A method for preparing vicinal diols by catalysis using titanium silicon molecular sieve

Abstract

The present invention discloses a method for preparing a vicinal diol, characterized in that an olefin, hydrogen peroxide, an acid, and a solvent are subjected to a contact reaction in the presence of a titanium silicalite catalyst to obtain a liquid product containing the vicinal diol, and the vicinal diol is separated. The titanium silicalite catalyst is a halogen-containing titanium silicalite. The method for preparing the vicinal diol has the advantages of mild reaction conditions, a simple operation process, high raw material conversion rate, high vicinal diol selectivity, and high effective utilization rate of hydrogen peroxide.

Description

Technical Field

[0001] The present invention relates to a method for preparing vicinal diols, and more specifically, to a method for preparing vicinal diols by catalyzing olefins with titanium silicon molecular sieve. Background Art

[0002] A vicinal diol is a hydrocarbon organic compound containing hydroxyl groups between two adjacent carbon atoms. Common vicinal diols include 1,2-ethylene glycol (ethylene glycol), 1,2-propylene glycol (propylene glycol), 1,2-butylene glycol (butylene glycol), and 1,2-hexanediol (hexanediol). These diols have important applications. For example, ethylene glycol can be used as a solvent, antifreeze, and synthetic polyester. Propylene glycol can be used to synthesize unsaturated polyester resins and as an antifreeze and moisturizer. Hexanediol can be used in the production of high-end cosmetics. These diols have broad market applications and are produced in large quantities. For example, global propylene glycol production capacity reached 1.8 million tons per year in 2018.

[0003] The primary production method for vicinal diols is through the hydrolysis of upstream epoxides under certain conditions. For example, ethylene oxide is hydrolyzed to produce ethylene glycol, propylene oxide to produce propylene glycol, and hexylene oxide to produce hexylene glycol. Propylene glycol can also be produced through the co-production of dimethyl carbonate and propylene glycol. This method, which requires the hydrolysis of epoxides, requires the initial preparation of the epoxide. This process increases process complexity, reduces raw material utilization, and leads to waste gas, waste gas, and wastewater discharge, directly leading to increased costs. The co-production method also requires the initial production of the epoxide, and the prices of the co-products are often subject to market fluctuations.

[0004] US10214471 and US20180354878A1 disclose a method for reacting propylene and hydrogen peroxide in a reactor to obtain propylene glycol under the action of a heteropolyacid and a phase transfer catalyst. In this method, the heteropolyacid and hydrogen peroxide form a peroxyheteropolyacid salt in the aqueous phase, and the organic phase soluble salt is formed by the phase transfer catalyst and the peroxyheteropolyacid salt. In this method, an alkylated aromatic organic solvent having 8-12 carbon atoms increases the proportion of the heteropolyacid salt in the organic phase to complete the oxidation of propylene to produce propylene oxide. The heteropolyacid is dissolved in water and continues to react with hydrogen peroxide. 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, the propylene oxide is hydrolyzed under the action of the aqueous phase acid to obtain propylene glycol. This method is actually just a two-step reaction of propylene epoxidation to produce propylene oxide and propylene oxide hydrolysis and ring opening to produce propylene glycol under the action of acid, which is carried out 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. This method involves reacting propylene with hydrogen peroxide to produce propylene oxide, which also produces propylene glycol as a byproduct. The resulting propylene oxide is then reacted at 180-220°C and 15-25 bar to produce propylene glycol, which is then separated. This method physically integrates the two-step epoxidation and hydrolysis reactions, which inevitably results in low reaction efficiency and demanding hydrolysis conditions.

[0006] WO2019029808A1 discloses a method for preparing terminal 1,2-alkanediols with 5-12 carbon atoms. The method involves mixing the corresponding terminal olefin with formic acid and hydrogen peroxide to produce a monoformate or diformate, which is then decomposed in the presence of a decarbonization catalyst to produce the corresponding diol and carbon monoxide. This method has low selectivity and poses significant safety risks due to the presence of organic peroxides.

[0007] CN103570493A discloses a method for synthesizing 1,2-vicinal diols using a solid-supported heteropolyacid phase transfer catalytic oxidation process. The method involves reacting an acid, a terminal olefin, hydrogen peroxide, and a heteropolyacid phase transfer catalyst, followed by separation to obtain an epoxidation mixture. Alkaline solution is then added to maintain the pH at 10-12, followed by ester extraction and reduced pressure distillation to obtain the vicinal diols. This method has a lengthy operational process and low product yields.

[0008] CN107879893A discloses a method for preparing vicinal diol compounds by catalytic oxidation. The method involves preparing vicinal diols by reacting an olefin, an oxidant, and a bifunctional catalyst. The bifunctional catalyst comprises a silicoaluminophosphate molecular sieve, aluminum oxide, and a titanium silicon molecular sieve. This method uses an aluminum-containing catalyst, resulting in low hydrogen peroxide utilization.

[0009] CN102452899A discloses a method for producing propylene glycol from propylene. The method involves subjecting a titanium silicate composite catalyst, propylene, and hydrogen peroxide to an epoxidation ring-opening hydration reaction to produce propylene glycol. The titanium silicate composite catalyst comprises a titanium silicate, an acidic molecular sieve, and a resin. This method has a low hydrogen peroxide utilization rate.

[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 produce diols. This method has a low hydrogen peroxide utilization rate. Summary of the Invention

[0011] The present invention aims to address the problems of low selectivity for target products and low utilization rate of hydrogen peroxide in the prior art of generating vicinal diol products through the catalytic reaction of hydrogen peroxide and olefins, and to provide a method for preparing vicinal diols by direct oxidation of olefins, which has mild reaction conditions, a simple operation process, a high raw material conversion rate, high selectivity for target products and high utilization rate of hydrogen peroxide.

[0012] To achieve the above object, the present invention provides a method for preparing vicinal diols by catalysis of titanium silicalite, characterized in that olefins, hydrogen peroxide, acid and solvent are contacted and reacted in the presence of titanium silicalite catalyst to obtain a liquid product containing vicinal diols and the vicinal diols are separated, wherein the titanium silicalite is a halogen-containing titanium silicalite, and the halogen-containing titanium silicalite has R XRF / R XPS Value greater than 2, R XRF is the atomic ratio of halogen to silicon in the molecular sieve bulk analyzed by XRF, R XPS is the atomic ratio of halogen to silicon on the molecular sieve surface analyzed by XPS, which is characterized by infrared spectroscopy, I 3740 / I 3530 4 to 10, I 3740 The hydroxyl group of molecular sieve is 3740 cm -1 The absorption peak intensity at I 3530 The hydroxyl group of molecular sieve is 3530 cm -1 The absorption peak intensity at the acid is selected from one or more of organic carboxylic acid, substituted benzenesulfonic acid, phosphoric acid, nitric acid and sulfuric acid.

