CN107235871A

CN107235871A - A kind of sulfide oxidation method

Info

Publication number: CN107235871A
Application number: CN201610186769.6A
Authority: CN
Inventors: 林民; 史春风; 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: 2016-03-29
Filing date: 2016-03-29
Publication date: 2017-10-10
Anticipated expiration: 2036-03-29
Also published as: CN107235871B

Abstract

The invention discloses a kind of sulfide oxidation method, including：Step (1 1), by isopropylbenzene and oxygen haptoreaction, catalytic condition causes the content of cumyl hydroperoxide in the reactant mixture that haptoreaction is obtained to be more than 1 weight %；Optional step (1 2), the reactant mixture that step (1 1) is obtained is mixed with inorganic acid；Step (2), under conditions of being enough sulfide oxidation, the reactant mixture and the raw mixture of thioether and HTS haptoreaction that will be obtained containing step (1 1), or the mixture and the raw mixture of thioether and HTS haptoreaction that will be obtained containing step (1 2).This method is conducive to improving the effective treating capacity of device, and can obtain higher thioether rate and desirable oxidation selectivity of product.This method directly installs sulfide oxidation reaction unit additional at the material outlet end of existing isopropyl benzene oxidation unit, it is easy to implement.

Description

A kind of sulfide oxidation method

Technical field

The present invention relates to a kind of sulfide oxidation method.

Background technology

Sulfoxides are important sulfur-containing compounds, and such as dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, It is colourless transparent liquid under normal temperature, with the characteristic such as highly polar, high-hygroscopicity, flammable and higher boiling be non-proton.Dimethyl Sulfoxide is dissolved in water, ethanol, acetone, ether and chloroform, is the strong atent solvent of polarity, is widely used as solvent and reaction is tried Agent.Also, dimethyl sulfoxide (DMSO) has very high selective extraction method ability, it can be used as the extraction that alkane separates with aromatic hydrocarbon molten Agent, for example：Dimethyl sulfoxide (DMSO) can be used for the extracting of aromatic hydrocarbons or butadiene, and process solvent is used as in acrylonitrile polymerization reaction With the solvent that reels off raw silk from cocoons, as the synthetic and the solvent that reels off raw silk from cocoons of polyurethane, as polyamide, fluoroaluminate glasses, polyimides and The synthetic of polysulfones.Meanwhile, in medical industry, dimethyl sulfoxide (DMSO) not only can directly as some drugses raw material And carrier, and the effect such as anti-inflammatory analgetic, diuresis, calmness can also be played, therefore frequently as the active component of analgesic drug product Make an addition in medicine.In addition, dimethyl sulfoxide (DMSO) can also be extracted as capacitor dielectric, antifreezing agent, brake fluid, rare metal Agent etc..

Sulfoxides are typically prepared using sulfide oxidation method, according to the difference of used oxidant and mode of oxidizing, are led to Often include nitric acid oxidation method, peroxide oxidation method, Ozonation, anodizing and nitrogen dioxide oxidizing process.Nitre The deficiency that acid oxidation is present is that reaction is whard to control, and equipment corrosion is serious, while environmental pollution is heavier.Ozone oxidation There is the problem of dimethyl sulfide conversion ratio is low in rule.Anodizing is unsuitable for extensive implementation.Nitrogen dioxide oxidizing process The problem of then there is environmental pollution.The reaction condition of peroxide oxidation method is gentle, and equipment and process route are simple, product Alkali is not needed to be neutralized, and it is substantially pollution-free to environment.But, it is used as oxygen the most frequently used in peroxide oxidation method Agent, hydrogen peroxide is provided generally in the form of hydrogen peroxide, and its commodity concentration is general between 20-50 weight %, so exists A large amount of water are inevitably introduced in reaction system, although water can play a part of solvent, the sulphur of reactant are used as Meltage of the ether in water is still limited, and in order to improve the meltage of thioether, the large usage quantity or needs of water are used cooperatively Organic solvent, this unavoidably reduces the effective treating capacity of device.

The content of the invention

It is an object of the invention to provide a kind of method of oxidizing sulfur ether, this method is conducive to the device improved effectively to handle Amount；This method can also obtain higher thioether rate and desirable oxidation selectivity of product simultaneously.

The invention provides a kind of sulfide oxidation method, the method comprising the steps of (1-1), step (2) and optional step Suddenly (1-2)：

In step (1-1), by isopropylbenzene and oxygen haptoreaction, the catalytic condition causes haptoreaction to obtain Reactant mixture in cumyl hydroperoxide content be more than 1 weight %；

In step (1-2), the reactant mixture that step (1-1) is obtained is mixed with inorganic acid；

In step (2), under conditions of being enough sulfide oxidation, the reactant mixture that will be obtained containing step (1-1) With the raw mixture and HTS haptoreaction of thioether, or the mixture and sulphur that will be obtained containing step (1-2) The raw mixture of ether and HTS haptoreaction.

The method according to the invention, the amount for additionally introducing solvent is low or even can not introduce, and is conducive to improving the effective of device Treating capacity.Also, the method according to the invention can obtain higher thioether rate.Meanwhile, the method according to the invention Higher desirable oxidation selectivity of product can also be obtained.The method according to the invention, what cumene oxidation was formed contains peroxide The reactant mixture of change hydrogen isopropylbenzene need not isolate cumyl hydroperoxide therein and can be used to step (2), on the one hand The loss of material that separation process is caused is reduced, technological process is on the other hand simplified.Using the method for the present invention by thioether During oxidation, directly sulfide oxidation reaction unit is installed additional at the material outlet end of existing isopropyl benzene oxidation unit, it is easy to Implement.

Embodiment

It is " optional " to represent inessential, it can be understood as " with or without ", " including or not including " in the present invention.

In step (1-1), isopropylbenzene and oxygen haptoreaction obtain cumene oxidation containing cumyl hydroperoxide Reactant mixture, the reactant mixture without carry out separation can directly as sulfide oxidation react oxidant use, And result in high thioether rate and desirable oxidation selectivity of product；Unreacted isopropyl in simultaneous reactions mixture Benzene is either still respectively provided with certain dissolubility to thioether to desirable oxidation product, so as to slacken for extra solvent Demand, even without extra solvent, be conducive to improving the effective treating capacity of device.

In the method according to the invention, step (1-1), the reaction mixing that the catalytic condition is typically obtained The content of cumyl hydroperoxide is more than 1 weight % in thing, such as 2-95 weight %, and the content of isopropylbenzene is 99 weight % Hereinafter, such as 5-98 weight %.From the further angle for improving reaction effect, step (1-1), the contact is anti- The condition answered causes the content of cumyl hydroperoxide in obtained reactant mixture to be preferably 10-70 weight %, more preferably 20-60 weight %, more preferably 25-50 weight %；The content of isopropylbenzene is preferably 30-90 weight %, more preferably 40-80 weight %, more preferably 50-75 weight %.

Hydrogen peroxide isopropyl can be obtained by adjusting ratio and catalytic condition between isopropylbenzene and oxygen The content of benzene meets the reactant mixture of above-mentioned requirements.Specifically, the mol ratio of isopropylbenzene and oxygen can be 1：0.1-20, Preferably 1：0.2-10, more preferably 1：0.5-8, more preferably 1：1-5, such as 1：2-4.The haptoreaction It can enter at a temperature of 50-180 DEG C, preferably 80-160 DEG C, more preferably 90-140 DEG C, further preferred 110-130 DEG C OK.The pressure carried out in the catalytic reactor can be in 0-5MPa scope, preferably in 0-3MPa scope It is interior, more preferably in 1-2.5MPa scope, the pressure is in terms of gauge pressure.In the present invention, statement " ×-× scope It is interior " include two endpoint values.

In step (1-1), oxygen can use the oxygen of pure state, can also use oxygen-containing gas.The oxygen-containing gas one As contain oxygen and carrier gas, the carrier gas for example can be nitrogen and/or group 0 element gas (such as argon gas).It is described oxygen-containing The consumption of oxygen typically can be 0.1-99 volume %, more preferably preferably 10-90 volumes %, 15-80 volumes in gas %, more preferably 15-30 volumes %.The oxygen-containing gas can be by the way that pure oxygen is obtained by mixing with carrier gas Gaseous mixture, can also directly use air.

In step (1-1), contact of the isopropylbenzene with oxygen is carried out preferably in the presence of at least one peroxide, described Peroxide plays a part of accelerator, can further improve reaction efficiency, improves the selectivity of cumyl hydroperoxide. The mol ratio of the peroxide and isopropylbenzene can be 0.0001-0.1：1, preferably 0.0005-0.05：1, such as 0.001-0.01：1.The peroxide refers to the compound for containing-O-O- keys in molecular structure, can for hydrogen peroxide and / or organic peroxide, the organic peroxide refers to that one or both of hydrogen peroxide molecule structure hydrogen atom is organic Material formed by substituent group.The instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, tertiary fourth Base hydrogen peroxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, Peracetic acid, Perpropionic Acid, cumyl peroxide, Di-t-butyl peroxide, dibenzoyl peroxide and dilauroyl peroxide.In the present invention, the organic peroxide is preferred

For R₁-O-O-R₂, R₁And R₂It is identical or different, can be each H, C₄-C₁₂Straight or branched alkyl or R₃For C₄-C₁₂Straight or branched alkyl, R₁And R₂It is asynchronously H.

