CN107556220B

CN107556220B - A kind of sulfide oxidation method and a kind of method for producing sulfoxide and sulfone simultaneously

Info

Publication number: CN107556220B
Application number: CN201610512084.6A
Authority: CN
Inventors: 史春风; 林民; 朱斌
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-06-30
Filing date: 2016-06-30
Publication date: 2019-09-24
Anticipated expiration: 2036-06-30
Also published as: CN107556220A

Abstract

The invention discloses a kind of sulfide oxidation methods, are included under oxidation reaction condition, and raw mixture is contacted at least one titanium Si-Al molecular sieve, and the raw mixture contains thioether, at least one oxidant and optional at least one solvent.The invention also discloses a kind of methods for producing sulfoxide and sulfone simultaneously, it is included under oxidation reaction condition, raw mixture is contacted at least one titanium Si-Al molecular sieve, the raw mixture contains thioether, at least one oxidant and optional at least one solvent, and the molar ratio of the oxidant and the thioether is lower than 2.In the presence of titanium Si-Al molecular sieve, by sulfide oxidation, the selectivity to sulfone can be significantly improved.

Description

A kind of sulfide oxidation method and a kind of method for producing sulfoxide and sulfone simultaneously

Technical field

The present invention relates to a kind of sulfide oxidation methods, and the invention further relates to a kind of methods for producing sulfoxide and sulfone simultaneously.

Background technique

Sulfoxides are important sulfur-containing compound.As the Typical Representative of sulfoxides, dimethyl sulfoxide (DMSO) it is a kind of organic compounds containing sulfur, is colourless transparent liquid under room temperature, there is highly polar, high-hygroscopicity, flammable and high The characteristics such as boiling point is non-proton.Dimethyl sulfoxide is dissolved in water, ethyl alcohol, acetone, ether and chloroform, is the strong atent solvent of polarity, extensively It is general to be used as solvent and reaction reagent, for example, as process solvent and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as polyurethane Synthetic and the solvent that reels off raw silk from cocoons, the synthetic as polyamide, fluoroaluminate glasses, polyimides and polysulfones.Also, dimethyl Sulfoxide has very high selective extraction method ability, can be used as the Extraction solvent that alkane is separated with aromatic hydrocarbon, such as: dimethyl sulfoxide It can be used for the extracting of aromatic hydrocarbons or butadiene.Meanwhile in medical industry, dimethyl sulfoxide not only can be directly as some drugs Raw material and carrier, and the effects of anti-inflammatory analgetic, diuresis and calmness can also be played, therefore frequently as the active group of analgesic drug product Divide and makes an addition in drug.In addition, dimethyl sulfoxide also can be used as capacitor dielectric, antifreezing agent, brake fluid and rare metal extracting agent Deng.

As the Typical Representative of sulfone substance, dimethyl sulfone is white crystalline powder, soluble easily in water, ethyl alcohol, benzene, methanol and Acetone is slightly soluble in ether.Potassium permanganate cannot be made to change colour under room temperature, dimethyl sulfone can be oxidized to methanesulfonic acid by strong oxidizer.Diformazan Base sulfone be used as in the industry organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, food additives and Drug.Dimethyl sulfone is as a kind of organic sulfur compound, the ability that there is enhancing human body to generate insulin, while the metabolism to carbohydrate Also there is facilitation, be the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound healing, also can be to new old Vitamin B, vitamin C, the synthesis of biotin and activation needed for metabolism and neurological health are worked, and referred to as " are beautified naturally Carbonizable substance ".All contain dimethyl sulfone in the skin of human body, hair, nail, bone, muscle and each organ, dimethyl sulfone is in nature It is primarily present in Yu Haiyang and soil in boundary, is absorbed in plant growth as nutriment, the mankind can be from vegetables, water It is absorbed in the foods such as fruit, fish, meat, egg, milk, is that human body maintains biology once health disorders will be caused or disease occurs by lacking The main matter of element sulphur balance has therapeutic value and healthcare function to human body diseases, is human survival and health care Indispensable drug.

Summary of the invention

It is an object of the present invention to provide a kind of sulfide oxidation method, this method can obtain the thioether of raising Rate, oxidant effective rate of utilization and selectivity of product.

It is another object of the present invention to provide a kind of method for producing sulfoxide and sulfone simultaneously, this method can not only with compared with Sulfide oxidation can be obtained higher sulfone selectivity while generating sulfoxide by high conversion ratio.

According to the first aspect of the invention, the present invention provides a kind of sulfide oxidation method, this method is included in oxidation Under reaction condition, raw mixture is contacted at least one titanium Si-Al molecular sieve, the raw mixture contains thioether, at least A kind of oxidant and optional at least one solvent.

According to the second aspect of the invention, the present invention provides a kind of sulfide oxidation method, this method is included in oxidation Under reaction condition, raw mixture is contacted at least one titanium Si-Al molecular sieve, the raw mixture contains thioether, at least A kind of oxidant and optional at least one solvent, the titanium Si-Al molecular sieve are made using method comprising the following steps:

(1) by Titanium Sieve Molecular Sieve and acid solution 10-200 DEG C at a temperature of contact, separated from the mixture that contact obtains Solid phase out；

(2) hydro-thermal process is carried out after mixing the isolated solid phase of step (1) with silicon source, titanium source and alkali source.

The method of first aspect and the second aspect according to the present invention, using titanium Si-Al molecular sieve as catalyst by thioether Oxidation, can improve thioether rate and oxidant effective rate of utilization, while can also significantly improve the selectivity for sulfone.

According to the third aspect of the present invention, the present invention provides a kind of method for producing sulfoxide and sulfone simultaneously, this method It is included under oxidation reaction condition, raw mixture is contacted at least one titanium Si-Al molecular sieve, the raw mixture contains There are thioether, at least one oxidant and an optional at least one solvent, the molar ratio of the oxidant and the thioether is low In 2, preferably 1 hereinafter, the molar ratio of the oxidant and the thioether is 0.1 or more, preferably 0.2 or more.

According to the fourth aspect of the present invention, the present invention provides a kind of method for producing sulfoxide and sulfone simultaneously, this method It is included under oxidation reaction condition, raw mixture is contacted at least one titanium Si-Al molecular sieve, the raw mixture contains There are thioether, at least one oxidant and an optional at least one solvent, the molar ratio of the oxidant and the thioether is low In 2, preferably 1 hereinafter, the molar ratio of the oxidant and the thioether is 0.1 or more, preferably 0.2 or more, the titanium silicon Aluminum molecular screen is made using method comprising the following steps:

Method in terms of third and in terms of the 4th according to the present invention can effectively improve the selectivity of sulfone, realize and exist While producing sulfoxide, and produce sulfone.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

In the present invention, "at least one" indicates one or more kinds of.It is " optional " to indicate inessential in the present invention, it can be with It is interpreted as with or without including or not including.

The titanium Si-Al molecular sieve contains aluminium element, titanium elements, element silicon, and aluminium element and titanium elements replace lattice framework In part element silicon.Based on the element, in the titanium Si-Al molecular sieve, element silicon: titanium elements: the molar ratio of aluminium element can be 100:0.1-10:0.1-8, preferably 100:0.2-8:0.2-6, more preferably 100:0.5-7:0.3-2.In the present invention, titanium silicon The content of element is determined using x ray fluorescence spectrometry in aluminum molecular screen.

The titanium Si-Al molecular sieve can be the common titanium Si-Al molecular sieve with various topological structures, such as: it is described Titanium Si-Al molecular sieve can for selected from MFI structure titanium Si-Al molecular sieve (such as TS-1), MEL structure titanium Si-Al molecular sieve (such as TS-2), the titanium Si-Al molecular sieve (such as Ti-Beta) of BEA structure, the titanium Si-Al molecular sieve (such as Ti-MCM-22) of MWW structure, six The titanium Si-Al molecular sieve (such as Ti-MCM-41, Ti-SBA-15) of square structure, MOR structure titanium Si-Al molecular sieve (such as Ti-MOR), One of titanium Si-Al molecular sieve (such as Ti-TUN) and the titanium Si-Al molecular sieve (such as Ti-ZSM-48) of other structures of TUN structure Or it is two or more.

Preferably, the titanium Si-Al molecular sieve divides for the titanium sial of titanium Si-Al molecular sieve, MEL structure selected from MFI structure One or more of son sieve, the titanium Si-Al molecular sieve of BEA structure and titanium Si-Al molecular sieve of hexagonal structure.More preferably Ground, the titanium Si-Al molecular sieve are the titanium Si-Al molecular sieve of MFI structure.

According to the method for the present invention, in a preferred embodiment, go out from the angle for further increasing catalytic activity Hair, the Kong Rongwei 0.3cm of the titanium Si-Al molecular sieve³/ g or more, total specific surface area are 200m²/ g or more, external surface area are 30m²/ g or more, and the ratio of the total specific surface area of external surface area Zhan is 7-55%；The titanium Si-Al molecular sieve is in 25 DEG C, P/P₀= 0.10 and adsorption time be 1h under conditions of the benzene adsorbance that measures be at least 65mg/g molecular sieve, by N₂Static Adsorption test Determine the micropore that the titanium Si-Al molecular sieve has pore-size distribution in 0.9-2nm range.

In the preferred embodiment, it is preferably 0.34-0.7cm that the hole of the titanium Si-Al molecular sieve, which holds,³/ g, such as 0.34-0.5cm³/ g, more preferably 0.35-0.4cm³/g.The Kong Rong uses N₂Static adsorptive method measurement.

In the preferred embodiment, total specific surface area of the titanium Si-Al molecular sieve is preferably 200-450m²/ g, more Preferably 270-430m²/ g, further preferably 300-420m²/ g is still more preferably 350-410m²/g；External surface area is excellent It is selected as 30-150m²/ g, more preferably 40-120m²/ g, further preferably 40-80m²/g.The total specific surface area of external surface area Zhan Ratio is preferably 7-35%, more preferably 10-30%, further preferably 11-22%.Total specific surface area of titanium Si-Al molecular sieve Refer to the total specific surface area of BET, external surface area refers to the surface area of the outer surface of titanium Si-Al molecular sieve, can be also simply referred to as outer surface Product, total specific surface area and external surface area are measured according to method specified in ASTM D4222-98.

In the preferred embodiment, the titanium Si-Al molecular sieve is in 25 DEG C, P/P₀=0.10 and adsorption time be The benzene adsorbance measured under conditions of 1h is preferably at least 75mg/g molecular sieve, more preferably 80-110mg/g molecular sieve, into one Step is preferably 90-110mg/g molecular sieve.In the present invention, benzene adsorbance uses N₂Static adsorptive method measurement.

In the preferred embodiment, the micropore size of the titanium Si-Al molecular sieve is in addition within the scope of 0.4-0.7nm Have outside pore-size distribution specific to typical micro porous molecular sieve (if the aperture of MFI topological structure molecular sieve is near 0.55nm), It is also distributed within the scope of 0.9-2nm.It is necessary to be noted that in poromerics field, if within the scope of 0.9-2nm Micropore size be distributed the total micropore size abundance of Zhan ratio < 1% when, then the pore size distribution of this partial pore is generally ignored, Think to be distributed within the scope of 0.9-2nm without micropore.Therefore, of the present invention in N₂Static Adsorption test is lower to have 0.9- The micropore size of 2nm range refer to the micropore size within the scope of 0.9-2nm distribution the total micropore size abundance of Zhan ratio > 1% the case where.