[0013] In the method, the olefin has a carbon number of C2-C30 and contains at least one double bond. The olefin may further contain one or more functional groups selected from alkyl, aryl, ester, nitro, hydroxyl, carboxyl, aldehyde, ketone, cyano, ether, amino, imino, and halogen substituents, as well as heteroatoms containing oxygen, nitrogen, sulfur, phosphorus, and halogen. Preferably, the olefin is one or more of ethylene, vinyl chloride, propylene, allyl chloride, allyl bromide, acrylonitrile, acrylic acid, acrolein, allyl alcohol, vinyl acetate, crotonic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, methylcyclopentene, 1,4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, hexadiene, 1-heptene, cycloheptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, styrene, oleic acid, methyl oleate, ricinoleic acid, and methyl ricinoleate. More preferably, the olefin is one or more of propylene, 1-butene, 1-hexene, cyclohexene, and allyl chloride.

[0014] In the method, the halogen-containing titanium silicalite molecular sieve contains 0.5%-5% and 0.5%-4% of halogen and carbon, respectively, based on the total weight of the molecular sieve, preferably 1%-3% and 0.8%-2.5%, respectively. The halogen is one of fluorine, chlorine, bromine, and iodine.

[0015] In the method, the halogen-containing titanium silicon molecular sieve is preferably R XRF / R XPSThe value is 2.5-4, I 3740 / I 3530 5-8.

[0016] The halogen-containing titanium silicate molecular sieve has an MFI, BEA, MEL, MWW or MOR framework structure. Preferably, the halogen-containing titanium silicate molecular sieve has an MFI framework structure.

[0017] In the halogen-containing titanium-silicon molecular sieve, the molar ratio of titanium to silicon is (0.001-0.05):1.

[0018] The micropore specific surface area of ​​the halogen-containing titanium silicate is 350-420m 2 / g, and the micropore volume is 0.130-0.170mL / g.

[0019] In the method, the solvent is one or more of water, C2-C20 ethers, C2-C20 acids, C2-C30 esters and derivatives; preferably, the solvent is water.

[0020] The hydrogen peroxide and solvent preferably have a molar ratio of 1:(3-200). The hydrogen peroxide and olefin preferably have a molar ratio of (0.1-20):1. The halogen-containing titanium silicalite and hydrogen peroxide preferably have a weight ratio of (0.01-10):1. The acid preferably provides a pH value of the reaction solution system of 1-4, preferably 1.5-3.

[0021] The halogen-containing titanium silicon molecular sieve is distributed in the reaction zone in the form of a fixed bed or in the form of a slurry.

[0022] The contact reaction is carried out under the following conditions: a temperature of 5°C to 100°C and a pressure of normal pressure to 5 MPa.

[0023] Preferably, the acid is selected from one or more of phosphoric acid, nitric acid and sulfuric acid.

[0024] The method for preparing vicinal diols using titanium silicalite catalysis provided by the present invention can catalyze olefins to produce products containing vicinal diols in a single step within a single reactor. Compared with existing methods, this method eliminates the need for prior preparation of epoxy compounds, simplifies the operation, operates under mild reaction conditions, achieves high feedstock conversion, achieves high selectivity for vicinal diols, and effectively utilizes hydrogen peroxide, making the process safer and more efficient, making it suitable for large-scale industrial production. DETAILED DESCRIPTION

[0025] The method for preparing vicinal diols by catalysis of titanium silicalite provided by the present invention is characterized in that olefins, hydrogen peroxide, acid and solvent are subjected to contact reaction in the presence of titanium silicalite catalyst to obtain a liquid product containing vicinal diols and the vicinal diols are separated, wherein the titanium silicalite is a halogen-containing titanium silicalite, and the halogen-containing titanium silicalite has R XRF / R XPS Value greater than 2, R XRF is the atomic ratio of halogen to silicon in the molecular sieve bulk analyzed by XRF, R XPS is the atomic ratio of halogen to silicon on the molecular sieve surface analyzed by XPS, which is characterized by infrared spectroscopy, I 3740 / I 3530 4 to 10, I 3740 The hydroxyl group of molecular sieve is 3740 cm -1 The absorption peak intensity at I 3530 The hydroxyl group of molecular sieve is 3530 cm -1 The absorption peak intensity at the position; the acid is selected from one or more of organic carboxylic acid, substituted benzenesulfonic acid, phosphoric acid, nitric acid and sulfuric acid.

[0026] In the method of the present invention, there is no limitation on the type of olefin used, which may be a monoolefin or a polyolefin. The olefin may be an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon, and may have a substituent, for example, one or more of an alkyl group, an aryl group, an ester group, a nitro group, a hydroxyl group, a carboxyl group, an aldehyde group, a ketone group, a cyano group, an ether group, an amino group, an imino group, or a halogen substituent, or may further contain oxygen, nitrogen, sulfur, phosphorus, or a halogen heteroatom. Preferably, the olefin is a C2-C30 monoolefin or polyolefin, for example, one or more of ethylene, vinyl chloride, propylene, allyl chloride, allyl bromide, acrylonitrile, acrylic acid, acrolein, allyl alcohol, vinyl acetate, butenoic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, methylcyclopentene, 1,4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, hexadiene, 1-heptene, cycloheptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, styrene, oleic acid, methyl oleate, ricinoleic acid, and methyl ricinoleate. More preferably, the olefin is C2-C18, and more preferably, C3-C8. Most preferably, the olefin is one or more of propylene, 1-butene, 1-hexene, cyclohexene, styrene, and allyl chloride.

[0027] In the method of the present invention, the olefin may be a pure component olefin, an olefin in a mixed component, a mixture of different olefins, or a mixture of an olefin and an inert component, such as nitrogen, argon, helium, neon, air, oxygen, hydrogen, methane, ethane, propane, or butane. The molar content of the olefin is preferably greater than 20%, more preferably greater than 50%, further preferably greater than 70%, and most preferably greater than 90%. For safety reasons, the oxygen and hydrogen contents of the olefin in the mixed component are controlled, preferably with the molar contents being less than 5%, further preferably less than 2%, and more preferably less than 1%.