The method according to the invention, step (1-2) is optional step, i.e.,：The reaction that step (1-1) can be obtained Mixture is sent directly into step (2) and thioether and HTS haptoreaction；Step (1-1) can also be obtained Reactant mixture feeding step (1-2) in mix with inorganic acid after, then the mixture feeding step that step (1-2) is obtained Suddenly in (2) with thioether and HTS haptoreaction.The reactant mixture that step (1-1) is obtained is sent directly into step Suddenly in (2), the operation terseness of the inventive method can be improved；The reactant mixture feeding that step (1-1) is obtained In step (1-2), the reactant mixture for then obtaining step (1-2) is sent into step (2), can further be carried The conversion ratio and the selectivity of desirable oxidation product of thioether in high step (2).It should be noted that regardless of whether being walked Suddenly (1-2), as the case may be, the reactant mixture that step (1-1) is obtained can be concentrated or diluted, with Meet the requirement of step (2).

In step (1-2), peroxidating in the reactant mixture that the consumption of inorganic acid can be obtained according to step (1-1) The content of hydrogen isopropylbenzene is selected.Usually, hydrogen peroxide in the reactant mixture that inorganic acid is obtained with step (1-1) The mol ratio of isopropylbenzene can be 0.00001-0.1：1, preferably 0.0001-0.05：1, more preferably 0.001-0.01：1, More preferably 0.001-0.005：1.

From the further angle for improving thioether rate and desirable oxidation selectivity of product in step (2), step (1-1) The mixing of obtained reactant mixture and inorganic acid preferably 20-100 DEG C, more preferably 20-80 DEG C, further preferably exist Carried out at a temperature of 20-60 DEG C (such as 30-50 DEG C).Mixed in the reactant mixture for obtaining step (1-1) with inorganic acid When, the pressure in reactor mixed can be 0-2MPa, preferably 0-0.5MPa, and the pressure is in terms of gauge pressure. The time of the mixing can be typically more than 0.1 hour, and preferably 0.1-5 hours, more preferably 0.5-4 hours (such as 2-4 hours).

The inorganic acid can be more than common various inorganic acids, such as one or both of halogen acids, sulfuric acid and phosphoric acid. Preferably, the inorganic acid is halogen acids, so resulted in step (2) the thioether rate that further improves and Desirable oxidation selectivity of product.It is highly preferred that the inorganic acid is HCl and/or HBr.

The inorganic acid can be provided in form of an aqueous solutions, and the content of inorganic acid can be conventional choosing in the aqueous solution Select, typically can be 20-40 weight %.

In step (2), HTS is the total of a class zeolite of a part of silicon atom in titanium atom substitution lattice framework Claim, chemical formula xTiO can be used₂·SiO₂Represent.The present invention is not limited especially for the content of titanium atom in HTS It is fixed, can be the conventional selection of this area.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, it is more excellent Elect 0.015-0.025 as.

The HTS can be the common HTS with various topological structures, for example：The titanium silicon point Son sieve can for the HTS (such as TS-1) selected from MFI structure, the HTS (such as TS-2) of MEL structures, The HTS (such as Ti-Beta) of BEA structures, the HTS (such as Ti-MCM-22) of MWW structures, six sides The HTS (such as Ti-MCM-41, Ti-SBA-15) of structure, the HTS (such as Ti-MOR) of MOR structures, One in the HTS (such as Ti-TUN) of TUN structures and the HTS (such as Ti-ZSM-48) of other structures Plant or two or more.

Preferably, the HTS be the HTS selected from MFI structure, the HTS of MEL structures, It is more than one or both of the HTS of BEA structures and the HTS of hexagonal structure.It is highly preferred that described HTS is the HTS of MFI structure, such as titanium-silicon molecular sieve TS-1 and/or hollow HTS.It is described Hollow HTS is the HTS of MFI structure, and the crystal grain of the HTS is hollow-core construction, the hollow knot The radical length of the chamber portion of structure is 5-300 nanometers, and the HTS is in 25 DEG C, P/P₀=0.10, adsorption time It is at least 70 milligrams per grams, the suction of the nitrogen absorption under low temperature of the HTS for the benzene adsorbance that is measured under conditions of 1 hour There is hysteresis loop between attached thermoisopleth and desorption isotherm.The hollow HTS is commercially available (such as commercially available The molecular sieve for being HTS from the trade mark of Hunan Jianchang Petrochemical Co., Ltd), can also be according to public in CN1132699C The method opened is prepared.

The method according to the invention, when the HTS uses template in preparation process, the HTS Can be the HTS that experienced the process (such as roasting process) for removed template method, or do not undergo use Can also be both mixtures in the HTS of the process (such as roasting process) of removed template method.

The method according to the invention, at least part HTS is titanium-silicon molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 Surface silicon titanium ratio be not less than body phase silicon titanium ratio, can so obtain the catalytic performance further improved, further extension titanium silicon The single trip use life-span of molecular sieve.Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2. It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5.It is further preferred that the surface Silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5 (such as 2.2-4.5).It is further preferred that the surface silicon titanium Than with the body phase silicon titanium than ratio be 2-3, such as 2.2-2.8.

In the present invention, mol ratio of the silicon titanium than referring to silica and titanium oxide, surface silicon titanium ratio uses x-ray photoelectron energy Spectrometry is determined, and body phase silicon titanium ratio uses x-ray fluorescence spectrometry.

The method according to the invention, from the further catalytic performance for improving HTS and further extends the single trip use longevity The angle of life is set out, and at least part HTS is titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1, which is used, to be included It is prepared by the method for following steps：

(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively supplements water, obtained In dispersion liquid, the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：(0.5-8)：(5-30)： (100-2000), the inorganic silicon source is with SiO₂Meter, the titanium source is with TiO₂Meter, the alkali source template is with OH^-Or N Meter is (in alkali source template Nitrogen element, in terms of N；In alkali source template not Nitrogen element, with OH^-Meter)；

(II) alternatively, the dispersion liquid is stood into 6-24h at 15-60 DEG C；

(III) dispersion liquid that the dispersion liquid or step (II) obtained step (I) is obtained order in sealing reactor Experience stage (1), stage (2) and stage (3) carry out crystallization, and the stage (1) was in 80-150 DEG C of crystallization 6-72 hours (h), the stage (2) is cooled to after not higher than 70 DEG C and residence time at least 0.5h, and the stage (3) is warming up to 120-200 DEG C Crystallization 6-96h again.

The alkali source template can be various templates usually used during synthesis of titanium silicon molecular sieve, for example：Institute It can be more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine to state alkali source template.The quaternary ammonium base Can be various organic level Four ammonium alkali, the aliphatic amine can be various NH₃In at least one hydrogen by aliphatic alkyl The compound formed after (such as alkyl) substitution, the aliphatic hydramine can be various NH₃In at least one hydrogen by containing The compound formed after aliphatic group (such as alkyl) substitution of hydroxyl.

Specifically, the alkali source template can represent for the quaternary ammonium base that is represented selected from Formulas I, Formula II aliphatic amine and formula It is more than one or both of aliphatic hydramine that III is represented.

In Formulas I, R₁、R₂、R₃And R₄Respectively C₁-C₄Alkyl, including C₁-C₄Straight chained alkyl and C₃-C₄'s Branched alkyl, R₁、R₂、R₃And R₄Instantiation can include but is not limited to methyl, ethyl, n-propyl, isopropyl, Normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.

R⁵(NH₂)_n(Formula II)

In Formula II, n is 1 or 2 integer.When n is 1, R⁵For C₁-C₆Alkyl, including C₁-C₆Straight chained alkyl And C₃-C₆Branched alkyl, its instantiation can include but is not limited to methyl, ethyl, n-propyl, isopropyl, just Butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.N is 2 When, R⁵For C₁-C₆Alkylidene, including C₁-C₆Straight-chain alkyl-sub and C₃-C₆Branched alkylidene, its instantiation Methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl can be included but is not limited to.

(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, its instantiation can include but is not limited to methylene, ethylidene, sub- n-propyl and it is sub- just Butyl；M is 1,2 or 3.

