CN106631931A

CN106631931A - Thioether oxidation method

Info

Publication number: CN106631931A
Application number: CN201510725869.7A
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: 2015-10-29
Filing date: 2015-10-29
Publication date: 2017-05-10
Anticipated expiration: 2035-10-29
Also published as: CN106631931B

Abstract

The invention discloses a thioether oxidation method. The method comprises the following steps: (1-1), ethylbenzene and oxygen are subjected to a contact reaction, and the content of EBHP in a reaction mixture obtained by the contact reaction under contact reaction condition is more than 1 weight%; optional (1-2), the reaction mixture in the step (1-1) is mixed with inorganic acid; (2), under condition that thioether is oxidized, a raw material mixture containing the reaction mixture obtained in the step (1-1) and thioether is subjected to a contact reaction with a titanium silicon molecular sieve, or a raw material mixture containing the mixture in the step (1-2) and thioether is subjected to the contact reaction with the titanium silicon molecular sieve. The method is in favor of increasing effective processing amount of equipment, and can obtain high thioether conversion rate and target oxidation product selectivity. The method can directly install a thioether oxidation reaction apparatus at a material outlet end of a current ethylbenzene oxidation apparatus, and is easy to carry out.

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) is a kind of organic compounds containing sulfur, It is colourless transparent liquid under room temperature, with the characteristic such as highly polar, high-hygroscopicity, flammable and high boiling point 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 examination Agent.Also, dimethyl sulfoxide has very high selective extraction method ability, can be used as alkane extraction detached with aromatic hydrocarbon molten Agent, for example：Dimethyl sulfoxide can be used for the extracting of aromatic hydrocarbons or butadiene, as process solvent in acrylonitrile polymerization reaction With the solvent that reels off raw silk from cocoons, the synthetic and the solvent that reels off raw silk from cocoons as polyurethane, as polyamide, fluoroaluminate glasses, polyimides and The synthetic of polysulfones.Meanwhile, in medical industry, dimethyl sulfoxide not only can be directly as the raw material of some drugses 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 also can be extracted as capacitor dielectric, antifreezing agent, brake fluid, rare metal Agent etc..

Sulfoxide type is typically prepared using sulfide oxidation method, according to the difference of the oxidant and mode of oxidizing for being used, is generally wrapped Include nitric acid oxidation method, peroxide oxidation method, Ozonation, anodizing and nitrogen dioxide oxidizing process.Nitric Acid Oxidation The deficiency that change method is present is that reaction is wayward, and equipment corrosion is serious, while environmental pollution is heavier.Ozone oxidation rule There is a problem of that dimethyl sulfide conversion ratio is low.Anodizing is unsuitable for extensive enforcement.Nitrogen dioxide oxidation rule is deposited In the problem of environmental pollution.The reaction condition of peroxide oxidation method is gentle, and equipment and process route are simple, and product is not required to Alkali is wanted to be neutralized, and it is substantially pollution-free to environment.But, as oxidant the most frequently used in peroxide oxidation method, Hydrogen peroxide is provided generally in the form of hydrogen peroxide, its commodity concentration typically between 20-50 weight %, so in reactant A large amount of water are inevitably introduced in system, although water can play a part of solvent, as reactant thioether in water In meltage it is still limited, in order to improve the meltage of thioether, the large usage quantity of water or need with the use of organic molten Agent, 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, the method is conducive to the device effective process for improving Amount；The 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 walk Suddenly (1-2)：

In step (1-1), ethylbenzene and oxygen haptoreaction, the catalytic condition are caused into what haptoreaction was obtained In reactant mixture, the content of ethylbenzene hydroperoxide is more than 1 weight %；

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

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

The method according to the invention, the amount for additionally introducing solvent are low or even can not introduce, and are conducive to the device for improving effective 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, ethylbenzene oxidation formed containing ethylbenzene mistake The reactant mixture of hydrogen oxide need not be isolated ethylbenzene hydroperoxide therein and can be used for step (2), on the one hand reduce The loss of material that separation process is caused, on the other hand simplifies technological process.During using the method for the present invention by sulfide oxidation, Directly sulfide oxidation reaction unit is installed additional at the material outlet end of existing ethylbenzene oxidation device, it is easy to implement.