[0028] In the method provided by the present invention, the halogen-containing titanium silicate molecular sieve has the following characteristics:

[0029] (1) XRF characterization shows that the molecular sieve contains silicon, titanium, oxygen, carbon, and halogen elements, wherein the halogen atoms account for 0.5%-5%, preferably 1%-3% of the total weight of the molecular sieve, and the carbon atoms account for 0.5%-4%, 0.8%-2.5% of the total weight of the molecular sieve. The halogen is one of fluorine, chlorine, bromine, and iodine, preferably chlorine;

[0030] (2) The halogen-containing material is analyzed by XRF to determine the bulk halogen / silicon atomic ratio of R XRF , XPS analysis of the surface halogen / silicon atomic ratio is R XPS , R XRF / R XPS The value is greater than 2, indicating that the halogen atoms are mainly distributed on the inner surface of the molecular sieve, i.e., in the pores, preferably 2.5-4; characterized by infrared spectroscopy, the ratio of the characteristic peak intensity I 3740 / I 3530 4 to 10, preferably 5 to 8, I 3740 The infrared hydroxyl spectrum of the molecular sieve is 3740 cm -1 The maximum absorption peak intensity near the molecular sieve represents the content of terminal hydroxyl groups, I 3530 The infrared hydroxyl spectrum of the molecular sieve is 3530 cm -1 The maximum absorption peak intensity near the hydroxyl group represents the content of nested hydroxyl groups. The higher the ratio, the fewer defect sites in the molecular sieve (Catalysis Today, 1997, 37(4): 353-366). The halogen-containing titanium silicon molecular sieve of the present invention has a higher I 3740 / I 3530 ratio.

[0031] (3) The halogen-containing titanium silicon molecular sieve does not limit the titanium-silicon molar ratio of the halogen-containing titanium silicon molecular sieve. Among them, the molecular sieve titanium-silicon molar ratio is (0.001-0.05): 1, and further preferably (0.01-0.03): 1. There is no limitation on the skeleton structure of the molecular sieve, which can be a skeleton structure such as MFI, BEA, MEL, MWW, SVR, MOR, EWT, etc. The skeleton structure of the molecular sieve is preferably an MFI skeleton structure. The specific surface area and pore volume of the molecular sieve were measured by low-temperature nitrogen adsorption desorption method, and the micropore specific surface area was 350-420m 2 / g, preferably 360-400m 2 / g, and the micropore volume is 0.130-0.170mL / g, preferably 0.140-0.160mL / g. The BET specific surface area and micropore volume of the halogen-containing titanium silicate molecular sieve of the present invention are lower than those of conventional titanium silicate molecular sieves, indicating that the halogen-containing groups enter the pores of the molecular sieve, resulting in a decrease in both values.

[0032] The halogen-containing titanium silicalite described in the present invention can be obtained by the following preparation method: the titanium silicalite molecular sieve after calcination to remove the template is contacted with a solution of an organic amine with a carbon number of C1-C3 at 40-100°C, and the separated solid product is washed and dried; then the solid product is contacted with a solution containing a small molecule silanization agent at 50-120°C, and then separated and dried.

[0033] In the preparation method of the halogen-containing titanium silicalite, the titanium silicalite can be synthesized by a traditional hydrothermal method, a dry gel method, a post-insertion method, or a rearrangement method. In the titanium silicalite from which the template is removed by calcination, the organic matter content is less than 0.01% of the weight of the molecular sieve. The calcination to remove the template can be carried out at a temperature greater than 300°C in an oxygen-rich or oxygen-poor atmosphere, or in a water vapor, ammonia atmosphere, an alcoholamine atmosphere, or an alcohol atmosphere, as long as the organic matter content in the titanium silicalite is reduced to less than 0.01% of the weight of the molecular sieve. The preferred calcination temperature is 350-800°C, more preferably 400-600°C, and the time is 0.5-6h.

[0034] In the preparation method of the halogen-containing titanium silicalite, the titanium silicalite molecular sieve, which has been calcined to remove the template, is contacted with a solution of an organic amine with a carbon number of C1-C3 at 40-100°C to clean the pores of the titanium silicalite molecular sieve, which has a good effect on activating the titanium silicalite molecular sieve framework. The organic amine with a carbon number of C1-C3 includes primary amines, secondary amines, tertiary amines, alcoholamines, and diamines; preferably, the organic amine with a carbon number of C1-C3 is selected from one or more of methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, ethanolamine, propanolamine, ethylenediamine, and propylenediamine.

[0035] In the preparation method of the halogen-containing titanium silicon molecular sieve, the solvent in the organic amine solution with a carbon number of C1-C3 is selected from water, C1-C10 alcohols, C2-C10 esters, or C3-C8 ketones. For example, it can be methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, cyclopentanol, n-hexanol, cyclohexanol, n-octanol, methyl formate, ethyl acetate, isopropyl acetate, n-butyl acetate, acetone, butanone, cyclopentanone, cyclohexanone, cycloheptanone, or cyclooctanone. Preferably, the organic amine solution with a carbon number of C1-C3 is an aqueous solution of an organic amine with a carbon number of C1-C3.

[0036] In the preparation method of the halogen-containing titanium silicon molecular sieve, the mass fraction of the organic amine in the organic amine solution having a carbon number of C1-C3 is preferably 0.1%-1.5%, preferably 0.2%-1%.

[0037] In the preparation method of the halogen-containing titanium silicalite, the step of "contacting the titanium silicalite from which the template has been calcined to remove it with a solution of an organic amine having carbon numbers of C1-C3 at 40-100°C, and then washing and drying the separated solid product" is preferably carried out at 60-80°C for 30-120 minutes. The separation process may be performed by centrifugation, evaporation, membrane separation, filtration, or the like. The washing is preferably performed with water or an alcohol solution until the liquid pH is less than 8, followed by drying. The drying temperature is preferably 80-200°C for 0.5-12 hours.

[0038] In the preparation method of the halogen-containing titanium silicon molecular sieve, the small molecule silanization agent has the following structure: R 1(m) -Si-OR 2(n) , or R 1(m) -Si-X (n) , where the general formula of R1 is C x H y X z, R2 is methyl or ethyl, m and n are positive integers, and m+n=4, y+z=2x+1, and x is a positive integer from 1 to 3, and X is at least one of fluorine, chlorine, bromine, and iodine. Preferably, m=1, R2 is methyl, z=1 or 2, more preferably 1, and the halogen is chlorine. More specifically, but not limited to, the small molecule silanization agent is selected from chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, chloromethyltriethoxysilane, chloroethyltrimethoxysilane, chloroethyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, dichloromethyldimethoxysilane, dichloromethyldiethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloroethyltriethoxysilane, 1,2-dichloropropyltrimethoxysilane, 1,2-dichloropropyltriethoxysilane, chloromethyltrichlorosilane, dichloromethyldichlorosilane, chloroethyltrichlorosilane, dichloromethyldimethoxysilane, dichloromethyldiethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloropropyltrimethoxysilane, 1,2-dichloropropyltriethoxysilane, chloromethyltrichlorosilane, dichloromethyldichlorosilane, chloroethyltrichlorosilane, dichloromethyldi ... Ethyldichlorosilane, chloropropyltrichlorosilane, dichloropropyldichlorosilane, 1,2-dichloroethyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, bis(1,2-dichloropropyl)dichlorosilane, bis(1,2-dichloropropyl)dichlorosilane; preferred small molecule silanization agents are chloromethyltrimethoxysilane, chloroethyltrimethoxysilane, chloropropyltrimethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloropropyltrimethoxysilane, chloromethyltrichlorosilane, chloroethyltrichlorosilane, chloropropyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, and 1,2-dichloropropyltrichlorosilane.

