Titanium silicalite molecular sieve, preparation method thereof, catalyst for catalyzing olefin oxidation to prepare vicinal diol and application of catalyst

Abstract

The invention relates to a titanium silicalite molecular sieve, a preparation method thereof, a catalyst for catalyzing olefin oxidation to prepare vicinal diol and application of the catalyst. The titanium silicalite molecular sieve comprises a sulfonic acid group; the molar ratio of Ti element to S element in the titanium silicalite molecular sieve is (0.1-100): 1. The problems of corrosivity and difficult separation caused by acidity of a homogeneous catalyst in the prior art, and the problems of low catalytic efficiency and low effective utilization rate of hydrogen peroxide of a heterogeneous catalyst can be solved.

Description

Technical Field

[0001] The present disclosure relates to the technical field of molecular sieves, and in particular, to a titanium silicon molecular sieve and a preparation method thereof, a catalyst for catalyzing olefin oxidation to prepare vicinal diols and an application thereof. Background Art

[0002] A vicinal diol refers to a hydrocarbon organic compound in which two adjacent carbon atoms have hydroxyl groups. Common vicinal diols include 1,2-ethylene glycol (hereinafter referred to as ethylene glycol), 1,2-propylene glycol (hereinafter referred to as propylene glycol), 1,2-butylene glycol (hereinafter referred to as butylene glycol), 1,2-hexanediol (hereinafter referred to as hexanediol), etc. Viscous diols have important uses. For example, ethylene glycol can be used as a solvent, antifreeze, synthetic polyester, etc. Propylene glycol can be used to synthesize unsaturated polyester resins, used as antifreeze, moisturizer, etc. Hexanediol can be used in the production of high-end cosmetics, etc. Viscous diols have broad market applications and their output is also large. Taking propylene glycol as an example, the global propylene glycol production capacity reached 1.8 million tons / year in 2018.

[0003] The main production method of vicinal diols is to hydrolyze the upstream epoxides under certain conditions. For example, ethylene oxide is hydrolyzed to obtain ethylene glycol, propylene oxide is hydrolyzed to obtain propylene glycol, and hexylene oxide is hydrolyzed to obtain hexylene glycol. In addition, propylene glycol can also be obtained through the dimethyl carbonate / propylene glycol co-production method. The method of hydrolyzing epoxides must first prepare epoxides. The entire process increases the complexity of the process, low raw material utilization, and three wastes are discharged, which directly leads to increased costs. The co-production method also requires the production of epoxides first. In addition, the prices of co-production products are always affected by market fluctuations.

[0004] US10214471 and US20180354878A1 disclose a method for obtaining propylene glycol by reacting propylene and hydrogen peroxide in a reactor under the action of a heteropoly acid and a phase transfer catalyst. In the method, the heteropoly acid and hydrogen peroxide form a peroxy heteropoly acid salt in the aqueous phase, and form an organic phase soluble salt with the peroxy heteropoly acid salt through a phase transfer catalyst. In the method, an alkylated aromatic hydrocarbon organic solvent having 8 to 12 carbon atoms increases the proportion of the heteropoly acid salt in the organic phase to complete the oxidation of propylene to produce propylene oxide. The heteropoly acid is dissolved in water and continues to react with hydrogen peroxide, and the generated propylene oxide can enter the aqueous phase. Since the pH value of the aqueous phase is maintained in the range of 1-3.5, propylene oxide is hydrolyzed under the action of the aqueous phase acid to obtain propylene glycol. The method is actually only a two-step reaction of propylene epoxidation to produce propylene oxide, and propylene oxide is hydrolyzed and ring-opened to produce propylene glycol under the action of acid in one reactor. A large amount of solvent is required during the reaction process, the catalyst system is complex, and the operation is difficult.

[0005] EP1527057A1 discloses a method for continuously preparing propylene glycol. In this method, propylene is reacted with hydrogen peroxide to generate propylene oxide, and propylene glycol is generated as a byproduct. The generated propylene oxide is then reacted at 180-220°C and 15-25 bar to generate propylene glycol, which is then separated to obtain propylene glycol. This method is a physical integration of two-step reactions of epoxidation and hydrolysis, and cannot avoid the problems of low reaction efficiency and harsh hydrolysis treatment conditions.

[0006] WO2019029808A1 discloses a method for preparing terminal 1,2-alkanediols having 5 to 12 carbon atoms, which comprises mixing the corresponding terminal olefins with formic acid and hydrogen peroxide to obtain monoformate or diformate, and then decomposing them under the action of a decarbonization catalyst to obtain the corresponding diols and carbon monoxide.

[0007] CN103570493A discloses a method for synthesizing 1,2-vicinal diol by phase transfer catalytic oxidation of a solid-supported heteropoly acid, characterized in that an acid, a terminal olefin, hydrogen peroxide, and a heteropoly acid phase transfer catalyst are mixed and reacted, separated to obtain an epoxidation mixture, and then an alkali solution is added to maintain the pH at 10-12, and then ester extraction and reduced pressure distillation are performed to obtain the vicinal diol. The method has a long operation process and a low product yield.

[0008] CN107879893A discloses a method for preparing vicinal diol compounds by catalytic oxidation, wherein olefins, an oxidant and a bifunctional catalyst are used to prepare vicinal diols, wherein the bifunctional catalyst contains silicoaluminophosphate molecular sieves, alumina and titanium silicon molecular sieves. This method uses an aluminum-containing catalyst, and the utilization rate of hydrogen peroxide is low.

[0009] CN102452899A discloses a method for preparing propylene glycol from propylene, which comprises subjecting a titanium silicon molecular sieve composite catalyst, propylene and hydrogen peroxide to an epoxidation ring-opening hydration reaction to prepare propylene glycol, wherein the titanium silicon molecular sieve composite catalyst comprises a titanium silicon molecular sieve, an acidic molecular sieve and a resin. The method has a low utilization rate of hydrogen peroxide.

[0010] CN104447204A discloses a method for preparing diols, which uses a titanium silicon molecular sieve loaded with rare earth oxides as a catalyst to promote the reaction of olefins and an oxidant to generate diols. The method has a low utilization rate of hydrogen peroxide. Summary of the invention

[0011] The purpose of the present disclosure is to provide a titanium silicon molecular sieve and a preparation method thereof, a catalyst for catalyzing the oxidation of olefins to prepare vicinal diols and its application, so as to solve the problems of corrosiveness and difficulty in separation caused by the acidity of homogeneous catalysts in the prior art, as well as the problems of low catalytic efficiency of heterogeneous catalysts and low effective utilization rate of hydrogen peroxide.

[0012] In order to achieve the above-mentioned object, the first aspect of the present disclosure provides a titanium silicon molecular sieve, which contains a sulfonic acid group; the molar ratio of the Ti element to the S element in the titanium silicon molecular sieve is (0.1-100):1.

[0013] Optionally, the molar ratio of Ti element to S element in the titanium silicon molecular sieve is (0.5-70):1, preferably (0.8-30):1; more preferably (1-15):1, and more preferably (1.5-6):1;

[0014] Optionally, in the titanium silicon molecular sieve, the molar ratio of Ti element to Si element is (0.001-0.05):1, preferably (0.01-0.04):1, and more preferably (0.015-0.03):1;

[0015] Preferably, the sulfonic acid groups in the titanium silicalite molecular sieve include benzenesulfonic acid groups.

[0016] Optionally, the titanium silicate molecular sieve contains C, O and S elements, and the thermal gravimetric analysis shows that the thermal loss weight of the titanium silicate molecular sieve is 0.5-8 wt%, preferably 1-6 wt%, more preferably 1.5-5 wt%, and further preferably 2-4 wt%.

[0017] Optionally, in the infrared spectrum of the titanium silicate molecular sieve, at 1060-1260 cm -1 The first characteristic peak exists in the wavenumber range; at 1455±5cm -1 There is a second characteristic peak at the wave number position; at 1882±10cm -1 There is a third characteristic peak at the wavenumber position;

[0018] Preferably, the peak area of ​​the first characteristic peak is recorded as A 第一特征峰 , the peak area of ​​the second characteristic peak is recorded as A 第二特征峰 , the peak area of ​​the third characteristic peak is recorded as A 第三特征峰 , will be located at 800±5cm -1 The peak area of ​​the signal peak at position is recorded as A 800 , the titanium silicalite molecular sieve has the following infrared spectral characteristics:

[0019] A 第一特征峰 : A 800 (10-30): 1, A 第二特征峰 : A 800 (0.005~0.05):1,A 第三特征峰 : A 800 is (0.05-0.3): 1; preferably, A 第一特征峰 : A 800 (15-25): 1, A 第二特征峰: A 800 (0.01~0.03):1,A 第三特征峰 : A 800 is (0.08~0.2):1.

[0020] Optionally, the average particle size of the titanium silicate molecular sieve is 50 to 600 nm, preferably 150 to 500 nm; the BET specific surface area is 300 to 550 m 2 / g, preferably 400 to 500 m 2 / g; total pore volume is 0.25~0.40cm 3 / g, preferably 0.27 to 0.36 cm 3 / g; mesopore volume is 0.08~0.25cm 3 / g, preferably 0.15 to 0.20 cm 3 / g;

[0021] Optionally, the configuration of the titanium silicalite molecular sieve is selected from one or more of MFI, MEL, BEA, MWW and MOR.

[0022] The second aspect of the present disclosure provides a method for preparing titanium silicon molecular sieve, comprising the following steps:

[0023] S1, contacting a titanium silicon molecular sieve raw material with an epoxy group donor, performing a first mixing treatment, and obtaining a first product having an epoxy group, wherein the epoxy group donor comprises a silanization agent containing an epoxy group;

[0024] S2, contacting the first product with a first sulfonic acid group donor, performing a second mixing treatment, to obtain a second titanium silicon molecular sieve having a sulfonic acid group, wherein the first sulfonic acid group donor comprises a sulfonic acid compound containing a hydroxyl group; or

[0025] The first product is contacted with a second sulfonic acid group donor and subjected to a third mixing treatment to obtain a third titanium silicon molecular sieve product having a sulfonate group, wherein the second sulfonic acid group donor includes a sulfonate compound containing a hydroxyl group; the third titanium silicon molecular sieve product having a sulfonate group is contacted with an acid solution and subjected to an acidification treatment.

[0026] Optionally, in step S1, the molar ratio of the titanium silicon molecular sieve raw material to the epoxy group donor is 1: (0.001-0.1), preferably 1: (0.005-0.08), more preferably 1: (0.01-0.6), and most preferably 1: (0.015-0.04), wherein the titanium silicon molecular sieve raw material is SiO 2 The epoxy group donor is calculated in terms of Si;

[0027] Optionally, the titanium silicate molecular sieve raw material is directly contacted with the epoxy group donor, or is contacted in the presence of a first solvent; preferably, it is contacted in the presence of a first solvent;

[0028] Preferably, the molar ratio of the titanium silicon molecular sieve raw material to the first solvent is 1: (5-100), preferably 1: (10-80), more preferably 1: (15-60), more preferably 1: (20-50), wherein the titanium silicon molecular sieve raw material is SiO 2 count;

[0029] Optionally, the first solvent is selected from one or more of ketone compounds with carbon atoms of 3 to 8, ester compounds with carbon atoms of 2 to 10 and hydrocarbon compounds with carbon atoms of 6 to 12; preferably, the first solvent is selected from one or more of acetone, butanone, cyclopentanone, cyclohexanone, acetylacetone, cycloheptanone, cyclooctanone, acetophenone, methyl formate, ethyl acetate, isopropyl acetate, butyl acetate, n-hexane, cyclohexane, n-heptane, n-octane, n-decane, benzene, toluene, ethylbenzene, isopropylbenzene, xylene and trimethylbenzene; further preferably, the first solvent is selected from one or more of acetone, butanone, cyclopentanone and acetylacetone.

