Method for preparing vicinal diol

Abstract

The invention discloses a method for preparing vicinal diol, which comprises the following steps: carrying out contact reaction on raw materials containing olefin, an oxidant and halogenated alcohol in the presence of a titanium silicalite molecular sieve catalyst and a hydration catalyst to obtain a vicinal diol-containing product, and has the advantages of mild reaction conditions, simple operation process and high yield. The method has the characteristics of high oxidant conversion rate and effective utilization rate, high vicinal diol selectivity and low product separation energy consumption.

Description

A method for preparing vicinal diols Technical Field

[0001] This invention relates to a method for preparing vicinal diols, and more specifically to a method for preparing vicinal diols by oxidizing olefins. Background Technology

[0002] vicinal glycols are hydrocarbon organic compounds in which hydroxyl groups are present on two adjacent carbon atoms. Common vicinal glycols include 1,2-ethylene glycol (hereinafter referred to as ethylene glycol), 1,2-propanediol (hereinafter referred to as propylene glycol), 1,2-butanediol (hereinafter referred to as butanediol), and 1,2-hexanediol (hereinafter referred to as hexanediol). Vicinal glycols have important applications. For example, ethylene glycol can be used as a solvent, antifreeze, and in the synthesis of polyester; propylene glycol can be used to synthesize unsaturated polyester resins and as an antifreeze and moisturizer; and hexanediol can be used in the production of high-end cosmetics. Vicinal glycols have broad market applications and large production volumes. For example, in 2018, the global production capacity of propylene glycol reached 1.8 million tons per year.

[0003] The main production method for vicinal glycols involves the hydrolysis of upstream epoxides under specific conditions. For example, ethylene oxide hydrolyzes to ethylene glycol, propylene oxide hydrolyzes to propylene glycol, and hexane oxide hydrolyzes to hexanediol. Propylene glycol can also be obtained through a dimethyl carbonate / propylene glycol co-production method. The epoxide hydrolysis method requires the prior preparation of the epoxide compound, increasing process complexity, reducing raw material utilization, and causing waste emissions, directly leading to increased costs. The co-production method also requires the prior production of the epoxide compound; furthermore, the price of co-produced products is always 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 reacts with hydrogen peroxide in the aqueous phase to form a peroxide salt. The peroxide salt is then reacted with the phase transfer catalyst to form a soluble salt in the organic phase. An alkylated aromatic organic solvent with 8-12 carbon atoms is used to increase the proportion of heteropolytungstate in the organic phase, thereby completing the oxidation of propylene to propylene oxide. The heteropolyacid then dissolves in water and continues to react with hydrogen peroxide. The resulting propylene oxide enters the aqueous phase, and because the pH of the aqueous phase is maintained in the range of 1-3.5, the propylene oxide is hydrolyzed under the action of the acid in the aqueous phase to obtain propylene glycol. This method is essentially just a two-step reaction in which propylene is epoxidized to produce propylene oxide, and then propylene oxide is hydrolyzed and ring-opened to produce propylene glycol under acid. This process is carried out in a single reactor and requires a large amount of solvent. Moreover, the catalyst system is complex and the operation is difficult.

[0005] EP1527057A1 discloses a method for the continuous preparation of propylene glycol. This method involves reacting propylene with hydrogen peroxide to produce propylene oxide, simultaneously generating propylene glycol as a byproduct. The generated propylene oxide is then reacted at 180-220°C and 15-25 bar to produce propylene glycol, which is then separated. This method is essentially a physical integration of two steps: epoxidation and hydrolysis. However, it cannot avoid the problems of 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 reacting the corresponding terminal olefin with formic acid and hydrogen peroxide to obtain a monoformate or diformate, followed by decomposition under the action of a decarbonization catalyst to yield the corresponding diol and carbon monoxide. This method has low selectivity and poses significant safety risks associated with organic peroxides.

[0007] CN103570493A discloses a method for synthesizing 1,2-vicinal diol via phase transfer catalytic oxidation using a supported heteropolyacid. The method involves mixing and reacting an acid, a terminal alkene, hydrogen peroxide, and a heteropolyacid phase transfer catalyst, followed by separation to obtain an epoxidized mixture. An alkaline solution is then added to maintain the pH at 10-12, and the mixture is subsequently subjected to ester extraction and vacuum distillation to obtain the vicinal diol. This method has a long operational process and low product yield.

[0008] CN107879893A discloses a method for preparing vicinal diols via catalytic oxidation. This method involves preparing vicinal diols through the action of an olefin, an oxidant, and a bifunctional catalyst. The bifunctional catalyst contains silica-alumina molecular sieves, alumina, and titanium-silicon molecular sieves. This method uses an aluminum-containing catalyst, resulting in low utilization of hydrogen peroxide.

[0009] CN102452899A discloses a method for producing propylene glycol from propylene. This method involves an epoxidation ring-opening hydration reaction of a titanium-silicon molecular sieve composite catalyst, propylene, and hydrogen peroxide to prepare propylene glycol. The titanium-silicon molecular sieve composite catalyst includes a titanium-silicon molecular sieve, an acidic molecular sieve, and a resin. However, this method has low hydrogen peroxide utilization.

[0010] CN104447204A discloses a method for preparing diols, which uses titanium-silicon molecular sieves supported on rare earth oxides as catalysts to promote the reaction of olefins and oxidants to produce diols. However, this method has low hydrogen peroxide utilization.

[0011] CN116803966A discloses a method for reacting olefins, hydrogen peroxide, an acid, and a solvent in the presence of a halogen-containing titanium-silicon molecular sieve catalyst to obtain a liquid product containing a vicinal diol, which is then separated. The catalyst preparation for this method is relatively complex.

[0012] CN116789523A discloses a method for reacting olefins, an oxidant, and a substituted benzenesulfonic acid solution in the presence of a catalyst containing a titanium silicate molecular sieve to obtain vicinal diols.

[0013] CN116789522A discloses a method for obtaining vicinal diols by contacting a double-bonded compound, an oxidant, and a solvent in the presence of a catalyst containing a titanium-silicon molecular sieve and a cation exchange resin. Summary of the Invention

[0014] The purpose of this invention is to provide a method for the direct oxidation of olefins to prepare vicinal diols, which features mild reaction conditions, simple operation, high selectivity for vicinal diols, high oxidant conversion rate, and high oxidant utilization rate.