Preferably, in the titanium Si-Al molecular sieve, the micropore size within the scope of 0.4-0.7nm is distributed the total micropore size of Zhan Ratio≤95% of abundance, within the scope of 0.9-2nm micropore size distribution the total micropore size abundance of Zhan ratio >= 5%.It is highly preferred that the micropore size distribution total micropore size of Zhan point in the titanium Si-Al molecular sieve, within the scope of 0.4-0.7nm Ratio≤90% of cloth amount, preferably 75-88%, the total micropore size distribution of micropore size distribution Zhan within the scope of 0.9-2nm Ratio >=6% of amount, preferably 8-25%.The micropore size uses N₂Static adsorptive method measurement.

In the present invention, the ratio of the total micropore size abundance of the micropore size Zhan of 0.9-2nm range is calculated as follows: [the quantity of the micropore size of 0.9-2nm range/(micro- in the quantity+0.4-0.7nm range of the micropore size of 0.9-2nm range The quantity in hole aperture)] × 100%.

According to the method for the present invention, the titanium Si-Al molecular sieve can be original powder, or molding titanium Si-Al molecular sieve. Molding titanium Si-Al molecular sieve is typically contained as the titanium Si-Al molecular sieve of active constituent and as the carrier of binder, wherein titanium The content of Si-Al molecular sieve can be conventional selection.Generally, on the basis of the total amount of the molding titanium Si-Al molecular sieve, titanium silicon The content of aluminum molecular screen can be 5-95 weight %, preferably 10-95 weight %, more preferably 70-95 weight %, further it is excellent It is selected as 80-90 weight %；The content of the carrier can be 5-95 weight %, preferably 5-90 weight %, more preferably 5-30 Weight %, further preferably 10-20 weight %.The carrier of the molding titanium Si-Al molecular sieve can be conventional selection, such as oxygen Change aluminium and/or silica.The method for preparing the molding titanium Si-Al molecular sieve is it is known in the art, being no longer described in detail herein. The granular size of the molding titanium Si-Al molecular sieve is also not particularly limited, and can be made appropriate choice according to concrete shape. Specifically, the average grain diameter of the molding titanium Si-Al molecular sieve can be 4-10000 microns, preferably 5-5000 microns, more excellent It is selected as 40-4000 microns, further preferably 50-1000 microns, such as 100-500 microns.The average grain diameter is average for volume Partial size can be measured using laser particle analyzer.

For the titanium Si-Al molecular sieve as catalyst, dosage, which is subject to, can be realized catalysis, can be according to reaction The type of device is selected.Specifically, when being reacted in fixed bed reactors, the weight (hourly) space velocity (WHSV) of thioether can be 0.1- 500h^-1, preferably 10-400h^-1, more preferably 50-300h^-1, further preferably 80-250h^-1；By titanium Si-Al molecular sieve It is mixed to form slurry with the raw mixture, so that the mass ratio of thioether and titanium Si-Al molecular sieve respectively may be used when being reacted Think 0.05-100:1, preferably 0.1-50:1, more preferably 1-40:1, is still more preferably 5-20:1.In the present invention, weight When air speed with the total amount of catalyst in whole catalyst beds (when for molded molecular sieve, being counted using the total amount of molded molecular sieve) as base It is quasi-.

The titanium Si-Al molecular sieve is commercially available, and can also be synthesized using the conventional method of this field.

In one embodiment, it is hydrolyzed after silicon source, silicon source, titanium source and alkali source being mixed, hydrolysis is obtained Mixture carry out hydrothermal crystallizing, to obtain titanium Si-Al molecular sieve.

In this embodiment, the silicon source that source of aluminium can be usually used for technical field of molecular sieve preparation is specific Example can include but is not limited to one or more of Aluminum sol, aluminium salt, aluminium hydroxide and aluminium oxide.The aluminium salt can Think that inorganic aluminate and/or organic aluminium salt, specific example can include but is not limited to aluminum sulfate, sodium metaaluminate, aluminium chloride, nitre Sour aluminium and C₁-C₁₀Organic aluminium salt (such as aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and isooctanol One or more of aluminium).Silicon source: the molar ratio of silicon source can be 100:0.01-10, preferably 100:0.1-5.It is described Silicon source is with Al₂O₃Meter, the silicon source is with SiO₂Meter.

In this embodiment, the titanium source that the titanium source can be usually used for technical field of molecular sieve preparation.Specifically, The titanium source can be organic titanium source (such as organic titanate) and/or inorganic ti sources (such as inorganic titanium salt).The inorganic titanium Source can be TiCl₄、Ti(SO₄)₂、TiOCl₂, titanium hydroxide, titanium oxide, one of nitric acid titanium salt and phosphoric acid titanium salt etc. or more Kind.The organic titanium source can be one of fatty alcohol titanium and organic titanate or a variety of.The titanium source is preferably organic titanium Source, further preferably organic titanate, further preferably formula M₄TiO₄Shown in organic titanate, wherein 4 M can be with It is identical, it can also be different, respectively preferably C₁-C₄Alkyl.The titanium source is still more preferably tetraisopropyl titanate, metatitanic acid One of four n-propyls, butyl titanate and tetraethyl titanate are a variety of.

Silicon source: the molar ratio of titanium source can be 100:0.01-10, preferably 100:0.1-5.The titanium source is with TiO₂Meter, The silicon source is with SiO₂Meter.

In this embodiment, the alkali source that the alkali source can be usually used for technical field of molecular sieve preparation.Specifically, The alkali source can be one or more of amine, hydramine and quaternary ammonium base.

The quaternary ammonium base can be various organic level Four ammonium alkali, and the amine can be various NH₃In at least one hydrogen quilt The compound that alkyl (preferably alkyl) is formed after replacing, the hydramine can be various NH₃In at least one hydrogen by contain hydroxyl The compound that the alkyl (preferably alkyl) of base is formed after replacing.

Specifically, the quaternary ammonium base can be quaternary ammonium base shown in Formulas I,

In Formulas I, R₁、R₂、R₃And R₄It is identical or different, respectively C₁-C₄Alkyl, including C₁-C₄Straight chained alkyl and C₃- C₄Branched alkyl, such as: R₁、R₂、R₃And R₄Respectively can for methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, Isobutyl group or tert-butyl.

The aliphatic amine that the amine can indicate for Formula II,

R⁵(NH₂)_n(Formula II)

In Formula II, n is an integer of 1 or 2.When n is 1, R⁵For C₁-C₆Alkyl, including C₁-C₆Straight chained alkyl and C₃-C₆ Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, new penta Base, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R⁵For C₁-C₆Alkylidene, including C₁-C₆Straight-chain alkyl-sub and C₃-C₆ Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.

The aliphatic hydramine that the hydramine can indicate for formula III,

(HOR⁶)_mNH_(3-m)(formula III)

In formula III, m R⁶It is identical or different, respectively C₁-C₄Alkylidene, including C₁-C₄Straight-chain alkyl-sub and C₃- C₄Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is further preferred that the aliphatic Alcohol amine compound is one of monoethanolamine, diethanol amine and triethanolamine or a variety of.

The specific example of the alkali source can include but is not limited to tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, 4 third Base ammonium hydroxide (including four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), tetrabutylammonium hydroxide (including four positive fourths Base ammonium hydroxide, four sec-butyl ammonium hydroxide, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide), four pentyl hydroxide One of ammonium, ethamine, n-butylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine and triethanolamine are a variety of.

Silicon source: the molar ratio of alkali source can be 100:1-50, preferably 100:5-25.The alkali source is with N or OH^-Meter, In, when the alkali source contains nitrogen, the alkali source in terms of N, the alkali source not Nitrogen element when, the alkali source is with OH^-Meter, institute Silicon source is stated with SiO₂Meter.

In this embodiment, the silicon source can be inorganic silicon source and/or organic silicon source.The inorganic silicon source includes silicon Glue and/or silica solution.SiO in the silica gel₂Content is generally 90 weight % or more, preferably 95 weight % or more, more excellent It is selected as 99 weight % or more.SiO in the silica solution₂Content is generally 10-40 weight %, preferably 15-30 weight %.Institute Stating organic silicon source can be the various substances that silica is capable of forming under the conditions of hydrolytic condensation, such as can be for shown in formula IV Silicon-containing compound,

In formula IV, R₇、R₈、R₉And R₁₀Respectively C₁-C₄Alkyl.The C₁-C₄Alkyl include C₁-C₄Straight chained alkyl And C₃-C₄Branched alkyl, specific example can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, secondary Butyl, isobutyl group and tert-butyl.Preferably, the organic silicon source is selected from methyl orthosilicate, ethyl orthosilicate, positive silicic acid positive third Ester, positive isopropyl silicate and positive silicic acid N-butyl.

In this embodiment, the dosage of water can be conventional selection.Generally, silicon source: the molar ratio of water can be 100:100-3000, preferably 100:200-2000.The silicon source is with SiO₂Meter.

The hydrolysis can carry out under normal conditions.Generally, the hydrolysis can 10-80 DEG C at a temperature of It carries out, the time of the hydrolysis, which is subject to, can be such that silicon source all hydrolyzes, such as can be 0.1-5 hours (h).

The mixture that hydrolysis obtains can carry out hydrothermal crystallizing under normal conditions.Generally, the hydro-thermal process Can 100-200 DEG C at a temperature of carry out, preferably 120-180 DEG C at a temperature of carry out, more preferably in 140-170 DEG C of temperature Degree is lower to carry out.The duration of the hydro-thermal process can be selected according to the temperature of hydro-thermal process.Generally, the hydro-thermal The duration of processing can be 0.5-100 hours, preferably 10-90 hours.The hydro-thermal process carries out in confined conditions. The hydro-thermal process can carry out under pressure itself, can also carry out under conditions of additionally increasing pressure, preferably at itself It is carried out under pressure.In the actual operation process, the hydro-thermal process can be carried out in a high pressure reaction kettle.

The mixture that hydro-thermal process obtains can be handled using conventional method, to obtain titanium Si-Al molecular sieve.Tool Body, the mixture that hydro-thermal process can be obtained is separated by solid-liquid separation, and is dried after obtained solid phase is washed And optional roasting, to obtain the titanium Si-Al molecular sieve.The drying can carry out under normal conditions, generally, The drying can 25-200 DEG C at a temperature of carry out, preferably 50-180 DEG C at a temperature of carry out, more preferably in 80-150 It is carried out at a temperature of DEG C.The roasting can 300-800 DEG C at a temperature of carry out, preferably 550-600 DEG C at a temperature of into Row.The duration of the roasting can be 2-12 hours, preferably 2-4 hours.The roasting can in air atmosphere into Row, can also carry out in inert atmosphere.

It, can be using described in the second aspect of the present invention for titanium Si-Al molecular sieve described in preferred embodiment above Prepared by the preparation method of titanium Si-Al molecular sieve involved in method, preparation method is by explanation in greater detail below.