[0030] Optionally, in step S1, the epoxy group donor is selected from one or more of the compounds having the structure shown in the following formula (1):

[0031]

[0032] In formula (1), R 1 , R 2 , R 3 Each independently selected from an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group, preferably each independently selected from a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, and a chlorine group; R 4 One selected from an alkylene group having 1 to 6 carbon atoms, an ether group having 1 to 6 carbon atoms, an alkenylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 9 carbon atoms, and a halogenated arylene group having 6 to 9 carbon atoms, preferably one selected from an alkylene group having 1 to 4 carbon atoms, an ether group having 1 to 4 carbon atoms, and a halogenated alkylene group having 1 to 4 carbon atoms; R 5 is H or one selected from an alkyl group having 1 to 5 carbon atoms, preferably H; R a and R b Each is independently selected from one or more of H, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an ether group and an ester group. Preferably, R a and R b is H;

[0033] Preferably, the epoxy group donor is selected from 5,6-epoxy-1-hexyltrimethoxysilane, 4,5-epoxy-1-pentyltrimethoxysilane, 3,4-epoxy-1-butyltrimethoxysilane, 2,3-epoxy-1-propyltrimethoxysilane, 5,6-epoxy-1-hexyltriethoxysilane, 4,5-epoxy-1-pentyltriethoxysilane, 3,4-epoxy-1-butyltrimethoxysilane, Ethoxysilane, 2,3-epoxy-1-propyltriethoxysilane, 5,6-epoxy-1-hexyltrichlorosilane, 4,5-epoxy-1-pentyltrichlorosilane, 3,4-epoxy-1-butyltrichlorosilane, 2,3-epoxy-1-propyltrichlorosilane, (3-glycidyl ether propyl) methyldimethoxysilane, (3-glycidyl ether ethyl) methyldimethoxysilane, (3-glycidyl ether ethyl) methyldimethoxysilane 2,3-epoxy-1-propyltrimethoxysilane;

[0034] Optionally, the molar ratio of titanium element to silicon element in the titanium silicalite raw material is (0.001-0.1):1, preferably (0.005-0.05):1, more preferably (0.01-0.04):1, and further preferably (0.015-0.03):1.

[0035] Optionally, in step S1, the conditions of the first mixing treatment include: treating at 5-100° C. for 0.5-24 h; preferably, treating at 20-90° C. for 2-18 h; further preferably, treating at 40-80° C. for 5-12 h;

[0036] Optionally, the treatment pressure (gauge pressure) is -0.8 to 2 MPa, preferably 0 to 0.5 MPa.

[0037] Optionally, in step S2, the molar ratio of the first sulfonic acid group donor to the epoxy group donor in step S1 or the molar ratio of the second sulfonic acid group donor to the epoxy group donor in step S1 is independently (0.5-3):1, preferably (1-2.5):1, and further preferably (1.2-2):1, wherein the first sulfonic acid group donor and the second sulfonic acid group donor are calculated as S, and the epoxy group donor is calculated as Si;

[0038] Optionally, the first product is contacted with the first sulfonic acid group donor or the second sulfonic acid group donor in the presence of a second solvent; preferably, the molar ratio of the first product to the second solvent is 1:(5-100), more preferably 1:(20-80), more preferably 1:(30-60), and the first product is SiO 2 count;

[0039] Optionally, the second solvent is selected from one or more of ketone compounds with carbon atoms of 3 to 8, ester compounds with carbon atoms of 2 to 10 and hydrocarbon compounds with carbon atoms of 6 to 12; preferably, the second solvent is selected from one or more of acetone, butanone, cyclopentanone, cyclohexanone, acetylacetone, cycloheptanone, cyclooctanone, acetophenone, methyl formate, ethyl acetate, isopropyl acetate, butyl acetate, n-hexane, cyclohexane, n-heptane, n-octane, n-decane, benzene, toluene, ethylbenzene, isopropylbenzene, xylene and trimethylbenzene.

[0040] Optionally, in step S2, the first sulfonic acid group donor and the second sulfonic acid group donor are each independently selected from one or more compounds having a structure represented by the following formula (2):

[0041]

[0042] In formula (2), R 6 is selected from a single bond, an alkyl group having 1 to 6 carbon atoms, an ether group having 1 to 6 carbon atoms, and a halogenated alkyl group having 1 to 6 carbon atoms, preferably R 6 is a single bond; R 7 One selected from a single bond, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a hydroxyl group having 1 to 6 carbon atoms, and an ether group having 1 to 6 carbon atoms, preferably one selected from a single bond, an alkyl group substituted with a hydroxyl group having 1 to 3 carbon atoms; in the first sulfonic acid group donor, M is H; in the second sulfonic acid group donor, M is selected from one of Na and K;

[0043] Preferably, the first sulfonic acid group donor is selected from one or more of o-hydroxybenzenesulfonic acid, o-dihydroxybenzenesulfonic acid, p-hydroxybenzenesulfonic acid, m-hydroxybenzenesulfonic acid, m-dihydroxybenzenesulfonic acid, o-hydroxymethylbenzenesulfonic acid, o-hydroxyethylbenzenesulfonic acid, p-hydroxymethylbenzenesulfonic acid, p-hydroxyethylbenzenesulfonic acid, and m-hydroxyethylbenzenesulfonic acid, preferably one or more of p-hydroxybenzenesulfonic acid, p-hydroxymethylbenzenesulfonic acid, p-hydroxyethylbenzenesulfonic acid, m-hydroxybenzenesulfonic acid, and m-hydroxymethylbenzenesulfonic acid;

[0044] The second sulfonic acid group donor is selected from sodium o-hydroxybenzene sulfonate, potassium o-hydroxybenzene sulfonate, sodium o-dihydroxybenzene sulfonate, potassium o-dihydroxybenzene sulfonate, sodium p-hydroxybenzene sulfonate, potassium p-hydroxybenzene sulfonate, sodium m-hydroxybenzene sulfonate, potassium m-hydroxybenzene sulfonate, sodium m-dihydroxybenzene sulfonate, potassium m-dihydroxybenzene sulfonate, sodium o-hydroxymethylbenzene sulfonate, potassium o-hydroxymethylbenzene sulfonate, sodium o-hydroxyethylbenzene sulfonate, potassium o-hydroxyethylbenzene sulfonate, sodium p-hydroxymethylbenzene sulfonate, p-hydroxymethylbenzene sulfonate, The present invention relates to one or more of potassium benzene sulfonate, sodium p-hydroxyethylbenzene sulfonate, potassium p-hydroxyethylbenzene sulfonate, sodium m-hydroxyethylbenzene sulfonate and potassium m-hydroxyethylbenzene sulfonate, preferably one or more of sodium p-hydroxybenzene sulfonate, potassium p-hydroxybenzene sulfonate, sodium p-hydroxymethylbenzene sulfonate, potassium p-hydroxymethylbenzene sulfonate, sodium p-hydroxyethylbenzene sulfonate, potassium p-hydroxyethylbenzene sulfonate, sodium m-hydroxybenzene sulfonate, potassium m-hydroxybenzene sulfonate, sodium m-hydroxymethylbenzene sulfonate and potassium m-hydroxymethylbenzene sulfonate.

[0045] Optionally, in step S2, the conditions of the second mixing treatment and the third mixing treatment each independently include: treating at 20-100° C. for 0.5-24 h, preferably treating at 40-90° C. for 2-18 h, and more preferably treating at 50-80° C. for 5-12 h;

[0046] Optionally, the treatment pressure (gauge pressure) is -0.8 to 2 MPa, preferably 0 to 0.5 MPa.

[0047] Optionally, in step S2, the acid solution is selected from one or more of an inorganic acid solution or an organic acid solution with a pH value of 5 or less;

[0048] Optionally, the inorganic acid is selected from one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, chloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, metaphosphoric acid, perphosphoric acid and pyrophosphoric acid; the organic acid is selected from one or more of carboxylic acids having 2 to 10 carbon atoms;

[0049] Preferably, relative to 1g of the third product of the titanium silicalite molecular sieve having sulfonate groups, the amount of the acid solution used is 1 to 50mL, preferably 3 to 20mL; the conditions for the acidification treatment include: temperature of 5 to 100°C, time of 0.05 to 24h, preferably, temperature of 30 to 60°C, time of 0.1 to 6h.

[0050] A third aspect of the present disclosure provides a titanium silicon molecular sieve prepared according to the method described in the second aspect of the present disclosure.

[0051] The fourth aspect of the present disclosure provides a catalyst for catalyzing the oxidation of olefins to prepare vicinal diols, comprising the titanium silicon molecular sieve described in the first aspect or the third aspect of the present disclosure; the content of the titanium silicon molecular sieve is 5 to 100 weight % based on the total weight of the catalyst.

[0052] The fifth aspect of the present disclosure provides use of the catalyst described in the fourth aspect of the present disclosure in catalyzing the oxidation of olefins to prepare vicinal diols.

[0053] Optionally, the catalytic olefin oxidation reaction to prepare vicinal diols comprises the following steps:

[0054] The catalyst is contacted with an olefin compound, an oxidant and an aqueous solvent to carry out a catalytic reaction to obtain a product containing a vicinal diol;

[0055] Preferably, the molar ratio of the oxidant to the olefin compound is (0.1-20):1, preferably (0.5-10):1, and more preferably (0.8-5):1; the molar ratio of the catalyst to the oxidant is (0.01-10):1, preferably (0.05-5):1, and more preferably (0.1-2):1, and the catalyst is SiO 2 count;

[0056] Optionally, the olefin compound is selected from one or more of monoolefin compounds having 2 to 30 carbon atoms and polyolefin compounds having 2 to 30 carbon atoms; preferably, the olefin compound is selected from one or more of ethylene, vinyl chloride, propylene, allyl chloride, acrylonitrile, acrylic acid, acrolein, allyl alcohol, butenoic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, 1,4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, styrene, oleic acid, methyl oleate, ricinoleic acid and methyl ricinoleate;

[0057] The oxidant is selected from one or more of inorganic peroxides, organic peroxides and ozone; optionally, the inorganic peroxide is one or more of hydrogen peroxide, urea peroxide, potassium permonosulfate, potassium persulfate, sodium percarbonate, percarbonamide and sodium perborate; the organic peroxide is selected from one or more of tert-butyl hydroperoxide, cyclohexyl hydroperoxide, isopropyl peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl peroxypivalate, isopropyl hydroperoxide, tert-amyl hydroperoxide and di-tert-butyl peroxide; preferably, the oxidant is hydrogen peroxide;

[0058] Preferably, the conditions of the catalytic reaction include: reaction temperature of 5 to 100° C., preferably 20 to 80° C.; reaction time of 1 min to 24 h, preferably 1 h to 12 h; reaction pressure of 0.5 to 10 Mpa, preferably 1 to 4 Mpa.

[0059] Through the above technical scheme, the present disclosure provides a titanium silicalite and a preparation method thereof, a catalyst for catalyzing olefin oxidation to prepare vicinal diols and an application thereof. The titanium silicalite provided by the present disclosure has both a skeleton titanium active center and a sulfonic acid group active center, that is, it has both epoxidation and hydrolysis ring-opening reaction centers, and has good performance in catalyzing olefin oxidation to prepare vicinal diols; and the preparation method is simple; and in the reaction of catalyzing olefin oxidation to prepare vicinal diols, there is no equipment corrosion and catalyst separation problems caused by heterogeneous acid catalysis, and compared with active centers such as silicon-aluminum active centers and oxides, the catalytic activity is high, the hydrogen peroxide utilization rate is high, and the vicinal diol selectivity is high; the process is safer and more efficient, and is suitable for large-scale industrial production applications.

[0060] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings:

[0062] Figure 1 This is the infrared spectrum of the titanium silicon molecular sieve of Example 1.

[0063] Figure 2 This is the infrared spectrum of the TS-1 molecular sieve of Preparation Example 1. DETAILED DESCRIPTION

[0064] The specific embodiments of the present disclosure are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, and are not used to limit the present disclosure.