[0039] In the method for preparing the halogen-containing titanium silicon molecular sieve, the solvent in the solution containing the small molecule silanization agent is selected from C3-C8 ketones, C2-C10 esters, or C6-C12 alkanes. Examples include 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. Ketones are preferred as the solvent, and more preferably, the solvent is one or more of acetone, butanone, cyclopentanone, and acetylacetone.

[0040] In the preparation method of the halogen-containing titanium silicalite, the molar ratio of the small molecule silanization agent to the titanium silicalite is preferably (0.001-0.05):1, preferably (0.005-0.03):1; the molar ratio of the solvent containing the small molecule silanization agent to the titanium silicalite is preferably (5-100):1, preferably (20-60):1, the silanization agent is calculated as Si, and the titanium silicalite is calculated as SiO2.

[0041] In the preparation method of the halogen-containing titanium silicon molecular sieve, the contact between the titanium silicon molecular sieve and the organic amine solution with a carbon number of C1-C3 is preferably carried out at 60-90°C for 2-8h; the calcination temperature is preferably 350-800°C, more preferably 400-600°C, and the time is 0.5-6h; the drying is preferably at a temperature of 80-200°C and a time of 0.5-12h.

[0042] In the preparation method of vicinal diols provided by the present invention, the halogen-containing titanium silicalite can be used directly as a catalyst, or can be mixed with other catalysts, co-catalysts, carriers, etc., and can be used after being formed. The mass content of the halogen-containing titanium silicalite in the formed catalyst is preferably greater than 5%.

[0043] The present invention provides a method for preparing vicinal diols using a titanium silicalite molecular sieve containing halogen atoms and organic groups within its pores as a catalyst. This method effectively improves the compatibility of the titanium silicalite molecular sieve with organic substrates, thereby exhibiting excellent performance in catalytic reactions or adsorption separations. The weight ratio of the halogen-containing titanium silicalite molecular sieve to hydrogen peroxide is (0.01-10):1, preferably (0.05-5):1, and more preferably (0.1-2):1.

[0044] In the method for preparing vicinal diols provided by the present invention, the molar ratio of hydrogen peroxide to olefin is (0.1-20):1, preferably (0.5-10):1, and further preferably (0.8-5):1.

[0045] In the method for preparing vicinal diols provided herein, hydrogen peroxide is typically used in the reaction in the form of an aqueous solution, i.e., hydrogen peroxide. There are no specific requirements for the mass concentration of the hydrogen peroxide. Preferably, the hydrogen peroxide has a mass concentration of 2% to 70%, more preferably 10% to 50%, and even more preferably 20% to 45%.

[0046] In the method for preparing vicinal diols provided by the present invention, the acid comprises an organic acid and / or an inorganic acid. The organic acid can be a carboxylic acid, such as formic acid, acetic acid, trifluoroacetic acid, difluoroacetic acid, monofluoroacetic acid, propionic acid, butyric acid, succinic acid, cyclohexyl acid, benzoic acid and its derivatives, or a substituted benzenesulfonic acid, such as one or more of benzenesulfonic acid, methylbenzenesulfonic acid, dimethylbenzenesulfonic acid, ethylbenzenesulfonic acid, diethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, pentylbenzenesulfonic acid, cyclohexylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, phenylbenzenesulfonic acid, and p-chlorobenzenesulfonic acid. The inorganic acid can be one or more of phosphoric acid, nitric acid, and sulfuric acid. The acid is preferably one or more of phosphoric acid, nitric acid, and sulfuric acid.

[0047] In the method for preparing vicinal diols provided by the present invention, the acid is ionized in the solvent to generate hydrogen protons, preferably so that the pH value of the solution system is 1-4, and more preferably the pH value is 1.5-3.

[0048] In the method for preparing vicinal diols provided by the present invention, the solvent can be selected from one or more of water, C2-C20 ethers, C2-C20 acids, C2-C30 esters, and derivatives thereof. For example, the solvent can be 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. The molar ratio of hydrogen peroxide to solvent is 1:(3-200), preferably 1:(5-80), and more preferably 1:(10-40). Considering that the addition of organic solvents requires additional solvent separation, purification, 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 the above-mentioned organic solvents but to use only water as the solvent for the contact reaction.

[0049] It is understandable that the heterogeneous mass transfer resistance present in the reaction process can be achieved by selecting a suitable reactor, adding internal components, adjusting the existing technical methods such as process parameters, and will not be repeated here. In the preparation method of vicinal diol provided by the present invention, the reaction can be realized in batch or continuous reaction in reactors of different forms such as kettle reactor, fixed bed reactor, shell and tube reactor, fluidized bed reactor, suspended bed reactor, microchannel reactor, etc., and the different reactor forms are only to adapt to the corresponding purpose requirements, so as to achieve a better effect of directly preparing vicinal diol by one-step reaction of olefins, and preferably with a catalyst of the corresponding form for use in conjunction with a reactor, for example, a fixed bed reactor and a shell and tube reactor use a shaped catalyst, a kettle reactor uses molecular sieve raw powder, a microchannel reactor uses molecular sieve raw powder or the catalyst is immobilized in a microchannel, which can achieve a relatively better reaction effect, and should all be regarded as the content of the present invention.

[0050] In the method for preparing vicinal diols provided by the present invention, optionally, the halogen-containing titanium silicon molecular sieve catalyst is distributed in the reaction zone in the form of a fixed bed, and the reaction liquid flows through the catalyst bed to obtain a liquid containing an epoxy compound. The mass space velocity of hydrogen peroxide is preferably 0.1-5h -1 , further preferably 0.3-2h -1The advantages of using a fixed bed are that it facilitates the separation of liquids and solids and is highly operable, especially when the reaction liquid is homogeneous. To achieve optimal reaction results, the catalyst can be distributed in the reaction zone using multiple beds, multiple tubes, or a combination thereof. Heat extraction methods such as inter-bed heat exchange and inter-tube heat exchange can be used.