[0015] To achieve the above objectives, the present invention provides a method for preparing vicinal diols, characterized in that the method comprises reacting a raw material containing an olefin, an oxidant, and a haloalcohol in the presence of a titanium silicate molecular sieve and a hydrated catalyst to obtain a product containing vicinal diols.

[0016] The haloalcohol has m carbon atoms, where m is a positive integer from 1 to 12, and the halogen element, hydroxyl group, and hydrogen are bonded to the carbon atoms; the halogen element is one or more of fluorine, chlorine, bromine, and iodine, and its number does not exceed 2m+1, and the number of hydroxyl groups does not exceed 5.

[0017] The halogen element is fluorine.

[0018] The haloalcohol is selected from one or more of the following: 2,2,3,3-tetrafluoropropanol, 1H,1H-pentafluoropropanol, 3-fluoropropanol, hexafluoroisopropanol, 2-allylhexafluoroisopropanol, 1,3-difluoro-2-propanol, hexafluoro-2-methylisopropanol, perfluorotert-butanol, 2-trifluoromethyl-2-propanol, 2,2-bis(trifluoromethyl)propanol, 2,2-difluoropropanol, 1-(4-fluoropropoxy)-2-propanol, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol, and 2-vinylhexafluoroisopropanol.

[0019] The olefin is a monoolefin or polyolefin of C2-C30.

[0020] The molar ratio of the oxidant to the olefin is 1:(0.05-20).

[0021] The oxidant is selected from at least one of inorganic peroxides, organic peroxides, and ozone.

[0022] The inorganic peroxide is selected from at least one of hydrogen peroxide, urea peroxide, potassium persulfate, potassium persulfate, sodium percarbonate, percarbonamide, and sodium perborate; the organic peroxide is selected from at least one of tert-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl perpentyl peroxide, isopropyl hydroperoxide, tert-amyl hydroperoxide, and di-tert-butyl peroxide. Preferably, the oxidant is hydrogen peroxide.

[0023] The raw material contains water, and the molar ratio of water to the oxidant is (0.1–100):1. The molar ratio of the haloalcohol to the oxidant is (0.01–100):1.

[0024] The titanium-silicon molecular sieve is at least one of MFI type titanium-silicon molecular sieve, MEL type titanium-silicon molecular sieve, BEA type titanium-silicon molecular sieve, MWW type titanium-silicon molecular sieve, MOR type titanium-silicon molecular sieve, TON type titanium-silicon molecular sieve, TUN type titanium-silicon molecular sieve and hexagonal structure titanium-silicon molecular sieve, with the preferred titanium-silicon molecular sieve being MFI type titanium-silicon molecular sieve.

[0025] The weight ratio of the titanium-silicon molecular sieve to the oxidant is (0.001-10):1, the titanium-silicon molecular sieve is calculated as TiO2, and the oxidant is calculated based on the amount of substance that actually exerts the oxidizing effect.

[0026] The hydration catalyst is a catalyst that reacts epoxides with water to produce vicinal diols, including liquid acids, liquid bases, solid acids, and solid bases.

[0027] The molar ratio of active centers of the titanium-silicon molecular sieve to the hydrated catalyst is 1:(0.05-20), wherein the titanium-silicon molecular sieve is calculated as TiO2 and the hydrated catalyst is calculated as acid or base centers.

[0028] The contact reaction is carried out at a temperature of 5℃ to 100℃, a pressure of atmospheric pressure to 5MPa, and a time of 1min to 24h.

[0029] The method provided by this invention does not require the prior preparation of epoxy compounds, has mild reaction conditions, simple operation process, high oxidant conversion rate and effective utilization rate, high selectivity of vicinal diol, and low energy consumption for product separation, making it suitable for large-scale industrial production applications. Detailed Implementation

[0030] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0031] The present invention provides a method for preparing vicinal diols, characterized in that the method includes contacting a raw material containing an olefin, an oxidant and a haloalcohol in the presence of a titanium silicate molecular sieve and a hydrated catalyst to obtain a product containing vicinal diols.

[0032] In this invention, the haloalcohol refers to a hydrocarbon molecule compound having both halogen substituents and hydroxyl substituents. Because halogen atoms have strong electronegativity and electron-withdrawing ability, in haloalcohol molecules, when the halogen-substituted carbon atom is close to the hydroxyl-substituted carbon atom, the hydroxyl group has a stronger tendency to dissociate hydrogen protons than a typical hydroxyl group without nearby halogen substituents, thus exhibiting weaker acidity. Therefore, such compounds facilitate the ring-opening of epoxides to generate vicinal diols, improving the selectivity of vicinal diol products, requiring little or no hydration catalyst. Simultaneously, the ring-opening reaction promotes the epoxidation of olefins, increasing the conversion and utilization efficiency of the oxidant. Using haloalcohols reduces the amount of water used in the reaction process, and haloalcohols generally have lower boiling points, resulting in lower energy consumption for product separation.

[0033] In this invention, the haloalcohol has m carbon atoms, where m is preferably a positive integer from 1 to 12, more preferably 2 to 8, and even more preferably 3 to 6. In the haloalcohol, a halogen element, a hydroxyl group, and hydrogen are bonded to carbon atoms. The halogen element can be one or more of fluorine, chlorine, bromine, and iodine, preferably one or more of fluorine and chlorine, and even more preferably fluorine. The number of halogens in the haloalcohol molecule does not exceed 2m+1, and the number of hydroxyl groups does not exceed 5, preferably not more than 3, and even more preferably 1. Atoms in the haloalcohol molecule can be substituted with their isotopes.