[0065] In a first aspect, the present disclosure provides a titanium silicon molecular sieve, which contains a sulfonic acid group; the molar ratio of the Ti element to the S element in the titanium silicon molecular sieve is (0.1-100):1.

[0066] The titanium silicon molecular sieve provided by the present invention has both a skeleton titanium active center and a sulfonic acid group active center, that is, it has both epoxidation and hydrolysis ring-opening reaction centers, and has good performance in catalyzing olefin oxidation to prepare vicinal diols; and the preparation method is simple; and in the reaction of catalyzing olefin oxidation to prepare vicinal diols, there is no equipment corrosion and catalyst separation problems caused by heterogeneous acid catalysis, and compared with active centers such as silicon aluminum active centers and oxides, the catalytic activity is high, the utilization rate of hydrogen peroxide is high, and the selectivity of vicinal diols is high; the process is safer and more efficient, and is suitable for large-scale industrial production applications.

[0067] The titanium silicon molecular sieve provided by the present disclosure can activate peroxides such as hydrogen peroxide and catalyze the epoxidation reaction of double-bond compounds due to its skeleton tetracoordinate titanium, so it has a wide range of uses in the preparation of epoxy compounds. The sulfonic acid group has a strongly acidic H proton, which can catalyze the ring-opening hydrolysis of epoxy compounds to generate vicinal diol products. The titanium silicon molecular sieve provided by the present disclosure contains both skeleton tetracoordinate titanium and sulfonic acid groups, and the two are closer in space, which is conducive to the occurrence of a series of reactions, so that the epoxidation product of olefin oxidation is rapidly ring-opened and hydrolyzed to obtain vicinal diols, reducing the side reactions occurring in the solution. At the same time, the heterogeneity of this heterogeneous catalyst is conducive to the separation of the catalyst, which can solve the problem of catalyst recycling. The present disclosure adopts sulfonic acid groups, which are more acidic and easy to immobilize. The sulfonic acid groups can be on the outer surface of the molecular sieve or inside the molecular sieve grains.

[0068] In a preferred embodiment, the molar ratio of the Ti element to the S element in the titanium silicalite is (0.5-70):1, preferably (0.8-30):1; further preferably (1-15):1, further preferably (1.5-6):1. The chemical composition of the titanium silicalite in the present disclosure can be analyzed by XRF, ICP and other methods. When the molar ratio of the Ti element to the S element of the titanium silicalite is within the optimized range of the present embodiment, the titanium silicalite has better catalytic performance and can obtain higher hydrogen peroxide utilization and vicinal diol selectivity.

[0069] In one embodiment, in the titanium silicon molecular sieve, the molar ratio of the Ti element to the Si element is (0.001-0.05):1, preferably (0.01-0.04):1, and more preferably (0.015-0.03):1.

[0070] In a preferred embodiment, the sulfonic acid groups in the titanium silicalite molecular sieve include benzenesulfonic acid groups.

[0071] In the present disclosure, the titanium silicon molecular sieve contains C, O, and S elements, and the elements can be confirmed by XRF, ICP and other methods. The sulfonic acid group of the titanium silicon molecular sieve disclosed in the present disclosure is bonded to the surface of the molecular sieve by organic matter, so elements such as C and O are introduced during the preparation process. According to thermogravimetric characterization, organic matter and other substances will undergo thermal weight loss under oxygen or air atmosphere, and the thermal weight loss of the titanium silicon molecular sieve is 0.5 to 8% by weight, preferably 1 to 6% by weight, more preferably 1.5 to 5% by weight, and more preferably 2 to 4% by weight.

[0072] In one embodiment, in the infrared spectrum of the titanium silicate molecular sieve, the -1 The first characteristic peak exists in the wavenumber range; at 1455±5cm -1 There is a second characteristic peak at the wave number position, at 1882±10cm -1 There is a third characteristic peak at the wavenumber position.

[0073] In a preferred embodiment, the peak area of ​​the first characteristic peak is recorded as A 第一特征峰 , the peak area of ​​the second characteristic peak is recorded as A 第二特征峰 , the peak area of ​​the third characteristic peak is recorded as A 第三特征峰 , will be located at 800±5cm -1 The peak area of ​​the signal peak at position is recorded as A 800 , the titanium silicalite molecular sieve has the following infrared spectral characteristics:

[0074] A 第一特征峰 : A 800 (10-30): 1, A 第二特征峰 : A 800 (0.005~0.05):1,A 第三特征峰 : A 800 is (0.05-0.3): 1; preferably, A 第一特征峰 : A 800 (15-25): 1, A 第二特征峰 : A 800 (0.01~0.03):1,A 第三特征峰 : A 800 (0.08~0.2): 1. In the infrared spectrum, 800cm -1 The characteristic peak at 1060-1260cm is the characteristic peak of molecular sieve skeleton vibration. Infrared spectrum can characterize the presence of organic matter. According to the titanium silicon molecular sieve of the present invention, the titanium silicon molecular sieve is characterized by infrared spectrum. -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1There are C=C and CH vibration peaks of the benzene ring nearby. Since the titanium silicalite provided by the present disclosure contains sulfonic acid groups, the vibration peaks of the C=C bond and CH bond on the benzene ring can be observed. The benzene sulfonic acid group in the titanium silicalite disclosed by the present disclosure is connected to other groups through ether bonds, so the vibration of the COC bond can be found. In addition, the red spectrum can also be found at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple signal peaks appear in the range, and the existence of these peaks can indicate that the organic structure described in the present disclosure exists on the titanium silicon molecular sieve provided in the present disclosure.

[0075] In one embodiment, the titanium silicon molecular sieve of the present invention can also be characterized by the method of nuclear magnetic carbon spectrum for the presence of sulfonic acid groups. For example, under preferred conditions, there may be signal peaks of at least three carbon atoms of the benzene ring of the benzene sulfonic acid group in the range of 110 to 140 ppm (in DMSO-d6 solvent). It is understood that the signal peaks vary slightly with the precursors that provide the benzene sulfonic acid groups. For example, when the titanium silicon molecular sieve of the present invention is prepared using p-hydroxybenzenesulfonic acid as a raw material, absorption peaks of three carbon atoms of the benzene ring can be found near 136 ppm, 127 ppm and 114 ppm.

[0076] In a specific embodiment, the average particle size of the titanium silicate molecular sieve is 50 to 600 nm, preferably 150 to 500 nm; the BET specific surface area is 300 to 550 m 2 / g, preferably 400 to 500 m 2 / g; total pore volume is 0.25~0.40cm 3 / g, preferably 0.27 to 0.36 cm 3 / g; mesopore volume is 0.08~0.25cm 3 / g, preferably 0.15 to 0.20 cm 3 / g;

[0077] Optionally, the configuration of the titanium silicalite molecular sieve is selected from one or more of MFI, MEL, BEA, MWW and MOR.

[0078] The second aspect of the present disclosure provides a method for preparing titanium silicon molecular sieve, comprising the following steps:

[0079] S1, contacting a titanium silicon molecular sieve raw material with an epoxy group donor, performing a first mixing treatment, and obtaining a first product having an epoxy group, wherein the epoxy group donor comprises a silanization agent containing an epoxy group;

[0080] S2, contacting the first product with a first sulfonic acid group donor, performing a second mixing treatment, to obtain a second titanium silicon molecular sieve having a sulfonic acid group, wherein the first sulfonic acid group donor comprises a sulfonic acid compound containing a hydroxyl group; or

[0081] The first product is contacted with a second sulfonic acid group donor and subjected to a third mixing treatment to obtain a third titanium silicon molecular sieve product having a sulfonate group, wherein the second sulfonic acid group donor includes a sulfonate compound containing a hydroxyl group; the third titanium silicon molecular sieve product having a sulfonate group is contacted with an acid solution and subjected to an acidification treatment.

[0082] The present invention introduces a silanization agent containing an epoxy group into the titanium silicon molecular sieve, which is beneficial to produce special functional bonds on the surface of the molecular sieve that can anchor the sulfonic acid group-containing compound, and then the obtained first product with the epoxy group is contacted with the second sulfonic acid group donor or the third sulfonic acid group donor for reaction, so that the hydroxyl groups on the sulfonic acid group can react with the epoxy groups on the surface of the molecular sieve to form bonds, thereby anchoring the sulfonic acid group on the surface of the molecular sieve, and finally preparing the titanium silicon molecular sieve containing sulfonic acid groups.

[0083] In one embodiment, in step S1, the titanium silicon molecular sieve raw material (in the form of SiO 2 The molar ratio of the epoxy group donor (in terms of Si) to the epoxy group donor (in terms of Si) is 1:(0.001-0.1), preferably 1:(0.005-0.08), further preferably 1:(0.01-0.6), and most preferably 1:(0.015-0.04).

[0084] In one embodiment, the titanium silicalite raw material is directly contacted with the epoxy group donor, or is contacted in the presence of a first solvent; preferably, the contact is in the presence of a first solvent, which is conducive to uniform distribution of the silanization agent on the titanium silicalite raw material;

[0085] Optionally, the first solvent is selected from one or more of ketone compounds with carbon atoms of 3 to 8, ester compounds with carbon atoms of 2 to 10 and hydrocarbon compounds with carbon atoms of 6 to 12; preferably, the first solvent is selected from one or more of acetone, butanone, cyclopentanone, cyclohexanone, acetylacetone, cycloheptanone, cyclooctanone, acetophenone, methyl formate, ethyl acetate, isopropyl acetate, butyl acetate, n-hexane, cyclohexane, n-heptane, n-octane, n-decane, benzene, toluene, ethylbenzene, isopropylbenzene, xylene and trimethylbenzene; further preferably, the first solvent is selected from one or more of acetone, butanone, cyclopentanone and acetylacetone.

[0086] In one embodiment, the titanium silicon molecular sieve raw material used in the present disclosure is a titanium silicon molecular sieve that can provide a skeleton titanium species, activate hydrogen peroxide and catalyze the oxidation of olefin molecules. Considering the operability of the molecular sieve preparation, the configuration of the titanium silicon molecular sieve can be selected from one or more of MFI, MEL, BEA, MWW, and MOR, preferably an MFI structure. The titanium silicon molecular sieve can be various morphological structures, for example, it can be one or more of a microporous molecular sieve, a mesoporous molecular sieve, a macroporous molecular sieve, a multi-level pore molecular sieve, a hollow structure molecular sieve (such as HTS), a sponge-like molecular sieve, and a layered molecular sieve. The titanium silicon molecular sieve can be directly synthesized, such as hydrothermal synthesis, dry gel synthesis, or post-synthesis, such as dealumination titanium supplementation, gas phase titanium insertion, liquid phase titanium insertion, solid phase ion exchange titanium insertion, alkali treatment titanium insertion (rearrangement titanium insertion), etc. Preferably, before the titanium silicon molecular sieve is used in the present disclosure, it is washed, dried and roasted to remove organic matter and impurities in the pores. This process is a conventional treatment method, and the present disclosure will not repeat it.

[0087] In a specific embodiment, the titanium silicon molecular sieve raw material (SiO 2 The molar ratio of the first solvent to the second solvent is 1:(5-100), preferably 1:(10-80), more preferably 1:(15-60), and further preferably 1:(20-50).

[0088] In a specific embodiment, the molar ratio of titanium element to silicon element in the titanium silicon molecular sieve raw material is (0.001-0.1):1, preferably (0.005-0.05):1, further preferably (0.01-0.04):1, further preferably (0.015-0.03):1. The higher the skeleton titanium content of the titanium silicon molecular sieve raw material used in the present invention, the more conducive it is to the catalytic reaction. Preferably, the skeleton titanium content of the titanium silicon molecular sieve raw material accounts for more than 10% of the total titanium content, preferably greater than 30%, more preferably greater than 60%, and more preferably greater than 80%. The skeleton titanium content can be measured by the UV-Vis method to measure the bulk skeleton titanium ratio of the molecular sieve, and can also be measured by the XPS method to measure the surface skeleton titanium content ratio.