In step (1), Titanium Sieve Molecular Sieve is the total of a kind of zeolite of a part of silicon atom in titanium atom substitution lattice framework Claim, chemical formula xTiO can be used₂·SiO₂It indicates.The content of titanium atom in Titanium Sieve Molecular Sieve is not particularly limited in the present invention, It can be the conventional selection of this field.Specifically, x can be 0.0001-0.09, preferably 0.01-0.08, more preferably 0.01-0.05。

The Titanium Sieve Molecular Sieve can be the common Titanium Sieve Molecular Sieve with various topological structures, such as: the titanium silicon Molecular sieve can be the Titanium Sieve Molecular Sieve (such as TS-1) selected from MFI structure, the Titanium Sieve Molecular Sieve (such as TS-2) of MEL structure, BEA knot The Titanium Sieve Molecular Sieve (such as Ti-Beta) of structure, the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, hexagonal structure titanium silicon molecule Sieve (such as Ti-MCM-41, Ti-SBA-15), the Titanium Sieve Molecular Sieve (such as Ti-MOR) of MOR structure, the Titanium Sieve Molecular Sieve of TUN structure One or more of Titanium Sieve Molecular Sieve (such as Ti-ZSM-48) of (such as Ti-TUN) and other structures.

Preferably, the Titanium Sieve Molecular Sieve be Titanium Sieve Molecular Sieve selected from MFI structure, the Titanium Sieve Molecular Sieve of MEL structure, One or more of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve of hexagonal structure of BEA structure.It is highly preferred that the titanium silicon Molecular sieve is the Titanium Sieve Molecular Sieve of MFI structure, such as titanium-silicon molecular sieve TS-1.

The Titanium Sieve Molecular Sieve can be fresh titanium si molecular sieves and/or non-fresh Titanium Sieve Molecular Sieve.The fresh titanium silicon Molecular sieve refers to not yet for being catalyzed the Titanium Sieve Molecular Sieve of reaction；The non-fresh Titanium Sieve Molecular Sieve, which refers to, lives through catalysis reaction Titanium Sieve Molecular Sieve.The specific example of the non-fresh Titanium Sieve Molecular Sieve can include but is not limited to: in catalytic reaction process Temporary inactivation occurs, after regeneration the Titanium Sieve Molecular Sieve (hereinafter referred to as regenerative agent) of activation recovering；In catalytic reaction process Permanent inactivation occurs, its active Titanium Sieve Molecular Sieve (hereinafter referred to as drawing off agent) can not be restored being regenerated；And Regenerative agent and the combination for drawing off agent.Preferably, the Titanium Sieve Molecular Sieve is non-fresh Titanium Sieve Molecular Sieve.

The Titanium Sieve Molecular Sieve permanently inactivated drawn off from using Titanium Sieve Molecular Sieve as the device of catalyst, which is referred to as, unloads Agent out, drawing off the usual method of disposal of agent is accumulation landfill.The present inventor has found in the course of the research, it is described draw off agent can Using the raw material as production titanium Si-Al molecular sieve, and the titanium Si-Al molecular sieve prepared is in the catalyst reacted as sulfide oxidation In use, preferable catalysis reaction effect can be obtained.Therefore, in step (1), the Titanium Sieve Molecular Sieve more preferably draws off agent. It is described draw off agent can be to use Titanium Sieve Molecular Sieve to draw off agent as what is drawn off in the reaction unit of catalyst from various, such as can Think that is drawn off from oxidation reaction apparatus draws off agent.Specifically, described to draw off agent and be drawn off for Ammoximation reaction device Agent, hydroxylating device draw off agent and epoxidation reaction device draw off one of agent or a variety of.More specifically, described Draw off agent can for cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draws off agent and propylene epoxy That changes reaction unit draws off one of agent or a variety of.

It is described from the angle for the catalytic performance for further increasing the titanium Si-Al molecular sieve finally prepared, step (1) Titanium Sieve Molecular Sieve is more preferably the reaction unit using Titanium Sieve Molecular Sieve as catalyst reacted under alkaline environment Draw off agent.It is particularly preferred that described, to draw off agent be that Ammoximation reaction device draws off agent, such as cyclohexanone oxamidinating reaction unit Draw off agent.

It is described to draw off agent for before being contacted with acid solution, preferably progress high-temperature roasting and/or solvent washing to be to remove Attachment removal is drawing off the residuals in agent surface and/or duct.In one embodiment, it is described draw off agent with acid solution into Row contact before, roasted, the roasting can 300-800 DEG C at a temperature of carry out, preferably in 550-600 DEG C of temperature Lower progress.The duration of the roasting can be 2-12 hours, preferably 2-4 hours.The roasting can be in air atmosphere Middle progress can also carry out in inert atmosphere.The inert atmosphere can be for by nitrogen and/or group 0 element gas shape At atmosphere, the group 0 element gas such as argon gas.

The activity for drawing off agent is different according to its source.Generally, the activity for drawing off agent can be the titanium The 5-95% of activity (that is, activity of fresh Titanium Sieve Molecular Sieve) of si molecular sieves when fresh, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%.Preferably, it is unloaded through regenerated The activity of agent can be active 10-90% of Titanium Sieve Molecular Sieve when fresh out.It is further preferred that being drawn off through regenerated The activity of agent can be active 60% or less of Titanium Sieve Molecular Sieve when fresh.It is further preferred that being unloaded through regenerated The activity of agent can be active 30-55% of Titanium Sieve Molecular Sieve when fresh out.It is being through the regenerated activity for drawing off agent When active 30-55% of Titanium Sieve Molecular Sieve when fresh, during long-time continuous operation, better activity is shown Stability.It is further preferred that being active 35- of Titanium Sieve Molecular Sieve when fresh through the regenerated activity for drawing off agent 50%.The activity of the fresh Titanium Sieve Molecular Sieve is generally 90% or more, and usually 95% or more.

The activity measures by the following method: respectively will be through regenerated agent and the fresh Titanium Sieve Molecular Sieve of drawing off as hexamethylene Ketone oxamidinating reaction catalyst, the condition of the Ammoximation reaction are as follows: Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH₃Meter), The hydrogen peroxide of 30 weight % is (with H₂O₂Meter), the tert-butyl alcohol and cyclohexanone 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure In 80 DEG C of reaction 2h.Calculate separately using through it is regenerated draw off agent and fresh Titanium Sieve Molecular Sieve as catalyst when cyclohexanone conversion Rate, and using it as through the regenerated activity for drawing off agent and fresh Titanium Sieve Molecular Sieve, wherein the conversion ratio of cyclohexanone= [mole of the cyclohexanone of (mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/addition] × 100%.

In step (1), the acid solution refers to the aqueous solution containing acid.The acid is general acid, for inorganic acid and can be had One of machine acid is a variety of.The organic acid can be carboxylic acid and/or sulfonic acid, such as C₁-C₆Aliphatic carboxylic acid, C₆-C₁₂Virtue Fragrant race's carboxylic acid, C₁-C₆Aliphatic sulfonic and C₆-C₁₂Aromatic sulphonic acid.Preferably, the acid is HCl, H₂SO₄、HNO₃、 CH₃COOH、HClO₄And H₃PO₄One or more of.The acid preferably provides in form of an aqueous solutions, sour aqueous solution The concentration of middle acid can be selected according to the type of acid, be not particularly limited, generally, the concentration of sour aqueous acid medium can Think 0.5-20mol/L, preferably 1-15mol/L.

In step (1), Titanium Sieve Molecular Sieve: sour molar ratio can be 100:0.005-50, and preferably 100:0.1-30 is more Preferably 100:2-15.The Titanium Sieve Molecular Sieve is with SiO₂Meter, the acid is with H⁺Meter.

In step (1), by Titanium Sieve Molecular Sieve and acid solution 10-200 DEG C at a temperature of contact.Preferably, by titanium silicon Molecular sieve and acid solution 50-180 DEG C at a temperature of contacted.It is highly preferred that by Titanium Sieve Molecular Sieve and acid solution at 60-180 DEG C At a temperature of contacted.The duration of the contact can be selected according to the temperature of contact.Generally, the contact Duration can be 0.5-36 hours, preferably 1-24 hours, more preferably 1-12 hours.

In step (1), the contact can carry out in air atmosphere, can also carry out in inert atmosphere, preferably It is carried out in air atmosphere.

In step (1), solid phase can be isolated from the mixture that contact obtains using conventional method.For example, can incite somebody to action It contacts obtained mixture to be filtered and/or be centrifuged, to isolate solid phase therein.

In step (2), source of aluminium can be the usually used silicon source of technical field of molecular sieve preparation.The tool of source of aluminium Body example can include but is not limited to one or more of Aluminum sol, aluminium salt, aluminium hydroxide and aluminium oxide.The aluminium salt Can be inorganic aluminate and/or organic aluminium salt, specific example can include but is not limited to Aluminum sol, aluminium hydroxide, aluminum sulfate, Sodium metaaluminate, aluminium chloride, aluminum nitrate and C₁-C₁₀Organic aluminium salt (such as aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three special One or more of butoxy aluminium and isooctanol aluminium).

The isolated solid phase of step (1): the molar ratio of silicon source can be 100:0.1-10, preferably 100:0.2-5, more Preferably 100:0.5-2.Source of aluminium is with Al₂O₃Meter, the isolated solid phase of step (1) is with SiO₂Meter.

The titanium source can be the usually used titanium source of technical field of molecular sieve preparation.Specifically, the titanium source can be Organic titanium source (such as organic titanate) and/or inorganic ti sources (such as inorganic titanium salt).The inorganic ti sources can be TiCl₄、 Ti(SO₄)₂、TiOCl₂, titanium hydroxide, titanium oxide, one of nitric acid titanium salt and phosphoric acid titanium salt etc. or a variety of.The organic titanium Source can be one of fatty alcohol titanium and organic titanate or a variety of.The titanium source is preferably organic titanium source, further preferably For organic titanate, further preferably formula M₄TiO₄Shown in organic titanate, wherein 4 M can be identical, can also not Together, respectively preferably C₁-C₄Alkyl.The titanium source is still more preferably tetraisopropyl titanate, four n-propyl of metatitanic acid, metatitanic acid One of four butyl esters and tetraethyl titanate are a variety of.

The isolated solid phase of step (1): the molar ratio of titanium source can be 100:0.1-20, preferably 100:0.5-15, Preferably 100:1-10.The titanium source is with TiO₂Meter, the isolated solid phase of step (1) is with SiO₂Meter.

The alkali source can be the usually used alkali source of technical field of molecular sieve preparation.Specifically, the alkali source can be Organic alkali source and/or inorganic alkali source, wherein inorganic alkali source can be ammonia, cation is the alkali of alkali metal and cation is alkaline earth One or more of alkali of metal.The specific example of the inorganic alkali source can include but is not limited to ammonia, sodium hydroxide, One or more of potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and barium hydroxide.Organic alkali source can be with For one or more of urea, amine, hydramine and quaternary ammonium base.

The aliphatic amine that the amine can indicate for Formula II,

R⁵(NH₂)_n(Formula II)

The aliphatic hydramine that the hydramine can indicate for formula III,

(HOR⁶)_mNH_(3-m)(formula III)

The specific example of the alkali source can include but is not limited to ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, carbonic acid Sodium, potassium carbonate, barium hydroxide, urea, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide are (including four just Propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), tetrabutylammonium hydroxide (including 4-n-butyl ammonium hydroxide, four sec-butyls Ammonium hydroxide, four isobutyl group ammonium hydroxide and tetra-tert ammonium hydroxide), four pentyl ammonium hydroxide, ethamine, n-butylamine, fourth two One of amine, hexamethylene diamine, monoethanolamine, diethanol amine and triethanolamine are a variety of.

In a preferred embodiment, from the catalytic activity for further increasing the titanium Si-Al molecular sieve finally prepared Angle is set out, and the alkali source is preferably sodium hydroxide, ammonium hydroxide, ethylenediamine, n-butylamine, butanediamine, hexamethylene diamine, monoethanolamine, two One or more of ethanol amine, triethanolamine, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide.