Specific embodiment

In step (1-1), by ethylbenzene and oxygen haptoreaction, the catalytic condition causes the reaction for obtaining to mix In thing, the content of ethylbenzene hydroperoxide is more than 1 weight %；

In the present invention, " optional " and " alternatively " represents inessential, it can be understood as " with or without ", " include Or do not include ".

In step (1-1), by ethylbenzene and oxygen haptoreaction, ethylbenzene oxidation is obtained into the reaction containing ethylbenzene hydroperoxide Mixture, the reactant mixture are used directly as the oxidant that sulfide oxidation reacts by need not being separated, and energy High thioether rate and desirable oxidation selectivity of product are obtained enough；In simultaneous reactions mixture, unreacted ethylbenzene is either Still certain dissolubility is respectively provided with to desirable oxidation product to thioether, so as to slacken for the demand of extra solvent, Even without extra solvent, be conducive to improving the effective treating capacity of device.

The method according to the invention, in step (1-1), the reaction mixing that the catalytic condition is typically obtained In thing, the content of ethylbenzene hydroperoxide is more than 1 weight %, such as 2-95 weight %, and the content of ethylbenzene is below 99 weight %, Such as 5-98 weight %.From the angle for further improving reaction effect, in step (1-1), the catalytic bar Part causes the content of ethylbenzene hydroperoxide in the reactant mixture for obtaining to be preferably 3-60 weight %, more preferably 4-30 weight %, more preferably 8-20 weight %, the content of ethylbenzene are preferably 40-97 weight %, more preferably 70-96 weight %, More preferably 80-92 weight %.

Ethylbenzene hydroperoxide can be obtained by adjusting ratio and catalytic condition between ethylbenzene and oxygen Content meets the reactant mixture of above-mentioned requirements.Specifically, ethylbenzene and the mol ratio of oxygen can be 1：0.1-20, preferably For 1：0.2-10, more preferably 1：0.5-5, such as 1：0.8-2.The haptoreaction can be in 50-180 DEG C, preferred 80-160 DEG C, carry out at a temperature of more preferably 90-140 DEG C.The pressure carried out in the catalytic reactor can be in 0-5MPa Scope, preferably in the scope of 0-3MPa, 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, it is also possible to use oxygen-containing gas.The oxygen-containing gas one As contain oxygen and carrier gas, the carrier gas can for example be nitrogen and/or group 0 element gas (such as argon).It is described oxygen-containing In gas, the consumption of oxygen can typically be 0.1-99 volumes %, preferably 10-90 volumes %, more preferably 15-80 volumes %, more preferably 15-30 volumes %.The oxygen-containing gas can be by pure oxygen is obtained by mixing with carrier gas Gaseous mixture, it is also possible to directly using air.

In step (1-1), ethylbenzene is preferably carried out in the presence of at least one peroxide with the contact of oxygen, the mistake Oxide plays a part of accelerator, can further improve reaction efficiency, improves the selectivity of ethylbenzene hydroperoxide.Institute The mol ratio that peroxide is stated with ethylbenzene 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 containing-O-O- keys in molecular structure, can be hydrogen peroxide and/or organic peroxy Compound, the organic peroxide refer in hydrogen peroxide molecule structure one or two hydrogen atom replaced by organic group and The material of formation.The instantiation of the peroxide can be including but not limited to：Hydrogen peroxide, tert-butyl hydroperoxide, Ethylbenzene hydroperoxide, cumyl hydroperoxide, peracetic acid, Perpropionic Acid, cumyl peroxide, two uncle of peroxidating Butyl, dibenzoyl peroxide and dilauroyl peroxide.In the present invention, the organic peroxide is preferably R₁-O-O-R₂, R₁And R₂It is identical or different, can be each H, C₄-C₁₂Straight or branched alkyl orR₃For C₄-C₁₂ Straight or branched alkyl, R₁And R₂It is asynchronously H.