[0089] In one embodiment, in step S1, the epoxy group donor is selected from one or more of the compounds having the structure shown in the following formula (1):

[0090]

[0091] In formula (1), R 1 , R 2 , R 3Each independently selected from an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group, preferably each independently selected from a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, and a chlorine group; R 4 One selected from an alkylene group having 1 to 6 carbon atoms, an ether group having 1 to 6 carbon atoms, an alkenylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 9 carbon atoms, and a halogenated arylene group having 6 to 9 carbon atoms, preferably one selected from an alkylene group having 1 to 4 carbon atoms, an ether group having 1 to 4 carbon atoms, and a halogenated alkylene group having 1 to 4 carbon atoms; R 5 is H or one selected from an alkyl group having 1 to 5 carbon atoms, preferably H; R a and R b Each is independently selected from one or more of H, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an ether group and an ester group. Preferably, R a and R b For H.

[0092] In a preferred embodiment, the epoxy group donor is selected from 5,6-epoxy-1-hexyltrimethoxysilane, 4,5-epoxy-1-pentyltrimethoxysilane, 3,4-epoxy-1-butyltrimethoxysilane, 2,3-epoxy-1-propyltrimethoxysilane, 5,6-epoxy-1-hexyltriethoxysilane, 4,5-epoxy-1-pentyltriethoxysilane, 3,4-epoxy-1-butyltrimethoxysilane, -butyltriethoxysilane, 2,3-epoxy-1-propyltriethoxysilane, 5,6-epoxy-1-hexyltrichlorosilane, 4,5-epoxy-1-pentyltrichlorosilane, 3,4-epoxy-1-butyltrichlorosilane, 2,3-epoxy-1-propyltrichlorosilane, (3-glycidyl ether propyl) methyldimethoxysilane, (3-glycidyl ether ethyl) methyldimethoxysilane, (3-glycidyl ether ethyl) methyldimethoxysilane, Preferably, the epoxy group donor is selected from one or more of (3-glycidyl ether propyl) methyldimethoxysilane, (3-glycidyl ether propyl) trimethoxysilane, (3-glycidyl ether ethyl) trimethoxysilane, (3-glycidyl ether methyl) trimethoxysilane, (3-glycidyl ether propyl) triethoxysilane, (3-glycidyl ether ethyl) triethylmethoxysilane, (3-glycidyl ether methyl) triethoxysilane, (3-glycidyl ether propyl) trichlorosilane, (3-glycidyl ether ethyl) trichlorosilane, (3-glycidyl ether methyl) trichlorosilane; preferably, the epoxy group donor is selected from one or more of (3-glycidyl ether propyl) methyldimethoxysilane, (3-glycidyl ether methyl) trimethoxysilane, (3-glycidyl ether propyl) trimethoxysilane, (3-glycidyl ether methyl) trichlorosilane and 2,3-epoxy-1-propyltrimethoxysilane.

[0093] In the present disclosure, step S1 can be carried out under any conditions that meet the operating conditions and requirements. For example, it can be carried out at any temperature between the freezing point and the boiling point of the system under reduced pressure, normal pressure, or pressurized conditions, and the processing time can meet the processing requirements.

[0094] In a specific embodiment, in step S1, the conditions of the first mixing treatment include: treating at 5-100°C for 0.5-24h; preferably, treating at 20-90°C for 2-18h; more preferably, treating at 40-80°C for 5-12h;

[0095] Optionally, the treatment pressure (gauge pressure) is -0.8 to 2 MPa, preferably 0 to 0.5 MPa.

[0096] In one embodiment, in step S2, the molar ratio of the first sulfonic acid group donor (in terms of S) to the epoxy group donor in step S1 or the molar ratio of the second sulfonic acid group donor (in terms of S) to the epoxy group donor in step S1 is independently (0.5-3):1, preferably (1-2.5):1, and more preferably (1.2-2):1. In the preparation process of titanium silicalite, the molar ratio of the sulfonic acid group donor to the epoxy group donor is within the preferred range of this embodiment, which can conveniently control the amount of the grafted group, and the prepared titanium silicalite has higher catalytic activity in the reaction of olefin oxidation to prepare vicinal diols.

[0097] In a specific embodiment, the first product is contacted with the first sulfonic acid group donor or the second sulfonic acid group donor in the presence of a second solvent; contacting in the presence of the second solvent is beneficial to reduce the amount of benzenesulfonic acid or its salt containing hydroxyl groups.

[0098] Optionally, the second solvent is selected from one or more of ketone compounds with 3 to 8 carbon atoms, ester compounds with 2 to 10 carbon atoms, and hydrocarbon compounds with 6 to 12 carbon atoms; preferably, the second solvent is selected from one or more of acetone, butanone, cyclopentanone, cyclohexanone, acetylacetone, cycloheptanone, cyclooctanone, acetophenone, methyl formate, ethyl acetate, isopropyl acetate, butyl acetate, n-hexane, cyclohexane, n-heptane, n-octane, n-decane, benzene, toluene, ethylbenzene, isopropylbenzene, xylene and trimethylbenzene;

[0099] Preferably, the first product (in the form of SiO 2 The molar ratio of the first solvent to the second solvent is 1:(5-100), more preferably 1:(20-80), and even more preferably 1:(30-60).

[0100] In one embodiment, in step S2, the first sulfonic acid group donor and the second sulfonic acid group donor are each independently selected from one or more compounds having a structure represented by the following formula (2):

[0101]

[0102] In formula (2), R 6 is selected from a single bond, an alkyl group having 1 to 6 carbon atoms, an ether group having 1 to 6 carbon atoms, and a halogenated alkyl group having 1 to 6 carbon atoms, preferably R 6 is a single bond; R 7 One selected from a single bond, an alkyl group with 1 to 6 carbon atoms, an alkyl group substituted with a hydroxyl group with 1 to 6 carbon atoms, and an ether group with 1 to 6 carbon atoms, preferably one selected from a single bond, an alkyl group substituted with 1 to 3 carbon atoms; in the first sulfonic acid group donor, M is H; in the second sulfonic acid group donor, M is selected from one of Na and K. The sulfonic acid group donor used in the present disclosure minimizes the number and volume of benzene ring substituents, which can reduce the steric hindrance effect and promote the catalytic effect.

[0103] In a preferred embodiment, the first sulfonic acid group donor is selected from one or more of o-hydroxybenzenesulfonic acid, o-dihydroxybenzenesulfonic acid, p-hydroxybenzenesulfonic acid, m-hydroxybenzenesulfonic acid, m-dihydroxybenzenesulfonic acid, o-hydroxymethylbenzenesulfonic acid, o-hydroxyethylbenzenesulfonic acid, p-hydroxymethylbenzenesulfonic acid, p-hydroxyethylbenzenesulfonic acid, and m-hydroxyethylbenzenesulfonic acid, preferably one or more of p-hydroxybenzenesulfonic acid, p-hydroxymethylbenzenesulfonic acid, p-hydroxyethylbenzenesulfonic acid, m-hydroxybenzenesulfonic acid, and m-hydroxymethylbenzenesulfonic acid;

[0104] The second sulfonic acid group donor is selected from sodium o-hydroxybenzene sulfonate, potassium o-hydroxybenzene sulfonate, sodium o-dihydroxybenzene sulfonate, potassium o-dihydroxybenzene sulfonate, sodium p-hydroxybenzene sulfonate, potassium p-hydroxybenzene sulfonate, sodium m-hydroxybenzene sulfonate, potassium m-hydroxybenzene sulfonate, sodium m-dihydroxybenzene sulfonate, potassium m-dihydroxybenzene sulfonate, sodium o-hydroxymethylbenzene sulfonate, potassium o-hydroxymethylbenzene sulfonate, sodium o-hydroxyethylbenzene sulfonate, potassium o-hydroxyethylbenzene sulfonate, sodium p-hydroxymethylbenzene sulfonate, p-hydroxymethylbenzene sulfonate, The present invention relates to one or more of potassium benzene sulfonate, sodium p-hydroxyethylbenzene sulfonate, potassium p-hydroxyethylbenzene sulfonate, sodium m-hydroxyethylbenzene sulfonate and potassium m-hydroxyethylbenzene sulfonate, preferably one or more of sodium p-hydroxybenzene sulfonate, potassium p-hydroxybenzene sulfonate, sodium p-hydroxymethylbenzene sulfonate, potassium p-hydroxymethylbenzene sulfonate, sodium p-hydroxyethylbenzene sulfonate, potassium p-hydroxyethylbenzene sulfonate, sodium m-hydroxybenzene sulfonate, potassium m-hydroxybenzene sulfonate, sodium m-hydroxymethylbenzene sulfonate and potassium m-hydroxymethylbenzene sulfonate.

[0105] In the present disclosure, the operation of step S2 can be carried out under any conditions that meet the operating conditions and requirements. For example, it can be carried out at any temperature between the freezing point and the boiling point of the system under reduced pressure, normal pressure, or pressurized conditions, and the processing time can meet the processing requirements.

[0106] In a specific embodiment, in step S2, the conditions of the second mixing treatment and the third mixing treatment each independently include: treating at 20-100° C. for 0.5-24 h, preferably treating at 40-90° C. for 2-18 h, and more preferably treating at 50-80° C. for 5-12 h;

[0107] Optionally, the treatment pressure (gauge pressure) is -0.8 to 2 MPa, preferably 0 to 0.5 MPa.

[0108] When a salt compound of benzenesulfonic acid containing a hydroxyl group is used as a sulfonic acid group donor in step S2, it needs to be further acidified to convert it into a sulfonic acid group to obtain a titanium silicon molecular sieve having a sulfonic acid group.

[0109] In one embodiment, in step S2, the acid solution is selected from one or more of an inorganic acid solution or an organic acid solution with a pH value of 5 or less;

[0110] Optionally, the inorganic acid is selected from one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, chloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, metaphosphoric acid, perphosphoric acid and pyrophosphoric acid; the organic acid is selected from one or more of carboxylic acids having 2 to 10 carbon atoms;

[0111] Preferably, relative to 1g of the third product of the titanium silicalite molecular sieve having sulfonate groups, the amount of the acid solution used is 1 to 50mL, preferably 3 to 20mL; the conditions for the acidification treatment include: temperature of 5 to 100°C, time of 0.05 to 24h, preferably, temperature of 30 to 60°C, time of 0.1 to 6h.

[0112] In a specific embodiment, in steps S1, S2 and S3, solid-liquid separation can be used to obtain the corresponding solid molecular sieve, preferably by at least one method of centrifugation, filtration, sedimentation, and evaporation to obtain the molecular sieve, and the obtained molecular sieve is further dried. The drying can be carried out in the range of 80 to 180° C., in air, oxygen or inert gas atmosphere for 0.5 to 24 hours.

[0113] According to the present disclosure, steps S1 and S2 can be performed independently in two steps or continuously, that is, after step S1 is completed, the sulfonic acid group donor B containing a hydroxyl group can be directly added to perform step S2 without solid-liquid separation to shorten the reaction process.

[0114] A third aspect of the present disclosure provides a titanium silicon molecular sieve prepared according to the method described in the second aspect of the present disclosure.

[0115] The fourth aspect of the present disclosure provides a catalyst for catalyzing the oxidation of olefins to prepare vicinal diols, comprising the titanium silicon molecular sieve described in the first aspect or the third aspect of the present disclosure; the content of the titanium silicon molecular sieve is 5 to 100 weight % based on the total weight of the catalyst.

[0116] The titanium silicon molecular sieve provided by the present disclosure can be used alone as raw powder, or can be mixed with other components such as structural additives, electronic additives, binders, inert carriers, dispersants, etc., or can be used after molding. The molding can be spray molding, ball rolling molding, extrusion molding, oil column molding, etc., and the present invention has no special requirements. Other components such as silicon dioxide, aluminum oxide, titanium oxide, sesbania powder or other components may be introduced during the molding process.