The isolated solid phase of step (1): the molar ratio of alkali source can be 100:0.5-50, preferably 100:1-20, more Preferably 100:2-15.The alkali source is with N or OH^-Meter, wherein when the alkali source contains nitrogen, the alkali source is in terms of N, institute State alkali source not Nitrogen element when, the alkali source is with OH^-Meter, the isolated solid phase of step (1) is with SiO₂Meter.

In step (2), the sequence that the isolated solid phase of step (1), titanium source, silicon source, alkali source and water mix is not had It is particularly limited to.From the angle for the catalytic activity for further increasing the titanium Si-Al molecular sieve finally prepared, preferably by step (1) The mixture of isolated solid phase and titanium source is added in the aqueous solution containing silicon source and alkali source.

In step (2), Titanium Sieve Molecular Sieve and titanium source, silicon source and alkali source are subjected to hydro-thermal process.The dosage of water can be normal Rule selection.Generally, the isolated solid phase of step (1): the molar ratio of water can be 100:20-1000, preferably 100:30- 800, more preferably 100:50-600, the isolated solid phase of step (1) is with SiO₂Meter.

In step (2), the hydro-thermal process can 100-200 DEG C at a temperature of carry out, preferably in 120-180 DEG C of temperature Degree is lower to carry out, more preferably 140-170 DEG C at a temperature of carry out.The duration of the hydro-thermal process can be according to hydro-thermal process Temperature selected.Generally, the duration of the hydro-thermal process can be 0.5-24 hours, preferably 2-24 hours, More preferably 6-18 hours.

In step (2), hydro-thermal process carries out in confined conditions.The hydro-thermal process can carry out under pressure itself, It can also carry out under conditions of additionally increasing pressure, preferably be carried out under pressure itself.In the actual operation process, Ke Yi The hydro-thermal process is carried out in autoclave.

The mixture that step (2) hydro-thermal process obtains can be handled using conventional method, to obtain titanium sial point Son sieve.Specifically, the mixture that hydro-thermal process can be obtained is separated by solid-liquid separation, and will be done after the washing of obtained solid phase Dry and optional roasting, to obtain the titanium Si-Al molecular sieve.The drying can carry out under normal conditions, generally Ground, the drying can 25-200 DEG C at a temperature of carry out, preferably 50-180 DEG C at a temperature of carry out, more preferably in 80- Carried out at a temperature of 150 DEG C, further preferably 90-120 DEG C at a temperature of carry out.The roasting can be at 300-800 DEG C At a temperature of carry out, preferably 550-600 DEG C at a temperature of carry out.The duration of the roasting can be 2-12 hours, preferably It is 2-4 hours.The roasting can carry out in air atmosphere, can also carry out in inert atmosphere.

Sulfide oxidation method described in the second aspect according to the present invention, the titanium Si-Al molecular sieve as catalyst, Dosage, which is subject to, can be realized catalysis, can be selected according to the type of reactor.Specifically, in fixed bed reactors In when being reacted, the weight (hourly) space velocity (WHSV) of thioether can be 0.1-500h^-1, preferably 10-400h^-1, more preferably 50-300h^-1, Further preferably 80-250h^-1；Titanium Si-Al molecular sieve and the raw mixture are being mixed to form slurry, to carry out anti- At once, the mass ratio of thioether and titanium Si-Al molecular sieve respectively can be 0.05-100:1, preferably 0.1-50:1, more preferably 1- 40:1 is still more preferably 5-20:1.In the present invention, weight (hourly) space velocity (WHSV) in whole catalyst beds titanium Si-Al molecular sieve it is total On the basis of amount.

Method described in first aspect and the second aspect according to the present invention, the oxidant can for it is various be enough by The substance of sulfide oxidation.Method of the invention is particularly suitable for carry out the occasion of oxidizing sulfur ether using peroxide as oxidant.Institute It states peroxide and refers to the compound for containing-O-O- key in molecular structure, hydrogen peroxide, organic peroxide and mistake can be selected from Acid.The organic peroxide refers to that a hydrogen atom or two hydrogen atoms in hydrogen peroxide molecule are replaced by organic group Obtained from substance.The peracid refers to the organic oxacid for containing-O-O- key in molecular structure.The peroxide it is specific Example can include but is not limited to: hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide, cyclohexyl hydroperoxide, peroxide Acetic acid and Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide.The hydrogen peroxide can be commonly used in the art with each Hydrogen peroxide existing for kind form, the hydrogen peroxide provided such as in the form of hydrogen peroxide.

The dosage of the oxidant can be conventional selection, be not particularly limited.Generally, the oxidant and thioether Molar ratio can be 0.1:1 or more, preferably 0.2:1 or more.The molar ratio of the oxidant and thioether can be 20:1 hereinafter, Such as 10:1 hereinafter, preferably 5:1 hereinafter, more preferably 4:1 hereinafter, further preferably 3:1 or less.In a kind of embodiment In, the molar ratio of oxidant and thioether is 2 or more, preferably 2-5:1, such as 2-3:1.According to the embodiment, can obtain higher Sulfone selectivity, to obtain the oxidation product based on sulfone.

Method described in first aspect and the second aspect according to the present invention, the raw mixture can contain molten Agent can also not contain solvent.From further increase in reaction system between each reactant mixability, enhanced dispersion and The angle that more easily severe degree of reaction is adjusted is set out, and the raw mixture preferably comprises at least one molten Agent.The type of the solvent is not particularly limited.Generally, the solvent can be selected from water, C₁-C₆Alcohol, C₃-C₈Ketone and C₂-C₆Nitrile.The specific example of the solvent can include but is not limited to: water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, tertiary fourth Alcohol, isobutanol, acetone, butanone and acetonitrile.

The dosage of the solvent is not particularly limited, and can be conventional selection.Generally, the mass ratio of solvent and thioether can Think 1-200:1, preferably 5-100:1.Furthermore it is also possible to be contacted according to by thioether and oxidant with titanium Si-Al molecular sieve Form difference, adjustment appropriate is carried out to the dosage of solvent.

Method described in first aspect and the second aspect according to the present invention, thioether, which refers to, contains-S- in molecular structure Compound, the preferably described thioether is selected from the thioether that carbon atom number is 2-18, more preferably dimethyl sulfide or thioanisole.

Method described in first aspect and the second aspect, titanium Si-Al molecular sieve are mixed with the raw material according to the present invention The contact conditions of object are enough will be subject to sulfide oxidation.Generally, temperature can be 20-200 DEG C, preferably 25-180 DEG C, more excellent It is selected as 30-120 DEG C.In terms of gauge pressure, pressure in reactor can be 0-3MPa, preferably 0.1-2.5MPa, more preferably 0.1-1.5MPa.The method of first aspect and the second aspect according to the present invention, even if by the raw mixture and titanium silicon Aluminum molecular screen is contacted (as not higher than 60 DEG C, preferably no greater than 50 DEG C, more preferably no higher than 45 DEG C) at a lower temperature, Also the selectivity for sulfone can be effectively improved.

Method described in first aspect and the second aspect according to the present invention can also include that will export from reactor Reaction mixture separated, to obtain desirable oxidation product (such as sulfoxide and/or sulfone) and unreacted reactant.It will be anti- The method for answering mixture to be separated can be the conventional selection of this field, be not particularly limited.The unreacted original isolated Material can be recycled.

According to the third aspect of the present invention, the present invention provides a kind of method for producing sulfoxide and sulfone simultaneously, this method It is included under oxidation reaction condition, raw mixture is contacted at least one titanium Si-Al molecular sieve, the raw mixture contains There are thioether, at least one oxidant and an optional at least one solvent, the molar ratio of the oxidant and the thioether is low In 2.

The difference of method and method described in first aspect according to the present invention described in third aspect according to the present invention It is the dosage of oxidant, therefore only the dosage of oxidant is illustrated below, remaining is referred to first side of the invention Method described in face carries out.

The molar ratio of method described in third aspect according to the present invention, the oxidant and thioether is lower than 2, preferably 1.9 hereinafter, more preferably 1.6 hereinafter, further preferably 1.5 hereinafter, still more preferably for 1.2 hereinafter, particularly preferably 1 Below.The molar ratio of the oxidant and the thioether can be 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more. For example, the molar ratio of the oxidant and the thioether can for section [0.1,2) in a numerical value, preferably section [0.2, 1.8] numerical value in, more preferably a numerical value in section [0.2,1.6], further preferably section [0.3,1.5] In a numerical value, be still more preferably a numerical value in section [0.3,1].

According to the fourth aspect of the present invention, the present invention provides a kind of method for producing sulfoxide and sulfone simultaneously, this method It is included under oxidation reaction condition, raw mixture is contacted at least one titanium Si-Al molecular sieve, the raw mixture contains There are thioether, at least one oxidant and an optional at least one solvent, the molar ratio of the oxidant and the thioether is low In 2, the titanium Si-Al molecular sieve is made using method comprising the following steps:

The difference of method and method described in the second aspect according to the present invention described in 4th aspect according to the present invention It is the dosage of oxidant, therefore only the dosage of oxidant is illustrated below, remaining is referred to second side of the invention Method described in face carries out.

The molar ratio of method described in 4th aspect according to the present invention, the oxidant and thioether is lower than 2, preferably 1.9 hereinafter, more preferably 1.6 hereinafter, further preferably 1.5 hereinafter, still more preferably for 1.2 hereinafter, particularly preferably 1 Below.The molar ratio of the oxidant and the thioether can be 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more. For example, the molar ratio of the oxidant and the thioether can for section [0.1,2) in a numerical value, preferably section [0.2, 1.8] numerical value in, more preferably a numerical value in section [0.2,1.6], further preferably section [0.3,1.5] In a numerical value, be still more preferably a numerical value in section [0.3,1].

According to the present invention first, second, third and fourth aspect described in method, oxidation reaction in oxygen-containing atmosphere into Row, carries out preferably in air atmosphere.

Method described in first, second, third and fourth aspect according to the present invention, can be used only titanium Si-Al molecular sieve As catalyst, titanium Si-Al molecular sieve and other catalyst (such as Titanium Sieve Molecular Sieve) can also be applied in combination, by being catalyzed Titanium Si-Al molecular sieve is introduced in agent can significantly improve the selectivity for sulfone, especially in third and fourth side according to the present invention In method described in face, the selectivity for sulfone can be improved while producing sulfoxide.The titanium Si-Al molecular sieve is urged with other Ratio between agent can be selected according to the set goal oxidation product, the amount of the sulfoxide generated and sulfone can be made full Subject to the respective output of foot.By titanium Si-Al molecular sieve and other catalyst combinations in use, according to specific response style, can To mix titanium Si-Al molecular sieve with other catalyst, using the mixture as catalyst；It is carried out in fixed bed reactors anti- At once, Titanium Sieve Molecular Sieve and other catalyst intervals can also be loaded in the reactor.

As an example, titanium Si-Al molecular sieve can be applied in combination with Titanium Sieve Molecular Sieve.In this example, with titanium silicon On the basis of the total amount of aluminum molecular screen and Titanium Sieve Molecular Sieve, the content of the titanium Si-Al molecular sieve can be 1-99 weight %, preferably It is still more preferably 40-90 for 10-98 weight %, more preferably 20-95 weight %, further preferably 30-95 weight % Weight %, such as 50-80 weight %.

