH of 2.2 and the concentration of 1.5mol/L, drying at 90 ℃ for 8h, and roasting at 500 ℃ for 6h to obtain a titanium-silicon composite oxide sample with the number of A1.

And performing physicochemical characterization on A1.

Fig. 1 shows XRD analysis results, indicating that a1 is an amorphous structure.

FIG. 2 shows the result of pore distribution, and it can be seen that A1 has a distribution of mesopores in the range of 16-50 nm.

FIG. 3 is a UV-Vis spectrum for characterizing the titanium species state, which shows that the absorption is broad in the range of 200-250nm and weak above 300 nm.

Fig. 4 is an SEM, and it can be seen that a1 is formed by aggregation of a plurality of nanoparticles, and the average size of the individual nanoparticles is measured to be about 9 nm.

Other results such as titanium, silicon, oxygen element content, specific surface area, mesoporous volume, titanium dioxide content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L-acid and the like are shown in Table 1.

Preparation example 2

(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetraethylammonium hydroxide and water, and treating for 6 hours at 50 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetraethylammonium hydroxide and water of 1: 0.07: 0.13: 50;

(2) according to the molar ratio of TiO2 to chloride ion of 1: 1.7 adding tetraethyl ammonium chloride to obtain a second product;

(3) treating the second product at 125 ℃ for 30h to obtain gel;

(4) drying the gel obtained in the step (3) at 90 ℃ for 12h, roasting at 550 ℃ for 6h, recovering the first roasted product, treating at 70 ℃ for 6h according to the weight ratio of the first roasted product to ammonium nitrate solution with pH of 3.0 and concentration of 1.0mol/L of 1:30, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 4h to obtain the titanium-silicon composite oxide with the number of A2

A2 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, titanium, silicon, oxygen content, specific surface area, mesoporous volume, titanium dioxide content, particle size, mesoporous range, mesoporous to total pore ratio, and first peak of L acid (1450 + -5 cm)^-1) Second peak (1612. + -. 5 cm)^-1) Other results such as ratios are shown in Table 1.

Preparation example 3

(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetraethylammonium hydroxide and water, and treating for 6 hours at 50 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetraethylammonium hydroxide and water of 1: 0.05: 0.1: 45;

(2) according to the molar ratio of TiO2 to chloride ion of 1: 1.5 adding tetraethyl ammonium chloride to obtain a second product;

(3) treating the second product at 135 deg.C for 18h to obtain gel;

(4) firstly drying the gel obtained in the step (3) at 110 ℃ for 10h, firstly roasting at 600 ℃ for 5h, recovering a first roasted product, then treating at 75 ℃ for 7h according to the weight ratio of the first roasted product to an ammonium nitrate solution with the pH of 2.0 and the concentration of 2.0mol/L, and secondly drying the recovered product at 95 ℃ for 10h, and secondly roasting at 450 ℃ for 4h to obtain a titanium-silicon composite oxide with the number of A3;

a3 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.

Preparation example 4

(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetraethylammonium hydroxide and water, and treating at 35 ℃ for 10 hours to obtain a mixture with a molar composition of SiO2, TiO2, tetraethylammonium hydroxide and water of 1: 0.12: 0.14: 70;

(2) according to the molar ratio of TiO2 to chloride ion of 1:2 adding tetraethyl ammonium chloride to obtain a second product;

(3) treating the second product at 120 ℃ for 36h to obtain gel;

(4) drying the gel obtained in the step (3) at 90 ℃ for 8h, roasting at 450 ℃ for 4h, recovering a first roasted product, treating at 80 ℃ for 6h according to the weight ratio of the first roasted product to an ammonium nitrate solution with the pH of 2.6 and the concentration of 2.0mol/L, drying at 90 ℃ for 12h, and roasting at 550 ℃ for 5h to obtain a titanium-silicon composite oxide, wherein the number is A4;

a4 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.