[0034] In this invention, the carbon atom of the haloalcohol can be saturated carbon or unsaturated carbon, that is, the haloalcohol molecule can contain unsaturated chemical bonds such as double bonds, triple bonds, and benzene rings.Examples, but not limited to, of the haloalcohols mentioned above can be 2-fluoroethanol (371-62-0), trifluoroethanol (75-89-8), 1-chloro-2-propanol (127-00-4), 3-chloro-1-propanol (627-30-5), 2-chloro-1-propanol (78-89-7), 1,3-dichloropropanol (96-23-1), 2,3-dichloro-1-propanol (616-23-9), bromopropanol (627-18-9), 2,2,3,3-tetrafluoropropanol (76-37-9), 1H,1H-pentafluoropropanol (422-05-9), 3-fluoropropanol (462-43-1), hexafluoroisopropanol (920-66-1), 1,1,1,3,3,3-hexafluoro-2 -Deuterated propanol (38701-74-5), 2-allyl hexafluoroisopropanol (646-97-9), 1,3-difluoro-2-propanol (453-13-4), hexafluoro-2-methylisopropanol (1515-14-6), perfluorotert-butanol (2378-02-1), 1-chloro-3-fluoro-2-propanol (453-11-2), 3-bromo-1,1,1-trifluoro-2-propanol (431-34-5), 2-trifluoromethyl-2-propanol (507-52-8), 2,2-bis(trifluoromethyl)propanol (2927-17-5), 2,2-difluoropropanol (33420-52-9), 3-bromo-trifluoro-2-propanol (88378-50-1), 1,1, 1,3,3,3-Hexafluoro-2-phenyl-2-propanol (718-64-9), 3-(3-trifluoromethylphenyl)propanol (78573-45-2), 2-(4-fluorophenyl)-2-propanol (402-41-5), 2-[3,5-(bis(trifluoromethyl)phenyl)phenyl]2-propanol (28180-47-4), 1,3-bis(1,1,1,3,3,3-hexafluoro-2-propanol)benzene (802-93-7), 3-perfluorooctylpropanol (1651-41-8), 3-(perfluorohexyl)propanol (80806-68-4), (R)-(+)-1-chloro-3-(4-fluorophenoxy)-2-propanol (307532-04-3), 1-(4-fluoro Propoxy)-2-propanol (307532-03-2), 1,1,1-trifluoro-2-propanol (374-01-6), 3,3,3-trifluoro-1-propanol (2240-88-2), 2-vinylhexafluoroisopropanol (19701-19-0), 2-(4-aminobenzene)-1,1,1,3,3,3-hexafluoro-2-propanol (722-92-9), hexafluoro-2-(p-tolyl)isopropanol (2010-61-9), 1-(4-trifluoromethylphenyl)-1-propanol (67081-98-5), 3-perfluorobutyl-2-propanol (80233-96-1), 3-(perfluoro-7-methylhexyl)-2-iodopropanol (65726-35-4).

[0035] Preferably, the haloalcohol may be 1-chloro-2-propanol (127-00-4), 3-chloro-1-propanol (627-30-5), 2-chloro-1-propanol (78-89-7), 1,3-dichloropropanol (96-23-1), 2,3-dichloro-1-propanol (616-23-9), bromopropanol (627-18-9), or 2,2,3,3-tetrafluoropropanol (76- 37-9), 1H,1H-pentafluoropropanol (422-05-9), 3-fluoropropanol (462-43-1), hexafluoroisopropanol (920-66-1), 1,1,1,3,3,3-hexafluoro-2-deuterated propanol (38701-74-5), 2-allylic hexafluoroisopropanol (646-97-9), 1,3-difluoro-2-propanol (453-13-4), hexafluoro 2-Methylisopropanol (1515-14-6), perfluorotert-butanol (2378-02-1), 1-chloro-3-fluoro-2-propanol (453-11-2), 2-trifluoromethyl-2-propanol (507-52-8), 2,2-bis(trifluoromethyl)propanol (2927-17-5), 2,2-difluoropropanol (33420-52-9), 3-bromo-trifluoro-2-propanol Alcohols (88378-50-1), 1-(4-fluoropropoxy)-2-propanol (307532-03-2), 1,1,1-trifluoro-2-propanol (374-01-6), 3,3,3-trifluoro-1-propanol (2240-88-2), 2-vinylhexafluoroisopropanol (19701-19-0), 3-perfluorobutyl-2-propanol (80233-96-1).

[0036] More preferably, the haloalcohol may be 2,2,3,3-tetrafluoropropanol (76-37-9), 1H,1H-pentafluoropropanol (422-05-9), 3-fluoropropanol (462-43-1), hexafluoroisopropanol (920-66-1), 2-allyl hexafluoroisopropanol (646-97-9), 1,3-difluoro-2-propanol (453-13-4), hexafluoro-2-methylisopropanol (1515-14-6), or perfluorotert-butanol (2378-02-1). 2-Trifluoromethyl-2-propanol (507-52-8), 2,2-bis(trifluoromethyl)propanol (2927-17-5), 2,2-difluoropropanol (33420-52-9), 1-(4-fluoropropoxy)-2-propanol (307532-03-2), 1,1,1-trifluoro-2-propanol (374-01-6), 3,3,3-trifluoro-1-propanol (2240-88-2), 2-vinylhexafluoroisopropanol (19701-19-0).

[0037] In this invention, there are no restrictions on the type of olefin used; it can be a monoolefin or a polyolefin. The olefin can be an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon, and may contain substituents such as alkyl, aryl, ester, nitro, hydroxyl, carboxyl, aldehyde, ketone, cyano, ether, amino, imino, or halogen substituents. It may also contain oxygen, nitrogen, sulfur, phosphorus, or halogen heteroatoms. Preferably, the olefin is a C2-C30 monoolefin or polyolefin. For example, the olefin may be ethylene, vinyl chloride, propylene, propylene chloride, acrylonitrile, acrylic acid, acrolein, allyl alcohol, butenoic acid, isobutene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, 1,4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, 1-decene, cyclododecene, cyclododecanetriene, styrene, styrene, oleic acid, methyl oleate, castor oil acid, methyl ricinoleate. Preferably, the olefin is a C2-C18 olefin, and more preferably a C3-C8 olefin.

[0038] In this invention, the olefin can be a pure olefin, a mixed olefin, a mixture of different olefins, or a mixture of olefins and inert components, such as nitrogen, argon, helium, neon, air, oxygen, hydrogen, methane, ethane, propane, and 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 content in the mixed olefin is controlled, preferably with each molar content below 5%, further preferably below 2%, and more preferably below 1%.

[0039] In this invention, the oxidant can be at least one of inorganic peroxides, organic peroxides, and ozone. The inorganic peroxide is selected from at least one of hydrogen peroxide, urea peroxide, potassium persulfate, potassium persulfate, sodium percarbonate, percarbonamide, and sodium perborate; the organic peroxide is selected from at least one of tert-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl perpentyl peroxide, isopropyl hydroperoxide, tert-amyl hydroperoxide, and di-tert-butyl peroxide. Hydrogen peroxide is preferred as the oxidant. This invention does not have specific requirements for the mass concentration of hydrogen peroxide; preferably, the mass concentration of hydrogen peroxide is 2%-70%, more preferably 10%-50%, and even more preferably 20%-45%.

[0040] In this invention, the molar ratio of the oxidant (based on the substance that actually exerts the oxidizing effect) to the olefin can be 1:(0.05-20), preferably 1:(0.8-10), and more preferably 1:(1-5).