[0117] The fifth aspect of the present disclosure provides use of the catalyst described in the fourth aspect of the present disclosure in catalyzing olefin oxidation to prepare vicinal diols.

[0118] In a specific implementation, the application includes the following steps:

[0119] The catalyst is contacted with an olefin compound, an oxidant and a water-containing solvent to carry out a catalytic reaction to obtain a product containing vicinal diols.

[0120] In one embodiment, the molar ratio of the oxidant to the olefin compound is 0.1 to 20:1, preferably 0.5 to 10:1, and more preferably 0.8 to 5:1; the catalyst (SiO 2 The molar ratio of the oxidant to the oxidant is 0.01 to 10:1, preferably 0.05 to 5:1, and more preferably 0.1 to 2:1.

[0121] According to the disclosure, the olefin compounds used in the raw materials can be monoolefins or polyolefins, and the olefins can be aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and can have substituents, such as alkyl, aryl, ester, nitro, hydroxyl, carboxyl, aldehyde, ketone, cyano, ether, amino, imino, halogen substituents, and can contain oxygen, nitrogen, sulfur, phosphorus, halogen heteroatoms. Preferably, the olefin compounds are selected from one or more of monoolefin compounds with 2 to 30 carbon atoms and polyolefin compounds with 2 to 30 carbon atoms; preferably, the olefin compounds are selected from one or more of monoolefin compounds with 2 to 18 carbon atoms and polyolefin compounds with 2 to 18 carbon atoms; further preferably, the olefin compounds are selected from one or more of monoolefin compounds with 3 to 8 carbon atoms and polyolefin compounds with 3 to 8 carbon atoms.

[0122] In a specific embodiment, the olefin compound is selected from one or more of ethylene, vinyl chloride, propylene, allyl chloride, acrylonitrile, acrylic acid, acrolein, allyl alcohol, crotonic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, 1,4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, styrene, oleic acid, methyl oleate, ricinoleic acid and methyl ricinoleate.

[0123] In a specific embodiment, the olefin compound can be a single component olefin, a mixed component olefin, or a mixed olefin raw material of olefin and inert components, such as nitrogen, argon, helium, neon, air, oxygen, hydrogen, methane, ethane, propane, butane. In the mixed olefin raw material, the molar content of the olefin compound is preferably greater than 20%, more preferably greater than 50%, further preferably greater than 70%, and most preferably greater than 90%. For safety considerations, the oxygen content and hydrogen content in the mixed olefin raw material should be controlled. Preferably, the oxygen molar content and the hydrogen molar content are each less than 5%, preferably less than 2%, and more preferably less than 1%.

[0124] In one embodiment, the oxidant is selected from one or more of inorganic peroxides, organic peroxides and ozone; optionally, the inorganic peroxide is one or more of hydrogen peroxide, urea peroxide, potassium permonosulfate, potassium persulfate, sodium percarbonate, percarbonamide and sodium perborate; the organic peroxide is selected from one or more of tert-butyl hydroperoxide, cyclohexyl hydroperoxide, isopropyl peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl peroxypivalate, isopropyl hydroperoxide, tert-amyl hydroperoxide and di-tert-butyl peroxide; preferably, the oxidant is hydrogen peroxide. Hydrogen peroxide is used in the present disclosure in the form of hydrogen peroxide. Preferably, the hydrogen peroxide is a solution with a mass concentration of hydrogen peroxide of 2 to 70% by weight, more preferably 10 to 50% by weight, and further preferably 20 to 45% by weight.

[0125] In one embodiment, the catalyst is contacted with an olefin compound, an oxidant and an aqueous solvent in the presence of a third solvent;

[0126] Optionally, the third solvent is selected from one or more of water, ether compounds with 2 to 20 carbon atoms, acid compounds with 2 to 20 carbon atoms, ester compounds with 2 to 30 carbon atoms and derivatives thereof.

[0127] In a specific embodiment, the third solvent is selected from one or more of methyl ether, ethyl ether, methyl tert-butyl ether, methyl cyclohexyl ether, anisole, acetic acid, propionic acid, butyric acid, malonic acid, octanoic acid, nonanoic acid, methyl formate, ethyl acetate, ethyl formate, butyl acetate, isopropyl acetate, cyclohexyl acetate, methyl oleate, ethyl oleate and methyl ricinoleate. Preferably, the molar ratio of the oxidant to the third solvent is 1:3 to 200, preferably 1:5 to 80, and more preferably 1:10 to 40.

[0128] Considering that the addition of organic solvents requires the addition of solvent separation, refining and recovery units, resulting in increased process complexity and energy consumption, from the perspective of optimizing the reaction process, reducing energy consumption, reducing the discharge of three wastes, and improving the economic efficiency of the device, it is preferred not to add an organic solvent as the third solvent, but to use water as the third solvent for the reaction. The heterogeneous mass transfer resistance in the reaction process can be achieved by selecting a suitable reactor, adding internal components, adjusting process parameters and other existing technical methods, which will not be repeated here.

[0129] According to the method disclosed in the present invention, the conditions of the contact reaction are: the reaction temperature is 5 to 100°C, preferably 20 to 80°C, and the reaction pressure is from normal pressure to 5Mpa (gauge pressure). Within the reaction pressure range, the reaction system disclosed in the present invention can be a liquid-liquid-solid three-phase reaction, a gas-liquid-solid three-phase reaction, a liquid-solid two-phase reaction, or a gas-liquid-liquid-solid four-phase reaction. The reaction pressure can be the autogenous pressure formed by the reaction raw materials under the reaction conditions, or it can be the introduction of a gas component inert to the reaction. The gas component inert to the reaction includes, for example, but is not limited to nitrogen, argon, helium, neon, air, oxygen, methane, ethane, propane, butane, etc. For safety reasons, the oxygen content and hydrogen content in the reaction system are controlled, preferably the molar content of oxygen and hydrogen is respectively less than 5%, further preferably less than 2%, and more preferably less than 1%.

[0130] According to the method disclosed in the present invention, the reaction can be carried out under batch conditions or under continuous conditions. From the perspective of reducing labor intensity, improving product quality and technical feasibility and safety, it is preferred to carry out the reaction under continuous conditions. The contact reaction, the contact time, that is, the reaction time is preferably 1min to 24h, preferably 1 to 12h; the reaction pressure is 0.5 to 10Mpa, preferably 1 to 4; or the feed mass space velocity is preferably 0.02 to 5h in terms of oxide. -1 Preferably 0.5 to 2 hours -1 .

[0131] According to the method disclosed in the present invention, the reaction can be realized in batches or continuously in reactors of different forms such as kettle reactors, fixed bed reactors, shell-and-tube reactors, fluidized bed reactors, suspended bed reactors, and microchannel reactors. The different reactor forms are only to adapt to the corresponding purpose requirements and achieve a better effect of directly preparing vicinal diols by one-step reaction of olefins. At the same time, it is preferably used in conjunction with the reactor with a catalyst of the corresponding form. For example, a fixed bed reactor and a shell-and-tube reactor use a formed catalyst, a kettle reactor uses a molecular sieve raw powder, and a microchannel reactor uses a molecular sieve raw powder or the catalyst is immobilized in a microchannel, which can achieve a relatively better reaction effect, and all should be regarded as the content of the present invention.

[0132] According to the method disclosed in the present invention, the reaction process disclosed in the present invention mainly produces vicinal diols, vicinal diol condensation (i.e., condensation etherification products of two vicinal diol molecules), divicinal diol condensation (i.e., condensation etherification products of three vicinal diol molecules), aldehydes produced by the cleavage of double bonds of raw olefins, acids obtained by further oxidation of aldehydes, etc. The substituted benzenesulfonic acid used for the reaction can be separated by distillation or extraction, while the unreacted olefins and the generated aldehydes can be separated by distillation, and the generated vicinal diols, vicinal diol condensation, and divicinal diol condensation can be separated under reduced pressure or by extraction, and the overall separation energy consumption is low.

[0133] According to the method disclosed in the present invention, the separation of the reaction product and the catalyst can be achieved in a variety of ways. For example, when the original powdered titanium silicon molecular sieve is used as the catalyst, the separation of the product and the recovery and reuse of the catalyst can be achieved by sedimentation, filtration, centrifugation, evaporation, membrane separation, etc. Alternatively, the catalyst can be formed and loaded into a fixed bed reactor, and the catalyst can be recovered after the reaction is completed. Various catalyst separation and recovery methods are involved in many existing documents and will not be described here.

[0134] The present invention will be further described below by way of examples, but the contents of the present invention are not limited thereto.

[0135] Unless otherwise specified, the raw materials used in the examples are all chemically pure reagents.

[0136] In the preparation process of the present disclosure, "room temperature" means a temperature of 25°C.

[0137] Preparation Example 1

[0138] This preparation example is used to illustrate the preparation of titanium silicalite raw materials.

[0139] The preparation method of the titanium silicalite raw material TS-1 used in the embodiment is as follows (refer to the method of Zeolites, 1992, 12 (8), 943-50): tetrapropylammonium hydroxide (TPAOH, 20%, purchased from Aldrich Company, USA) solution is added to tetraethyl orthosilicate (TEOS) solution to obtain a liquid mixture with a pH of about 13, and then a required amount of n-butyl titanate [Ti(OBu) 4 ] anhydrous isopropanol solution, stirred for 15 minutes to obtain a clear liquid, and finally, the remaining TPAOH was slowly added to the clear liquid and stirred at 348-353K for about 3 hours to obtain a 0.03TiO 2 :SiO 2 :0.36TPA:35H 2 O sol, then crystallized at 443K for 3 days, then the obtained solid was filtered, washed with distilled water, dried at 373K for 5 hours, and then calcined at 823K for 10h to obtain a molecular sieve sample. Among them, the amount of TEOS used is 42g, the amount of TPAOH used is 73g, and the amount of Ti(OBu) 4 The amount of isopropanol used is 2g, the amount of anhydrous isopropanol used is 10g, and the amount of water used is 68g. In the prepared titanium silicon molecular sieve raw material TS-1, the molar ratio of Ti:Si is 0.03:1. The infrared spectrum of the titanium silicon molecular sieve TS-1 is as follows Figure 2 shown.

[0140] Preparation Example 2

[0141] The hollow titanium silicate molecular sieve HTS used in the example is prepared by referring to the method described in Example 1 of the specification of Chinese patent CN1301599A. In the HTS molecular sieve, the Ti:Si molar ratio is 0.03:1. TEM characterization shows that there is an obvious hollow structure in the molecular sieve crystal.

[0142] Example 1

[0143] TS-1 molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with sodium p-hydroxybenzenesulfonate and toluene in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to silanization agent was 1.5:1, and Z1 (in terms of SiO 2The molar ratio of 1:2 (toluene) to toluene is 1:30, and the mixture is treated at 60°C for 8 hours and filtered to separate. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with sodium benzenesulfonate salt. Z2 is mixed with a sufficient amount of hydrochloric acid solution with a pH value of 2 (the amount of acid solution is 15 mL relative to 1 g of Z2) and stirred at room temperature for 2 hours, and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0144] XRF analysis of Z3 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. The infrared spectrum of the titanium silicon molecular sieve containing sulfonic acid prepared in this example is shown in FIG. Figure 1 As shown, Figure 1 and Figure 2 (Infrared spectrum of the titanium silicon molecular sieve raw material TS-1 prepared in the preparation example) By comparison, it can be seen that the titanium silicon molecular sieve containing sulfonic acid prepared in this example has a wavelength of 1060-1260 cm -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0145] Comparative Example 1

[0146] This comparative example refers to the preparation method in Example 1, and the difference from Example 1 is that:

[0147] Without adding (3-glycidyl ether propyl) methyl dimethoxy silane (epoxy group donor), the titanium silicalite raw material is directly mixed with sodium p-hydroxybenzene sulfonate as Z1 to obtain the titanium silicalite molecular sieve.