The instantiation of the alkali source template can include but is not limited to：TMAH, tetraethyl ammonium hydroxide, TPAOH (includes the various isomers of TPAOH, such as four n-propyl ammonium hydroxide and tetra isopropyl Ammonium hydroxide), TBAH (include the various isomers of TBAH, such as 4-n-butyl ammonium hydroxide With four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, It is more than one or both of diethanol amine and triethanolamine.Preferably, the alkali source template be tetraethyl ammonium hydroxide, It is more than one or both of TPAOH and TBAH.It is highly preferred that the alkali source template is TPAOH.

The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can be with For TiCl₄、Ti(SO₄)₂And TiOCl₂One or both of more than；The organic titanate can be general formula R⁷ ₄TiO₄ The compound of expression, wherein, R⁷For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom, Such as butyl titanate.

The inorganic silicon source can be silica gel and/or Ludox, preferably silica gel.SiO in the Ludox₂Quality hundred It can be more than 10%, preferably more than 15%, more preferably more than 20% to divide content.It is preferable to carry out preparing according to this During the HTS of mode, without using organic silicon source, such as organosilan and organosiloxane.

In the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is preferably 100：(1-6)：(8-25)： (200-1500), more preferably 100：(2-5)：(10-20)：(400-1000).

The dispersion liquid that step (I) is obtained, which can be sent directly into step (III), carries out crystallization.Preferably, by step (I) 6-24h is stood at a temperature of 15-60 DEG C in obtained dispersion liquid feeding step (II).In step (I) and step (III) Between carry out step (II) the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 finally prepared can be significantly improved so that final system The surface silicon titanium ratio of standby HTS is not less than body phase silicon titanium ratio, can so significantly improve the titanium silicon molecule finally prepared The catalytic performance of sieve, extends its single trip use life-span.Usually, by being set between step (I) and step (III) Step (II), the surface silicon titanium of the HTS finally prepared than with body phase silicon titanium than ratio can 1.2-5 scope It is interior, preferably in the range of 1.5-4.5 (such as in the range of 2.2-4.5), more preferably (such as in 2.2-2.8 in the range of 2-3 In the range of).The standing is carried out more preferably at a temperature of 20-50 DEG C, is carried out at a temperature of such as 25-45 DEG C.

In step (II), when being stood, dispersion liquid can be placed in sealing container, unlimited appearance can also be placed in Stood in device.Preferably, step (II) is carried out in sealing container, can so avoid during standing to point Foreign matter is introduced into dispersion liquid or causes moieties volatilization in dispersion liquid to be lost in.

After the completion of step (II) described standing, directly the dispersion liquid through standing can be sent into reactor and carry out crystallization, Crystallization is carried out in feeding reactor after dispersion liquid through standing can also being carried out into redisperse, preferably carries out sending into after redisperse In reactor, the dispersing uniformity for the dispersion liquid for carrying out crystallization so can be further improved.The method of the redisperse can be with For conventional method, such as combination of one or both of stirring, ultrasonically treated and vibration above.The redisperse is held The continuous time is defined so that the dispersion liquid through standing can be made to form uniform dispersion liquid, typically can be 0.1-12h, such as 0.5-2h. The redisperse can be carried out at ambient temperature, be carried out at a temperature of such as 15-40 DEG C.

In step (III), temperature is adjusted can be according to specific use to the heating rate of each phase temperature and rate of temperature fall The type of crystallization device selected, be not particularly limited.In general, temperature is increased into stage (1) crystallization The heating rate of temperature can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By the stage (1) temperature to stage (2) temperature rate of temperature fall can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably For 5-10 DEG C/min.Can be 1-50 DEG C/min by the heating rate of stage (2) temperature to stage (3) temperature, preferably For 2-40 DEG C/min, more preferably 5-20 DEG C/min.

In step (III), the crystallization temperature in stage (1) is preferably 110-140 DEG C, more preferably 120-140 DEG C, is entered One step is preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.Stage (2) Temperature be preferably not higher than 50 DEG C.The residence time in stage (2) is preferably at least 1h, more preferably 1-5h.Stage (3) crystallization temperature is preferably 140-180 DEG C, more preferably 160-170 DEG C.The stage crystallization time of (3) is preferably 12-20h, more preferably 12-16h.

In step (III), in a preferred embodiment, the crystallization temperature in stage (1) is less than the stage (3) Crystallization temperature, so can further improve the catalytic performance of the HTS of preparation.Preferably, the crystallization in stage (1) Temperature is lower 10-50 DEG C than the crystallization temperature in stage (3).It is highly preferred that the crystallization temperature in stage (1) is than stage (3) Crystallization temperature it is low 20-40 DEG C.In step (III), in another preferred embodiment, the crystallization in stage (1) Time is less than the crystallization time in stage (3), so can further improve the catalytic performance of the HTS finally prepared. Preferably, crystallization time short 5-24h of the crystallization time in stage (1) than the stage (3).It is highly preferred that the stage (1) Crystallization time than the stage (3) the short 6-12h of crystallization time, such as short 6-8h.In step (III), both are preferred Embodiment be may be used alone, can also be used in combination, and preferred compositions are used, i.e. stage (1) and stage (3) Crystallization temperature and crystallization time meet the requirement of both preferred embodiments simultaneously.

In step (III), another preferred embodiment in, the temperature in stage (2) is not higher than 50 DEG C, and Residence time is at least 0.5h, such as 0.5-6h, so can further improve the catalytic performance of the HTS finally prepared. Preferably, the residence time in stage (2) is at least 1h, such as 1-5h.This preferred embodiment can be with foregoing two kinds Preferred embodiment it is used separately, can also be applied in combination, preferred compositions are used, be i.e. stage (1) and stage (3) Crystallization temperature and the temperature and residence time in crystallization time and stage (2) simultaneously meet above-mentioned three kinds of preferred embodiments Requirement.

HTS is reclaimed in the mixture that can be obtained using conventional method from step (III) crystallization.Specifically, may be used After alternatively being filtered and washed with the mixture for obtaining step (III) crystallization, solid matter is dried and roasted Burn, so as to obtain HTS.The drying and the roasting can be carried out under normal conditions.Usually, it is described Drying can be in environment temperature (such as 15 DEG C) to carrying out at a temperature of 200 DEG C.The drying can be in environmental pressure (one As be 1 standard atmospheric pressure) under carry out, can also carry out at reduced pressure.The duration of the drying can root Selected, be not particularly limited according to the mode of dry temperature and pressure and drying.For example, in the drying in ring When being carried out under the pressure of border, temperature is preferably 80-150 DEG C, more preferably 100-120 DEG C, and the dry duration is preferably 0.5-5h, more preferably 1-3h.The roasting can be carried out at a temperature of 300-800 DEG C, preferably at 500-700 DEG C At a temperature of carry out, carry out, carried out further preferably at a temperature of 550-600 DEG C more preferably at a temperature of 550-650 DEG C. The duration of the roasting can select according to the temperature being calcined, and typically can be 2-12h, preferably 2-5h.Institute Roasting is stated to carry out preferably in air atmosphere.

The method according to the invention, at least part HTS is preferably modified processing before for step (2). The modification comprises the following steps：Using as the HTS of raw material with containing nitric acid (that is, HNO₃) and at least A kind of modification liquid contact of peroxide.The raw material HTS refers to the titanium silicon molecule as the raw material of modification Sieve, can be the HTS without going through the modification, or live through the modification but need The HTS of the modification is carried out again.The HTS that above-mentioned modification is lived through in the present invention claims For modified HTS, the HTS that above-mentioned modification is not lived through is referred to as unmodified HTS. In step (2), can whole HTSs live through above-mentioned modification, or modified HTS With the mixture of unmodified HTS.Preferably, on the basis of the total amount of HTS described in step (2), At least more than 50 weight % HTS lives through the titanium silicon of the modification, more preferably at least more than 60 weight % Molecular sieve lives through the modification, and such as 60-90 weight % HTS lives through the modification.

In the modification, peroxide can be selected from hydrogen peroxide, hydroperoxides and peracid.At the modification In reason, the instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, ethylbenzene hydroperoxide, the tert-butyl group Hydrogen peroxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxygen Agent is hydrogen peroxide.The hydrogen peroxide can be the hydrogen peroxide existed in a variety of manners commonly used in the art.

Can be 1 as the HTS of raw material and the mol ratio of the peroxide in the modification： 0.01-5, preferably 1：0.05-2, more preferably 1：0.1-1.The consumption of the nitric acid can be according to the peroxide Consumption is selected.Usually, the mol ratio of the peroxide and the nitric acid can be 1：0.01-50, preferably 1： 0.1-20, more preferably 1：0.2-10, more preferably 1：0.5-5, particularly preferably 1：0.6-3.5, such as 1：0.7-3, The HTS is in terms of silica.