[0041] In this invention, the raw materials may contain water. Water may be introduced along with the olefin, oxidant, haloalcohol, or catalyst, or it may be added separately. The molar ratio of water to oxidant is preferably (0.1–100):1, more preferably (3–35):1, and even more preferably (5–20):1.

[0042] In this invention, the molar ratio of haloalcohol to oxidant is preferably (0.01-100):1, more preferably (0.1-30):1, and even more preferably (0.5-8):1.

[0043] The titanium species in the framework of titanium-silicon molecular sieves exhibit excellent performance in activating hydrogen peroxide to catalyze the epoxidation of olefin molecules. In this invention, the titanium-silicon molecular sieve is a common type, such as MFI-type (e.g., TS-1), MEL-type (e.g., TS-2), BEA-type (e.g., Ti-β), MWW-type (e.g., Ti-MCM-22), MOR-type (e.g., Ti-MOR), TUN-type (e.g., Ti-TUN), hexagonal titanium-silicon molecular sieves (e.g., Ti-MCM-41, Ti-SBA-15), and other structural titanium-silicon molecular sieves (e.g., Ti-ZSM-48). Preferably, the titanium-silicon molecular sieve is selected from at least one of MFI-type, MEL-type, and BEA-type titanium-silicon molecular sieves. More preferably, the titanium-silicon molecular sieve is an MFI-type titanium-silicon molecular sieve. Preferably, the MFI-structured titanium-silicon molecular sieve can be a TS-1 molecular sieve prepared by conventional methods such as hydrothermal synthesis or post-processing synthesis, a titanium-silicon molecular sieve with a multi-level pore structure, a hollow titanium-silicon molecular sieve HTS with a hollow crystal structure, or a titanium-silicon molecular sieve with a plate-like, spherical, hexagonal prism shape and an open surface. The present invention does not impose any specific limitations.

[0044] In this invention, the titanium-silicon molecular sieve can be used directly as a catalyst from raw molecular sieve powder, or it can be shaped before use, for example, by pressing into tablets, by rolling to prepare microspheres or small spheres, by extrusion to prepare strip catalysts, by spray drying to prepare spherical catalysts, etc. Alternatively, the titanium-silicon molecular sieve can be added directly to the reaction of this invention simultaneously or sequentially with other catalysts, co-catalysts, and inert matrix supports without being shaped. This invention does not impose any limitations on this. The titanium-silicon molecular sieve can also be used as a main active component and binder, co-catalyst, pore expander, inert matrix support, etc. The weight content of the titanium-silicon molecular sieve in the catalyst is preferably 20%-100%, more preferably 50%-100%, and even more preferably 80%-100%.

[0045] According to the present invention, the molar ratio of the titanium-silicon molecular sieve (calculated as TiO2) to the oxidant (calculated as effective substance) can be (0.001-10):1, preferably (0.005-1):1, and more preferably (0.01-0.5):1.

[0046] According to the present invention, the hydration catalyst is a catalyst that enables the epoxy compound intermediate generated by the reaction of titanium silicate molecular sieve with an oxidant to undergo a ring-opening reaction with water to generate a vicinal diol. Such catalysts include liquid acids, liquid bases, solid acids, and solid bases. The liquid acids include inorganic acids and organic acids. The inorganic acids can be one or more of phosphoric acid, sulfuric acid, nitric acid, and hydrochloric acid. The organic acids include saturated fatty acids and unsaturated fatty acids with 1 to 20 carbon atoms, such as formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, succinic acid, cyclopentanoic acid, cyclopentanoic acid, adipic acid, heptanoic acid, octanoic acid, benzoic acid, benzenesulfonic acid, and substituted benzenesulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid, one or more of these. The liquid alkali includes inorganic alkali and organic alkali. The inorganic alkali can be one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium carbonate, and sodium phosphate. The organic alkali can be organic amines, including primary amines, secondary amines, tertiary amines, and quaternary ammonium bases. For example, it can be one or more of methylamine, ethylamine, propylamine, butylamine, ethylenediamine, ethanolamine, hexamethylenediamine, tri-n-propylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, allyltripropylammonium hydroxide, propenyltripropylammonium hydroxide, butenyltributylammonium hydroxide, hexadecyltrimethylammonium hydroxide, and hexadecyltripropylammonium hydroxide. The solid acid includes Brønsted acid molecular sieves, such as one or more of silica-alumina molecular sieves (ZSM-5, β-molecular sieves, Y-type molecular sieves, X-type molecular sieves, and MOR molecular sieves), Lewis acid molecular sieves (at least one or more of MFI-type, BEA-type, MWW-type, and MOR-type molecular sieves containing at least one of tin, zirconium, hafnium, and lead), and one or more of acidic cation exchange resins. The solid alkali includes basic anion exchange resins. The Brønsted acid or Lewis acid molecular sieve can be a modified molecular sieve, such as a molecular sieve modified by silanization pore expansion, alkali treatment pore expansion, acid treatment modification, or silane surface modification; there are no particular limitations in this invention.

[0047] Preferably, the hydration catalyst is one or more of liquid acid and solid acid. More preferably, the hydration catalyst is one or more of phosphoric acid, sulfuric acid, and nitric acid and / or L-acid molecular sieves (at least one or more of MFI, MEL, BEA, MWW, and MOR type molecular sieves containing at least one of tin, zirconium, hafnium, and lead). More preferably, it is one or more of phosphoric acid, sulfuric acid, Sn-MFI molecular sieves, Sn-β molecular sieves, and Sn-Ti-MFI molecular sieves.

[0048] According to the method of the present invention, the molar ratio of the active centers of the titanium silicate molecular sieve (calculated as TiO2) to the hydrated catalyst (calculated as acid or base centers) is preferably 1:(0.05-20), more preferably 1:(0.1-6), and even more preferably 1:(0.2-1).

[0049] According to the method of the present invention, the reaction conditions are as follows: the reaction temperature is 5–100°C, preferably 20–80°C, and more preferably 40–60°C. The reaction is preferably carried out under a pressure ranging from atmospheric pressure to 5 MPa (gauge pressure). Within the preferred 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 self-generated pressure formed by the reactants under the reaction conditions, or it can be achieved by introducing inert gas components, such as, but not limited to, nitrogen, argon, helium, neon, air, oxygen, methane, ethane, propane, and 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 with each molar content below 5%, more preferably below 2%, and more preferably below 1%. The method of the present invention can be carried out under intermittent or continuous conditions. From the perspective of reducing labor intensity, improving product quality, and considering the feasibility and safety of the technology, continuous reaction conditions are preferred. The contact reaction, i.e., the reaction time, is preferably 1 min to 24 h, or the feed space velocity, calculated in terms of oxides, is preferably 0.01 to 5 h. -1 .