Preparation example 5

(1) Mixing propyl orthosilicate, tetraethyl titanate, tetramethylammonium hydroxide and water, and treating at 20 ℃ for 18 hours to obtain a mixture with a molar composition of SiO2, TiO2, tetramethylammonium hydroxide and water of 1: 0.035: 0.09: 35;

(2) according to the molar ratio of TiO2 to chloride ion of 1: 1.2 adding tetramethylammonium chloride to obtain a second product;

(3) treating the second product at 110 ℃ for 48h to obtain gel;

(4) firstly drying the gel obtained in the step (3) at 110 ℃ for 6h, firstly roasting the gel at 400 ℃ for 8h, recovering a first roasted product, then treating the gel at 85 ℃ for 9h according to the weight ratio of the first roasted product to an ammonium chloride solution with the pH of 1.3 and the concentration of 0.5mol/L, and secondly drying the recovered product at 110 ℃ for 18h, and secondly roasting the gel at 700 ℃ for 3h to obtain a titanium-silicon composite oxide with the number of A5;

a5 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.

Preparation example 6

(1) Mixing n-butyl silicate, tetrapropyl titanate, hexadecyl trimethyl ammonium hydroxide and water, and treating for 4 hours at the temperature of 60 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, hexadecyl trimethyl ammonium hydroxide and water of 1: 0.13: 0.15: 80;

(2) according to the molar ratio of TiO2 to chloride ion of 1: 2.2 adding hexadecyl trimethyl ammonium chloride to obtain a second product;

(3) treating the second product at 140 ℃ for 12h to obtain gel;

(4) firstly drying the gel obtained in the step (3) at 110 ℃ for 6h, firstly roasting the gel at 600 ℃ for 3h, recovering a first roasted product, then treating the gel at 90 ℃ for 4h according to the weight ratio of the first roasted product to an ammonium chloride solution with the pH of 4.5 and the concentration of 3.0mol/L of 1:40, and secondly drying the recovered product at 100 ℃ for 6h, and secondly roasting the recovered product at 550 ℃ for 3h to obtain a titanium-silicon composite oxide with the number of A6;

a6 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.

Preparation example 7

(1) Mixing tetrabutyl orthosilicate, tetrapropyl titanate, tetramethylammonium hydroxide and water, and treating for 18 hours at 25 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetramethylammonium hydroxide and water of 1: 0.02: 0.08: 25;

(2) according to the molar ratio of TiO2 to chloride ion of 1:0.8 adding tetramethylammonium chloride to obtain a second product;

(3) treating the second product at 110 ℃ for 12h to obtain gel;

(4) firstly drying the gel obtained in the step (3) at 80 ℃ for 18h, firstly roasting at 550 ℃ for 8h, recovering a first roasted product, then treating at 90 ℃ for 12h according to the weight ratio of the first roasted product to an ammonium chloride solution with the pH of 5.0 and the concentration of 0.8mol/L, and secondly drying the recovered product at 80 ℃ for 12h, and secondly roasting at 600 ℃ for 6h to obtain a titanium-silicon composite oxide with the number of A7;

a7 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.

Preparation example 8

(1) Mixing n-butyl silicate, tetrapropyl titanate, sodium hydroxide and water, and treating at 70 ℃ for 24 hours to obtain a mixture with a molar composition of SiO2, TiO2, sodium hydroxide and water of 1: 0.2: 0.2: 100;

(2) according to the molar ratio of TiO2 to chloride ion of 1: 0.5 adding sodium chloride to obtain a second product;

(3) treating the second product at 100 ℃ for 72h to obtain gel;

(4) firstly drying the gel obtained in the step (3) at 120 ℃ for 24h, firstly roasting at 500 ℃ for 10h, recovering a first roasted product, then treating at 90 ℃ for 18h according to the weight ratio of the first roasted product to an ammonium chloride solution with the pH of 1.1 and the concentration of 5.0mol/L, and secondly drying the recovered product at 130 ℃ for 24h, and secondly roasting at 600 ℃ for 10h to obtain a titanium-silicon composite oxide with the number of A8;

a8 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.