[0148] Comparative Example 2

[0149] This comparative example refers to the preparation method in Example 1, and the difference from Example 1 is that sodium p-hydroxybenzenesulfonate is replaced by sulfuric acid, and the rest of the process is the same as Example 1 to obtain titanium silicon molecular sieve.

[0150] Comparative Example 3

[0151] This comparative example refers to the preparation method in Example 1, and the difference from Example 1 is that:

[0152] TS-1 molecular sieve, (3-glycidyl ether propyl) methyl dimethoxy silane, acetone, sodium p-hydroxybenzenesulfonate and toluene are all mixed together, then treated at 60°C for 8 hours and filtered to separate. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with sodium benzenesulfonate salt; Z2 is mixed with a sufficient amount of hydrochloric acid solution with a pH value of 2 and stirred at room temperature for 2 hours, and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0153] Example 2

[0154] TS-1 molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with sodium p-hydroxybenzenesulfonate and n-hexane in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to silane reagent was 1.2:1, and Z1 (in terms of SiO 2 The molar ratio of 1:50 of n-hexane is 1:50, and the mixture is treated at 80°C for 6 hours, and then filtered and separated. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with sodium benzenesulfonate salt; Z2 is mixed with a sufficient amount of hydrochloric acid solution with a pH value of 2 (the amount of acid solution is 10 mL relative to 1 g of Z2) and stirred at room temperature for 2 hours, and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0155] XRF analysis of Z3 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0156] Example 3

[0157] TS-1 molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with p-hydroxymethylbenzenesulfonic acid and cyclohexane in a three-necked flask with condensation reflux, wherein the molar ratio of p-hydroxymethylbenzenesulfonic acid to silanization agent was 1:1, and Z1 (in terms of SiO 2 The molar ratio of the reaction mixture to cyclohexane was 1:80, and the mixture was treated at 80°C for 12 hours and separated by filtration. The solid was dried at 120°C for 8 hours to obtain titanium silicalite Z2 with benzenesulfonic acid.

[0158] XRF analysis of Z2 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0159] Example 4

[0160] TS-1 molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with potassium p-hydroxybenzenesulfonate and toluene in a three-necked flask with condensation reflux, wherein the molar ratio of potassium p-hydroxybenzenesulfonate to silanization agent was 2.5:1, and Z1 (in terms of SiO 2The molar ratio of 1 g of Z2 to toluene is 1:20, and the mixture is treated at 80°C for 12 hours and then filtered and separated. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with potassium benzenesulfonate. Z2 is mixed with a sufficient amount of nitric acid solution with a pH value of 2 and stirred at room temperature for 2 hours (the amount of acid solution is 12 mL relative to 1 g of Z2), and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0161] XRF analysis of Z3 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0162] Example 5

[0163] TS-1 molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with sodium p-hydroxybenzenesulfonate and toluene in a three-necked flask with condensation and reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to silane reagent was 1.8:1, and the molar ratio of Z1 (based on SiO2) to toluene was 1:50, and after being treated at 50°C for 8 hours, it was filtered and separated, and the solid was dried at 120°C for 8 hours to obtain titanium silicon molecular sieve Z2 with sodium benzenesulfonate; Z2 was mixed with a sufficient amount of nitric acid solution with a pH value of 2 and stirred at room temperature for 2 hours (relative to 1g of Z2, the amount of acid solution was 15mL), and then filtered to obtain titanium silicon molecular sieve Z3 with benzenesulfonic acid. After the reaction is completed, the catalyst and the liquid product are separated by filtration.

[0164] XRF analysis of Z3 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the-1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0165] Example 6

[0166] TS-1 molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with sodium p-hydroxybenzenesulfonate and cyclohexane in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to silanization agent was 2:1, and Z1 (in terms of SiO 2 The molar ratio of cyclohexane to cyclohexane is 1:60, and the mixture is treated at 70°C for 12 hours and filtered to separate. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with sodium benzenesulfonate salt; Z2 is mixed with a sufficient amount of nitric acid solution with a pH value of 2 and stirred at room temperature for 2 hours (the amount of acid solution is 10 mL relative to 1 g of Z2), and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0167] XRF analysis of Z3 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0168] Example 7

[0169] HTS molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with sodium p-hydroxybenzenesulfonate and toluene in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to silanization agent was 1.5:1, and Z1 (in terms of SiO 2 The molar ratio of 1 g of Z2 to toluene is 1:30, and the mixture is treated at 60°C for 8 hours and filtered to separate. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with sodium benzenesulfonate salt. Z2 is mixed with a sufficient amount of hydrochloric acid solution with a pH value of 2 and stirred at room temperature for 2 hours (the amount of acid solution is 5 mL relative to 1 g of Z2), and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0170] XRF analysis of Z2 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0171] Example 8

[0172] HTS molecular sieve (SiO 2The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with potassium p-hydroxybenzenesulfonate and cyclohexane in a three-necked flask with condensation reflux, wherein the molar ratio of potassium p-hydroxybenzenesulfonate to silanization agent was 1.7:1, and Z1 (in terms of SiO 2 The molar ratio of cyclohexane to cyclohexane is 1:40, and the mixture is treated at 50°C for 12 hours and then filtered and separated. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with potassium benzenesulfonate. Z2 is mixed with a sufficient amount of hydrochloric acid solution with a pH value of 2 and stirred at room temperature for 2 hours (the amount of acid solution is 10 mL relative to 1 g of Z2), and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0173] XRF analysis of Z3 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0174] Example 9

[0175] HTS molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with sodium p-hydroxybenzenesulfonate and toluene in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to silanization agent was 1.5:1, and Z1 (in terms of SiO 2The molar ratio of 1 g of Z2 to toluene is 1:50, and the mixture is treated at 60°C for 8 hours and filtered to separate. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with sodium benzenesulfonate salt. Z2 is mixed with a sufficient amount of hydrochloric acid solution with a pH value of 2 and stirred at room temperature for 2 hours (the amount of acid solution is 15 mL relative to 1 g of Z2), and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0176] XRF analysis of Z3 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the -1 There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0177] Example 10

[0178] HTS molecular sieve (SiO 2 The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with sodium p-hydroxybenzenesulfonate and n-hexane in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to silane reagent was 2:1, and Z1 (in terms of SiO 2 The molar ratio of 1 g of Z2 to n-hexane is 1:60, and the mixture is treated at 80°C for 6 hours and filtered to separate. The solid is dried at 120°C for 8 hours to obtain titanium silicalite Z2 with sodium benzenesulfonate salt. Z2 is mixed with a sufficient amount of hydrochloric acid solution with a pH value of 2 and stirred at room temperature for 2 hours (the amount of acid solution is 15 mL relative to 1 g of Z2), and then filtered to obtain titanium silicalite Z3 with benzenesulfonic acid.

[0179] XRF analysis of Z3 revealed the presence of Ti, Si, O, S, and C in the molecular sieve. Infrared spectroscopy revealed that the -1There is a COC bond vibration peak at 1455cm -1 、1882cm -1 There are C=C and CH vibration peaks of benzene ring nearby, at 2780-3030cm -1 There is a CH bond vibration peak at 1800-2080cm -1 、400~500cm -1 Multiple organic group signal peaks appeared in the range. Characterization by NMR carbon spectrum showed that there were signal peaks of at least 3 carbon atoms in the benzene ring of the benzenesulfonic acid group in the range of 110-140ppm (in DMSO-d6 solvent). Other characterization results and the reaction results of catalytic olefin oxidation to vicinal diols are shown in Table 2. After the reaction, the catalyst and the liquid product were separated by filtration.

[0180] Embodiment 11

[0181] This example refers to the preparation method in Example 1, and the difference from Example 1 is that:

[0182] TS-1 molecular sieve (SiO 2 Mix Z1 with sodium p-hydroxybenzenesulfonate and toluene in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to the silanization agent is 3:1, and Z1 (in terms of SiO 2 The molar ratio of 1:1 to toluene is 1:5, and the rest of the process is the same as in Example 1 to obtain titanium silicon molecular sieve Z3 with benzenesulfonic acid.

[0183] Example 12

[0184] This example refers to the preparation method in Example 1, and the difference from Example 1 is that:

[0185] TS-1 molecular sieve (SiO 2 Mix Z1 with sodium p-hydroxybenzenesulfonate and toluene in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to the silanization agent is 5:1, and Z1 (in terms of SiO 2 The molar ratio of 1:1 (in terms of weight) to toluene is 1:1, and the remaining process is the same as in Example 1 to obtain titanium silicon molecular sieve Z3 with benzenesulfonic acid.

[0186] Example 13

[0187] TS-1 molecular sieve (SiO 2The mixture was filtered and separated, and the solid was dried at 120°C for 6 hours to obtain titanium silicon molecular sieve Z1 with epoxy groups; Z1 was mixed with sodium p-hydroxybenzenesulfonate and toluene in a three-necked flask with condensation reflux, wherein the molar ratio of sodium p-hydroxybenzenesulfonate to silanization agent was 1.5:1, and Z1 (in terms of SiO 2 The molar ratio of 1:2 (toluene) to toluene is 1:30, and the mixture is treated at 30°C for 0.5h and then filtered and separated. The solid is dried at 120°C for 8h to obtain titanium silicalite Z2 with sodium benzenesulfonate salt; Z2 is mixed with a sufficient amount of hydrochloric acid solution with a pH value of 2 (the amount of acid solution is 15mL relative to 1g of Z2) and stirred at 100°C for 24h, and then filtered to obtain titanium silicalite Z13 with benzenesulfonic acid.

[0188] The molar ratios of the elements, weight loss on heat and structural parameters of the molecular sieves prepared in the above examples and comparative examples are listed in the following Table 1-1, and the infrared spectral characteristics of the molecular sieves are listed in the following Table 1-2.

[0189] Table 1-1

[0190]

[0191] According to the data in Table 1-1 above, we can see that:

[0192] The molar ratio of Ti element to S element in the titanium silicon molecular sieves prepared in Examples 1 to 3 and 5 to 10 is in the range of (1.5 to 6):1, and the thermal weight loss is in the range of 2 to 4 weight %.

[0193] Table 1-2

[0194] Example No. <![CDATA[A 第一特征峰 :A 800 ]]> <![CDATA[A 第二特征峰 :A 800 ]]> <![CDATA[A 第三特征峰 :A 800 ]]> 1 17:1 0.018 0.11 Comparative Example 1 12:1 0 0.01 Comparative Example 2 13:1 0 0.01 Comparative Example 3 13:1 0.002 0.03 2 16:1 0.017 0.09 3 14:1 0.009:1 0.07:1 4 13:1 0.008:1 0.07:1 5 16:1 0.018 0.10 6 15:1 0.019 0.11 7 18:1 0.025 0.13 8 20:1 0.021 0.14 9 21:1 0.023 0.14 10 20:1 0.024 0.13 11 10:1 0.006:1 0.06:1 12 8:1 0.004:1 0.05:1 13 28:1 0.04:1 0.26:1

[0195] Among them, after peak area integral calculation, taking the molecular sieve prepared in Example 1 as an example, in the infrared spectrum of the molecular sieve, the peak area A of the first characteristic peak is 第一特征峰 is 867, the peak area of ​​the second characteristic peak is A 第二特征峰 is 0.9, the peak area A of the third characteristic peak 第三特征峰 5.6, located at 800±5cm -1 The peak area A of the signal peak at position 800 is 51.