[0050] According to the method of the present invention, the reaction can be carried out in batch or continuous reactions in different types of reactors such as batch reactors, fixed-bed reactors, tubular reactors, fluidized-bed reactors, suspended-bed reactors, and microchannel reactors. Different reactor types are only used to adapt to the corresponding purpose requirements and achieve better results in the one-step direct preparation of vicinal diols from olefins. At the same time, it is preferred to use appropriate catalysts in conjunction with the reactors. For example, fixed-bed reactors and tubular reactors use shaped catalysts, batch reactors use molecular sieve powder, and microchannel reactors use molecular sieve powder or immobilize the catalyst in the microchannels to achieve relatively better reaction results. All of these should be considered as part of the present invention.

[0051] According to the method of the present invention, the reaction process mainly produces vicinal diols, mono-vicinal diols (i.e., condensation etherification products of 2 vicinal diol molecules), di-vicinal diols (i.e., condensation etherification products of 3 vicinal diol molecules), aldehydes generated from the double bond cleavage of the starting olefin, and acids obtained by further oxidation of the aldehydes. The haloalcohols added to the reaction can be separated by distillation or extraction, reducing the amount of water required for separation; unreacted olefins and generated aldehydes can be separated by distillation; the generated vicinal diols, mono-vicinal diols, and di-vicinal diols can be separated under reduced pressure or by extraction, resulting in low overall separation energy consumption.

[0052] According to the method of the present invention, the separation of the product from the catalyst can be achieved in a variety of ways. For example, when the original powdered titanium silicate molecular sieve is used as the catalyst, the product can be separated and the catalyst can be recycled and reused by sedimentation, filtration, centrifugation, evaporation, membrane separation, etc. Alternatively, the catalyst can be shaped and loaded into a fixed bed reactor, and the catalyst can be recovered after the reaction is completed. Various methods for the separation and recovery of catalysts are involved in the existing literature, and will not be described in detail here.

[0053] The present invention will be further illustrated by the following embodiments, but these embodiments do not limit the scope of the invention.

[0054] The preparation method of TS-1 molecular sieve used in the examples is as follows (refer to the method in Zeolites, 1992, 12(8), 943-50): about 3 / 4 of the amount of tetrapropylammonium hydroxide (TPAOH, 20%, purchased from Aldrich, USA) solution was added to tetraethyl orthosilicate (TEOS) solution to obtain a liquid mixture with a pH of about 13. Then, under vigorous stirring, the required amount of tetrabutyl titanate [Ti(OBu)4] was added dropwise to the obtained liquid mixture. A solution of aqueous isopropanol was stirred for 15 minutes to obtain a clear liquid. Finally, the remaining TPAOH was slowly added to the clear liquid, and the mixture was stirred at 348-353 K for approximately 3 hours to obtain a sol with a chemical composition of 0.025TiO2:SiO2:0.3TPA:35H2O. This sol was then crystallized at 443 K for 3 days. The resulting solid was filtered, washed with distilled water, dried at 373 K for 5 hours, and then calcined at 823 K for 10 hours to obtain the molecular sieve sample. The amounts of TEOS, TPAOH, Ti(OBu)4, anhydrous isopropanol, and water were 42 g, 61 g, 1.67 g, 10 g, and 68 g, respectively. The final TS-1 molecular sieve had a Ti:Si molar ratio of 0.026:1.

[0055] The hollow titanium-silicon molecular sieve (HTS) was prepared according to the method described in Example 1 of Chinese Patent CN1301599A, and the Ti:Si molar ratio of the HTS molecular sieve was 0.026:1.

[0056] The Ti-β molecular sieve preparation method used in this example is as follows (referring to the method in Journal of Physical Chemistry B, 1998, 102:75-88): A certain amount of tetraethyl orthosilicate (TEOS) is added to a solution of tetraethylammonium hydroxide (TEAOH, 20%) and hydrogen peroxide, and hydrolyzed for 2 hours under stirring. Then, a weighed solution of anhydrous isopropanol of tetrabutyl titanate [Ti(OBu)4] is added to the hydrolysate of tetraethyl orthosilicate, and stirring is continued for 3 hours to remove alcohol, finally yielding a sol with the chemical composition TiO2:60SiO2:33TEAOH:400H2O:20H2O2. Finally, dealuminized molecular sieve seed crystals are added and stirred vigorously (the amount of seed crystals added is based on the sol as silica, 4g of seed crystals for every 100g of silica). The resulting mixture was crystallized at 413 K for 14 days. The resulting slurry was filtered, washed with water, dried at 373 K for 6 hours, and then calcined at 823 K for 12 hours to obtain a molecular sieve sample. The amounts of TEOS, TEAOH, Ti(OBu)₄, anhydrous isopropanol, and hydrogen peroxide were 42 g, 81 g, 1.16 g, 10 g, and 7.5 g, respectively. The final Ti-β molecular sieve had a Ti:Si molar ratio of 0.016:1.

[0057] The Sn-MFI molecular sieve used in the examples was prepared using the following method. Tetraethyl orthosilicate (TEOS), tin tetrachloride, and tetrapropylammonium hydroxide (TPAOH, 26.5 wt%) solutions were mixed at a molar ratio of 1 SiO2:0.02 SnO2:0.36 TPAOH:35 H2O. After stirring for 15 min, a clear liquid was obtained. Water was then added to the clear liquid, and the mixture was stirred at 348–353 K for approximately 3 h to obtain a clear sol. This sol was then crystallized at 443 K for 3 days. The resulting solid was filtered, washed with distilled water, dried at 373 K for 5 h, and then calcined at 823 K for 10 h to obtain the Sn-MFI molecular sieve. The amounts of TEOS used were 125.0 g, tin tetrachloride 5.2 g, TPAOH 172.1 g, and water 285.3 g.

[0058] The Sn-MEL molecular sieve used in the examples was prepared using the following method. The difference from the preparation method of Sn-MFI molecular sieve is that tetrapropylammonium hydroxide solution (TPAOH, 26.5 wt%) was replaced with tetrabutylammonium hydroxide solution (TBAOH, 20 wt%), and the amount of TBAOH used was 156.0 g. The materials were mixed according to the molar ratio of SiO2:0.02SnO2:0.20TBAOH:35H2O to obtain the Sn-MEL molecular sieve.