In the modification liquid, the concentration of the peroxide and nitric acid can be each 0.1-50 weight %.From further carrying The angle of the catalytic performance of the HTS for the modification that height is finally prepared is set out, preferably 0.5-25 weight %.More preferably In ground, the modification liquid, the concentration of the peroxide and nitric acid is respectively 1-15 weight %.It is further preferred that institute State in modification liquid, the concentration of the peroxide and nitric acid is respectively 2-10 weight %.

The solvent of the modification liquid various can simultaneously dissolve the solvent of nitric acid and the peroxide to be common.It is preferred that Ground, the solvent of the modification liquid is water.

In the modification, it can be carried out as the HTS and modification liquid of raw material at a temperature of 10-350 DEG C Contact.From the angle of the catalytic performance for the HTS for further improving the modification finally prepared, the contact is excellent Contacted at a temperature of being selected in 20-300 DEG C.It is highly preferred that the contact is carried out at a temperature of 50-250 DEG C.Enter one Preferably, the contact is carried out step at a temperature of 60-200 DEG C, is such as contacted at a temperature of 70-170 DEG C.Institute State in modification, the pressure in container that will be contacted as the HTS of raw material with the modification liquid can root Selected according to Contact Temperature, can be environmental pressure, or pressurization.Usually, the titanium silicon point of raw material will be used as The pressure in container that son sieve is contacted with the modification liquid can be 0-5MPa.Preferably, under pressure will Contacted as the HTS of raw material with the modification liquid.It is highly preferred that in closed container under self-generated pressure will make Contacted for the HTS of raw material with the modification liquid.

In the modification, as the HTS of raw material and the exposure level of the modification liquid preferably so that, with On the basis of the HTS of raw material, in ultraviolet-visible spectrum, modified HTS 230-310nm it Between absworption peak peak area reduction by more than 2%, the pore volume of modified HTS reduces more than 1%.Modified titanium silicon The peak area of absworption peak of the molecular sieve between 230-310nm preferably reduces 2-30%, more preferably reduces 2.5-15%, enters one The preferred reduction 3-6% of step.The pore volume of modified HTS preferably reduces 1-20%, more preferably reduces 2-10%, enters one Step is preferred to reduce 2.5-5%.The pore volume is using static determination of nitrogen adsorption.

In the various commercial plants using HTS as catalyst, such as Ammoximation reaction device, hydroxylating In device and epoxidation reaction device, generally plant running for a period of time after, the catalytic activity of catalyst declines, and needs Carry out in device or ex-situ regeneration, even if when carrying out regeneration and also being difficult to obtain satisfied activity, it is necessary to by catalyst from dress Drawn off in putting (that is, more catalyst changeout), and the current processing side of the catalyst (that is, drawing off agent or dead catalyst) drawn off Method is typically that accumulation is buried, and on the one hand occupies the land resource and inventory space of preciousness, the life of another aspect HTS Produce cost higher, directly pass into disuse and also result in great waste.The present inventor has found in research process, If these are drawn off is used in step (2) after agent (that is, the HTS drawn off) is regenerated, remain able to obtain Preferable catalytic performance is obtained, while in continuous running for a long time, showing more preferable activity stability.Therefore, The method according to the invention, at least partly described HTS is preferably used as catalyst through regeneration using HTS Reaction unit (in addition to thioether oxidation unit) draw off agent.It is described that to draw off agent can be from various use HTSs As the agent that draws off drawn off in the reaction unit of catalyst, for example, it can draw off agent for what is drawn off from oxidation reaction apparatus. Specifically, it is described draw off agent for Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation is anti- Answer the one or more drawn off in agent of device.More specifically, described, to draw off agent can be cyclohexanone oxamidinating reaction unit Draw off agent, one kind drawn off in agent or many for drawing off agent and propylene ring oxidation reaction device of phenol hydroxylation reaction unit Kind.

The condition that agent regenerated will be drawn off to be not particularly limited, appropriate selection can be carried out according to the source for drawing off agent, For example：High-temperature roasting and/or solvent washing.

The activity for drawing off agent through regeneration is different according to its source.Usually, the activity for drawing off agent through regeneration can Think the 5-95% of activity (that is, the activity of fresh HTS) of the HTS when fresh.Preferably, The active 10-90% that the activity for drawing off agent through regeneration can be the HTS when fresh, more preferably exists Active 30-50% when fresh.It is that the HTS is active when fresh in the activity for drawing off agent through regeneration During 30-50%, in continuous running for a long time, more preferable activity stability is shown.Preferably, through regeneration Draw off the active 35-45% that the activity of agent is the HTS when fresh.The activity one of the fresh HTS As be more than 90%, usually more than 95%.

The activity is determined by the following method：Respectively agent and fresh HTS will be drawn off as cyclohexanone through regeneration The catalyst of Ammoximation reaction, the condition of the Ammoximation reaction is：HTS, 36 weight % ammoniacal liquor are (with NH₃ Meter), 30 weight % hydrogen peroxide is (with H₂O₂Meter), the tert-butyl alcohol and cyclohexanone in mass ratio 1：7.5：10：7.5：10, At atmosheric pressure 2h is reacted in 80 DEG C.Calculate respectively using through regeneration when drawing off agent and fresh HTS as catalyst The conversion ratio of cyclohexanone, and using it as the activity for drawing off agent and fresh HTS through regeneration, wherein, ring Cyclohexanone that the conversion ratio of hexanone=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/is added rubs You measure] × 100%.

At least part HTS be the reaction unit through regeneration draw off agent when, using the total amount of the HTS as Benchmark, the content that the reaction unit through regeneration draws off agent is preferably more than 5 weight %.The method according to the invention, even if Whole HTSs are that the reaction unit through regeneration draws off agent (that is, the content for drawing off agent of the reaction unit through regeneration is 100 weight %) when, remain able to obtain preferable catalytic effect.

It is particularly preferably in the method according to the invention, the HTS of the modification as the HTS of raw material State and draw off agent through regeneration, the agent that draws off through regeneration is subjected to the modification, can further be improved through regeneration The single trip use life-span of agent is drawn off, and the desirable oxidation selectivity of product for drawing off agent through regeneration can be significantly improved.

In the method according to the invention, step (2), the reactant mixture or step that step (1-1) can be obtained The mixture that (1-2) is obtained is mixed to form slurry with thioether and HTS, to carry out haptoreaction；Can also be by titanium Si molecular sieves are seated in the beds of fixed bed reactors, liquid material is flowed through beds, so as to carry out Haptoreaction.

In step (2), the HTS can be the former powder of HTS, or shaping HTS, Preferably it is molded HTS.The shaping HTS typically contains the HTS and work as active component For the carrier of binding agent, wherein, the content of HTS can be conventional selection.Usually, with the shaping titanium silicon On the basis of the total amount of molecular sieve, the content of HTS can be 5-95 weight %, preferably 10-95 weight %, more Preferably 70-90 weight %；The content of the carrier can be 5-95 weight %, preferably 5-90 weight %, more preferably For 10-30 weight %.The carrier of the shaping HTS can be conventional selection, such as aluminum oxide and/or silica. The method for preparing the shaping HTS is it is known in the art, being no longer described in detail herein.The shaping titanium silicon molecule The granular size of sieve is also not particularly limited, and appropriate selection can be carried out according to concrete shape.Usually, the shaping The average grain diameter of HTS can be 4-10000 microns, and preferably 5-5000 microns, more preferably 40-4000 is micro- Rice, such as 100-2000 microns.The average grain diameter is volume average particle size, can be determined using laser particle analyzer.

In step (2), the HTS is as catalyst, and its consumption, can realize that catalysis is defined Selected with carrying out catalytic concrete mode according to HTS and the liquid material.For example：By titanium silicon Molecular sieve is mixed to form slurry with the liquid material, so that when carrying out haptoreaction, the weight of thioether and HTS Than that can be 0.01-100：1, preferably 1-100：1, more preferably 5-50：1, such as 10-30：1；In titanium silicon molecule When sieve contact with the liquid material is carried out in fixed bed reactors, the weight (hourly) space velocity (WHSV) of thioether can be 0.1-100h^-1, Preferably 20-80h^-1.In the present invention, weight (hourly) space velocity (WHSV) is on the basis of whole HTSs in beds.

The method according to the invention, beds can only load HTS, can also load HTS and Inactive filler.Inactive filler is loaded in beds to be carried out to the amount of HTS in beds Adjustment, so that the speed to reaction is adjusted.When beds contain HTS and inactive filler, urge The content of inactive filler can be 5-95 weight % in agent bed.The inactive filler refers to do not have to oxidation reaction Or the basic filler without catalytic activity, its instantiation can include but is not limited to：Quartz sand, ceramic ring and ceramics are broken One or more in piece.