[0196] Reaction Example 1

[0197] The catalyst performance was evaluated under the following conditions: titanium silicon molecular sieve catalyst, propylene, 30% by mass hydrogen peroxide solution and water were put into a reactor, wherein the titanium silicon molecular sieve (SiO 2 The molar ratio of hydrogen peroxide to propylene was 0.2:1, the molar ratio of hydrogen peroxide to propylene was 2:1, and the molar ratio of hydrogen peroxide to water was 1:20. The mixture in the reactor was then reacted at 60°C and 2.5MPa for 4h. After the reaction was completed, the temperature was lowered and samples were taken for analysis.

[0198] The composition of the reaction product in the embodiment was analyzed by gas chromatography, and the analysis results were quantitatively analyzed by external standard method. The analysis conditions of the chromatography were: Agilent-6890 chromatograph, HP-5 capillary column, injection volume 0.5 μL, injection port temperature 280°C. The column temperature was maintained at 100°C for 2 min, then increased to 250°C at a rate of 15°C / min and maintained for 15 min. FID detector, detector temperature 280°C.

[0199] The content of hydrogen peroxide in the examples is measured by sodium thiosulfate indirect titration, and the amount of hydrogen peroxide is calculated based on hydrogen peroxide.

[0200] The following indicators were mainly investigated in each embodiment and comparative example, and the analysis results are listed in the following Table 2:

[0201] Olefin conversion rate (%) = the number of moles of olefins consumed in the production of each substance in the product / the number of moles of olefins in the feedstock × 100%;

[0202] Selectivity of vicinal diol (%) = mole number of vicinal diol in the product / mole number of olefins consumed to generate main and by-products × 100%;

[0203] Effective utilization rate of hydrogen peroxide (%) = the number of moles of hydrogen peroxide consumed in converting propylene into organic products / the total number of moles of hydrogen peroxide consumed in the raw materials measured by titration analysis × 100%.

[0204] Comparative Reaction Example 1

[0205] In this comparative example, TS-1 molecular sieve was used as the catalyst, and the analysis results are listed in Table 2.

[0206] Comparative Reaction Example 2

[0207] In this comparative example, TS-1 molecular sieve and sulfuric acid were used for catalytic reaction. 2 The molar ratio of 2-nitropropene to 2-nitropropene was 0.03:1, and the analysis results are listed in Table 2. In this comparative example, sulfuric acid could not be separated from the reaction product by filtration.

[0208] Reaction Comparative Example 3

[0209] This comparative example is different from comparative example 2 in that p-toluenesulfonic acid is used instead of sulfuric acid, and no TS-1 molecular sieve is added for catalytic reaction, and the analysis results are listed in Table 2. In this comparative example, p-toluenesulfonic acid cannot be separated from the reaction product by filtration.

[0210] Comparative Reaction Example 4

[0211] According to the method of Example 1 of Chinese Patent CN104447204A, TS-1 molecular sieve loaded with cerium dioxide was prepared, and CeO 2 / TS-1 was used as the catalyst for reaction evaluation, and the analysis results are listed in Table 2.

[0212] Reaction Example 2

[0213] This reaction example refers to the method for preparing vicinal diols by catalytic oxidation of olefins in reaction example 1, and the difference from reaction example 1 is that the reaction is carried out under the following conditions:

[0214] The titanium silicon molecular sieve prepared in Example 1 was used as a catalyst, wherein the titanium silicon molecular sieve (SiO 2 The molar ratio of hydrogen peroxide to propylene was 0.01:1, the molar ratio of hydrogen peroxide to propylene was 20:1, and the molar ratio of hydrogen peroxide to water was 1:20. Then the mixture in the reactor was reacted at 100°C and 0.5MPa for 0.5h. After the reaction was completed, the temperature was lowered and samples were taken for analysis. The analysis results are listed in Table 2.

[0215] Reaction Example 3

[0216] This reaction example refers to the method for preparing vicinal diols by catalytic oxidation of olefins in reaction example 1, and the difference from reaction example 1 is that the reaction is carried out under the following conditions:

[0217] The titanium silicon molecular sieve prepared in Example 1 was used as a catalyst, wherein the titanium silicon molecular sieve (SiO 2 The molar ratio of hydrogen peroxide to propylene was 15:1, the molar ratio of hydrogen peroxide to propylene was 30:1, and the molar ratio of hydrogen peroxide to water was 1:20. Then the mixture in the reactor was reacted at 120°C and 0.2MPa for 30h. After the reaction was completed, the temperature was lowered and samples were taken for analysis. The analysis results are listed in Table 2.

[0218] Table 2

[0219]

[0220]

[0221] According to the data in Table 2 above, we can see that:

[0222] Compared with the reaction results using the molecular sieves prepared in Comparative Examples 1 to 3 as catalysts, the titanium silicon molecular sieves prepared by the method provided by the present disclosure in Examples 1 to 13 have better catalytic activity in the reaction of olefin oxidation to prepare vicinal diols, and can obtain higher olefin conversion rate, vicinal diol selectivity and effective utilization rate of hydrogen peroxide;

[0223] Compared with comparative reaction examples 1 to 4, in the reaction of preparing vicinal diols by olefin oxidation in Examples 1 to 13, the titanium silicon molecular sieve provided by the present disclosure is used as a catalyst, the catalytic reaction is simple (no need to use reaction reagents such as sulfuric acid that are not easy to separate), and a higher olefin conversion rate, vicinal diol selectivity and effective utilization rate of hydrogen peroxide can be obtained;

[0224] According to the data in Table 1-2, it can be seen that the A of the catalyst prepared in Example 12 第一特征峰 : A 800 , A 第二特征峰 : A 800 The value is not within the scope of the present disclosure. The olefin conversion rate of the catalysts prepared in Examples 1 to 11 and 13 in the olefin oxidation to prepare vicinal diol reaction is significantly higher than that of the catalyst in Example 12; further, in the infrared spectra of the catalysts prepared in Examples 1 to 2 and Examples 5 to 10, A 第一特征峰 : A 800 is a preferred value within the range of (15 to 25): 1, A 第二特征峰 : A 800 The preferred value is (0.01 to 0.03): 1, A 第三特征峰 : A 800 The catalysts prepared in Examples 1 to 2 and 5 to 10 have a higher olefin conversion rate in the olefin oxidation reaction to prepare vicinal diols than the catalysts in Examples 11 and 13 which are not within the preferred range.

[0225] By comparing Example 11 with Example 12, it can be seen that in the preparation process of the titanium silicalite in Example 11, the molecular sieve is synthesized according to the raw material ratio range provided in the present disclosure, and the titanium silicalite prepared in Example 11 can obtain higher olefin conversion rate, vicinal diol selectivity and effective utilization rate of hydrogen peroxide in the reaction of olefin oxidation to prepare vicinal diols; further, by comparing Example 1 with Example 11, it can be seen that in the preparation process of the titanium silicalite in Example 1, the raw material addition ratio is within the optimized range provided in the present disclosure, and the titanium silicalite prepared in Example 1 is used as a catalyst in the reaction of olefin oxidation to prepare vicinal diols, which can obtain higher olefin conversion rate, vicinal diol selectivity and effective utilization rate of hydrogen peroxide;

[0226] By comparing Example 1 with Example 13, it can be seen that the catalyst of Example 1 is prepared according to the preferred preparation conditions in the present disclosure, and the catalyst of Example 1 has higher olefin conversion rate and effective utilization rate of hydrogen peroxide than the catalyst of Example 13.

[0227] Under the condition of using the same catalyst, according to the comparison between Reaction Example 2 and Reaction Example 3, it can be seen that Reaction Example 2 performs olefin oxidation to prepare vicinal diols according to the range of conditions for the catalytic reaction provided by the present disclosure, and the olefin conversion rate, vicinal diol selectivity and effective utilization rate of hydrogen peroxide in Reaction Example 2 are higher; further comparison between Reaction Example 2 and Reaction Example 1 shows that the olefin conversion rate, vicinal diol selectivity and effective utilization rate of hydrogen peroxide in Reaction Example 1 (preparing vicinal diols according to the preferred reaction conditions) are higher.

[0228] The preferred embodiments of the present disclosure are described in detail above; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0229] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0230] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A titanium silicon molecular sieve, characterized in that: The titanium silicon molecular sieve contains sulfonic acid groups; the molar ratio of the Ti element to the S element in the titanium silicon molecular sieve is (0.1-100):

1.

2. The titanium silicon molecular sieve according to claim 1, characterized in that: The molar ratio of the Ti element to the S element in the titanium silicon molecular sieve is (0.5-70):1, preferably (0.8-30):1; more preferably (1-15):1, and more preferably (1.5-6):1; Optionally, in the titanium silicon molecular sieve, the molar ratio of Ti element to Si element is (0.001-0.05):1, preferably (0.01-0.04):1, and more preferably (0.015-0.03):1; Preferably, the sulfonic acid groups in the titanium silicalite molecular sieve include benzenesulfonic acid groups.

3. The titanium silicon molecular sieve according to claim 1, characterized in that: The titanium silicate molecular sieve contains C, O and S elements. According to thermogravimetric analysis, the thermal loss weight of the titanium silicate molecular sieve is 0.5 to 8% by weight, preferably 1 to 6% by weight, more preferably 1.5 to 5% by weight, and more preferably 2 to 4% by weight.

4. The titanium silicon molecular sieve according to claim 1, characterized in that: In the infrared spectrum of the titanium silicate molecular sieve, in the range of 1060-1260cm -1 The first characteristic peak exists in the wavenumber range; at 1455±5cm -1 There is a second characteristic peak at the wavenumber position; at 1882±10cm -1 There is a third characteristic peak at the wavenumber position; Preferably, the peak area of ​​the first characteristic peak is recorded as A 第一特征峰 , the peak area of ​​the second characteristic peak is recorded as A 第二特征峰 , the peak area of ​​the third characteristic peak is recorded as A 第三特征峰 , will be located at 800±5cm -1 The peak area of ​​the signal peak at position is recorded as A 800 , the titanium silicalite molecular sieve has the following infrared spectral characteristics: A 第一特征峰 : A 800 (10-30): 1, A 第二特征峰 : A 800 (0.005~0.05):1,A 第三特征峰 : A 800 is (0.05-0.3): 1; preferably, A 第一特征峰 : A 800 (15-25): 1, A 第二特征峰 : A 800 (0.01~0.03):1,A 第三特征峰 : A 800 is (0.08~0.2):

1.

5. The titanium silicon molecular sieve according to claim 1, characterized in that: The average particle size of the titanium silicate molecular sieve is 50 to 600 nm, preferably 150 to 500 nm; the BET specific surface area is 300 to 550 m 2 / g, preferably 400 to 500 m 2 / g; total pore volume is 0.25~0.40cm 3 / g, preferably 0.27 to 0.36 cm 3 / g; mesopore volume is 0.08~0.25cm 3 / g, preferably 0.15 to 0.20 cm 3 / g; Optionally, the configuration of the titanium silicalite molecular sieve is selected from one or more of MFI, MEL, BEA, MWW and MOR.

6. A method for preparing titanium silicon molecular sieve, characterized in that: The following steps are involved: S1, contacting a titanium silicon molecular sieve raw material with an epoxy group donor, performing a first mixing treatment, and obtaining a first product having an epoxy group, wherein the epoxy group donor comprises a silanization agent containing an epoxy group; S2, contacting the first product with a first sulfonic acid group donor, and performing a second mixing treatment to obtain a second titanium silicon molecular sieve having a sulfonic acid group, wherein the first sulfonic acid group donor comprises a sulfonic acid compound containing a hydroxyl group; or The first product is contacted with a second sulfonic acid group donor and subjected to a third mixing treatment to obtain a third titanium silicon molecular sieve product having a sulfonate group, wherein the second sulfonic acid group donor includes a sulfonate compound containing a hydroxyl group; the third titanium silicon molecular sieve product having a sulfonate group is contacted with an acid solution and subjected to an acidification treatment.