[0051] In the method for preparing vicinal diols provided by the present invention, optionally, the halogen-containing titanium silicalite catalyst is distributed in the reaction zone in the form of a slurry. This reaction form can adopt a slurry bed reactor, a fluidized bed reactor, a microchannel reactor, a moving bed reactor, or a supergravity reactor. The mass fraction of the titanium silicalite in the slurry is preferably 1%-30%, and more preferably 5%-15%. The advantage of using a catalyst slurry form is that it facilitates the enhancement of mass transfer and heat transfer processes. Liquid and solid separation can be achieved by sedimentation, membrane separation, filtration, centrifugation, and other operating methods, especially when the reaction liquid is heterogeneous. Its contact time, that is, the reaction time, is preferably 1 min-24 h.

[0052] In the method for preparing vicinal diols provided by the present invention, the contact is preferably carried out at a temperature of 5°C-100°C and a pressure of normal pressure to 5 MPa. Within the pressure range, the reaction system of 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 pressure can be the autogenous pressure formed by the reaction raw materials under the reaction conditions, or can be the introduction of a gas component inert to the reaction, for example, including but not limited to nitrogen, argon, helium, neon, air, oxygen, methane, ethane, propane, butane, to maintain the reaction pressure and carry out the reaction of the present invention under conditions that do not violate objective laws. For safety reasons, the oxygen content and hydrogen content are controlled, preferably the molar content of oxygen and hydrogen is less than 5%, more preferably less than 2%, and more preferably less than 1%, respectively.

[0053] The method for preparing vicinal diols provided by the present invention can be carried out under batch conditions or 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.

[0054] In the method for preparing vicinal diols provided by the present invention, the reaction process mainly produces vicinal diols, diol monocondensates (i.e., condensation etherification products of two vicinal diol molecules), diol dicondensates (i.e., condensation etherification products of three vicinal diol molecules), aldehydes produced by cleavage of double bonds of the raw olefins, and acids obtained by further oxidation of the aldehydes. The unreacted olefins and the produced aldehydes can be separated by distillation, while the produced vicinal diols, diol monocondensates, and diol dicondensates can be separated under reduced pressure or by extraction, resulting in low overall separation energy consumption.

[0055] The present invention will be further described below by way of examples, but the present invention is not limited thereto.

[0056] In the preparation example, the X-ray powder diffraction (XRD) spectrum of the titanium silicate molecular sieve was measured on a Siemens D5005 X-ray diffractometer. XRF was measured using a 3013 X-ray fluorescence spectrometer produced by Rigaku Corporation of Japan. XPS was measured using an ESCALab250 X-ray photoelectron spectrometer produced by ThermoFisher Scientific. The infrared hydroxyl spectrum of the titanium silicate molecular sieve was measured on a Nicolet 870 Fourier transform infrared spectrometer. The sample was pressed into a self-supporting sheet, placed in an infrared cell, and heated at 1×10 -3 The samples were treated at 450 °C for 3 h under Pa conditions, and the infrared hydroxyl spectrum of the samples was measured.

[0057] In the preparation example, the carbon content of the titanium silicalite molecular sieve was measured using a CS-844 high-frequency infrared carbon-sulfur analyzer (LECO Analytical Instruments, Inc., USA). The weighed sample and flux were placed in a high-frequency induction furnace, ventilated with oxygen, and then burned at high temperature. The resulting CO2 gas was detected by an infrared detector, and the carbon content of the titanium silicalite molecular sieve was calculated. (Reference: Shen Shanwen et al. Determination of Carbon and Sulfur in Precious Metal Catalysts by High-Frequency Infrared Absorption Method, Precious Metals, 2001).

[0058] The raw materials used in the examples and comparative examples were all commercially available and of analytical grade.

[0059] The concentration of hydrogen peroxide was measured by iodine titration.

[0060] Olefin conversion rate = moles of olefins consumed in the production of each substance / moles of olefins in the feedstock × 100%

[0061] Selectivity of vicinal diol = moles of vicinal diol in the product / moles of olefins consumed to generate main and by-products × 100%

[0062] Effective utilization rate of hydrogen peroxide = moles of hydrogen peroxide consumed to generate organic matter in the product / (moles of hydrogen peroxide in the raw material before the reaction - moles of hydrogen peroxide in the product after the reaction) × 100%

[0063] Preparation Example 1

[0064] In this preparation example, TS-1 molecular sieve having an MFI structure was prepared according to the method of Zeolites, 1992, Vol. 12, pages 943-950.

[0065] At room temperature, the above substances are mixed under stirring according to the molar ratio of 1:0.03:0.2:25 of ethyl orthosilicate (calculated as SiO2): tetrabutyl titanate (calculated as TiO2): tetrapropylammonium hydroxide (calculated as N): deionized water. The mixture is then transferred to a pressure-resistant stainless steel reactor and crystallized at 170°C under autogenous pressure for 72 hours. The solid product is then filtered, washed and recovered. The obtained solid product is dried in an oven at 120°C for 12 hours and then calcined at 550°C in an air atmosphere for 6 hours. The organic matter content is less than 0.01% of the weight of the molecular sieve, and a titanium silicon molecular sieve numbered TS-1-A is obtained.

[0066] XRF, XPS, low temperature nitrogen adsorption and desorption characterization results, infrared spectrum characterization characteristic peak intensity ratio I 3740 / I 3530 See Table 1.

[0067] Preparation Examples 2-6 illustrate the preparation of halogen-containing titanium silicate molecular sieves in the method of the present invention.

[0068] Preparation Example 2

[0069] (1) The titanium silicate molecular sieve TS-1-A obtained in Preparation Example 1 was mixed with an aqueous solution of methylamine, wherein the mass fraction of the organic amine was 0.5%. The mixture was then treated at 80°C for 120 minutes. The TS-1-A molecular sieve was then separated and washed with deionized water until the pH was less than 8, and then dried at 120°C for 12 hours.

[0070] (2) The titanium silicate molecular sieve obtained in step (1) is mixed with a butanone solution containing chloromethyltrimethoxysilane, and treated at 80°C for 6 hours, wherein the silanization agent (calculated as Si): titanium silicate molecular sieve (calculated as SiO2) = 0.02:1 (molar ratio), and the solvent: titanium silicate molecular sieve (calculated as SiO2) = 60:1 (molar ratio). Then the molecular sieve is separated and dried at 120°C for 12 hours to obtain a halogen-containing titanium silicate molecular sieve.

[0071] XRF, XPS, low temperature nitrogen adsorption and desorption characterization results, infrared spectrum characterization characteristic peak intensity ratio I 3740 / I 3530 See Table 1.

[0072] Preparation Example 3

[0073] (1) The titanium silicate molecular sieve TS-1-A obtained in Preparation Example 1 was mixed with an aqueous solution of ethylamine, wherein the mass fraction of the organic amine was 1.0%. The mixture was then treated at 80°C for 90 minutes. The TS-1-A molecular sieve was then separated and washed with deionized water until the pH was less than 8, and then dried at 120°C for 12 hours.