The method according to the invention, step (1-2) are optional step, i.e.,：The reaction that step (1-1) can be obtained Mixture is sent directly in step (2) and thioether and HTS haptoreaction；Step (1-1) can also be obtained Reactant mixture send into step (1-2) in mix with mineral acid after, then the mixture that step (1-2) is obtained sends into and walks Suddenly in (2) with thioether and HTS haptoreaction.The reactant mixture that step (1-1) is obtained is sent directly into into step Suddenly the operation terseness of the inventive method can in (2), be improved；The reactant mixture that step (1-1) is obtained is sent into In step (1-2), the reactant mixture for then obtaining step (1-2) is sent in step (2), further can 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 is diluted, with Meet the requirement of step (2).

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

From the angle for further improving thioether rate and desirable oxidation selectivity of product in step (2), step (1-1) The mixing of the reactant mixture that obtains and mineral acid preferably 20-100 DEG C, more preferably 20-80 DEG C, further preferably exist Carry out at a temperature of 20-60 DEG C (such as 30-40 DEG C).The reactant mixture that step (1-1) is obtained is being mixed with mineral acid When, the pressure in reactor for being 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 be (such as 2-4 hours).

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

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

In step (2), HTS is the total of the class zeolite that titanium atom replaces a part of silicon atom in lattice framework Claim, chemical formula xTiO can be used₂·SiO₂Represent.The present invention is not especially limited 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 structure, for example：The titanium silicon point Son sieve can be selected from the HTS (such as TS-1) of 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, In the HTS (such as Ti-ZSM-48) of the HTS (such as Ti-TUN) and other structures of TUN structures one Plant or two or more.

Preferably, the HTS be selected from the HTS of MFI structure, the HTS of MEL structures, One or more in the HTS of the HTS and hexagonal structure of BEA structures.It is highly preferred that described HTS of the HTS for MFI structure, such as titanium-silicon molecular sieve TS-1 and/or hollow HTS.It is described HTS of the hollow HTS for MFI structure, 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 Benzene adsorbance to measure under conditions of 1 hour is at least 70 milligrams per grams, the suction of the nitrogen absorption under low temperature of the HTS There is hysteresis loop between attached isothermal line and desorption isotherm.The hollow HTS is commercially available (such as commercially available Molecular sieve from the trade mark of Hunan Jianchang Petrochemical Co., Ltd is HTS), it is also possible to according to public in CN1132699C The method opened is prepared.

The method according to the invention, at least part of HTS be 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, the catalytic performance that so further can be improved further extends titanium silicon The single trip use life-span of molecular sieve.Preferably, the surface silicon titanium ratio and the ratio of the body phase silicon titanium ratio are more than 1.2. It is highly preferred that the surface silicon titanium ratio is 1.2-5 with the ratio of the body phase silicon titanium ratio.It is further preferred that the surface Silicon titanium ratio is 1.5-4.5 with the ratio of the body phase silicon titanium ratio (such as 2.5-4.5).It is further preferred that the surface silicon titanium Than being 2-3 with the ratio of the body phase silicon titanium ratio.

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

The method according to the invention, extends the single trip use longevity from the catalytic performance for further improving HTS and further The angle of life is set out, and at least part of HTS is titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1 is adopted 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 Dispersion liquid, in 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) for obtaining step (I) is obtained order in sealed reactor Experience stage (1), stage (2) and stage (3) carry out crystallization, and the stage (1) is in 80-150 DEG C of crystallization 6-72 hour H (), after the stage (2) is cooled to not higher than 70 DEG C and the time of staying at least 0.5h, the stage (3) is warming up to 120-200 DEG C Crystallization 6-96h again.