In step (2), hydrogen peroxide isopropyl in the reactant mixture that the consumption of thioether can be obtained according to step (1-1) The content of cumyl hydroperoxide is selected in the reactant mixture that benzene or step (1-2) are obtained.Usually, thioether Mol ratio with cumyl hydroperoxide can be 1：0.1-10.Furthermore it is also possible to according to the set goal oxidation product pair The mol ratio of thioether and cumyl hydroperoxide is optimized.For example, being that (such as dimethyl is sub- for sulfoxide in desirable oxidation product Sulfone) when, the mol ratio of thioether and cumyl hydroperoxide is preferably 1：0.1-2, such as 1：0.3-2.

The method according to the invention, the thioether can be the various compounds containing-S- keys, and the thioether is preferably selected from carbon Atomicity is 2-18 thioether, such as dimethyl sulfide and/or thioanisole.

In step (2), mixture and thioether that the reactant mixture or step (1-2) that step (1-1) is obtained are obtained Contact with HTS is carried out under conditions of being enough sulfide oxidation.Usually, can 0-120 DEG C, preferably The reactant mixture or step (1-2) for obtaining step (1-1) at a temperature of 20-90 DEG C, more preferably 40-80 DEG C are obtained Mixture and thioether and HTS haptoreaction.The pressure in reactor contacted can 0-5MPa model In enclosing, preferably in the range of 0.1-3.5MPa, such as in the range of 0.3-2MPa, the pressure is in terms of gauge pressure.

The method according to the invention, the reactant mixture that step (2) is obtained contains the desirable oxidation production of sulfide oxidation formation Thing (such as sulfoxide), can be separated using conventional method to it, so that desirable oxidation product (such as sulfoxide) is obtained, point The unreacted reactant separated out can be recycled.

Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.

In following examples and comparative example, agents useful for same is commercial reagent, and pressure is gauge pressure.

In following examples and comparative example, the content of each composition in obtained reaction solution is analyzed using gas-chromatography, herein On the basis of below equation is respectively adopted calculate thioether rate and sulfoxide selectivity.

X_Thioether=[(m^o _Thioether- m_Thioether)/m^o _Thioether] × 100%

Wherein, X_ThioetherRepresent thioether rate；

m^o _ThioetherRepresent the mole of thioether added；

m_ThioetherRepresent the mole of unreacted thioether.

S_Sulfoxide=[n_Sulfoxide/(n^o _Thioether- n_Thioether)] × 100%

Wherein, S_SulfoxideRepresent sulfoxide selectivity；

n^o _ThioetherRepresent the mole of thioether added；

n_ThioetherRepresent the mole of unreacted thioether；

n_SulfoxideRepresent the mole of the sulfoxide of reaction generation.

In following examples and comparative example, static nitrogen adsorption method is respectively adopted and solid ultraviolet-visible diffuses spectrometry to changing The pore volume and ultraviolet absorption peak of HTS before and after property are characterized.Wherein, solid ultraviolet-visible diffusing reflection spectrum (UV-Vis) analysis is carried out on SHIMADZU UV-3100 type ultraviolet-visible spectrometers；Static nitrogen adsorption analysis exists Carried out on the static n2 absorption apparatus of the types of ASAP 2405 of Micromeritics companies.

It is related to drawing off in the embodiment and comparative example of agent through regeneration below, HTS (bag is determined using following methods Include regenerative agent and fresh dose) activity：By HTS, 36 weight % ammoniacal liquor (with NH₃Meter), 30 weight % Hydrogen peroxide (with H₂O₂Meter), the tert-butyl alcohol and cyclohexanone be by weight=1：7.5：10：7.5：In air after 10 mixing In after 80 DEG C of stirring reactions 2 hours under pressure, reactant is filtered, liquid phase analyzed with gas-chromatography, use with Lower formula calculates the conversion ratio of cyclohexanone and as the activity of HTS,

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

In embodiment and comparative example included below the step of prepare HTS, X-ray diffraction is analyzed in Siemens On D5005 type X-ray diffractometers carry out, using sample and authentic specimen between 2 θ is 22.5 ° -25.0 ° the five fingers diffractive features The ratio of diffracted intensity (peak height) sum at peak represents crystallinity of the sample relative to authentic specimen；Fourier transform is red External spectrum analysis is carried out on the type Fourier transformation infrared spectrometers of Nicolet 8210；Silicon titanium ratio refers to silica and titanium oxide Mol ratio, surface silicon titanium is than the ESCALab250 type x-ray photoelectron power spectrums using Thermo Scientific companies Instrument is determined, and body phase silicon titanium ratio is determined using Rigaku Electric Co., Ltd 3271E types Xray fluorescence spectrometer.

Embodiment 1-20 is used for the method for illustrating the present invention.

Embodiment 1

(1-1) is 120 DEG C in temperature by isopropylbenzene and oxygen and pressure is haptoreaction under conditions of 1MPa, is contained There is the reactant mixture of cumyl hydroperoxide, the composition of the reactant mixture is analyzed with gas-chromatography, it is determined that The content of hydrogen oxide isopropylbenzene is 40 weight %.Wherein, the mol ratio of isopropylbenzene and oxygen is 1：3；Oxygen is with oxygenous The form of body is provided, in oxygen-containing gas, and the content of oxygen is 21 volume %, and the content of nitrogen is 79 volume %.

The reactant mixture that (1-2) obtains step (1-1) is with hydrochloric acid (HCl concentration is 36.5 weight %) in high pressure Mixed in reactor, wherein, cumyl hydroperoxide and HCl mol ratio in the reactant mixture that step (1-1) is obtained For 1：0.004, by the temperature control in autoclave be 50 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 standard atmospheric pressure), incorporation time is 3h.

(2) titanium-silicon molecular sieve TS-1 is with reference to Zeolites, 1992, the Vol.12 method system described in the 943-950 pages Standby, specific method is as follows.

(20 DEG C), the TPAOH of 22.5g tetraethyl orthosilicates and 7.0g as template is mixed at room temperature Close, and add 59.8g distilled water, stirring mixing obtains the water of tetraethyl orthosilicate after normal pressure and 60 DEG C of hydrolysis 1.0h Solve solution.With vigorous stirring, it is slowly added into the hydrating solution anhydrous different with 5.0g by 1.1g butyl titanates The solution that propyl alcohol is constituted, stirs 3h at 75 DEG C by gained mixture, obtains clear colloid.This colloid is placed in not Become rusty in steel sealing reactor, constant temperature places 36h at a temperature of 170 DEG C, obtains the mixture of crystallization product.By what is obtained Mixture is filtered, and is collected after obtained solid matter water used wash, in 110 DEG C of dry 1h, is then calcined 6h at 500 DEG C, So as to obtain titanium-silicon molecular sieve TS-1, its titanium oxide content is 2.8 weight %.

The reactant mixture that step (1-2) is obtained is placed in autoclave with dimethyl sulfide and titanium-silicon molecular sieve TS-1 In, it is stirred reaction.Wherein, the weight ratio of dimethyl sulfide and HTS is 12：1, step (1-2) To reactant mixture in cumyl hydroperoxide and dimethyl sulfide mol ratio be 1：1, by autoclave Temperature control is 40 DEG C, is 0.3MPa by Stress control.React after 2h, stop reaction, will be anti-in autoclave Answer mixture to be filtered, obtain liquid material and the HTS reclaimed, analyze the composition of obtained liquid material, Dimethyl sulfide conversion ratio and dimethyl sulfoxide (DMSO) selectivity are calculated, the HTS of recovery is re-fed into step (2) Recycle.Reaction result when titanium-silicon molecular sieve TS-1 is used for the 1st time and the 30th time is listed in table 1.

Embodiment 2

Dimethyl sulfide is aoxidized using method same as Example 1, unlike, without step (1-2), step Suddenly the reactant mixture that (1-1) is obtained is sent directly into step (2).Titanium-silicon molecular sieve TS-1 the 1st time and the 25th time Reaction result when using is listed in table 1.

Embodiment 3

Dimethyl sulfide is aoxidized using method same as Example 1, unlike, in step (2), titanium silicon point Son sieve TS-1 is prepared using following methods.

First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：4： 12：400, silicon source is with SiO₂Meter, titanium source is with TiO₂Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker 24h is stood in room temperature (being 25 DEG C, similarly hereinafter) after being sealed using sealed membrane, is stirred followed by magnetic agitation at 35 DEG C 2h is mixed, is allowed to disperse again.Again the dispersion liquid after disperseing is transferred in sealing reactor, first is undergone at 140 DEG C Stage crystallization 6h, is then cooled to 30 DEG C of experience second stage by mixture and stops after 2h, continue in sealing reactor Phase III crystallization 12h is undergone at a temperature of 170 DEG C (wherein, by the heating of room temperature to first stage crystallization temperature Speed is 2 DEG C/min, is 5 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by the Two-stage treatment temperature to phase III crystallization temperature heating rate be 10 DEG C/min), by gained crystallization product take out after not Through filtering and washing step, 2h directly is dried in 110 DEG C, 3h is then calcined at 550 DEG C, molecular sieve is obtained.Gained The XRD crystalline phases figure of sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), and illustrate to obtain is tool There is the titanium-silicon molecular sieve TS-1 of MFI structure；In FFIR figure, in 960cm^-1Nearby there is absworption peak, Show that titanium has been enter into framework of molecular sieve, in the HTS, titanium oxide content is 3.5 weight %, surface silicon titanium ratio/body Phase silicon titanium ratio is that 2.58 (in HTS prepared by embodiment 1,1.05) surface silicon titanium ratio/body phase silicon titanium ratio is.Titanium Reaction result when silicalite TS-1 is used for the 1st time and the 60th time is listed in table 1.