The Titanium Sieve Molecular Sieve is the general name that titanium atom replaces a kind of zeolite of a part of silicon atom in lattice framework, can be with With chemical formula xTiO₂·SiO₂It indicates.The content of titanium atom in Titanium Sieve Molecular Sieve is not particularly limited in the present invention, Ke Yiwei The conventional selection of this field.Specifically, x can be 0.0001-0.09, preferably 0.01-0.08, more preferably 0.01-0.05.

Preferably, the Titanium Sieve Molecular Sieve be Titanium Sieve Molecular Sieve selected from MFI structure, the Titanium Sieve Molecular Sieve of MEL structure, One or more of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve of hexagonal structure of BEA structure.It is highly preferred that the titanium silicon Molecular sieve is the Titanium Sieve Molecular Sieve of MFI structure, such as titanium-silicon molecular sieve TS-1 and/or hollow Titanium Sieve Molecular Sieve.The hollow titanium silicon Molecular sieve is the Titanium Sieve Molecular Sieve of MFI structure, and the crystal grain of the Titanium Sieve Molecular Sieve is hollow structure, the chamber portion of the hollow structure Radical length be 5-300 nanometers, and the Titanium Sieve Molecular Sieve is in 25 DEG C, P/P₀=0.10, adsorption time is under conditions of 1 hour The benzene adsorbance measured is at least 70 milligrams per grams, the adsorption isotherm and desorption isothermal of the nitrogen absorption under low temperature of the Titanium Sieve Molecular Sieve There are hysteresis loops between line.The hollow Titanium Sieve Molecular Sieve, which is commercially available, (such as to be commercially available from Hunan and builds feldspathization share and have The trade mark of limit company be HTS molecular sieve), can also the method according to disclosed in CN1132699C be prepared.

When the Titanium Sieve Molecular Sieve uses template during the preparation process, the Titanium Sieve Molecular Sieve can be that experienced to be used for The Titanium Sieve Molecular Sieve of the process (such as roasting process) of removed template method, or do not undergo the process for removed template method The Titanium Sieve Molecular Sieve of (such as roasting process) can also be the mixture of the two.

The Titanium Sieve Molecular Sieve can be fresh titanium si molecular sieves, or non-fresh Titanium Sieve Molecular Sieve can also be The mixture of fresh Titanium Sieve Molecular Sieve and non-fresh Titanium Sieve Molecular Sieve.The non-fresh Titanium Sieve Molecular Sieve has been carried out above Detailed description, and will not be described here in detail.

The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.

In following embodiment and comparative example, pressure is gauge pressure.

In following embodiment and comparative example, X-ray diffraction (XRD) is analyzed in Siemens D5005 type x-ray diffractometer Upper progress, with sample and authentic specimen the diffracted intensity (peak height) that 2 θ are the five fingers diffractive features peak between 22.5 ° -25.0 ° it The ratio of sum indicates crystallinity of the sample relative to authentic specimen, using the sample prepared with reference to preparation example 1 as benchmark sample, Crystallinity is calculated as 100%.

In following embodiment and comparative example, benzene adsorbance, Kong Rong, pore-size distribution, total specific surface area and external surface area exist It is measured on Micromeritics company ASAP2405 static state n2 absorption apparatus；Mole composition of molecular sieve is in Rigaku motor strain It is measured on formula commercial firm 3271E type Xray fluorescence spectrometer.

In following embodiment and comparative example, the content of each ingredient in the reaction solution analyzed using gas chromatography, Following formula is respectively adopted on this basis to calculate thioether rate, sulfoxide selectivity and sulfone selectivity:

Thioether rate (%)=[(mole of the unreacted thioether of the mole-of the thioether of addition)/sulphur being added The mole of ether] × 100%；

Sulfoxide selectivity (%)=[mole for the sulfoxide that reaction generates/(mole-of the thioether of addition is unreacted Thioether mole)] × 100%；

Sulfone selectivity (%)=[mole/(the unreacted thioether of the mole-of the thioether of addition for the sulfone that reaction generates Mole)] × 100%.

In following embodiment and comparative example, using the activity of following methods measurement Titanium Sieve Molecular Sieve.

By Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH₃Meter), the hydrogen peroxide of 30 weight % is (with H₂O₂Meter), the tert-butyl alcohol With cyclohexanone in mass ratio=1:7.5:10:7.5:10 mixing after at atmosheric pressure after 80 DEG C are stirred to react 2h, will react Object filtering, analyzed with composition of the gas chromatography to liquid phase, be calculated using the following equation the conversion ratio of cyclohexanone and by its As the activity of Titanium Sieve Molecular Sieve,

The conversion ratio of cyclohexanone=[(mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/it is added Cyclohexanone mole] × 100%.

With reference to preparation example 1

Authentic specimen is used to prepare with reference to preparation example 1.

Tetraethyl orthosilicate, isopropyl titanate are mixed with tetrapropylammonium hydroxide, and appropriate distilled water is added and is stirred, In reaction system, tetraethyl orthosilicate is (with SiO₂Meter): isopropyl titanate is (with TiO₂Meter): tetrapropylammonium hydroxide (in terms of N): water =100:5:10:200 (molar ratio)；1h is hydrolyzed at normal pressure and 60 DEG C, then stirs 3h at 75 DEG C, is then put into mixed liquor Stainless steel seals reaction kettle, places 3d in 170 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product；By this mixture mistake It filters, be washed with water, and in 110 DEG C of dry 60min, molecular screen primary powder is obtained, by molecular screen primary powder in 550 DEG C of roasting temperature 3h obtains the Titanium Sieve Molecular Sieve of hydro-thermal direct crystallization, and the TS-1 molecular sieve of MFI structure is determined that it is by XRD analysis.

Preparation embodiment 1-19 is used to prepare titanium Si-Al molecular sieve.

Prepare embodiment 1

Tetraethyl orthosilicate, aluminium isopropoxide, isopropyl titanate are mixed with four n-propyl ammonium hydroxide, and appropriate distillation is added Water is stirred, and in reaction system, tetraethyl orthosilicate is (with SiO₂Meter): tetraisopropyl titanate is (with TiO₂Meter): aluminium isopropoxide (with Al₂O₃Meter): four n-propyl ammonium hydroxide (in terms of N): water=100:5:2:10:200 (molar ratio)；At normal pressure and 60 DEG C 1h is hydrolyzed, then stirs 3h at 75 DEG C, mixed liquor is then put into stainless steel sealing reaction kettle, in 170 DEG C of at a temperature of constant temperature 3d is placed, the mixture of crystallization product is obtained；It by the filtering of this mixture, is washed with water, and in 110 DEG C of dry 60min, is divided Son sieve original powder obtains the titanium Si-Al molecular sieve of hydro-thermal direct crystallization by molecular screen primary powder in 550 DEG C of roasting temperature 3h, XRD crystalline phase figure and reference preparation example 1 are consistent, are MFI structure.

Prepare comparative example 1

Titanium Sieve Molecular Sieve prepared by reference preparation example 1 is mixed with sodium metaaluminate aqueous solution, wherein Titanium Sieve Molecular Sieve and partially The molar ratio of sodium aluminate and water is 10:2:25, and obtained mixture is stirred 6h at normal pressure and 60 DEG C, then mixed by what is obtained After closing object filtering, solid phase is washed with water, by washed solid phase after 110 DEG C of dry 60min, in 550 DEG C of roasting temperatures 3h obtains the Titanium Sieve Molecular Sieve that load has aluminium.

Prepare embodiment 2

What this preparation embodiment used, which draw off agent, draws off agent (for TS-1 for what is drawn off from cyclohexanone oxamidinating reaction unit Molecular sieve is prepared using method identical with reference preparation example 1), which is 35% (fresh TS-1 molecular sieve 95%) activity is.

(1) under environment temperature (20 DEG C) and normal pressure (0.1MPa), the combined of agent and 1mol/L will be drawn off Mashing, by obtained mixed serum 80 DEG C at a temperature of be stirred to react 12h.After the reaction was completed, mixture is filtered, is received Collect solid phase.Wherein, agent is drawn off (with SiO₂Meter) with HCl (with H⁺Meter) molar ratio be 100:10.

(2) the whole solid phases for obtaining step (1) and the aluminum sulfate as silicon source, the titanium sulfate as titanium source and hydrogen-oxygen Change sodium water solution mixing, mixed liquor be placed in stainless steel sealing reaction kettle, handles 12h under pressure itself at 170 DEG C, In, agent is drawn off (with SiO₂Meter is the amount for drawing off agent in step (1) as raw material): titanium source is (with TiO₂Meter): silicon source (with Al₂O₃Meter): alkali source is (with OH^-Meter): water=100:1:1:5:250 (molar ratio).After the completion of processing, the reaction mixture that will obtain It is filtered, after collecting solid phase and being washed with water, by solid phase in 110 DEG C of dry 120min, is then roasted in 550 DEG C of air atmospheres 3h is burnt, titanium Si-Al molecular sieve according to the present invention is obtained.The XRD crystalline phase figure and reference preparation example 1 of the titanium Si-Al molecular sieve are consistent, Show it with MFI structure, nature parameters are listed in table 1.

Prepare comparative example 2

Agent (identical as preparation embodiment 2) will be drawn off to mix with sodium metaaluminate aqueous solution, wherein draw off agent and sodium metaaluminate It is 10:0.5:10 with the molar ratio of water, obtained mixture is stirred into 6h at a temperature of normal pressure and 60 DEG C, then will obtains After mixture filtering, solid phase is washed with water, by washed solid phase after 110 DEG C of dry 60min, is roasted at a temperature of 550 DEG C 3h is burnt, the molecular sieve that load has aluminium is obtained, nature parameters are listed in table 1.

Prepare comparative example 3

The solid phase that 2 step of embodiment (1) obtains will be prepared to mix with aluminum sulfate aqueous solution, wherein preparation 2 step of embodiment (1) solid phase obtained is (with SiO₂Meter) it with the molar ratio of aluminum sulfate and water is 10:2:20, by obtained mixture in normal pressure and 60 6h is stirred at a temperature of DEG C, then by after the filtering of obtained mixture, solid phase is washed with water, by washed solid phase 110 After DEG C dry 60min, in 550 DEG C of roasting temperature 3h, the molecular sieve that load has aluminium is obtained, nature parameters are listed in table 1.

Prepare embodiment 3

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 2, unlike, without step (1), and It is that will draw off agent to be sent directly into step (2).The XRD crystalline phase figure and reference preparation example 1 for the molecular sieve being prepared are consistent, show It is listed in table 1 with MFI structure, nature parameters.

Prepare embodiment 4

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 2, unlike, step (1) is middle to be formed The fresh TS-1 for drawing off agent in preparation embodiment 2 replaces drawing off agent.The XRD crystalline phase figure for the molecular sieve being prepared and reference are made Standby example 1 is consistent, shows it with MFI structure, nature parameters are listed in table 1.

Prepare comparative example 4

There is the molecular sieve of aluminium using method preparation load identical with preparation comparative example 2, unlike, draw off agent preparation Fresh TS-1 in embodiment 4 is replaced, and nature parameters are listed in table 1.

Prepare comparative example 5

There is the molecular sieve of aluminium using method preparation load identical with preparation comparative example 3, unlike, prepare embodiment 2 The solid phase that step (1) obtains is replaced with the solid phase that preparation 4 step of embodiment (1) obtains, and nature parameters are listed in table 1.