[0074] (2) The titanium silicate obtained in step (1) is mixed with a cyclopentanone solution containing chloropropyltrimethoxysilane, and treated at 70°C for 6 hours, wherein the silanization agent (calculated as Si): titanium silicate (calculated as SiO2) = 0.01:1 (molar ratio), and the solvent: titanium silicate (calculated as SiO2) = 40:1 (molar ratio). Then the molecular sieve is separated and dried at 120°C for 12 hours to obtain a halogen-containing titanium silicate.

[0075] XRF, XPS, low temperature nitrogen adsorption and desorption characterization results, infrared spectrum characterization characteristic peak intensity ratio I 3740 / I 3530 See Table 1.

[0076] Preparation Example 4

[0077] (1) The titanium silicate molecular sieve TS-1-A obtained in Preparation Example 1 was mixed with an aqueous solution of ethanolamine, wherein the mass fraction of the organic amine was 0.5%. The mixture was then treated at 80°C for 60 minutes. The TS-1-A molecular sieve was then separated and washed with deionized water until the pH was less than 8, and then dried at 120°C for 12 hours.

[0078] (2) The titanium silicate obtained in step (1) is mixed with an acetylacetone solution containing chloroethyltrichlorosilane, and treated at 90°C for 4 hours, wherein the silanization agent (calculated as Si): titanium silicate (calculated as SiO2) = 0.005:1 (molar ratio), and the solvent: titanium silicate (calculated as SiO2) = 20:1 (molar ratio). Then the molecular sieve is separated and dried at 120°C for 12 hours to obtain a halogen-containing titanium silicate.

[0079] XRF, XPS, low temperature nitrogen adsorption and desorption characterization results, infrared spectrum characterization characteristic peak intensity ratio I 3740 / I 3530 See Table 1.

[0080] Preparation Example 5

[0081] (1) The titanium silicate molecular sieve TS-1-A obtained in Preparation Example 1 was mixed with an aqueous solution of ethylenediamine, wherein the mass fraction of the organic amine was 0.2%. The mixture was then treated at 80°C for 120 minutes. The TS-1-A molecular sieve was then separated and washed with deionized water until the pH was less than 8, and then dried at 120°C for 12 hours.

[0082] (2) The titanium silicate obtained in step (1) is mixed with a butanone solution containing chloroethyltrimethoxysilane, and treated at 70°C for 2 hours, wherein the silanization agent (calculated as Si): titanium silicate (calculated as SiO2) = 0.03:1 (molar ratio), and the solvent: titanium silicate (calculated as SiO2) = 40:1 (molar ratio). Then the molecular sieve is separated and dried at 120°C for 12 hours to obtain a halogen-containing titanium silicate.

[0083] XRF, XPS, low temperature nitrogen adsorption and desorption characterization results, infrared spectrum characterization characteristic peak intensity ratio I 3740 / I 3530 See Table 1.

[0084] Preparation Example 6

[0085] (1) The titanium silicate molecular sieve TS-1-A obtained in Preparation Example 1 was mixed with an aqueous solution of dimethylamine, wherein the mass fraction of the organic amine was 1.0%. The mixture was then treated at 60°C for 120 minutes. The TS-1-A molecular sieve was then separated and washed with deionized water until the pH was less than 8, and then dried at 120°C for 12 hours.

[0086] (2) The titanium silicate molecular sieve obtained in step (1) is mixed with an acetone solution containing 1,2-dichloropropyltrichlorosilane, and treated at 60°C for 8 hours, wherein the silanization agent (calculated as Si): titanium silicate molecular sieve (calculated as SiO2) = 0.025:1 (molar ratio), and the solvent: titanium silicate molecular sieve (calculated as SiO2) = 20:1 (molar ratio). Then the molecular sieve is separated and dried at 120°C for 12 hours to obtain a halogen-containing titanium silicate molecular sieve.

[0087] XRF, XPS, low temperature nitrogen adsorption and desorption characterization results, infrared spectrum characterization characteristic peak intensity ratio I 3740 / I 3530 See Table 1.

[0088] Table 1

[0089]

[0090] As can be seen from Table 1, the prepared halogen-containing titanium silicon molecular sieve contains halogen atoms and organic groups, and the R XRF / R XPS Greater than 2, I 3740 / I 3530 Greater than 4, micropore specific surface area is 350-420m 2 / g, and the micropore volume is 0.130-0.170mL / g, both lower than the results of conventional sample TS-1-A, which indicates that in the halogen-containing titanium silicate molecular sieve, the halogen atoms and organic groups are mainly present in the pores of the molecular sieve.

[0091] Comparative Example 1

[0092] The titanium silicalite obtained in Preparation Example 1, propylene, 30% hydrogen peroxide, and water were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.2:1, the molar ratio of hydrogen peroxide to propylene was 2.5:1, and the molar ratio of hydrogen peroxide to solvent was 1:15. The mixture was reacted at 60°C and 2 MPa for 3 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0093] Comparative Example 2

[0094] The titanium silicalite obtained in Preparation Example 1, propylene, 30% hydrogen peroxide, and an aqueous solution containing phosphoric acid were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.2:1, the molar ratio of hydrogen peroxide to propylene was 2.5:1, the pH of the solution was 2.0, and the molar ratio of hydrogen peroxide to solvent was 1:15. The mixture was reacted at 60°C and 2 MPa for 3 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0095] Comparative Example 3

[0096] Propylene, 30% hydrogen peroxide, and an aqueous solution containing phosphoric acid were placed in a reactor. The molar ratio of hydrogen peroxide to propylene was 2.5:1, the pH of the solution was 2.0, and the molar ratio of hydrogen peroxide to solvent was 1:15. The mixture was reacted at 60°C and 2 MPa for 3 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0097] Comparative Example 4

[0098] A TS-1 molecular sieve loaded with ceria was prepared according to the method of Example 1 of Chinese Patent CN104447204A, and the reaction evaluation was performed according to the method of Example 1, wherein phosphoric acid was not added during the reaction and CeO2 / TS-1 was used as the catalyst. The analytical results after the reaction are shown in Table 2.

[0099] Example 1

[0100] The titanium silicalite obtained in Preparation Example 2, propylene, 30% hydrogen peroxide, and an aqueous solution containing phosphoric acid were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.2:1, the molar ratio of hydrogen peroxide to propylene was 2.5:1, the pH of the solution was 2.0, and the molar ratio of hydrogen peroxide to solvent was 1:15. The mixture was reacted at 60°C and 2 MPa for 3 hours to obtain a product. The composition of the product was analyzed, and the results are shown in Table 2.