Embodiment 4

Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), preparing During titanium-silicon molecular sieve TS-1, the crystallization temperature of phase III is also 140 DEG C.The XRD crystalline phases figure of gained sample is with implementing Titanium-silicon molecular sieve TS-1 prepared by the step of example 1 (2) is consistent, and illustrate to obtain is the TS-1 molecules with MFI structure Sieve；In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, should In HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 4.21, and titanium oxide content is 3.1 weight %.HTS Reaction result when TS-1 is used for the 1st time and the 45th time is listed in table 1.

Embodiment 5

Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), preparing During titanium-silicon molecular sieve TS-1, the crystallization temperature of first stage is 110 DEG C.The XRD crystalline phases figure of gained sample and embodiment 1 Titanium-silicon molecular sieve TS-1 prepared by step (2) is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure； In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, the titanium silicon In molecular sieve, surface silicon titanium ratio/body phase silicon titanium ratio is 2.37, and titanium oxide content is 3.2 weight %.Titanium-silicon molecular sieve TS-1 Reaction result when using for the 1st time and the 50th time is listed in table 1.

Embodiment 6

Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), the first rank The crystallization time of section is 12h.The HTS that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1 Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio For 3.78, titanium oxide content is 3.4 weight %.Reaction result when titanium-silicon molecular sieve TS-1 is used for the 1st time and the 45th time Listed in table 1.

Embodiment 7

Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), second-order Section is to be cooled to 70 DEG C of stop 2h.The titanium silicon molecule that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) Sieve that TS-1 is consistent, illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body Phase silicon titanium ratio is 2.75, and titanium oxide content is 3.1 weight %.When titanium-silicon molecular sieve TS-1 is used for the 1st time and the 50th time Reaction result is listed in table 1.

Embodiment 8

Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), second-order Section is to be cooled to 30 DEG C of stop 0.2h.The titanium silicon point that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) Son sieve TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body Phase silicon titanium ratio is 1.14, and titanium oxide content is 2.4 weight %.When titanium-silicon molecular sieve TS-1 is used for the 1st time and the 25th time Reaction result is listed in table 1.

Embodiment 9

Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), without Second stage.The XRD crystalline phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), Illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Nearby occur Absworption peak, shows that titanium has been enter into framework of molecular sieve, in the HTS, and surface silicon titanium ratio/body phase silicon titanium ratio is 1.08, Titanium oxide content is 2.5 weight %.Reaction result when titanium-silicon molecular sieve TS-1 is used for the 1st time and the 25th time is in table 1 List.

Embodiment 10

Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), moisture dissipates Liquid does not stand 24h at room temperature, but is sent directly into reactor and carries out crystallization.The XRD crystalline phases figure and reality of gained sample The titanium-silicon molecular sieve TS-1 for applying the step of example 1 (2) preparation is consistent, and illustrate to obtain is that the TS-1 with MFI structure divides Son sieve；In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, In the HTS, titanium oxide content is 3.5 weight %, and surface silicon titanium ratio/body phase silicon titanium ratio is 1.18.Titanium silicon molecule Reaction result when sieve TS-1 is used for the 1st time and the 40th time is listed in table 1.

Embodiment 11

Dimethyl sulfide is aoxidized using method same as Example 1, unlike, in step (2), titanium silicon point Son sieve TS-1 is modified processing before as catalyst using following methods.

Using as the titanium-silicon molecular sieve TS-1 of the preparation of raw material and containing HNO₃(HNO₃Mass concentration for 10%) and The aqueous solution mixing of hydrogen peroxide (mass concentration of hydrogen peroxide is 7.5%), by obtained mixture in closed container In 70 DEG C of stirring reaction 5h, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid matter Dried at 120 DEG C to constant weight, obtain modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂Meter, titanium silicon The mol ratio of molecular sieve and hydrogen peroxide is 1：0.1.Compared with raw material HTS, the titanium silicon molecule of obtained modification The peak area of absworption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.5%, is surveyed by static nitrogen adsorption method Fixed pore volume reduces 2.6%.Reaction result when titanium-silicon molecular sieve TS-1 is used for the 1st time and the 65th time is listed in table 1.

Embodiment 12

Dimethyl sulfide is aoxidized using with the identical method of embodiment 11, unlike, in modification, it is used as original What is expected is titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 of being drawn off from phenol hydroxylation reaction unit through regeneration Using with the step of embodiment 1 (2) identical method prepare, the titanium-silicon molecular sieve TS-1 drawn off at a temperature of 570 DEG C in 5h is calcined in air atmosphere and is regenerated, the activity after regeneration is 35%, and 96%) activity when fresh is.With raw material titanium silicon Molecular sieve is compared, the peak of the absworption peak in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm Area reduces 3.3%, and 2.8% is reduced by the pore volume of static determination of nitrogen adsorption.Titanium-silicon molecular sieve TS-1 the 1st time and the 75th Secondary reaction result when using is listed in table 1.

Embodiment 13

Dimethyl sulfide is aoxidized using with the identical method of embodiment 12, unlike, it will directly make in embodiment 11 It is used as catalyst for the titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit through regeneration of raw material, i.e., does not enter Row modification.Reaction result when titanium-silicon molecular sieve TS-1 is used for the 1st time and the 60th time is listed in table 1.

Comparative example 1

Dimethyl sulfide is aoxidized using with the step of embodiment 1 (2) identical method, unlike, without step (1-1) and step (1-2), in step (2) using cumyl hydroperoxide cumene solution (in the cumene solution, Cumyl hydroperoxide in the reactant mixture that the concentration of cumyl hydroperoxide is obtained with the step of embodiment 1 (1) it is dense Degree is identical) replace step (1-2) obtained reactant mixture.When titanium-silicon molecular sieve TS-1 is used for the 1st time and the 30th time Reaction result listed in table 1.

Table 1

Embodiment 14

(1-1) (mol ratio of cumyl hydroperoxide and isopropylbenzene is 0.003 by isopropylbenzene and cumyl hydroperoxide：1) It is 110 DEG C in temperature with oxygen and pressure is haptoreaction under conditions of 2.5MPa, obtains containing cumyl hydroperoxide Reactant mixture, is analyzed the composition of the reactant mixture with gas-chromatography, determines the content of cumyl hydroperoxide For 30 weight %.Wherein, the mol ratio of isopropylbenzene and oxygen is 1：2, oxygen is provided in the form of oxygen-containing gas, oxygen-containing In gas, the content of oxygen is 20 volume %, and the content of nitrogen is 80 volume %.

The reactant mixture that (1-2) obtains step (1-1) is with hydrobromic acid (HBr concentration is 30 weight %) in high pressure Mixed in reactor, wherein, cumyl hydroperoxide and HBr mol ratio in the reactant mixture that step (1-1) is obtained For 1：0.001, by the temperature control in autoclave be 35 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 standard atmospheric pressure), incorporation time is 2h.

(2) as raw material HTS be purchased from Hunan Jianchang Petrochemical Co., Ltd the trade mark be HTS sky Heart HTS, its titanium oxide content is 2.5 weight %.

By hollow HTS with containing HNO₃(HNO₃Mass concentration 10%) and hydrogen peroxide (peroxidating for The mass concentration of hydrogen for 5%) the aqueous solution mixing, by obtained mixture in closed container under 120 DEG C of pressure itselfs Stirring reaction 4h, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid matter 120 DEG C dry to constant weight, obtain modified HTS.Wherein, hollow HTS is with SiO₂Meter, HTS Mol ratio with hydrogen peroxide is 1：0.4.Compared with raw material HTS, the HTS of obtained modification The peak area of absworption peak in UV-Vis spectrum between 230-310nm reduces 4.6%, by the hole of static determination of nitrogen adsorption Hold and reduce 3.8%.The mixture of modified hollow HTS and non-modified hollow HTS is (mixed with this On the basis of the total amount of compound, the content of modified hollow HTS is 60 weight %) it is seated in miniature fixed bed reaction In device, beds are formed.