The alkali source template can be the various template that are usually used during synthesis of titanium silicon molecular sieve, for example：Institute State alkali source template can be quaternary ammonium base, aliphatic amine and aliphatic hydramine in one or more.The quaternary ammonium base Can be various organic level Four ammonium alkali, the aliphatic amine can be various NH₃At least one of hydrogen by aliphatic alkyl The compound that (such as alkyl) is formed after replacing, the aliphatic hydramine can be various NH₃At least one of hydrogen contained The compound that the aliphatic group (such as alkyl) of hydroxyl is formed after replacing.

Specifically, the alkali source template can be the aliphatic amine and formula that the quaternary ammonium base that represents selected from Formulas I, Formula II are represented One or more in the 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-pro-pyl, 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-pro-pyl, 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-pro-pyl, 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 just can include but is not limited to methylene, ethylidene, sub- n-pro-pyl and Asia Butyl；M is 1,2 or 3.

The instantiation of the alkali source template can be including but not limited to：Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH (includes the various isomers of TPAOH, such as four n-pro-pyl 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, monoethanolamine, One or more in diethanolamine and triethanolamine.Preferably, the alkali source template be tetraethyl ammonium hydroxide, One or more in 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 TiOCl₂In one or more；The organic titanate can be general formula R⁷ ₄TiO₄ The compound of expression, wherein, R⁷It is the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom.

The inorganic silicon source can be silica gel and/or Ludox, preferably silica gel.SiO in the Ludox₂Quality hundred Divide content be more than 10%, preferably more than 15%, more preferably more than 20%.It is preferable to carry out according to this preparing During the HTS of mode, organic silicon source, such as organosilan and organosiloxane are not used.

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 carries out crystallization in being sent directly into step (III).Preferably, by step (I) The dispersion liquid for obtaining stands 6-24h in sending into step (II) at a temperature of 15-60 DEG C.In step (I) and step (III) Between carry out the surface silicon titanium ratio that step (II) can significantly improve the titanium-silicon molecular sieve TS-1 of final preparation so that it is final to make 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 of final preparation The catalytic performance of sieve, extends its single trip use life-span.Usually, by arranging between step (I) and step (III) Step (II), the surface silicon titanium ratio of the final HTS for preparing can be in the scopes of 1.2-5 with the ratio of body phase silicon titanium ratio It is interior, preferably in the range of 1.5-4.5 (such as in the range of 2.5-4.5), more preferably in the range of 2-3.It is described quiet Putting more preferably is carried out 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, it is also possible to be placed in unlimited appearance Stood in device.Preferably, step (II) is carried out in sealing container, can so avoid during standing to point Moieties volatilization in foreign matter being introduced in dispersion liquid or causing dispersion liquid is lost in.

After the completion of step (II) standing, the dispersion liquid that directly can be stood Jing carries out crystallization in sending into reactor, Dispersion liquid Jing standing can also be carried out sending in reactor after redispersion and carry out crystallization, be sent into after preferably carrying out redispersion In reactor, the dispersing uniformity of the dispersion liquid for carrying out crystallization so can be further improved.The method of the redispersion can be with For conventional method, such as one or more the combination in stirring, supersound process and vibration.The redispersion is held The continuous time is defined so that the dispersion liquid that Jing stands can be made to form uniform dispersion liquid, can typically be 0.1-12h, such as 0.5-2h. The redispersion 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 to the heating rate and rate of temperature fall of each phase temperature and can be adopted according to concrete The type of crystallization device selected, be not particularly limited.In general, temperature is increased to 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, enters 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 time of staying 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。

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) Crystallization time of the time less than the stage (3), so can further improve the catalytic performance of the HTS of final preparation. Preferably, the crystallization time in stage (1) 5-24h shorter than the crystallization time in stage (3).It is highly preferred that the stage (1) Crystallization time 6-12h shorter than the crystallization time in stage (3), such as short 6-8h.In step (III), both are preferred Embodiment may be used alone, can also be used in combination, preferred compositions use, i.e. stage (1) and stage (3) Crystallization temperature and crystallization time meet the requirement of both preferred implementations simultaneously.