Prepare embodiment 5

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 4, unlike, without step (1), and It is to be sent directly into fresh titanium-silicon molecular sieve TS-1 in step (2).It is prepared by the XRD crystalline phase figure for the molecular sieve being prepared and reference Example 1 is consistent, shows it with MFI structure, nature parameters are listed in table 1.

Prepare embodiment 6

What this preparation embodiment used, which draw off agent, draws off agent (for TS-1 for what is drawn off from cyclohexanone oxamidinating reaction unit Molecular sieve is prepared referring to the method with reference to preparation example 1, wherein titanium oxide content is 2.4 moles of %), which is 45% (activity of fresh TS-1 molecular sieve is 95%).

(1) under environment temperature (20 DEG C) and normal pressure (0.1MPa), agent and the hydrochloric acid water of 5mol/L are drawn off by what is be fired Solution is mixed with beating, by obtained mixed serum 60 DEG C at a temperature of be stirred to react 1h.After the reaction was completed, mixture is carried out Solid phase is collected in filtering.Wherein, agent is drawn off (with SiO₂Meter) with HCl (with H⁺Meter) molar ratio be 100:15.

(2) the whole solid phases for obtaining step (1) and the Aluminum sol (Al as silicon source₂O₃Content is 20%), as titanium source Butyl titanate and tetrapropylammonium hydroxide solution mixing, by mixed liquor be placed in stainless steel sealing reaction kettle in, 150 DEG C 12h is handled under pressure itself, wherein draw off agent (with SiO₂Meter is the amount for drawing off agent in step (1) as raw material): Titanium source is (with TiO₂Meter): silicon source is (with Al₂O₃Meter): alkali source is (with OH^-Meter): water=100:2:0.5:15:200 (molar ratio).Processing After the completion, obtained reaction mixture is filtered, after collecting solid phase and being washed with water, by solid phase in 110 DEG C of dryings Then 120min roasts 3h in 550 DEG C of air atmospheres, obtain titanium Si-Al molecular sieve according to the present invention.The titanium silicoaluminophosphate molecular The XRD crystalline phase figure of sieve and consistent with reference to preparation example 1 shows it with MFI structure, and nature parameters are listed in table 1.

Prepare embodiment 7

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 6, unlike, it draws off agent and is being sent into step (1) before, first roasted, roast 570 DEG C at a temperature of carry out in air atmosphere, the duration of roasting is 4 hours.Through The activity for drawing off agent of roasting is 52%.The XRD crystalline phase figure and reference preparation example 1 of the titanium Si-Al molecular sieve of preparation are consistent, show It is listed in table 1 with MFI structure, nature parameters.

Prepare embodiment 8

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 6, unlike, raw material in step (2) Order by merging are as follows: after mixing silicon source with tetrapropylammonium hydroxide solution, solid phase and titanium source that step (1) obtains are added to In mixed liquor, finally obtained mixture is placed in stainless steel sealing reaction kettle and is handled.The titanium Si-Al molecular sieve of preparation XRD crystalline phase figure and consistent with reference to preparation example 1, show it with MFI structure, nature parameters are listed in table 1.

Prepare embodiment 9

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 6, unlike, in step (1), HCl is used Etc. quality H₃PO₄Instead of.The XRD crystalline phase figure and reference preparation example 1 of the titanium Si-Al molecular sieve of preparation are consistent, show it with MFI Structure, nature parameters are listed in table 1.

Prepare embodiment 10

What this preparation embodiment used, which draw off agent, draws off agent (for TS-1 for what is drawn off from cyclohexanone oxamidinating reaction unit Molecular sieve is prepared referring to the method with reference to preparation example 1, wherein titanium oxide content is 3.9 moles of %), which is 36% (activity of fresh TS-1 molecular sieve is 95%).

(1) under environment temperature (20 DEG C) and normal pressure (0.1MPa), agent will be drawn off and mixed with the aqueous solution of nitric acid of 8mol/L Mashing, by obtained mixed serum 100 DEG C at a temperature of be stirred to react 2h.After the reaction was completed, mixture is filtered, is received Collect solid phase.Wherein, agent is drawn off (with SiO₂Meter) and HNO₃(with H⁺Meter) molar ratio be 100:10.

(2) the whole solid phases for obtaining step (1) and the aluminium hydroxide as silicon source, the titanium tetrachloride as titanium source and Mixed liquor is placed in stainless steel sealing reaction kettle, handles 18h under pressure itself at 140 DEG C by ethylenediamine solution mixing, In, agent is drawn off (with SiO₂Meter is the amount for drawing off agent in step (1) as raw material): titanium source is (with TiO₂Meter): silicon source (with Al₂O₃Meter): alkali source is (with OH^-Meter): water=100:5:2:5:150 (molar ratio).After the completion of processing, the reaction mixture that will obtain It is filtered, after collecting solid phase and being washed with water, by solid phase in 110 DEG C of dry 120min, is then roasted in 550 DEG C of air atmospheres 3h is burnt, titanium Si-Al molecular sieve according to the present invention is obtained.The XRD crystalline phase figure and reference preparation example 1 of the titanium Si-Al molecular sieve are consistent, Show it with MFI structure, nature parameters are listed in table 1.

Prepare embodiment 11

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 10, unlike, step (1) is middle to be formed The fresh TS-1 for drawing off agent in preparation embodiment 10 replaces drawing off agent.The XRD crystalline phase figure and reference for the molecular sieve being prepared Preparation example 1 is consistent, shows it with MFI structure, nature parameters are listed in table 1.

Prepare embodiment 12

What this preparation embodiment used, which draw off agent, draws off agent (for TS-1 for what is drawn off from cyclohexanone oxamidinating reaction unit Molecular sieve is prepared referring to the method with reference to preparation example 1, wherein titanium oxide content is 1.3 moles of %), which is 41% (activity of fresh TS-1 molecular sieve is 95%).

(1) under environment temperature (30 DEG C) and normal pressure (0.1MPa), agent will be drawn off and mixed with the aqueous sulfuric acid of 5mol/L Mashing, is stirred to react 1h at 120 DEG C for obtained mixed serum.After the reaction was completed, mixture is filtered, is collected solid Phase.Wherein, agent is drawn off (with SiO₂Meter) and H₂SO₄(with H⁺Meter) molar ratio be 100:2.

(2) the whole solid phases for obtaining step (1) and the aluminium chloride as silicon source, the tetraisopropyl titanate as titanium source with And the mixing of n-butylamine aqueous solution, mixed liquor is placed in stainless steel sealing reaction kettle, handles 12h under pressure itself at 170 DEG C, Wherein, agent is drawn off (with SiO₂Meter is the amount for drawing off agent in step (1) as raw material): titanium source is (with TiO₂Meter): silicon source (with Al₂O₃Meter): alkali source is (with OH^-Meter): water=100:1:1:2:50 (molar ratio).After the completion of processing, the reaction mixture that will obtain It is filtered, after collecting solid phase and being washed with water, by solid phase in 110 DEG C of dry 120min, is then roasted in 550 DEG C of air atmospheres 3h is burnt, titanium Si-Al molecular sieve according to the present invention is obtained.The XRD crystalline phase figure and reference preparation example 1 of the titanium Si-Al molecular sieve are consistent, Show it with MFI structure, nature parameters are listed in table 1.

Prepare embodiment 13

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 12, unlike, step (1) is middle to be formed The fresh TS-1 for drawing off agent in preparation embodiment 12 replaces drawing off agent.The XRD crystalline phase figure and reference for the molecular sieve being prepared Preparation example 1 is consistent, shows it with MFI structure, nature parameters are listed in table 1.

Prepare embodiment 14

It is identical as preparation embodiment 2 that this preparation embodiment used draws off agent.

(1) under environment temperature (35 DEG C) and normal pressure (0.1MPa), agent will be drawn off and mixed with the phosphate aqueous solution of 15mol/L Mashing, is stirred to react 3h at 180 DEG C for obtained mixed serum.After the reaction was completed, mixture is filtered, is collected solid Phase.Wherein, agent is drawn off (with SiO₂Meter) and H₃PO₄(with H⁺Meter) molar ratio be 100:10.

(2) the whole solid phases for obtaining step (1) and the aluminum nitrate as silicon source, the titanium sulfate as titanium source and hydrogen-oxygen Change sodium water solution mixing, mixed liquor be placed in stainless steel sealing reaction kettle, handles 6h under pressure itself at 150 DEG C, wherein Agent is drawn off (with SiO₂Meter is the amount for drawing off agent in step (1) as raw material): titanium source is (with TiO₂Meter): silicon source is (with Al₂O₃ Meter): alkali source is (with OH^-Meter): water=100:10:1:15:600 (molar ratio).After the completion of processing, by obtained reaction mixture into Row filtering, by solid phase in 110 DEG C of dry 120min, then roasts in 550 DEG C of air atmospheres after collecting solid phase and being washed with water 3h obtains titanium Si-Al molecular sieve according to the present invention.The XRD crystalline phase figure of the titanium Si-Al molecular sieve and consistent, the table with reference to preparation example 1 It is bright its with MFI structure, nature parameters are listed in table 1.

Prepare embodiment 15

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 14, unlike, it draws off agent and is being sent into step Suddenly it before (1), is first roasted, roasting carries out in air atmosphere at 570 DEG C, and the duration of roasting is 4 hours.It is fired The activity for drawing off agent is 39%.The XRD crystalline phase figure and reference preparation example 1 of the titanium Si-Al molecular sieve of preparation are consistent, show that it has MFI structure, nature parameters are listed in table 1.

Prepare embodiment 16

Prepare titanium Si-Al molecular sieve using with the identical method of preparation embodiment 14, unlike, use draw off agent for What is drawn off from phenol hydroxylation reaction unit draws off agent (for TS-1 molecular sieve, using method system identical with reference preparation example 1 It is standby), which is 36% (activity of fresh TS-1 molecular sieve is 95%).The XRD of the titanium Si-Al molecular sieve of preparation Crystalline phase figure and consistent with reference to preparation example 1 shows it with MFI structure, and nature parameters are listed in table 1.

Prepare embodiment 17

Prepare titanium Si-Al molecular sieve using with the identical method of preparation embodiment 14, unlike, use draw off agent for What is drawn off from epoxidation of propylene device draws off agent (for TS-1 molecular sieve, preparing using method identical with reference preparation example 1), The activity for drawing off agent is 34% (activity of fresh TS-1 molecular sieve is 95%).The XRD crystal phase of the titanium Si-Al molecular sieve of preparation Figure is consistent with reference to preparation example 1, shows it with MFI structure, nature parameters are listed in table 1.

Prepare embodiment 18

Titanium Si-Al molecular sieve is prepared using method identical with preparation embodiment 14, unlike, drawing off in step (1) Agent is the hollow Titanium Sieve Molecular Sieve drawn off from cyclohexanone oxamidinating reaction unit, which is 40%, when fresh Activity be 97%.The nature parameters of the titanium Si-Al molecular sieve of preparation are listed in table 1.

Prepare embodiment 19

Titanium Si-Al molecular sieve is prepared using method identical with embodiment 18, unlike, step (1) is not used and is drawn off Agent, but (Hunan Jianchang Petrochemical Co., Ltd is commercially available from using the fresh hollow Titanium Sieve Molecular Sieve for drawing off agent is formed The trade mark is the molecular sieve of HTS).The nature parameters of the titanium Si-Al molecular sieve of preparation are listed in table 1, and table 1 lists file names with fresh sky The relevant parameter of heart Titanium Sieve Molecular Sieve is as reference.