[0059] Unless otherwise specified, all raw materials used in the examples are analytical grade reagents.

[0060] The reaction products were analyzed by gas chromatography, and the results were quantified using the external standard method. The chromatographic conditions were as follows: Agilent-6890 chromatograph, HP-INNOWAX capillary column, injection volume 1 μL, injection port temperature 280℃. Column temperature was maintained at 50℃ for 5 min, then increased to 250℃ at a rate of 10℃ / min and held for 15 min. An FID detector was used, with a detector temperature of 280℃.

[0061] The hydrogen peroxide content was measured using an indirect titration method with sodium thiosulfate.

[0062] The following indicators were mainly examined in each embodiment and comparative example:

[0063] Hydrogen peroxide conversion rate = (Number of moles of hydrogen peroxide consumed in the reaction) / (Number of moles of hydrogen peroxide initially added to the reaction) × 100%

[0064] vicinal diol selectivity = (moles of vicinal diol in the product) / (moles of olefin consumed in the formation of main and by-products) × 100%

[0065] Hydrogen peroxide effective utilization rate = (Number of moles of hydrogen peroxide consumed in the production of main and by-products) / (Number of moles of hydrogen peroxide consumed in the reaction) × 100%

[0066] Comparative Example 1

[0067] TS-1 molecular sieve, phosphoric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.016:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to phosphoric acid (based on phosphoric acid) was 1:0.7, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:5, and the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 44:1. The mixture in the reactor was then stirred and reacted at 50℃ and 2MPa for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0068] Comparative Example 2

[0069] TS-1 molecular sieve, phosphoric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.016:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to phosphoric acid (based on phosphoric acid) was 1:0.7, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:5, and the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 22:1. The mixture in the reactor was then stirred and reacted at 50℃ and 2MPa for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0070] Comparative Example 3

[0071] HTS molecular sieve, phosphoric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, isopropanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.016:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to phosphoric acid (based on phosphoric acid) was 1:0.7, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:5, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 31:1, and the molar ratio of isopropanol to hydrogen peroxide (based on hydrogen peroxide) was 0.7:1. The mixture in the reactor was then stirred and reacted at 50℃ and 2MPa for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0072] Example 1

[0073] TS-1 molecular sieve, phosphoric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, hexafluoroisopropanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.016:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to phosphoric acid (based on phosphoric acid) was 1:0.7, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:5, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 31:1, and the molar ratio of hexafluoroisopropanol to hydrogen peroxide (based on hydrogen peroxide) was 0.7:1. The mixture in the reactor was then stirred and reacted at 50℃ and 2MPa for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0074] Example 2

[0075] TS-1 molecular sieve, sulfuric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, hexafluoro-2-methylisopropanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.2:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to sulfuric acid (based on sulfuric acid) was 1:0.3, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:3, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 21:1, and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 8:1. The mixture in the reactor was then stirred and reacted at 40℃ and 1.5 MPa for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0076] Example 3

[0077] TS-1 molecular sieve, Sn-MFI molecular sieve, 30% (w / w) hydrogen peroxide aqueous solution, propylene, perfluorotert-butanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.4:1; the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to Sn-MFI molecular sieve (based on SnO2) was 1:0.4; the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:2; the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 25:1; and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 5:1. The mixture in the reactor was then stirred and reacted at 60℃ and 3MPa for 4 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0078] Example 4

[0079] HTS molecular sieve, sulfuric acid, 40% (w / w) hydrogen peroxide aqueous solution, ethylene, hexafluoroisopropanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.1:1; the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to sulfuric acid (based on sulfuric acid) was 1:0.5; the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to ethylene was 1:2; the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 20:1; and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 1:1. The mixture in the reactor was then stirred and reacted at 30°C and 2 MPa for 2 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0080] Example 5

[0081] HTS molecular sieve, phosphoric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, hexafluoroisopropanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.016:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to phosphoric acid (based on phosphoric acid) was 1:0.7, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:5, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 31:1, and the molar ratio of hexafluoroisopropanol to hydrogen peroxide (based on hydrogen peroxide) was 0.7:1. The mixture in the reactor was then stirred and reacted at 50℃ and 2MPa for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0082] Example 6

[0083] HTS molecular sieve, Sn-MEL molecular sieve, 30% (w / w) hydrogen peroxide aqueous solution, 1-butene, perfluorotert-butanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.3:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to Sn-MEL molecular sieve (based on SnO2) was 1:0.8, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to 1-butene was 1:4, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 20:1, and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 3:1. The mixture in the reactor was then stirred and reacted at 50℃ and 0.5MPa for 4 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0084] Example 7

[0085] HTS molecular sieve, Sn-MFI molecular sieve, 30% (w / w) hydrogen peroxide aqueous solution, allyl chloride, hexafluoroisopropanol, and the required amount of water were mixed and added to a microchannel reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.01:1; the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to Sn-MFI molecular sieve (based on SnO2) was 1:0.2; the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to allyl chloride was 1:1; the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 5:1; and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 0.5:1. The mixture in the reactor was then allowed to react continuously at 50°C and atmospheric pressure for 5 minutes, followed by sampling and analysis. The analytical results are shown in Table 1.

[0086] Example 8

[0087] HTS molecular sieve, phosphoric acid, 30% (w / w) aqueous hydrogen peroxide solution, 1-hexene, hexafluoroisopropanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.3:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to phosphoric acid (based on phosphoric acid) was 1:0.5, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to 1-hexene was 1:3, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 8:1, and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 5:1. The mixture in the reactor was then stirred and reacted at 60°C and atmospheric pressure for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0088] Example 9

[0089] HTS molecular sieve, Sn-MFI molecular sieve, 30% (w / w) aqueous hydrogen peroxide solution, propylene, perfluorotert-butanol, and the required amount of water were mixed and added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.15:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to Sn-MFI molecular sieve (based on SnO2) was 1:0.6, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:2, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 6:1, and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 7:1. The mixture in the reactor was then reacted at 40℃ and 1.5 MPa for 2 hours before sampling and analysis. The analytical results are shown in Table 1.