[0101] Example 2

[0102] The titanium silicalite obtained in Preparation Example 2, 1-butene, 40% hydrogen peroxide, and an aqueous solution containing phosphoric acid were placed in a reaction kettle. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.2:1, the molar ratio of hydrogen peroxide to 1-butene was 2:1, the pH of the solution was 2.0, and the molar ratio of hydrogen peroxide to solvent was 1:20. The mixture was reacted at 50°C and 1 MPa for 5 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0103] Example 3

[0104] The titanium silicalite obtained in Preparation Example 2, allyl chloride, 30% hydrogen peroxide, and an aqueous solution containing phosphoric acid were placed in a microchannel reactor. The weight ratio of titanium silicalite to hydrogen peroxide was 0.5:1, the molar ratio of hydrogen peroxide to allyl chloride was 1.2:1, the pH of the solution was 3.0, and the molar ratio of hydrogen peroxide to solvent was 1:15. The mixture was reacted at 30°C and 0.5 MPa for 5 minutes to obtain a product. The composition of the product was analyzed, and the results are shown in Table 2.

[0105] Example 4

[0106] The titanium silicalite obtained in Preparation Example 2, 1-hexene, 27% hydrogen peroxide, and an aqueous solution containing sulfuric acid were placed in a reactor. The weight ratio of the titanium silicalite to the hydrogen peroxide was 1:1, the molar ratio of the hydrogen peroxide to the 1-hexene was 0.8:1, the pH of the solution was 1.5, and the molar ratio of the hydrogen peroxide to the solvent was 1:10. The mixture was reacted at 80°C and 0.2 MPa for 3 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0107] Example 5

[0108] The titanium silicalite obtained in Preparation Example 2, propylene, 30% hydrogen peroxide, and an aqueous solution containing nitric acid were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.5:1, the molar ratio of hydrogen peroxide to propylene was 1.5:1, the pH of the solution was 1.5, and the molar ratio of hydrogen peroxide to solvent was 1:20. The mixture was reacted at 60°C and 3 MPa for 2 hours to obtain a product. The composition of the product was analyzed, and the results are shown in Table 2.

[0109] Example 6

[0110] The titanium silicate pellet obtained in Preparation Example 2 was crushed and loaded into a fixed-bed reactor. Propylene, 30% hydrogen peroxide, and a phosphoric acid aqueous solution were introduced into the fixed-bed reactor. The pH of the reaction solution was 2.0, the molar ratio of hydrogen peroxide to propylene was 1.5:1, and the molar ratio of hydrogen peroxide to solvent was 1:30. The reaction was continued at 50°C, 3 MPa, and a hydrogen peroxide feed mass space velocity of 0.7 h⁻¹ to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0111] Example 7

[0112] The titanium silicalite obtained in Preparation Example 2, propylene, 30% hydrogen peroxide, and an aqueous solution containing sulfuric acid were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.2:1, the molar ratio of hydrogen peroxide to propylene was 2:1, the pH of the solution was 2.5, and the molar ratio of hydrogen peroxide to solvent was 1:20. The mixture was reacted at 70°C and 3 MPa for 3 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0113] Example 8

[0114] The titanium silicalite obtained in Preparation Example 2, propylene, 30% hydrogen peroxide, and a methyl tert-butyl ether solution containing phosphoric acid were placed in a reaction kettle. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.5:1, the molar ratio of hydrogen peroxide to propylene was 1:1, the pH of the solution was 1.0, and the molar ratio of hydrogen peroxide to solvent was 1:5. The mixture was reacted at 60°C and 2 MPa for 3 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0115] Example 9

[0116] The titanium silicalite obtained in Preparation Example 3, propylene, 30% hydrogen peroxide, and an aqueous solution containing phosphoric acid were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.5:1, the molar ratio of hydrogen peroxide to propylene was 2:1, the pH of the solution was 2.0, and the molar ratio of hydrogen peroxide to solvent was 1:20. The mixture was reacted at 60°C and 2 MPa for 4 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0117] Example 10

[0118] The titanium silicalite obtained in Preparation Example 4, propylene, 30% hydrogen peroxide, and an aqueous solution containing sulfuric acid were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.2:1, the molar ratio of hydrogen peroxide to propylene was 2:1, the pH of the solution was 2.5, and the molar ratio of hydrogen peroxide to solvent was 1:15. The mixture was reacted at 70°C and 2 MPa for 3 hours to obtain a product. The composition of the product was analyzed, and the results are shown in Table 2.

[0119] Example 11

[0120] The titanium silicalite obtained in Preparation Example 5, propylene, 30% hydrogen peroxide, and an aqueous solution containing phosphoric acid were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.5:1, the molar ratio of hydrogen peroxide to propylene was 1.5:1, the pH of the solution was 1.5, and the molar ratio of hydrogen peroxide to solvent was 1:20. The mixture was reacted at 70°C and 3 MPa for 3 hours to obtain a product. The composition of the product was analyzed, and the results are shown in Table 2.

[0121] Example 12

[0122] The titanium silicalite obtained in Preparation Example 6, propylene, 30% hydrogen peroxide, and an aqueous solution containing phosphoric acid were placed in a reactor. The weight ratio of the titanium silicalite to hydrogen peroxide was 0.8:1, the molar ratio of hydrogen peroxide to propylene was 1.2:1, the pH of the solution was 2.0, and the molar ratio of hydrogen peroxide to solvent was 1:10. The mixture was reacted at 60°C and 3 MPa for 4 hours to obtain the product. The composition of the product was analyzed, and the results are shown in Table 2.

[0123] Table 2

[0124]

[0125] As can be seen from Table 2, the present invention can achieve higher olefin conversion rate, vicinal diol selectivity and effective utilization rate of hydrogen peroxide.