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

HTS can be reclaimed in adopting the mixture that obtains from step (III) crystallization of conventional method.Specifically, may be used After the mixture that step (III) crystallization is obtained alternatively is filtered and be washed, solid matter is dried and is 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 carried out at a temperature of 200 DEG C in ambient temperature (such as 15 DEG C).The drying can be in ambient pressure ( As be 1 normal atmosphere) under carry out, it is also possible to carry out at reduced pressure.The persistent period of the drying can be with root Selected according to the mode of dry temperature and pressure and drying, be not particularly limited.For example, in the drying in ring When carrying out under the pressure of border, temperature is preferably 80-150 DEG C, and more preferably 100-120 DEG C, the dry persistent period 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, more preferably carry out at a temperature of 550-650 DEG C, further preferably carry out at a temperature of 550-600 DEG C. The persistent period of the roasting can be selected according to the temperature for carrying out roasting, can typically be 2-12h, preferably 2-5h.Institute Stating roasting is carried out preferably in air atmosphere.

The method according to the invention, at least part of HTS were preferably modified process before for step (2). The modification is comprised the following steps：Using the HTS as raw material and 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 of the raw material as modification Sieve, can be without the HTS for going through the modification, or lives through the modification but needs The HTS of the modification is carried out again.The HTS that above-mentioned modification is lived through in the present invention claims For the HTS being modified, the HTS referred to as unmodified HTS of above-mentioned modification is not lived through. 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), HTSs more than at least 50 weight % lives through the modification, titanium silicon more than more preferably at least 60 weight % Molecular sieve lives through the modification, as the HTS of 50-90 weight % lives through the modification.

In the modification, peroxide can be selected from hydrogen peroxide, hydroperoxides and peracid.At the modified place In reason, the instantiation of the peroxide can be including but 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 commonly used in the art hydrogen peroxide for existing in a variety of manners.

In the modification, can be 1 as the mol ratio of HTS and the peroxide of raw material： 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 peroxide and the mol ratio of 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 silicon dioxide.

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 high final modified HTS for preparing is set out, preferably 0.5-25 weight %.More preferably Ground, in 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 can be the common various solvents that can dissolve nitric acid and the peroxide simultaneously.It is preferred that Ground, the solvent of the modification liquid is water.

In the modification, can carry out at a temperature of 10-350 DEG C as the HTS and modification liquid of raw material Contact.From the angle of the catalytic performance for further improving the final modified HTS for preparing, the contact is excellent It is selected at a temperature of 20-300 DEG C and is contacted.It is highly preferred that the contact is carried out at a temperature of 50-250 DEG C.Enter one Step preferably, the contact at a temperature of 70-200 DEG C under carry out, such as contacted at a temperature of 70-170 DEG C. In the modification, the pressure in container contacted with the modification liquid by the HTS as raw material can be with Selected according to Contact Temperature, can be ambient pressure, or pressurization.Usually, using the titanium silicon as raw material The pressure in container contacted with the modification liquid by molecular sieve can be 0-5MPa.Preferably, under pressure Contact the HTS as raw material with the modification liquid.It is highly preferred that will under self-generated pressure in hermetic container Contact with the modification liquid as the HTS of raw material.