[0090] Example 10

[0091] HTS molecular sieve, sulfuric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, hexafluoro-2-methylisopropanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.1:1; the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to sulfuric acid (based on sulfuric acid) was 1:0.3; the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:4; the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 5:1; and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 4:1. The mixture in the reactor was then stirred and reacted at 40℃ and 1.5 MPa for 4 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0092] Example 11

[0093] HTS molecular sieve, Sn-MEL molecular sieve, 30% (w / w) aqueous hydrogen peroxide solution, propylene, hexafluoro-2-methylisopropanol, and the required amount of water were mixed and added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.05:1; the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to Sn-MEL molecular sieve (based on SnO2) was 1:0.6; the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:3; the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 8:1; and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 8:1. The mixture in the reactor was then reacted at 50°C and 2 MPa for 4 hours, and samples were taken for analysis. The analytical results are shown in Table 1.

[0094] Example 12

[0095] Ti-β molecular sieve, sulfuric acid, 30% (w / w) aqueous hydrogen peroxide solution, methyl oleate, tetrafluoropropanol, and the required amount of water were added to a reaction vessel. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.5:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to sulfuric acid (based on sulfuric acid) was 1:1, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to methyl oleate was 1:1, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 10:1, and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 2:1. The mixture in the reaction vessel was then stirred and reacted at 80°C and atmospheric pressure for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0096] Example 13

[0097] TS-1 molecular sieve, phosphoric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, 1,3-dichloro-2-propanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.016:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to phosphoric acid (based on phosphoric acid) was 1:0.7, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:5, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 31:1, and the molar ratio of 1,3-dichloro-2-propanol to hydrogen peroxide (based on hydrogen peroxide) was 0.7:1. The mixture in the reactor was then stirred and reacted at 50℃ and 2MPa for 3 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0098] Example 14

[0099] HTS molecular sieve, sulfuric acid, 30% (w / w) hydrogen peroxide aqueous solution, propylene, 2,3-dichloro-1-propanol, and the required amount of water were added to a reactor. The molar ratio of titanium silicate molecular sieve (based on TiO2) to hydrogen peroxide (based on hydrogen peroxide) was 0.1:1, the molar ratio of active centers of titanium silicate molecular sieve (based on TiO2) to sulfuric acid (based on sulfuric acid) was 1:0.3, the molar ratio of hydrogen peroxide (based on hydrogen peroxide) to propylene was 1:4, the molar ratio of water to hydrogen peroxide (based on hydrogen peroxide) was 5:1, and the molar ratio of haloalcohol to hydrogen peroxide (based on hydrogen peroxide) was 4:1. The mixture in the reactor was then stirred and reacted at 40℃ and 1.5 MPa for 4 hours. After the reaction was completed, samples were taken for analysis, and the results are shown in Table 1.

[0100] Table 1

[0101]

[0102]

[0103] As can be seen from Comparative Examples 1, 3 and 1, using haloalcohols instead of water as a solvent can effectively improve the hydrogen peroxide conversion rate, vicinal diol selectivity and hydrogen peroxide utilization rate.

[0104] As can be seen from Examples 7-14, the use of haloalcohols can also reduce the amount of solvent water used, thereby reducing separation energy consumption in the subsequent product separation process.

[0105] As can be seen from the results of Examples 1-14 and Comparative Examples 1-3, the method of the present invention for preparing vicinal diols is simple to operate, has mild reaction conditions, high oxidant conversion and utilization rate, high selectivity for vicinal diols, can reduce the amount of water used, and is safe and controllable, making it suitable for large-scale industrial production applications.

Claims

1. A method for preparing vicinal diols, characterized in that, The method involves contacting a feedstock containing olefins, an oxidant, and a haloalcohol in the presence of a titanium silicate molecular sieve and a hydrated catalyst to obtain a product containing a vicinal diol.

2. The method according to claim 1, characterized in that, The haloalcohol has m carbon atoms, where m is a positive integer from 1 to 12, preferably 2 to 8, and more preferably 3 to 6. In the haloalcohol, the halogen element, hydroxyl group, and hydrogen are bonded to the carbon atoms. The halogen element is one or more of fluorine, chlorine, bromine, and iodine, and its number does not exceed 2m+1. The number of hydroxyl groups does not exceed 5, preferably not more than 3, and more preferably 1.

3. The method according to claim 2, characterized in that, The halogen element is fluorine.

4. The method according to claim 1, characterized in that, The haloalcohol is selected from 2-fluoroethanol, trifluoroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 2-chloro-1-propanol, 1,3-dichloropropanol, 2,3-dichloro-1-propanol, bromopropanol, 2,2,3,3-tetrafluoropropanol, 1H,1H-pentafluoropropanol, 3-fluoropropanol, hexafluoroisopropanol, 1,1,1,3,3,3-hexafluoro-2-deuterated propanol, 2-allyl hexafluoroisopropanol, 1, 3-Difluoro-2-propanol, hexafluoro-2-methylisopropanol, perfluorotert-butanol, 1-chloro-3-fluoro-2-propanol, 3-bromo-1,1,1-trifluoro-2-propanol, 2-trifluoromethyl-2-propanol, 2,2-bis(trifluoromethyl)propanol, 2,2-difluoropropanol, 3-bromo-trifluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol, 3-(3-trifluoromethylphenyl) 2-(4-fluorophenyl)-2-propanol (402-41-5), 2-[3,5-(bis(trifluoromethyl)phenyl)phenyl]2-propanol, 1,3-bis(1,1,1,3,3,3-hexafluoro-2-propanol)benzene, 3-perfluorooctylpropanol, 3-(perfluorohexyl)propanol, (R)-(+)-1-chloro-3-(4-fluorophenoxy)-2-propanol, 1-(4-fluoropropoxy)-2-propanol One or more of the following: 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol, 2-vinylhexafluoroisopropanol, 2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoro-2-propanol, hexafluoro-2-(p-tolyl)isopropanol, 1-(4-trifluoromethylphenyl)-1-propanol, 3-perfluorobutyl-2-propanol, and 3-(perfluoro-7-methylhexyl)-2-iodopropanol.

5. The method according to claim 1, characterized in that, The haloalcohol is selected from 1-chloro-2-propanol, 3-chloro-1-propanol, 2-chloro-1-propanol, 1,3-dichloropropanol, 2,3-dichloro-1-propanol, bromopropanol, 2,2,3,3-tetrafluoropropanol, 1H,1H-pentafluoropropanol, 3-fluoropropanol, hexafluoroisopropanol, 1,1,1,3,3,3-hexafluoro-2-deuterated propanol, 2-allyl hexafluoroisopropanol, 1,3-difluoro-2-propanol, hexafluoro-2- One or more of the following: methyl isopropanol, perfluorotert-butanol, 1-chloro-3-fluoro-2-propanol, 2-trifluoromethyl-2-propanol, 2,2-bis(trifluoromethyl)propanol, 2,2-difluoropropanol, 3-bromo-trifluoro-2-propanol, 1-(4-fluoropropoxy)-2-propanol, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol, 2-vinylhexafluoroisopropanol, and 3-perfluorobutyl-2-propanol.