The reactant mixture and dimethyl sulfide that step (1-2) is obtained send into reactor from the entrance positioned at reactor bottom In, flow through beds.Wherein, cumyl hydroperoxide and dimethyl in the reactant mixture that step (1) is obtained The mol ratio of thioether is 1.1：1, it is 40 DEG C by the temperature control in beds, is by the Stress control in reactor 1.5MPa, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 20h^-1。

The composition of the reactant mixture exported from reactor is monitored in course of reaction, dimethyl sulfide conversion ratio and two is calculated Methyl sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 520h and listed in table 2.

Embodiment 15

Using with the identical method cacodyl oxide base thioether of embodiment 14, unlike, what is loaded in beds is Non-modified hollow HTS.

The composition of the reactant mixture exported from reactor is monitored in course of reaction, dimethyl sulfide conversion ratio and two is calculated Methyl sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 350h and listed in table 2.

Embodiment 16

Using with the identical method cacodyl oxide base thioether of embodiment 14, unlike, prepare modified HTS When the raw material that uses be being drawn off from cyclohexanone oxamidinating reaction unit through regeneration hollow HTS (hollow titanium Si molecular sieves and the step of embodiment 14 (2) identical, the hollow titanium drawn off as the source of the hollow HTS of raw material Si molecular sieves are calcined 6h in air atmosphere at a temperature of 550 DEG C and regenerated, and the activity after regeneration is 40%, when fresh Activity for 97%).Compared with raw material HTS, in the UV-Vis spectrum of the HTS of obtained modification The peak area of absworption peak between 230-310nm reduces 4.8%, and 3.5% is reduced by the pore volume of static determination of nitrogen adsorption.

The composition of the reactant mixture exported from reactor is monitored in course of reaction, dimethyl sulfide conversion ratio and two is calculated Methyl sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 620h and listed in table 2.

Embodiment 17

(1-1) is 130 DEG C in temperature by isopropylbenzene and oxygen and pressure is haptoreaction under conditions of 2MPa, is contained There is the reactant mixture of cumyl hydroperoxide, the composition of the reactant mixture is analyzed with gas-chromatography, it is determined that The content of hydrogen oxide isopropylbenzene is 25 weight %.Wherein, the mol ratio of isopropylbenzene and oxygen is 1：2.5；Oxygen is with oxygen-containing The form of gas is provided, in oxygen-containing gas, and the content of oxygen is 25 volume %, and the content of nitrogen is 75 volume %.

The reactant mixture that (1-2) obtains step (1-1) and hydrochloric acid (HCl concentration is 25 weight %) are anti-in high pressure Answer in kettle and mix, wherein, cumyl hydroperoxide and HCl mol ratio are in the reactant mixture that step (1-1) is obtained 1：0.005, by the temperature control in autoclave be 30 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 standard atmospheric pressure), incorporation time is 4h.

(2) titanium-silicon molecular sieve TS-1 used in this step is prepared using following methods.

First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：2： 10：600, silicon source is with SiO₂Meter, titanium source is with TiO₂Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker 10h is stood at 40 DEG C after being sealed using sealed membrane, 0.5h is stirred at 25 DEG C followed by magnetic agitation, is allowed to again It is scattered.Again the dispersion liquid after disperseing is transferred in sealing reactor, first stage crystallization 8h is undergone at 130 DEG C, connects And mixture is cooled to after 50 DEG C of experience second stage stop 5h, continue the temperature in 170 DEG C in sealing reactor and pass through Go through phase III crystallization 16h (wherein, by room temperature to first stage crystallization temperature heating rate be 1 DEG C/min, by First stage crystallization temperature to second stage treatment temperature rate of temperature fall be 10 DEG C/min, by second stage treatment temperature to The heating rate of phase III crystallization temperature is 20 DEG C/min), without filtering and purge step after gained crystallization product is taken out Suddenly, 3h directly is dried in 120 DEG C, 2h is then calcined at 580 DEG C, obtain molecular sieve.The XRD crystalline phases of gained sample Figure is consistent with the titanium-silicon molecular sieve TS-1 of the step of embodiment 1 (2) preparation, and illustrate to obtain is the titanium with MFI structure Silicalite TS-1；In FFIR figure, in 960cm^-1Nearby there is absworption peak, show that titanium has been enter into In framework of molecular sieve, the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.25, and titanium oxide content is 2.6 weight %.

The titanium-silicon molecular sieve TS-1 of preparation is seated in micro fixed-bed reactor, beds are formed.By step The reactant mixture and dimethyl sulfide that (1-2) is obtained flow through and urged from positioned at the entrance of reactor bottom feeding reactor Agent bed.Wherein, cumyl hydroperoxide and dimethyl sulfide in the reactant mixture that step (1-1) is obtained rub You are than being 1：3, it is 60 DEG C by the temperature control in beds, is 1.2MPa by the Stress control in reactor,

The weight (hourly) space velocity (WHSV) of dimethyl sulfide is 40h^-1。

The composition of the reactant mixture exported from reactor is monitored in course of reaction, dimethyl sulfide conversion ratio and two is calculated Methyl sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 500h and listed in table 2.

Table 2

Embodiment 18

(1-1) is 120 DEG C in temperature by isopropylbenzene and oxygen and pressure is haptoreaction under conditions of 1.8MPa, obtains Reactant mixture containing cumyl hydroperoxide, is analyzed the composition of the reactant mixture with gas-chromatography, it is determined that The content of cumyl hydroperoxide is 50 weight %.Wherein, the mol ratio of isopropylbenzene and oxygen is 1：4；Oxygen is with oxygen-containing The form of gas is provided, in oxygen-containing gas, and the content of oxygen is 22 volume %, and the content of argon gas is 78 volume %.

The reactant mixture that (1-2) obtains step (1-1) and hydrochloric acid (HCl concentration is 20 weight %) are anti-in high pressure Answer in kettle and mix, wherein, cumyl hydroperoxide and HCl mol ratio are in the reactant mixture that step (1-1) is obtained 1：0.004, by the temperature control in autoclave be 35 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 standard atmospheric pressure), incorporation time is 2h.

(2) titanium-silicon molecular sieve TS-1 that this step is used is prepared using following methods.

First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：5： 18：1000, silicon source is with SiO₂Meter, titanium source is with TiO₂Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker After middle utilization sealed membrane sealing 8h is stood at 45 DEG C；Dispersion liquid through standing is transferred in sealing reactor, at 140 DEG C First stage crystallization 6h is undergone, mixture then is cooled into 40 DEG C of experience second stage stops after 1h, continues in sealing Phase III crystallization 12h is undergone (wherein, by room temperature to first stage crystallization temperature at a temperature of 160 DEG C in reactor The heating rate of degree is 5 DEG C/min, is to the rate of temperature fall of second stage treatment temperature by first stage crystallization temperature 5 DEG C/min, be 5 DEG C/min by the heating rate of second stage treatment temperature to phase III crystallization temperature), by gained crystallization Without filtering and washing step after product taking-up, 2h directly are dried in 110 DEG C, then 3h are calcined at 550 DEG C, obtained Molecular sieve.The XRD crystalline phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), says It is bright that obtain is the titanium-silicon molecular sieve TS-1 with MFI structure；In FFIR figure, in 960cm^-1It is attached Closely there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.71, titanium oxide content is 4.3 weight %.

The titanium-silicon molecular sieve TS-1 of preparation is seated in micro fixed-bed reactor, beds are formed.By step The mixture and thioanisole that (1-2) is obtained flow through catalyst bed from positioned at the entrance of reactor bottom feeding reactor Layer.Wherein, the mol ratio of cumyl hydroperoxide and thioanisole in the reactant mixture that step (1) is obtained is 2：1, By the temperature control in beds be 80 DEG C, by the Stress control in reactor be 2MPa, thioanisole it is heavy when Air speed is 80h^-1。

The composition of the reactant mixture exported from reactor is monitored in course of reaction, thioanisole conversion ratio and benzene first is calculated Sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 450h and listed in table 3.

Embodiment 19

Thioanisole is aoxidized using with the identical method of embodiment 18, unlike, the titanium-silicon molecular sieve TS-1 of preparation Before as catalyst, processing is modified using following methods.

By the titanium-silicon molecular sieve TS-1 of preparation with containing HNO₃(HNO₃Mass concentration 10%) and hydrogen peroxide (mistake for The mass concentration of hydrogen oxide is aqueous solution mixing 2%), and obtained mixture is stirred into anti-at 170 DEG C in closed container 2.5h is answered, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid matter in 120 DEG C of dryings To constant weight, modified HTS is obtained.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂Meter, HTS and mistake The mol ratio of hydrogen oxide is 1：1.Through characterizing, compared with raw material HTS, the HTS of obtained modification The peak area of absworption peak in UV-Vis spectrum between 230-310nm reduces 5.7%, by the hole of static determination of nitrogen adsorption Hold and reduce 4.1%.

The composition of the reactant mixture exported from reactor is monitored in course of reaction, thioanisole conversion ratio and benzene first is calculated Sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 550h and listed in table 3.