Table 1

*: the molar ratio of silicon, titanium and aluminium in the molecular sieve of preparation, based on the element；When silicon and titanium or al mole ratio are greater than When 1000, titanium or aluminium are in terms of 0.

*: being determined by solid-state nuclear magnetic resonance aluminium spectrum analysis, is non-framework aluminum.

Embodiment 1-35 is for illustrating method of the invention.

Embodiment 1-5

Respectively by prepare embodiment 1-5 preparation molecular sieve and dimethyl sulfide, as oxidant hydrogen peroxide (with 30 The form of the hydrogen peroxide of weight % provides) and methanol as solvent is after mixing, is sent into small-sized slurry bed reactor Oxidation reaction is carried out in air atmosphere, isolating catalyst circulation from the reaction mixture that slurry bed reactor exports makes With collection liquid phase mixture is sent into product reservoir.Wherein, the molar ratio of dimethyl sulfide and oxidant is 1:1, dimethyl The mass ratio of thioether and titanium Si-Al molecular sieve is 5:1, and the mass ratio of methanol and dimethyl sulfide is 50:1；Reaction temperature is 30 DEG C, pressure in reactor is 0.5MPa, and the combined feed speed of reaction mass is 100mL/min, is carried out continuously 24 hours anti- It answers.After reaction, after mixing evenly by the liquid mixture in product reservoir, sampling is analyzed with gas chromatography, and Dimethyl sulfide conversion ratio, dimethyl sulfoxide selectivity and dimethyl sulfone selectivity are calculated, takes 5 samples to be tested altogether, table 2 The result listed is the average value of 5 samples.

Comparative example 1-5

The molecular sieve for preparing comparative example 1-5 preparation is used as respectively by catalyst using method identical with embodiment 1-5, it will Dimethyl sulfide oxidation.Experimental result is listed in table 2.

Reference example 1

Catalyst is used as using the molecular sieve that method identical with embodiment 1-5 prepares reference preparation example 1, by dimethyl Sulfide oxidation.Experimental result is listed in table 2.

Table 2

Number	Catalyst source	Dimethyl sulfide conversion ratio (%)	Dimethyl sulfoxide selectivity (%)	Dimethyl sulfone selectivity (%)
					Reference example 1	With reference to preparation example 1	94	94	6
Embodiment 1	Prepare embodiment 1	91	84	16
					Comparative example 1	Prepare comparative example 1	85	91	9
Embodiment 2	Prepare embodiment 2	88	70	30
					Comparative example 2	Prepare comparative example 2	86	92	8
Comparative example 3	Prepare comparative example 3	87	93	7
					Embodiment 3	Prepare embodiment 3	92	82	18
Embodiment 4	Prepare embodiment 4	87	79	21
					Comparative example 4	Prepare comparative example 4	91	92	8
Comparative example 5	Prepare comparative example 5	92	90	10
					Embodiment 5	Prepare embodiment 5	90	86	14

Embodiment 6-9

Respectively by the molecular sieve of preparation embodiment 6-9 preparation and dimethyl sulfide, as the tert-butyl hydroperoxide of oxidant It hydrogen (in the form of the acetone soln of the tert-butyl hydroperoxide of 35 weight % provide) and is uniformly mixed as the acetone of solvent Afterwards, it is sent into small-sized slurry bed reactor and carries out oxidation reaction in air atmosphere, the reaction exported from slurry bed reactor is mixed It closes and isolates catalyst circulation use in object, collect liquid phase mixture, be sent into product reservoir.Wherein, dimethyl sulfide and oxygen The molar ratio of agent is 1:0.8, and the mass ratio of dimethyl sulfide and titanium Si-Al molecular sieve is 10:1, and acetone (does not include tert-butyl Acetone in the acetone soln of hydrogen peroxide) it with the mass ratio of dimethyl sulfide is 80:1；Reaction temperature is 35 DEG C, in reactor Pressure be 0.1MPa, the combined feed speed of reaction mass is 150mL/min, is carried out continuously reaction in 24 hours.Reaction terminates Afterwards, after mixing evenly by the liquid mixture in product reservoir, sampling is analyzed with gas chromatography, and calculates dimethyl disulfide Ether conversion ratio, dimethyl sulfoxide selectivity and dimethyl sulfone selectivity, take 5 samples to be tested, the result that table 3 is listed is altogether The average value of 5 samples.

Reference example 2

Catalyst is used as using the molecular sieve that method identical with embodiment 6-9 prepares reference preparation example 1, by dimethyl Sulfide oxidation.Experimental result is listed in table 3.

Table 3

Number	Catalyst source	Dimethyl sulfide conversion ratio (%)	Dimethyl sulfoxide selectivity (%)	Dimethyl sulfone selectivity (%)
					Reference example 2	With reference to preparation example 1	74	95	5
Embodiment 6	Prepare embodiment 6	72	78	22
					Embodiment 7	Prepare embodiment 7	67	72	28
Embodiment 8	Prepare embodiment 8	70	74	26
					Embodiment 9	Prepare embodiment 9	69	77	23

Embodiment 10-11

Respectively by prepare embodiment 6-9 preparation molecular sieve and dimethyl sulfide, as oxidant Perpropionic Acid (with 40 The form of the acetonitrile solution of the Perpropionic Acid of weight % provides) and acetonitrile as solvent is after mixing, is sent into small-sized silt Oxidation reaction is carried out in slurry bed reactor in air atmosphere, isolates and urges from the reaction mixture that slurry bed reactor exports Agent is recycled, and collects liquid phase mixture, is sent into product reservoir.Wherein, the molar ratio of dimethyl sulfide and oxidant is The mass ratio of 1:0.5, dimethyl sulfide and titanium Si-Al molecular sieve is 20:1, and acetonitrile (does not include in the acetonitrile solution of Perpropionic Acid Acetonitrile) with the mass ratio of dimethyl sulfide be 60:1；Reaction temperature is 40 DEG C, and the pressure in reactor is 0.3MPa, reaction The combined feed speed of material is 200mL/min, is carried out continuously reaction in 24 hours.After reaction, by the liquid in product reservoir Body mixture after mixing evenly, analyzed with gas chromatography by sampling, and calculates dimethyl sulfide conversion ratio, dimethyl sulfoxide Selectivity and dimethyl sulfone selectivity, take 5 samples to be tested altogether, and the result that table 4 is listed is the average value of 5 samples.

Reference example 3

Catalyst is used as using the molecular sieve that method identical with embodiment 10-11 prepares reference preparation example 1, by diformazan Base sulfide oxidation.Experimental result is listed in table 4.

Table 4

Number	Catalyst source	Dimethyl sulfide conversion ratio (%)	Dimethyl sulfoxide selectivity (%)	Dimethyl sulfone selectivity (%)
					Reference example 3	With reference to preparation example 1	46	96	4
Embodiment 10	Prepare embodiment 10	39	74	26
					Embodiment 11	Prepare embodiment 11	42	80	20

Embodiment 12-13

Respectively by prepare embodiment 12-13 preparation molecular sieve and dimethyl sulfide, as oxidant hydrogen peroxide (with The form of the hydrogen peroxide of 35 weight % provides) and the tert-butyl alcohol as solvent is after mixing, is sent into small-sized slurry-bed reaction Oxidation reaction is carried out in device in air atmosphere, isolates catalyst circulation from the reaction mixture that slurry bed reactor exports It uses, collects liquid phase mixture, be sent into product reservoir.Wherein, the molar ratio of dimethyl sulfide and oxidant be 1:0.3, two The mass ratio of Dimethyl sulfide and titanium Si-Al molecular sieve is 15:1, and the mass ratio of the tert-butyl alcohol and dimethyl sulfide is 40:1；Reaction temperature Degree is 45 DEG C, and the pressure in reactor is 0.4MPa, and the combined feed speed of reaction mass is 300mL/min, and it is small to be carried out continuously 24 When reaction.After reaction, after mixing evenly by the liquid mixture in product reservoir, sampling is divided with gas chromatography Analysis, and dimethyl sulfide conversion ratio, dimethyl sulfoxide selectivity and dimethyl sulfone selectivity are calculated, take 5 samples to be surveyed altogether Examination, the result that table 5 is listed are the average value of 5 samples.

Reference example 4

Catalyst is used as using the molecular sieve that method identical with embodiment 12-13 prepares reference preparation example 1, by diformazan Base sulfide oxidation.Experimental result is listed in table 5.

Table 5

Number	Catalyst source	Dimethyl sulfide conversion ratio (%)	Dimethyl sulfoxide selectivity (%)	Dimethyl sulfone selectivity (%)
					Reference example 4	With reference to preparation example 1	31	97	3
Embodiment 12	Prepare embodiment 12	25	82	18
					Embodiment 13	Prepare embodiment 13	27	88	12

Embodiment 14-19

Respectively by prepare embodiment 14-19 preparation molecular sieve and dimethyl sulfide, as oxidant hydrogen peroxide (with The form of the hydrogen peroxide of 25 weight % provides) and water as solvent is after mixing, is sent into small-sized slurry bed reactor Oxidation reaction is carried out in air atmosphere, isolates catalyst, collection liquid from the reaction mixture that slurry bed reactor exports Phase mixture is sent into product reservoir.Wherein, the molar ratio of dimethyl sulfide and oxidant is 1:0.9, dimethyl sulfide and titanium The mass ratio of Si-Al molecular sieve is 15:1, and the mass ratio of water (not including the water in hydrogen peroxide) and dimethyl sulfide is 40:1；Instead Answering temperature is 50 DEG C, and the pressure in reactor is 0.2MPa, and the combined feed speed of reaction mass is 160mL/min, is carried out continuously Reaction in 24 hours.After reaction, after mixing evenly by the liquid mixture in product reservoir, sampling gas chromatography into Row analysis, and calculate dimethyl sulfide conversion ratio, dimethyl sulfoxide selectivity and dimethyl sulfone selectivity, take altogether 5 samples into Row test, the result that table 6 is listed are the average value of 5 samples.

Reference example 5

Catalyst is used as using the molecular sieve that method identical with embodiment 14-19 prepares reference preparation example 1, by diformazan Base sulfide oxidation.Experimental result is listed in table 6.

Table 6

Number	Catalyst source	Dimethyl sulfide conversion ratio (%)	Dimethyl sulfoxide selectivity (%)	Dimethyl sulfone selectivity (%)
					Reference example 5	With reference to preparation example 1	83	92	8
Embodiment 14	Prepare embodiment 14	76	72	28
					Embodiment 15	Prepare embodiment 15	75	68	32
Embodiment 16	Prepare embodiment 16	74	84	16
					Embodiment 17	Prepare embodiment 17	75	78	22
Embodiment 18	Prepare embodiment 18	77	70	30
					Embodiment 19	Prepare embodiment 19	80	84	16

Embodiment 20-27

The molecular sieve for preparing the preparation of embodiment 1-4,10,11,18 and 19 is seated in micro fixed-bed reactor respectively, Form catalyst bed, wherein the quantity of catalyst bed is 1 layer.Dimethyl sulfide, oxidant and solvent are mixed, formed Liquid mixture.The liquid mixture is sent into micro fixed-bed reactor and is contacted with the catalyst bed containing molecular sieve Reaction.