6. The method according to claim 1, characterized in that, The haloalcohol is selected from one or more of the following: 2,2,3,3-tetrafluoropropanol, 1H,1H-pentafluoropropanol, 3-fluoropropanol, hexafluoroisopropanol, 2-allylhexafluoroisopropanol, 1,3-difluoro-2-propanol, hexafluoro-2-methylisopropanol, perfluorotert-butanol, 2-trifluoromethyl-2-propanol, 2,2-bis(trifluoromethyl)propanol, 2,2-difluoropropanol, 1-(4-fluoropropoxy)-2-propanol, 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol, and 2-vinylhexafluoroisopropanol.

7. The method according to claim 1, characterized in that, The olefin is a mono- or polyolefin of C2-C30, preferably C2-C18, and more preferably C3-C8.

8. The method according to claim 1, characterized in that, The olefin is an aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon; or the olefin is an aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon with substituents, wherein the substituents are alkyl, aryl, ester, nitro, hydroxyl, carboxyl, aldehyde, ketone, cyano, ether, amino, imino, or halogen.

9. The method according to claim 1, characterized in that, The olefins are ethylene, vinyl chloride, propylene, propylene chloride, acrylonitrile, acrylic acid, acrolein, allyl alcohol, butenoic acid, isobutene, 1-butene, 2-butene, butadiene, 1-pentene, cyclopentene, 1,4-pentadiene, cyclopentadiene, isoprene, 1-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, 1-decene, cyclododecene, cyclododecanetriene, styrene, styrene, oleic acid, methyl oleate, castor oil acid, and methyl castor oil.

10. The method according to claim 1, characterized in that, The molar ratio of the oxidant to the olefin is 1:(0.05-20), preferably 1:(0.8-10), and more preferably 1:(1-5).

11. The method according to claim 1, characterized in that, The oxidant is selected from at least one of inorganic peroxides, organic peroxides, and ozone.

12. The method according to claim 11, characterized in that, The inorganic peroxide is selected from at least one of hydrogen peroxide, urea peroxide, potassium peroxymonosulfate, potassium persulfate, sodium percarbonate, percarbonamide, and sodium perborate; the organic peroxide is selected from at least one of tert-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene peroxide, ethylbenzene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, tert-butyl perpentyl peroxide, isopropyl hydroperoxide, tert-amyl hydroperoxide, and di-tert-butyl peroxide; the preferred oxidant is hydrogen peroxide.

13. The method according to claim 1, characterized in that, The raw material contains water, and the molar ratio of water to the oxidant is (0.1-100):1, preferably (3-35):1, and more preferably (5-20):

1.

14. The method according to claim 1, characterized in that, The molar ratio of the haloalcohol to the oxidant is (0.01-100):1, preferably (0.1-30):1, and more preferably (0.5-8):

1.

15. The method according to claim 1, characterized in that, The titanium-silicon molecular sieve is at least one of MFI type titanium-silicon molecular sieve, MEL type titanium-silicon molecular sieve, BEA type titanium-silicon molecular sieve, MWW type titanium-silicon molecular sieve, MOR type titanium-silicon molecular sieve, TON type titanium-silicon molecular sieve, TUN type titanium-silicon molecular sieve and hexagonal structure titanium-silicon molecular sieve, with the preferred titanium-silicon molecular sieve being MFI type titanium-silicon molecular sieve.

16. The method according to claim 1, characterized in that, The weight ratio of the titanium-silicon molecular sieve to the oxidant is (0.001-10):1, preferably (0.005-1):1, and more preferably (0.01-0.5):

1. The titanium-silicon molecular sieve is calculated as TiO2, and the oxidant is calculated based on the amount of substance that actually exerts the oxidizing effect.

17. The method according to claim 1, characterized in that, The hydration catalyst is a catalyst that enables the reaction of an epoxy compound intermediate generated by the reaction of titanium silicon molecular sieves with olefins and oxidants to produce vicinal diols with water.

18. The method according to claim 17, characterized in that, The hydration catalyst is selected from inorganic acids, organic acids, inorganic bases, organic bases, solid acids, or solid bases.

19. The method according to claim 18, characterized in that, The inorganic acid is one or more of phosphoric acid, sulfuric acid, nitric acid, and hydrochloric acid; the organic acid is one or more of formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, succinic acid, cyclopentanoic acid, cyclopentanoic acid, adipic acid, heptanoic acid, octanoic acid, benzoic acid, benzenesulfonic acid, and substituted benzenesulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid; the inorganic base is one or more of sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, sodium carbonate, and sodium phosphate; the organic base is one or more of methylamine, ethylamine, propylamine, butylamine, ethylenediamine, ethanolamine, hexamethylenediamine, tri-n-propylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, allyltripropylammonium hydroxide, propenyltripropylammonium hydroxide, butenyltributylammonium hydroxide, hexadecyltrimethylammonium hydroxide, and hexadecyltripropylammonium hydroxide.

20. The method according to claim 18, characterized in that, The solid acid is one or more of Brønsted acid molecular sieves, Lewis acid molecular sieves, or acidic cation exchange resins.

21. The method according to claim 20, characterized in that, The Brønsted acid molecule is selected from one or more of ZSM-5, β-zeolite, Y-type zeolite, X-type zeolite, and MOR zeolite; the L-acetate molecule is selected from MFI-type, BEA-type, MWW-type, and MOR-type zeolites containing at least one of tin, zirconium, hafnium, and lead.

22. The method according to claim 18, characterized in that, The solid base includes a basic anion exchange resin.

23. The method according to claim 1, characterized in that, The molar ratio of the active centers of the titanium-silicon molecular sieve to the hydrated catalyst is 1:(0.05-20), preferably 1:(0.1-6), and more preferably 1:(0.2-1), wherein the titanium-silicon molecular sieve is calculated as TiO2 and the hydrated catalyst is calculated as acid or base centers.

24. The method according to claim 1, characterized in that, The contact reaction is carried out at a temperature of 5℃ to 100℃, a pressure of atmospheric pressure to 5MPa, and a time of 1min to 24h, or at a feed space velocity of 0.01 (based on oxides). ～ 5h -1 .

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