In the modification, as the HTS of raw material with the exposure level of the modification liquid preferably so that, with On the basis of as the HTS of raw material, in ultraviolet-visible spectrum, modified HTS 230-310nm it Between the peak area of absworption peak reduce 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 3-15%, enters one Step is preferred to reduce 3.5-6%.The pore volume of modified HTS preferably reduces 1-20%, more preferably reduces 2-10%, enters One step preferably reduces 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, hydroxylating and ring In oxidation reaction apparatus, generally plant running for a period of time after, the catalysis activity of catalyst declines, and needs to carry out device Interior or ex-situ regeneration, though when carry out regenerating also be difficult to obtain satisfied active when, need catalyst is drawn off from device (that is, more catalyst changeout), and catalyst (that is, drawing off agent or dead catalyst) the current processing method for drawing off is typically Pile up bury, on the one hand occupy preciousness land resource and inventory space, another aspect HTS production cost compared with Height, directly passes into disuse and also result in greatly waste.The present inventor had found in research process, if by this Draw off, remain able to obtain preferable Catalytic performance, while in the continuous running of long-time, showing more preferable activity stability.Therefore, according to this Bright method, at least partly reaction using HTS as catalyst of the HTS preferably Jing regeneration are filled That puts (in addition to thioether oxidation unit) draws off agent.It is described that to draw off agent can be to use HTS as catalysis from various What is drawn off in the reaction unit of agent draws off agent, can for example be draw off from oxidation reaction apparatus draw off agent.Specifically, It is described to draw off agent and draw off agent and epoxidation reaction device for the draw off agent, hydroxylating device of Ammoximation reaction device Draw off one or more in agent.More specifically, it is described draw off agent can be cyclohexanone oxamidinating reaction unit draw off agent, One or more drawn off in agent that draws off agent and propylene ring oxidation reaction device of phenol hydroxylation reaction unit.

The condition regenerated by agent 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 of Jing regeneration is different according to its source.Usually, the activity for drawing off agent of Jing regeneration can Think the 5-95% of activity (that is, the activity of fresh HTS) of HTS when fresh.Preferably, The activity for drawing off agent of Jing regeneration can be the 10-90% of activity of HTS when fresh, more preferably exist The 30-50% of activity when fresh.It is activity of HTS when fresh in the activity for drawing off agent of Jing regeneration During 30-50%, in the continuous running of long-time, more preferable activity stability is shown.Preferably, in Jing regeneration The activity for drawing off agent is the 35-45% of activity of 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：Agent and fresh HTS are drawn off as Ketohexamethylene by what Jing regenerated respectively The catalyst of Ammoximation reaction, the condition of the Ammoximation reaction is：HTS, the ammonia of 36 weight % are (with NH₃ Meter), the hydrogen peroxide of 30 weight % is (with H₂O₂Meter), the tert-butyl alcohol and Ketohexamethylene in mass ratio 1：7.5：10：7.5：10, 2h is reacted in 80 DEG C at atmosheric pressure.Calculated with Jing regeneration respectively when drawing off agent and fresh HTS as catalyst The conversion ratio of Ketohexamethylene, and using which as the activity for drawing off agent and fresh HTS of Jing regeneration, wherein, ring The conversion ratio of hexanone=[Ketohexamethylene of (mole of the mole of the Ketohexamethylene of addition-unreacted Ketohexamethylene)/add rubs You measure] × 100%.

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

The method according to the invention, the HTS in the modified HTS as raw material are particularly preferably That states Jing regeneration draws off agent, and the agent that draws off that the Jing regenerates is carried out the modification, can further improve Jing regeneration The single trip use life-span of agent is drawn off, and the desirable oxidation selectivity of product for drawing off agent of the Jing regeneration can be significantly improved.

The method according to the invention, in step (2), the reactant mixture that step (1-1) can be obtained or step (1-2) mixture for obtaining 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, make liquid material flow through beds, so as to carry out Haptoreaction.

In step (2), the HTS can be HTS original powder, or molding HTS, Preferably molding HTS.The molding 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 molding 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 molding HTS can be conventional selection, such as aluminium oxide and/or silicon oxide. The method for preparing the molding HTS is it is known in the art, no longer describing in detail herein.The molding titanium silicon molecule The granular size of sieve is also not particularly limited, and can carry out appropriate selection according to concrete shape.Usually, the molding The mean diameter of HTS can be 4-10000 microns, preferably 5-5000 microns, and more preferably 40-4000 is micro- Rice, such as 100-2000 microns.The mean diameter is volume average particle size, can be determined using laser particle analyzer.