7. The method according to claim 6, characterized in that In step S1, the molar ratio of the titanium silicon molecular sieve raw material to the epoxy group donor is 1: (0.001-0.1), preferably 1: (0.005-0.08), further preferably 1: (0.01-0.6), and most preferably 1: (0.015-0.04), wherein the titanium silicon molecular sieve raw material is calculated as SiO2, and the epoxy group donor is calculated as Si; Optionally, the titanium silicalite raw material is directly contacted with the epoxy group donor, or is contacted in the presence of a first solvent; preferably, it is contacted in the presence of a first solvent; Preferably, the molar ratio of the titanium silicon molecular sieve raw material to the first solvent is 1: (5-100), preferably 1: (10-80), more preferably 1: (15-60), more preferably 1: (20-50), wherein the titanium silicon molecular sieve raw material is calculated as SiO2; Optionally, the first solvent is selected from one or more of ketone compounds with carbon atoms of 3 to 8, ester compounds with carbon atoms of 2 to 10 and hydrocarbon compounds with carbon atoms of 6 to 12; preferably, the first solvent is selected from one or more of acetone, butanone, cyclopentanone, cyclohexanone, acetylacetone, cycloheptanone, cyclooctanone, acetophenone, methyl formate, ethyl acetate, isopropyl acetate, butyl acetate, n-hexane, cyclohexane, n-heptane, n-octane, n-decane, benzene, toluene, ethylbenzene, isopropylbenzene, xylene and trimethylbenzene; further preferably, the first solvent is selected from one or more of acetone, butanone, cyclopentanone and acetylacetone.

8. The method according to claim 6, characterized in that In step S1, the epoxy group donor is selected from one or more compounds having a structure represented by the following formula (1): In formula (1), R1, R2, and R3 are each independently selected from an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group, and are preferably each independently selected from a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, and a chlorine group; R4 is selected from an alkylene group having 1 to 6 carbon atoms, an ether group having 1 to 6 carbon atoms, an alkenylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 9 carbon atoms, and a halogenated arylene group having 6 to 9 carbon atoms, and is preferably selected from an alkylene group having 1 to 4 carbon atoms, an ether group having 1 to 4 carbon atoms, and a halogenated alkylene group having 1 to 4 carbon atoms; R5 is H or selected from an alkyl group having 1 to 5 carbon atoms, and is preferably H; R a and R b Each is independently selected from one or more of H, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an ether group and an ester group. Preferably, R a and R b is H; Preferably, the epoxy group donor is selected from 5,6-epoxy-1-hexyltrimethoxysilane, 4,5-epoxy-1-pentyltrimethoxysilane, 3,4-epoxy-1-butyltrimethoxysilane, 2,3-epoxy-1-propyltrimethoxysilane, 5,6-epoxy-1-hexyltriethoxysilane, 4,5-epoxy-1-pentyltriethoxysilane, 3,4-epoxy-1-butyltrimethoxysilane, Ethoxysilane, 2,3-epoxy-1-propyltriethoxysilane, 5,6-epoxy-1-hexyltrichlorosilane, 4,5-epoxy-1-pentyltrichlorosilane, 3,4-epoxy-1-butyltrichlorosilane, 2,3-epoxy-1-propyltrichlorosilane, (3-glycidyl ether propyl) methyldimethoxysilane, (3-glycidyl ether ethyl) methyldimethoxysilane, (3-glycidyl ether ethyl) methyldimethoxysilane 2,3-epoxy-1-propyltrimethoxysilane; Optionally, the molar ratio of titanium element to silicon element in the titanium silicalite raw material is (0.001-0.1):1, preferably (0.005-0.05):1, more preferably (0.01-0.04):1, and further preferably (0.015-0.03):

1.

9. The method according to claim 6, characterized in that In step S1, the conditions of the first mixing treatment include: treating at 5-100°C for 0.5-24h; preferably, treating at 20-90°C for 2-18h; more preferably, treating at 40-80°C for 5-12h; Optionally, the treatment pressure (gauge pressure) is -0.8 to 2 MPa, preferably 0 to 0.5 MPa.

10. The method according to claim 6, characterized in that In step S2, the molar ratio of the first sulfonic acid group donor to the epoxy group donor in step S1 or the molar ratio of the second sulfonic acid group donor to the epoxy group donor in step S1 is independently (0.5-3):1, preferably (1-2.5):1, and more preferably (1.2-2):1, wherein the first sulfonic acid group donor and the second sulfonic acid group donor are calculated as S, and the epoxy group donor is calculated as Si; Optionally, the first product is contacted with the first sulfonic acid group donor or the second sulfonic acid group donor in the presence of a second solvent; preferably, the molar ratio of the first product to the second solvent is 1:(5-100), more preferably 1:(20-80), more preferably 1:(30-60), the first product is calculated as SiO2; Optionally, the second solvent is selected from one or more of ketone compounds with carbon atoms of 3 to 8, ester compounds with carbon atoms of 2 to 10 and hydrocarbon compounds with carbon atoms of 6 to 12; preferably, the second solvent is selected from one or more of acetone, butanone, cyclopentanone, cyclohexanone, acetylacetone, cycloheptanone, cyclooctanone, acetophenone, methyl formate, ethyl acetate, isopropyl acetate, butyl acetate, n-hexane, cyclohexane, n-heptane, n-octane, n-decane, benzene, toluene, ethylbenzene, isopropylbenzene, xylene and trimethylbenzene.

11. The method according to claim 6, characterized in that In step S2, the first sulfonic acid group donor and the second sulfonic acid group donor are each independently selected from one or more compounds having a structure represented by the following formula (2): In formula (2), R6 is selected from a single bond, an alkyl group having 1 to 6 carbon atoms, an ether group having 1 to 6 carbon atoms, and a halogenated alkyl group having 1 to 6 carbon atoms, preferably R6 is a single bond; R7 is selected from a single bond, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a hydroxyl group having 1 to 6 carbon atoms, and an ether group having 1 to 6 carbon atoms, preferably a single bond, an alkyl group substituted with a hydroxyl group having 1 to 3 carbon atoms; in the first sulfonic acid group donor, M is H; in the second sulfonic acid group donor, M is selected from a single bond and K; Preferably, the first sulfonic acid group donor is selected from one or more of o-hydroxybenzenesulfonic acid, o-dihydroxybenzenesulfonic acid, p-hydroxybenzenesulfonic acid, m-hydroxybenzenesulfonic acid, m-dihydroxybenzenesulfonic acid, o-hydroxymethylbenzenesulfonic acid, o-hydroxyethylbenzenesulfonic acid, p-hydroxymethylbenzenesulfonic acid, p-hydroxyethylbenzenesulfonic acid, and m-hydroxyethylbenzenesulfonic acid, preferably one or more of p-hydroxybenzenesulfonic acid, p-hydroxymethylbenzenesulfonic acid, p-hydroxyethylbenzenesulfonic acid, m-hydroxybenzenesulfonic acid, and m-hydroxymethylbenzenesulfonic acid; The second sulfonic acid group donor is selected from sodium o-hydroxybenzene sulfonate, potassium o-hydroxybenzene sulfonate, sodium o-dihydroxybenzene sulfonate, potassium o-dihydroxybenzene sulfonate, sodium p-hydroxybenzene sulfonate, potassium p-hydroxybenzene sulfonate, sodium m-hydroxybenzene sulfonate, potassium m-hydroxybenzene sulfonate, sodium m-dihydroxybenzene sulfonate, potassium m-dihydroxybenzene sulfonate, sodium o-hydroxymethylbenzene sulfonate, potassium o-hydroxymethylbenzene sulfonate, sodium o-hydroxyethylbenzene sulfonate, potassium o-hydroxyethylbenzene sulfonate, sodium p-hydroxymethylbenzene sulfonate, p-hydroxymethylbenzene sulfonate, The present invention relates to one or more of potassium benzene sulfonate, sodium p-hydroxyethylbenzene sulfonate, potassium p-hydroxyethylbenzene sulfonate, sodium m-hydroxyethylbenzene sulfonate and potassium m-hydroxyethylbenzene sulfonate, preferably one or more of sodium p-hydroxybenzene sulfonate, potassium p-hydroxybenzene sulfonate, sodium p-hydroxymethylbenzene sulfonate, potassium p-hydroxymethylbenzene sulfonate, sodium p-hydroxyethylbenzene sulfonate, potassium p-hydroxyethylbenzene sulfonate, sodium m-hydroxybenzene sulfonate, potassium m-hydroxybenzene sulfonate, sodium m-hydroxymethylbenzene sulfonate and potassium m-hydroxymethylbenzene sulfonate.

12. The method according to claim 6, characterized in that In step S2, the conditions of the second mixing treatment and the third mixing treatment each independently include: treating at 20-100° C. for 0.5-24 h, preferably treating at 40-90° C. for 2-18 h, and more preferably treating at 50-80° C. for 5-12 h; Optionally, the treatment pressure (gauge pressure) is -0.8 to 2 MPa, preferably 0 to 0.5 MPa.

13. The method according to claim 6, characterized in that In step S2, the acid solution is selected from one or more of an inorganic acid solution or an organic acid solution with a pH value of 5 or less; Optionally, the inorganic acid is selected from one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, chloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, metaphosphoric acid, perphosphoric acid and pyrophosphoric acid; the organic acid is selected from one or more of carboxylic acids having 2 to 10 carbon atoms; Preferably, relative to 1g of the third product of the titanium silicalite molecular sieve having sulfonate groups, the amount of the acid solution used is 1 to 50mL, preferably 3 to 20mL; the conditions for the acidification treatment include: temperature of 5 to 100°C, time of 0.05 to 24h, preferably, temperature of 30 to 60°C, time of 0.1 to 6h.

14. Titanium silicon molecular sieve prepared according to the method according to any one of claims 6 to 13.

15. A catalyst for catalyzing olefin oxidation to prepare vicinal diols, characterized in that: Comprising the titanium silicon molecular sieve described in any one of claims 1 to 5 and 14; based on the total weight of the catalyst, the content of the titanium silicon molecular sieve is 5 to 100 weight %.

16. Use of the catalyst according to claim 15 in catalyzing the oxidation of olefins to produce vicinal diols.

17. The use according to claim 16, characterized in that The catalytic olefin oxidation reaction to prepare vicinal diols comprises the following steps: The catalyst is contacted with an olefin compound, an oxidant and an aqueous solvent to carry out a catalytic reaction to obtain a product containing a vicinal diol; Preferably, the molar ratio of the oxidant to the olefin compound is (0.1-20):1, preferably (0.5-10):1, and more preferably (0.8-5):1; the molar ratio of the catalyst to the oxidant is (0.01-10):1, preferably (0.05-5):1, and more preferably (0.1-2):1, and the catalyst is calculated as SiO2; Optionally, the olefin compound is selected from one or more of monoolefin compounds having 2 to 30 carbon atoms and polyolefin compounds having 2 to 30 carbon atoms; preferably, the olefin compound is selected from one or more of ethylene, vinyl chloride, propylene, allyl chloride, acrylonitrile, acrylic acid, acrolein, allyl alcohol, butenoic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, 1,4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, styrene, oleic acid, methyl oleate, ricinoleic acid and methyl ricinoleate; The oxidant is selected from one or more of inorganic peroxides, organic peroxides and ozone; optionally, the inorganic peroxide is one or more of hydrogen peroxide, urea peroxide, potassium permonosulfate, potassium persulfate, sodium percarbonate, percarbonamide and sodium perborate; the organic peroxide is selected from one or more of tert-butyl hydroperoxide, cyclohexyl hydroperoxide, isopropyl peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl peroxypivalate, isopropyl hydroperoxide, tert-amyl hydroperoxide and di-tert-butyl peroxide; preferably, the oxidant is hydrogen peroxide; Preferably, the conditions of the catalytic reaction include: reaction temperature of 5 to 100° C., preferably 20 to 80° C.; reaction time of 1 min to 24 h, preferably 1 h to 12 h; reaction pressure of 0.5 to 10 Mpa, preferably 1 to 4 Mpa.

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