Preparation of comparative example 1

(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetrapropylammonium hydroxide and water, and treating for 12 hours at the temperature of 30 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetrapropylammonium hydroxide, water, 1: 0.07: 0.13: 50;

(2) treating the product obtained in the step (1) at 170 ℃ for 72 h;

(3) filtering and washing the product obtained in the step (2), drying a filter cake at 90 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain a titanium-silicon molecular sieve with the number of D1;

physicochemical characterization of D1 revealed that the structure was MFI type, and other results, such as contents of titanium, silicon and oxygen elements, specific surface area, mesoporous volume, titanium dioxide content, particle size, mesoporous range, mesoporous to total pore ratio, and ratio of first peak to second peak of L acid, are shown in Table 1.

Preparation of comparative example 2

(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetrapropylammonium hydroxide and water, and treating for 12 hours at the temperature of 30 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetrapropylammonium hydroxide, water, 1: 0.07: 0.13: 50;

(2) treating the product obtained in the step (1) at 90 ℃ for 12 h;

(3) mixing the product obtained in the step (2) (calculated as SiO 2) with a silanization reagent according to the molar ratio of 1: 0.1 adding N-phenyl-3-aminopropyl trimethoxy silanization reagent and processing for 48h at 170 ℃;

(4) filtering and washing the product obtained in the step (3), drying a filter cake at 90 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain a silylation reagent expanded titanium silicalite molecular sieve with the number of D2;

physicochemical characterization of D2 revealed that the structure was MFI type, and other results, such as contents of titanium, silicon and oxygen elements, specific surface area, mesoporous volume, titanium dioxide content, particle size, mesoporous range, mesoporous to total pore ratio, and ratio of first peak to second peak of L acid, are shown in Table 1.

TABLE 1

The following examples illustrate the method of modifying vegetable fats and oils according to the present invention.

Example 1

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, tert-butyl hydroperoxide is taken as an oxidant, acetone is taken as a solvent, the molar ratio of oleic acid to tert-butyl hydroperoxide is 1:1, the molar ratio of the solvent to oleic acid is 10:1, the weight ratio of the catalyst to tert-butyl hydroperoxide is 0.1:1, the reaction temperature is 120 ℃, the reaction pressure is 0.1MPa, the reaction time is 50min, and the reaction results are shown in Table 2.

Example 2

A reaction kettle is used as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is used as a catalyst, tert-butyl hydroperoxide is used as an oxidant, cyclopentanone is used as a solvent, the molar ratio of oleic acid to tert-butyl hydroperoxide is 1:1, the molar ratio of the solvent to oleic acid is 10:1, the weight ratio of the catalyst to cumene hydroperoxide is 0.1:1, the reaction temperature is 120 ℃, the reaction pressure is 0.1MPa, the reaction time is 50min, and the reaction results are shown in Table 2.

Example 3

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, cyclohexyl hydrogen peroxide is taken as an oxidant, cyclohexanone is taken as a solvent, the molar ratio of methyl oleate to cyclohexyl hydrogen peroxide is 1:1, the molar ratio of the solvent to methyl oleate is 14:1, the weight ratio of the catalyst to the cyclohexyl hydrogen peroxide is 0.15:1, the reaction temperature is 125 ℃, the reaction pressure is 0.1MPa, the reaction time is 20min, and the reaction results are shown in Table 2.

Example 4

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, ethylbenzene hydroperoxide is taken as an oxidant, cyclopentanone is taken as a solvent, the molar ratio of oleic acid to ethylbenzene hydroperoxide is 1:1, the molar ratio of the solvent to oleic acid is 15:1, the weight ratio of the catalyst to ethylbenzene hydroperoxide is 0.08:1, the reaction temperature is 130 ℃, the reaction pressure is 0.1MPa, the reaction time is 30min, and the reaction results are shown in Table 2.

Example 5

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, tert-butyl hydroperoxide is taken as an oxidant, cycloheptanone is taken as a solvent, the molar ratio of oleic acid to tert-butyl hydroperoxide is 1:1, the molar ratio of the solvent to oleic acid is 10:1, the weight ratio of the catalyst to tert-butyl hydroperoxide is 0.1:1, the reaction temperature is 120 ℃, the reaction pressure is 0.1MPa, the reaction time is 50min, and the reaction result is shown in Table 2.