In step (2), used as catalyst, its consumption, can realize that catalysiss are defined for the HTS 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 as to carry out during haptoreaction, the weight of thioether and HTS Than being 0.01-100：1, preferably 1-100：1, more preferably 10-50：1, such as 15-30：1；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 1-80h^-1, such as 15-50h^-1.In the present invention, weight (hourly) space velocity (WHSV) with beds in whole HTSs be Benchmark.

The method according to the invention, beds can only load HTS, it is also possible to containing HTS and Inactive filler.Load in beds inactive filler can to beds in the amount of HTS carry out Adjustment, so as to the speed to reacting is adjusted.When beds contain HTS and inactive filler, urge In agent bed, the content of inactive filler can be 5-95 weight %.The inactive filler refers to that oxidation reaction is not had Or there is no substantially the filler of catalysis activity, its instantiation can be including but not limited to：Quartz sand, ceramic ring and ceramics are broken One or more in piece.

In step (2), ethylbenzene hydroperoxide in the reactant mixture that the consumption of thioether can be obtained according to step (1-1) Or the content of ethylbenzene hydroperoxide is selected in the reactant mixture that obtains of step (1-2).Usually, thioether and second The mol ratio of benzene hydrogen peroxide can be 1：0.1-10.Furthermore it is also possible to according to the set goal oxidation product to thioether with The mol ratio of ethylbenzene hydroperoxide is optimized.For example, when desirable oxidation product is sulfoxide (such as dimethyl sulfoxide), Thioether is preferably 1 with the mol ratio of ethylbenzene hydroperoxide：0.1-2, more preferably 1：0.3-1.5.

The method according to the invention, the thioether can be the various compounds containing-S- keys, and the thioether is preferably selected from carbon Thioether of the atomic number for 2-18, 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 is obtained Contact with HTS is carried out under conditions of it be enough to sulfide oxidation.Usually, can 0-120 DEG C, preferably The reactant mixture or step (1-2) at a temperature of 20-80 DEG C, more preferably 40-50 DEG C obtaining step (1-1) is obtained Mixture and thioether and HTS haptoreaction.The pressure in reactor for being contacted can be in the model of 0-5MPa In enclosing, preferably in the range of 0.1-3.5MPa, such as in the range of 0.5-2MPa, the pressure is in terms of gauge pressure.

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

Describe the present invention with reference to embodiments in detail, 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 in the reactant liquor that obtain each composition, here are analyzed using gas chromatogram On the basis of below equation is respectively adopted to 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 the thioether for adding；

m_ThioetherRepresent the mole of unreacted thioether.

n_SulfoxideRepresent the mole of the sulfoxide that reaction is generated.

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

Wherein, S_SulfoxideRepresent sulfoxide selectivity；

n^o _ThioetherRepresent the mole of the thioether for adding；

n_ThioetherRepresent the mole of unreacted thioether；

n_SulfoxideRepresent the mole of the sulfoxide that reaction is generated.

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 the HTS before and after property is 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 analyses exist Carry out on 2405 types of the ASAP static state n2 absorption apparatus of Micromeritics companies.

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

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

In embodiment and comparative example the step of prepare HTS included below, X-ray diffraction is analyzed in Siemens Carry out on D5005 type X-ray diffractometers, the five fingers diffractive features between 2 θ are as 22.5 ° -25.0 ° with sample and authentic specimen The ratio of diffracted intensity (peak height) sum at peak is representing degree of crystallinity of the sample relative to authentic specimen；Fourier transform is red External spectrum analysis is carried out on 8210 type Fourier infrared spectrographs of Nicolet；Silicon titanium is than referring to rubbing for silicon oxide and titanium oxide You compare, and surface silicon titanium ratio is surveyed using the ESCALab250 types x-ray photoelectron spectroscopy of Thermo Scientific companies Fixed, body phase silicon titanium ratio is determined using Rigaku Electric Co., Ltd 3271E types Xray fluorescence spectrometer.