Claims

1. A method for preparing vicinal diols by catalysis using titanium silicalite molecular sieve, characterized in that: The olefin, hydrogen peroxide, acid and solvent are contacted and reacted in the presence of a titanium silicalite catalyst to obtain a liquid product containing a vicinal diol and the vicinal diol is separated and obtained, wherein the titanium silicalite is a halogen-containing titanium silicalite, and the halogen-containing titanium silicalite has an R XRF / R XPS Value greater than 2, R XRF is the atomic ratio of halogen to silicon in the molecular sieve bulk analyzed by XRF, R XPS is the atomic ratio of halogen to silicon on the molecular sieve surface analyzed by XPS, which is characterized by infrared spectroscopy, I 3740 / I 3530 4 to 10, I 3740 The hydroxyl group of molecular sieve is 3740 cm -1 The absorption peak intensity at I 3530 The hydroxyl group of molecular sieve is 3530 cm -1 The absorption peak intensity at the halogen-containing titanium silicon molecular sieve is obtained by the following preparation method: the titanium silicon molecular sieve after calcination to remove the template agent is contacted with a solution of an organic amine with a carbon number of C1-C3 at 40-100°C, the separated solid product is washed and dried, and then contacted with a solution containing a small molecule silanization agent at 50-120°C, and then separated and dried, wherein the small molecule silanization agent has the following structure: R 1(m) -Si-OR 2(n) , or R 1(m) -Si-X (n) , where the general formula of R1 is C x H y X z , R2 is methyl or ethyl, m and n are positive integers, and m+n=4, y+z=2x+1, and x is a positive integer from 1 to 3, and X is at least one of fluorine, chlorine, bromine, and iodine; and the acid is selected from one or more of organic carboxylic acids, substituted benzenesulfonic acids, phosphoric acid, nitric acid, and sulfuric acid.

2. The method according to claim 1, wherein The olefin has a carbon number of C2-C30 and contains at least one double bond.

3. The method according to claim 2, wherein: The olefin further contains one or more functional groups selected from alkyl, aryl, ester, nitro, hydroxyl, carboxyl, aldehyde, ketone, cyano, ether, amino, imino, and halogen substituents, or further contains oxygen, nitrogen, sulfur, phosphorus, and halogen heteroatom groups.

4. The method according to claim 1, wherein The olefin is one or more of ethylene, vinyl chloride, propylene, allyl chloride, allyl bromide, acrylonitrile, acrylic acid, acrolein, allyl alcohol, vinyl acetate, butenoic acid, isobutylene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, methylcyclopentene, 1,4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, hexadiene, 1-heptene, cycloheptene, 1-octene, cyclooctene, 1-decene, cyclododecene, styrene, styrene, oleic acid, methyl oleate, ricinoleic acid, and methyl ricinoleate.

5. The method according to claim 1, wherein The olefin is one or more of propylene, 1-butene, 1-hexene, cyclohexene, and allyl chloride.

6. The method according to claim 1, wherein The halogen-containing titanium silicate molecular sieve contains 0.5%-5% of halogen and 0.5%-4% of carbon, respectively, accounting for the total weight of the molecular sieve.

7. The method according to claim 1, wherein The halogen-containing titanium silicate molecular sieve contains 1%-3% and 0.8%-2.5% of halogen and carbon respectively, accounting for the total weight of the molecular sieve.

8. The method according to claim 1, 6 or 7, wherein In the halogen-containing titanium silicon molecular sieve, the halogen is one of fluorine, chlorine, bromine and iodine.

9. The method according to claim 1, wherein In the halogen-containing titanium silicon molecular sieve, R XRF / R XPS The value is 2.5-4, I 3740 / I 3530 5-8.

10. The method according to claim 1, wherein The halogen-containing titanium silicalite molecular sieve has an MFI, BEA, MEL, MWW or MOR framework structure.

11. The method according to claim 1, wherein The halogen-containing titanium silicalite molecular sieve has an MFI framework structure.

12. The method according to claim 1, wherein In the halogen-containing titanium silicate molecular sieve, the molar ratio of titanium to silicon is (0.001-0.05):

1.

13. The method according to claim 1, wherein The halogen-containing titanium silicon molecular sieve has a micropore specific surface area of ​​350-420m 2 / g, and the micropore volume is 0.130-0.170mL / g.

14. The method according to claim 1, wherein The solvent is one or more of water, C2-C20 ether, C2-C20 acid, C2-C30 ester and derivatives.

15. The method according to claim 1, wherein The solvent is water.

16. The method according to claim 1, wherein The molar ratio of the hydrogen peroxide to the solvent is 1:(3-200).

17. The method according to claim 16, wherein The molar ratio of hydrogen peroxide to solvent is 1:(5-80).

18. The method according to claim 17, wherein The molar ratio of hydrogen peroxide to solvent is 1:(10-40).

19. The method according to claim 1, wherein The molar ratio of hydrogen peroxide to olefin is (0.1-20):

1.

20. The method according to claim 19, wherein The molar ratio of hydrogen peroxide to olefin is (0.5-10):

1.

21. The method according to claim 20, wherein The molar ratio of hydrogen peroxide to olefin is (0.8-5):

1.

22. The method according to claim 1, wherein The weight ratio of the halogen-containing titanium silicon molecular sieve to hydrogen peroxide is (0.01-10):

1.

23. The method according to claim 22, wherein The weight ratio of the halogen-containing titanium silicon molecular sieve to hydrogen peroxide is (0.05-5):

1.

24. The method according to claim 23, wherein The weight ratio of the halogen-containing titanium silicon molecular sieve to hydrogen peroxide is (0.1-2):

1.

25. The method according to claim 1, wherein The acid makes the pH value of the reaction solution system be 1-4.

26. The method according to claim 25, wherein The acid makes the pH value of the reaction solution system be 1.5-3.

27. The method according to claim 1, wherein The halogen-containing titanium silicon molecular sieve is distributed in the reaction zone in the form of a fixed bed.

28. The method according to claim 1, wherein The halogen-containing titanium silicon molecular sieve is distributed in the reaction zone in the form of slurry.

29. The method according to claim 1, wherein The contact reaction is carried out under the following conditions: a temperature of 5°C to 100°C and a pressure of normal pressure to 5 MPa.

30. The method according to claim 1, wherein: The acid is selected from one or more of phosphoric acid, nitric acid and sulfuric acid.

31. The method according to claim 1, wherein The small molecule silanization agent is selected from chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, chloromethyltriethoxysilane, chloroethyltrimethoxysilane, chloroethyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, dichloromethyldimethoxysilane, dichloromethyldiethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloroethyltriethoxysilane, 1,2-dichloropropyltrimethoxysilane, 1,2-dichloropropyltriethoxysilane, chloromethyltrichlorosilane, dichloromethyldichlorosilane, chloroethyltrichlorosilane, dichloroethyldichlorosilane, chloropropyltrichlorosilane, dichloropropyldichlorosilane, 1,2-dichloroethyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, bis(1,2-dichloropropyl)dichlorosilane, and bis(1,2-dichloropropyl)dichlorosilane.

32. The method of claim 1, wherein: The small molecule silanization reagent is chloromethyltrimethoxysilane, chloroethyltrimethoxysilane, chloropropyltrimethoxysilane, 1,2-dichloroethyltrimethoxysilane, 1,2-dichloropropyltrimethoxysilane, chloromethyltrichlorosilane, chloroethyltrichlorosilane, chloropropyltrichlorosilane, 1,2-dichloroethyltrichlorosilane, and 1,2-dichloropropyltrichlorosilane.

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