Wherein: in embodiment 20-23, solvent is methanol, and oxidant is hydrogen peroxide (with the shape of the hydrogen peroxide of 30 weight % Formula provides), in liquid mixture, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1:0.8, the matter of dimethyl sulfide and methanol For amount than being 1:12, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 220h^-1.Temperature in catalyst bed is 35 DEG C, fixed bed reactors Interior pressure is 0.5MPa；

In embodiment 24 and 25, solvent is acetone, and oxidant is tert-butyl hydroperoxide (with the tert-butyl mistake of 30 weight % The form of the acetone soln of hydrogen oxide provides), in liquid mixture, the molar ratio of dimethyl sulfide and tert-butyl hydroperoxide is The mass ratio of 1:0.6, dimethyl sulfide and acetone is 1:10, and the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 140h^-1.In catalyst bed Temperature be 40 DEG C, pressure in fixed bed reactors is 0.8MPa；

In embodiment 26 and 27, solvent is water, and oxidant is that hydrogen peroxide (is mentioned in the form of the hydrogen peroxide of 40 weight % For), in liquid mixture, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1:0.4, and dimethyl sulfide and water (do not include double Water in oxygen water) mass ratio be 1:10, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 80h^-1.Temperature in catalyst bed is 45 DEG C, the pressure in fixed bed reactors is 0.7MPa.

The product exported from reactor is collected, is sent into product reservoir.It is carried out continuously reaction in 48 hours.Reaction terminates Afterwards, after mixing evenly by the liquid mixture in product reservoir, sampling is analyzed with gas chromatography, and calculates dimethyl disulfide Ether conversion ratio, dimethyl sulfoxide selectivity and dimethyl sulfone selectivity, take 5 samples to be tested, the result that table 7 is listed is altogether The average value of 5 samples.

Reference example 6-8

Reference example 6 is used as catalysis using the molecular sieve that method identical with embodiment 20-23 prepares reference preparation example 1 Agent aoxidizes dimethyl sulfide；The molecule that reference example 7 is prepared reference preparation example 1 using method identical with embodiment 24-25 Sieve is used as catalyst, and dimethyl sulfide is aoxidized；Reference example 8 uses method identical with embodiment 26-27 by fresh hollow titanium Si molecular sieves (source is with preparation embodiment 19) are used as catalyst, and dimethyl sulfide is aoxidized.

Experimental result is listed in table 7.

Table 6

Number	Catalyst source	Dimethyl sulfide conversion ratio (%)	Dimethyl sulfoxide selectivity (%)	Dimethyl sulfone selectivity (%)
					Reference example 6	With reference to preparation example 1	72	93	7
Embodiment 20	Prepare embodiment 1	67	86	14
					Embodiment 21	Prepare embodiment 2	65	71	29
Embodiment 22	Prepare embodiment 3	63	79	21
					Embodiment 23	Prepare embodiment 4	69	82	18
Reference example 7	With reference to preparation example 1	55	95	5
					Embodiment 24	Prepare embodiment 10	51	74	26
Embodiment 25	Prepare embodiment 11	52	83	17
					Reference example 8	Hollow Titanium Sieve Molecular Sieve	37	96	4
Embodiment 26	Prepare embodiment 18	32	78	22
					Embodiment 27	Prepare embodiment 19	34	87	13

Embodiment 28-35

In embodiment 28-31, point that method identical with embodiment 20-23 will prepare embodiment 1-4 preparation is respectively adopted Son sieve is used as catalyst and aoxidizes dimethyl sulfide, unlike, in liquid mixture, dimethyl sulfide and hydrogen peroxide rub You are than being 1:2.5；

In embodiment 32-33, method identical with embodiment 24-25, which is respectively adopted, will prepare embodiment 10-11 preparation Molecular sieve is used as catalyst and aoxidizes dimethyl sulfide, unlike, in liquid mixture, dimethyl sulfide and t-butyl peroxy The molar ratio for changing hydrogen is 1:2；

In embodiment 34-35, method identical with embodiment 26-27, which is respectively adopted, will prepare embodiment 18-19 preparation Molecular sieve is used as catalyst and aoxidizes dimethyl sulfide, unlike, in liquid mixture, dimethyl sulfide and hydrogen peroxide Molar ratio is 1:3.

The product exported from reactor is collected, is sent into product reservoir.It is carried out continuously reaction in 48 hours.Reaction terminates Afterwards, after mixing evenly by the liquid mixture in product reservoir, sampling is analyzed with gas chromatography, and calculates dimethyl disulfide Ether conversion ratio, dimethyl sulfoxide selectivity and dimethyl sulfone selectivity, take 5 samples to be tested, the result that table 8 is listed is altogether The average value of 5 samples.

Comparative example 6-8

The agent that draws off in preparation embodiment 2 as raw material is used as by comparative example 6 using method identical with embodiment 28-31 Catalyst aoxidizes dimethyl sulfide.Experimental result is listed in table 8；

Comparative example 7 will be prepared in embodiment 10 using method identical with embodiment 32-33 and draw off agent use as raw material Make catalyst, dimethyl sulfide is aoxidized.Experimental result is listed in table 8；

Comparative example 8 will be prepared in embodiment 18 using method identical with embodiment 34-35 and draw off agent use as raw material Make catalyst, dimethyl sulfide is aoxidized.Experimental result is listed in table 8.

Reference example 9-11

Reference example 9 is used as catalysis using the molecular sieve that method identical with embodiment 28-31 prepares reference preparation example 1 Agent aoxidizes dimethyl sulfide.Experimental result is listed in table 8；

Reference example 10 is used as catalysis using the molecular sieve that method identical with embodiment 32-33 prepares reference preparation example 1 Agent aoxidizes dimethyl sulfide.Experimental result is listed in table 8；

Using method identical with embodiment 34-35, by fresh hollow Titanium Sieve Molecular Sieve, (source is same to prepare reality to reference example 11 Apply example 19) it is used as catalyst, dimethyl sulfide is aoxidized.Experimental result is listed in table 8.

Table 8

The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims

1. a kind of sulfide oxidation method, this method are included under oxidation reaction condition, by raw mixture and at least one titanium silicon Aluminum molecular screen contact, the raw mixture contains thioether, at least one oxidant and optional at least one solvent, described Titanium Si-Al molecular sieve is made using method comprising the following steps:

(1) by Titanium Sieve Molecular Sieve and acid solution 10-200 DEG C at a temperature of contact, isolated from the mixture that contact obtains solid Phase；

2. a kind of method for producing sulfoxide and sulfone simultaneously, this method are included under oxidation reaction condition, by raw mixture and extremely A kind of few titanium Si-Al molecular sieve contact, the raw mixture contain thioether, at least one oxidant and optional at least one The molar ratio of kind solvent, the oxidant and the thioether is lower than 2, and the molar ratio of the oxidant and the thioether is 0.1 More than, the titanium Si-Al molecular sieve is made using method comprising the following steps:

3. according to the method described in claim 2, wherein, the molar ratio of the oxidant and the thioether is 1 hereinafter, the oxygen Agent and the molar ratio of the thioether are 0.2 or more.

4. method according to claim 1 or 2, wherein in step (1), mole of the acid in Titanium Sieve Molecular Sieve and acid solution Than for 100:0.005-50, the Titanium Sieve Molecular Sieve is with SiO₂Meter, the acid is with H⁺Meter.

5. method according to claim 1 or 2, wherein in step (1), the acid is HCl, H₂SO₄、HNO₃、CH₃COOH、 HClO₄And H₃PO₄One or more of.

6. method according to claim 1 or 2, wherein in step (1), the duration of the contact is that 0.5-36 is small When.

7. method according to claim 1 or 2, wherein in step (2), the isolated solid phase of step (1): titanium source: aluminium Source: acid: alkali source: the molar ratio of water is 100:0.1-20:0.1-10:0.5-50:20-1000, the isolated solid phase of step (1) With SiO₂Meter, alkali source is with N or OH^-Meter, source of aluminium is with Al₂O₃Meter, the titanium source is with TiO₂Meter.

8. method according to claim 1 or 2, wherein in step (2), by step (1) isolated solid phase and titanium source Mixture be added in the aqueous solution containing silicon source and alkali source.

9. method according to claim 1 or 2, wherein in step (2), temperature of the hydro-thermal process at 100-200 DEG C Lower progress；The duration of the hydro-thermal process is 0.5-24 hours.

10. according to the method described in claim 9, wherein, in step (2), the hydro-thermal process 120-180 DEG C at a temperature of It carries out.

11. according to the method described in claim 10, wherein, in step (2), temperature of the hydro-thermal process at 140-170 DEG C Lower progress.

12. method according to claim 1 or 2, wherein the alkali source is ammonia, alkali, cation that cation is alkali metal For one or more of the alkali of alkaline-earth metal, aliphatic amine, aliphatic hydramine and quaternary ammonium base；

Source of aluminium is one or more of Aluminum sol, aluminium salt, aluminium hydroxide and aluminium oxide；

The titanium source is inorganic titanium salt and/or organic titanate.

13. method according to claim 1 or 2, wherein the Titanium Sieve Molecular Sieve is non-fresh Titanium Sieve Molecular Sieve.

14. according to the method for claim 13, wherein the non-fresh Titanium Sieve Molecular Sieve is using Titanium Sieve Molecular Sieve as urging The reaction unit of agent draws off agent.

15. according to the method for claim 14, wherein the non-fresh Titanium Sieve Molecular Sieve is to carry out instead under alkaline environment The reaction unit using Titanium Sieve Molecular Sieve as catalyst answered draws off agent.

16. according to the method for claim 15, wherein the non-fresh Titanium Sieve Molecular Sieve is using Titanium Sieve Molecular Sieve as urging The Ammoximation reaction device of agent draws off agent.

17. according to the method for claim 16, wherein the non-fresh Titanium Sieve Molecular Sieve is using Titanium Sieve Molecular Sieve as urging The cyclohexanone oxamidinating reaction unit of agent draws off agent.

18. according to the method for claim 13, wherein the activity of the non-fresh Titanium Sieve Molecular Sieve is it when fresh Active 5-95%.

19. according to the method for claim 18, wherein the activity of the non-fresh Titanium Sieve Molecular Sieve is it when fresh Active 10-90%.

20. according to the method for claim 19, wherein the activity of the non-fresh Titanium Sieve Molecular Sieve is it when fresh Active 60% or less.

21. according to the method for claim 20, wherein the activity of the non-fresh Titanium Sieve Molecular Sieve is it when fresh Active 30-55%.

22. according to the method for claim 21, wherein the activity of the non-fresh Titanium Sieve Molecular Sieve is it when fresh Active 35-50%.

23. method according to claim 1 or 2, wherein the Titanium Sieve Molecular Sieve is the Titanium Sieve Molecular Sieve of MFI structure.

24. method according to claim 1 or 2, wherein the oxidant is peroxide.

25. according to the method for claim 24, wherein the oxidant is hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene One or more of hydrogen peroxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.

26. method according to claim 1 or 2, wherein the solvent is water, C₁-C₆Alcohol, C₃-C₈Ketone and C₂-C₆ One or more of nitrile.

27. method according to claim 1 or 2, wherein the oxidation reaction condition includes: that temperature is 20-200 DEG C, excellent It is selected as not higher than 60 DEG C；Pressure is 0-0.3MPa, and the pressure is gauge pressure.

28. according to the method for claim 27, wherein the oxidation reaction condition includes: that temperature is not higher than 60 DEG C；Pressure Power is 0.1-2.5MPa, and the pressure is gauge pressure.

29. according to the method for claim 28, wherein the oxidation reaction condition includes: that temperature is not higher than 50 DEG C.

30. according to the method for claim 29, wherein the oxidation reaction condition includes: that temperature is not higher than 45 DEG C.