Embodiment 20

Thioanisole is aoxidized using with the identical method of embodiment 19, unlike, what it is as raw material is through regeneration (titanium-silicon molecular sieve TS-1 is used and embodiment 18 titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit Prepared by step (2) identical method, the titanium-silicon molecular sieve TS-1 drawn off is calcined at a temperature of 580 DEG C in air atmosphere 4h and regenerate, the activity after regeneration is 40%, and 95%) activity when fresh is.Compared with raw material HTS, obtain To modification HTS UV-Vis spectrum in the peak area of absworption peak between 230-310nm reduce 5.5%, 4.3% is reduced by the pore volume of static determination of nitrogen adsorption.

The composition of the reactant mixture exported from reactor is monitored in course of reaction, thioanisole conversion ratio and benzene first is calculated Sulfoxide selectivity, wherein, reaction proceeds to the reaction result obtained during 2h and 660h and listed in table 3.

Table 3

The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, can carry out a variety of simple variants to technical scheme, These simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned embodiment, in not contradiction In the case of, it can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is to various Possible combination no longer separately illustrates.

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 equally be considered as content disclosed in this invention.

Claims

1. a kind of sulfide oxidation method, the method comprising the steps of (1-1), step (2) and optional step (1-2)：

2. according to the method described in claim 1, wherein, in step (1-1), the catalytic condition causes In obtained reactant mixture the content of cumyl hydroperoxide be 2-95 weight %, preferably 10-70 weight %, it is more excellent Elect 20-60 weight %, more preferably 25-50 weight % as；The content of isopropylbenzene is 5-98 weight %, preferably 30-90 Weight %, more preferably 40-80 weight %, more preferably 50-75 weight %.

3. method according to claim 1 or 2, wherein, in step (1-1), mole of isopropylbenzene and oxygen Than for 1：0.1-20, preferably 1：0.2-10, more preferably 1：0.5-8, more preferably 1：1-5, the contact Reaction is 50-180 DEG C, preferably 80-160 DEG C, more preferably 90-140 DEG C in temperature, and pressure is 0-5MPa, preferably To be carried out under conditions of 0-3MPa, more preferably 1-2.5MPa, the pressure is in terms of gauge pressure.

4. the method according to any one in claim 1-3, wherein, in step (1-2), inorganic acid and mistake The mol ratio of hydrogen oxide isopropylbenzene is 0.00001-0.1：1, preferably 0.0001-0.05：1, more preferably 0.001-0.01： 1, more preferably 0.001-0.005：1.

5. the method according to any one in claim 1-4, wherein, it is described to be blended in step (1-2) Temperature be 20-100 DEG C, be preferably 20-80 DEG C, more preferably 20-60 DEG C, and pressure be 0-2MPa under conditions of enter OK, the pressure is in terms of gauge pressure；The time of the mixing is 0.1-5 hours, more preferably preferably 0.5-4 hours, 2-4 Hour.

6. the method according to any one in claim 1-5, wherein, in step (1-2), the inorganic acid For HCl and/or HBr.

7. the method according to any one in claim 1-6, wherein, in step (2), at least part titanium silicon Molecular sieve is the HTS of the modification of experience modification, and the modification is including will be used as the titanium silicon molecule of raw material Sieve is contacted with the modification liquid containing nitric acid and at least one peroxide.

8. method according to claim 7, wherein, in the modification, it is used as the titanium silicon molecule of raw material The mol ratio of sieve and the peroxide is 1：0.01-5, preferably 1：0.05-2, more preferably 1：0.1-1, the mistake The mol ratio of oxide and the nitric acid is 1：0.01-50, preferably 1：0.1-20, more preferably 1：0.2-10, enters one Step is preferably 1：0.5-5, the HTS is in terms of silica.

9. the method according to claim 7 or 8, wherein, in the modification liquid, peroxide and nitric acid it is dense Degree is respectively 0.1-50 weight %, more preferably preferably 0.5-25 weight %, more preferably 1-15 weight %, 2-10 Weight %.

10. the method according to any one in claim 7-9, wherein, in the modification, it is used as original The HTS of material and the modification liquid 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, it is further excellent Contacted at a temperature of selecting 60-200 DEG C, the contact in 0-5MPa container in pressure to carry out, and the pressure is Gauge pressure.

11. method according to any one of claims of claim 7-10, wherein, in the modification liquid, the peroxidating Thing is hydrogen peroxide.

12. the method according to any one in claim 7-11, wherein, in the modification, it is used as original The exposure level of the HTS of material and the modification liquid causes, using on the basis of the HTS as raw material, in purple In outside-visible spectrum, the peak area reduction by more than 2% of the absworption peak of modified HTS between 230-310nm, It is preferred that reducing 2-30%, 2.5-15% is more preferably reduced, 3-6% is further preferably reduced, the hole of modified HTS Hold and reduce more than 1%, preferably reduce 1-20%, more preferably reduce 2-10%, further preferably reduce 2.5-5%, the hole Hold using static determination of nitrogen adsorption.

13. the method according to any one in claim 7-12, wherein, using the total amount of the HTS as Benchmark, the content of the HTS of the modification is more than 50 weight %.

14. the method according to any one in claim 1-13, wherein, in step (2), at least part titanium Si molecular sieves are titanium-silicon molecular sieve TS-1, and the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 is not less than body phase silicon titanium ratio, institute Mol ratio of the silicon titanium than referring to silica and titanium oxide is stated, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, The body phase silicon titanium ratio uses x-ray fluorescence spectrometry；

Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2；

It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5；

It is further preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5；

It is further preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 2-3.

15. the method according to any one in claim 1-14, wherein, in step (2), at least part titanium Si molecular sieves are titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1 is prepared using the method comprised the following steps：

(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively supplements water, obtained In dispersion liquid, the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：(0.5-8)：(5-30)： (100-2000), the inorganic silicon source is with SiO₂Meter, the titanium source is with TiO₂Meter, the alkali source template is with OH^-Or N Meter；

(II) alternatively, the dispersion liquid is stood 6-24 hours at 15-60 DEG C；

(III) dispersion liquid that the dispersion liquid or step (II) obtained step (I) is obtained order in sealing reactor Experience stage (1), stage (2) and stage (3) to carry out crystallization, the stage (1) 80-150 DEG C, preferably 110-140 DEG C, More preferably at 120-140 DEG C, further preferably in 130-140 DEG C of crystallization 6-72 hours, preferably 6-8 hours；Stage (2) It is cooled to not higher than 70 DEG C and the residence time is at least 0.5 hour, preferably 1-5 hours；Stage (3) is warming up to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170 DEG C, then crystallization 6-96 hours, preferably 12-20 hours.

16. method according to claim 15, wherein, stage (1) and stage (3) are met in following condition One of or both：

Condition 1：The crystallization temperature in stage (1) is less than the crystallization temperature in stage (3), it is preferable that the crystalline substance in stage (1) Change temperature lower 10-50 DEG C than the crystallization temperature in stage (3), it is preferably low 20-40 DEG C；

Condition 2：The crystallization time in stage (1) is less than the crystallization time in stage (3), it is preferable that the crystalline substance in stage (1) The change time is shorter 5-24 hours than the crystallization time in stage (3), preferably short 6-12 hours.

17. the method according to claim 15 or 16, wherein, the stage (2) is cooled to not higher than 50 DEG C, and Residence time is at least 1 hour.

18. the method according to any one in claim 15-17, wherein, the titanium source be inorganic titanium salt and/ Or organic titanate；The alkali source template is more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine, Preferably quaternary ammonium base, more preferably TPAOH；The inorganic silicon source is silica gel and/or Ludox；

Preferably, the inorganic titanium salt is TiCl₄、Ti(SO₄)₂And TiOCl₂One or both of more than；It is described organic Titanate esters are selected from general formula R⁷ ₄TiO₄The compound of expression, R⁷Selected from the alkyl with 2-4 carbon atom.

19. the method according to any one in claim 1-18, wherein, at least part HTS is derived from At least one reaction unit draws off agent, described to draw off agent and draw off agent, hydroxylating device for Ammoximation reaction device Draw off agent and epoxidation reaction device draw off agent.

20. the method according to any one in claim 1-19, wherein, the thioether be dimethyl sulfide and/ Or thioanisole.

21. the method according to any one in claim 1-20, wherein, in step (2), step (1-1) The mol ratio of cumyl hydroperoxide and thioether in obtained reactant mixture is 0.1-10：1, preferably 0.1-2：1.

22. the method according to any one in claim 1-21, wherein, in step (2), the contact is anti- It should be 0-120 DEG C in temperature, be preferably 20-90 DEG C, be more preferably 40-80 DEG C, and pressure is 0-5MPa, is preferably Carried out under conditions of 0.1-3.5MPa, the pressure is in terms of gauge pressure.