Example 6

A reaction kettle is used as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is used as a catalyst, cumene hydroperoxide is used as an oxidant, acetone is used as a solvent, the molar ratio of methyl oleate to cumene hydroperoxide is 1:0.8, the molar ratio of the solvent to methyl oleate is 8:1, the weight ratio of the catalyst to cumene hydroperoxide is 0.05:1, the reaction temperature is 110 ℃, the reaction pressure is 0.1MPa, the reaction time is 80min, and the reaction result is shown in Table 2.

Example 7

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, cyclohexyl hydrogen peroxide is taken as an oxidant, acetone is taken as a solvent, the molar ratio of linoleic acid to cyclohexyl hydrogen peroxide is 1:1, the molar ratio of the solvent to the linoleic acid is 9:1, the weight ratio of the catalyst to the cyclohexyl hydrogen peroxide is 0.07:1, the reaction temperature is 100 ℃, the reaction pressure is 0.1MPa, the reaction time is 60min, and the reaction result is shown in Table 2.

Example 8

A reaction kettle is used as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is used as a catalyst, cumene hydroperoxide is used as an oxidant, acetone is used as a solvent, the molar ratio of linolenic acid to cumene hydroperoxide is 1:0.95, the molar ratio of the solvent to linolenic acid is 20:1, the weight ratio of the catalyst to the cumene hydroperoxide is 0.18:1, the reaction temperature is 105 ℃, the reaction pressure is 0.1MPa, the reaction time is 70min, and the reaction result is shown in Table 2.

Example 9

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, ethylbenzene hydroperoxide is taken as an oxidant, butanone is taken as a solvent, the molar ratio of methyl oleate to ethylbenzene hydroperoxide is 1:1, the molar ratio of the solvent to methyl oleate is 18:1, the weight ratio of the catalyst to ethylbenzene hydroperoxide is 0.16:1, the reaction temperature is 100 ℃, the reaction pressure is 0.1MPa, the reaction time is 90min, and the reaction results are shown in Table 2.

Example 10

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, tert-butyl hydroperoxide is taken as an oxidant, pentanone is taken as a solvent, the molar ratio of oleic acid to tert-butyl hydroperoxide is 1:0.85, the molar ratio of the solvent to oleic acid is 20:1, the weight ratio of the catalyst to tert-butyl hydroperoxide is 0.06:1, the reaction temperature is 135 ℃, the reaction pressure is 0.1MPa, the reaction time is 80min, and the reaction results are shown in Table 2.

Example 11

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, tert-butyl hydroperoxide is taken as an oxidant, pentanedione is taken as a solvent, the molar ratio of oleic acid to tert-butyl hydroperoxide is 1:0.9, the molar ratio of the solvent to oleic acid is 8:1, the weight ratio of the catalyst to tert-butyl hydroperoxide is 0.07:1, the reaction temperature is 140 ℃, the reaction pressure is 0.1MPa, the reaction time is 70min, and the reaction results are shown in Table 2.

Example 12

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, cyclohexyl hydrogen peroxide is taken as an oxidant, butanone is taken as a solvent, the molar ratio of oleic acid to cyclohexyl hydrogen peroxide is 1:0.65, the molar ratio of the solvent to oleic acid is 30:1, the weight ratio of the catalyst to cyclohexyl hydrogen peroxide is 0.01:1, the reaction temperature is 150 ℃, the reaction pressure is 1MPa, and the reaction time is 30min, wherein the reaction results are shown in Table 2.

Example 13

A reaction kettle is taken as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is taken as a catalyst, cyclohexyl hydrogen peroxide is taken as an oxidant, pentanone is taken as a solvent, the molar ratio of oleic acid to cyclohexyl hydrogen peroxide is 1:0.75, the molar ratio of the solvent to oleic acid is 5:1, the weight ratio of the catalyst to the cyclohexyl hydrogen peroxide is 0.04:1, the reaction temperature is 90 ℃, the reaction pressure is 0.1MPa, the reaction time is 30min, and the reaction results are shown in Table 2.

Example 14

A reaction kettle is used as a reactor, the titanium-silicon composite oxide A1 of preparation example 1 is used as a catalyst, tert-butyl hydroperoxide is used as an oxidant, pentanone is used as a solvent, the molar ratio of oleic acid to tert-butyl hydroperoxide is 1:0.6, the weight ratio of the catalyst to tert-butyl hydroperoxide is 0.2:1, the reaction temperature is 80 ℃, the reaction pressure is 0.1MPa, and the reaction time is 30min, wherein the reaction results are shown in Table 2.

Comparative example 1

A reaction kettle is taken as a reactor, D1 is taken as a catalyst, tert-butyl hydroperoxide is taken as an oxidant, acetone is taken as a solvent, the molar ratio of oleic acid to tert-butyl hydroperoxide is 1:1, the molar ratio of the solvent to oleic acid is 10:1, the weight ratio of the catalyst to tert-butyl hydroperoxide is 0.1:1, the reaction temperature is 120 ℃, the reaction pressure is 0.1Mpa, the reaction time is 50min, and the reaction results are shown in Table 2.

Comparative example 2

A reaction kettle is taken as a reactor, D2 is taken as a catalyst, tert-butyl hydroperoxide is taken as an oxidant, acetone is taken as a solvent, the molar ratio of oleic acid to tert-butyl hydroperoxide is 1:1, the molar ratio of the solvent to oleic acid is 10:1, the weight ratio of the catalyst to tert-butyl hydroperoxide is 0.1:1, the reaction temperature is 120 ℃, the reaction pressure is 0.1Mpa, the reaction time is 50min, and the reaction results are shown in Table 2.

TABLE 2

From the results of examples 1-14 and comparative examples 1-2, it can be seen that the method for modifying the epoxidized vegetable oil prepared by the epoxidation reaction of the vegetable oil and the organic peroxide has high conversion rate of the vegetable oil and the organic peroxide and good product selectivity, and when the cyclic ketone is used as the solvent, the conversion rate of the vegetable oil and the conversion rate of the organic peroxide are higher.

Example 15

The difference from example 1 is that the titanium silicon composite oxide was a2 sample. The reaction results are shown in Table 3.

Example 16

The difference from example 1 is that the titanium silicon composite oxide was a3 sample. The reaction results are shown in Table 3.

Example 17

The difference from example 1 is that the titanium silicon composite oxide was a4 sample. The reaction results are shown in Table 3.

Example 18

The difference from example 1 is that the titanium silicon composite oxide was a5 sample. The reaction results are shown in Table 3.

Example 19

The difference from example 1 is that the titanium silicon composite oxide was a6 sample. The reaction results are shown in Table 3.

Example 20

The difference from example 1 is that the titanium silicon composite oxide was a7 sample. The reaction results are shown in Table 3.

Example 21

The difference from example 1 is that the titanium silicon composite oxide was A8 sample. The reaction results are shown in Table 3.

TABLE 3

Example 22

The difference from example 2 is that the titanium silicon composite oxide was a2 sample. The reaction results are shown in Table 4.

Example 23

The difference from example 2 is that the titanium silicon composite oxide was a3 sample. The reaction results are shown in Table 4.

Example 24

The difference from example 2 is that the titanium silicon composite oxide was a4 sample. The reaction results are shown in Table 4.

Example 25

The difference from example 2 is that the titanium silicon composite oxide was a5 sample. The reaction results are shown in Table 4.

Example 26

The difference from example 2 is that the titanium silicon composite oxide was a6 sample. The reaction results are shown in Table 4.

Example 27

The difference from example 2 is that the titanium silicon composite oxide was a7 sample. The reaction results are shown in Table 4.

Example 28

The difference from example 2 is that the titanium silicon composite oxide was A8 sample. The reaction results are shown in Table 4.

TABLE 4

The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.

In addition, any combination of the various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present invention, as long as the combination does not depart from the spirit of the present disclosure.