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

Embodiment 1

(1-1) haptoreaction under conditions of temperature is 120 DEG C and pressure is 1MPa by ethylbenzene and oxygen, is contained The reactant mixture of ethylbenzene hydroperoxide, is analyzed to the composition of the reactant mixture with gas chromatogram, determines ethylbenzene mistake The content of hydrogen oxide is 15 weight %.Wherein, ethylbenzene and the mol ratio of oxygen are 1：2；Oxygen is in the form of oxygen-containing gas There is provided, in oxygen-containing gas, the content of oxygen is 21 volumes %, and the content of nitrogen is 79 volumes %.

(1-2) reactant mixture for obtaining step (1-1) and hydrochloric acid (HCl concentration is 36.5 weight %) are in high pressure Mix in reactor, wherein, in the reactant mixture that step (1-1) is obtained, ethylbenzene hydroperoxide with the mol ratio of HCl is 1：0.005, by the temperature control in autoclave be 40 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 normal atmosphere), incorporation time is 2h.

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

(20 DEG C), 22.5g tetraethyl orthosilicates are mixed as the TPAOH of template with 7.0g 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 Solution solution.With vigorous stirring, it is slowly added into in the hydrating solution anhydrous with 5.0g different by 1.1g butyl titanates Gained mixture is stirred 3h at 75 DEG C, obtains clear colloid by the solution constituted by propanol.This colloid is placed in not In rust steel sealed 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 after collecting the solid matter water used wash for obtaining, is dried 1h in 110 DEG C, then in 500 DEG C of roasting 6h, 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, dimethyl sulfide and the weight ratio of HTS are 15：1, step (1-2) To reactant mixture in the mol ratio of ethylbenzene hydroperoxide and dimethyl sulfide be 1：1, by the temperature in autoclave Degree is controlled to 45 DEG C, is 0.5MPa by Stress control.After reaction 2h, stopped reaction, by the reaction in autoclave Mixture is filtered, and obtains liquid material and the HTS for reclaiming, and analyzes the composition of the liquid material for obtaining, meter Dimethyl sulfide conversion ratio and dimethyl sulfoxide selectivity are calculated, the HTS of recovery is re-fed into following in step (2) Ring is used.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, except for the difference that, do not carry out step (1-2), walked Suddenly the reactant mixture that (1-1) is obtained is sent directly in step (2).Titanium-silicon molecular sieve TS-1 the 1st time and the 25th time Reaction result during use is listed in table 1.

Embodiment 3

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

First butyl titanate is dissolved in alkali source template TPAOH aqueous solution, silica gel is subsequently adding (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) using after sealed membrane sealing, stirred at 35 DEG C followed by magnetic agitation 2h is mixed, is allowed to disperse again.Again the dispersion liquid after disperseing is transferred in sealed reactor, first is experienced at 140 DEG C Mixture is then cooled to 30 DEG C of experience second stage and is stopped after 2h, continued in sealed reactor by stage crystallization 6h Phase III crystallization 12h is experienced at a temperature of 170 DEG C (wherein, by the intensification 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 segment treatment temperature, by second Phase process temperature to phase III crystallization temperature heating rate be 10 DEG C/min), by gained crystallization product take out after without Filter and washing step, directly 2h is dried in 110 DEG C, then the roasting 3h at 550 DEG C, obtain molecular sieve.Gained sample The titanium-silicon molecular sieve TS-1 that the XRD crystalline phases figure of product is prepared with 1 step of embodiment (2) is consistent, and illustrate to obtain is have The titanium-silicon molecular sieve TS-1 of MFI structure；In Fourier transform infrared spectroscopy 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 be 3.5 weight %, surface silicon titanium ratio/body Phase silicon titanium ratio be 2.58 (embodiment 1 prepare HTS in, surface silicon titanium ratio/body phase silicon titanium ratio be 1.05).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, except for the difference that, in step (2), prepared 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 and enforcement Titanium-silicon molecular sieve TS-1 prepared by 1 step of example (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, except for the difference that, in step (2), prepared During titanium-silicon molecular sieve TS-1, the crystallization temperature of first stage is 110 DEG C.The XRD crystalline phases figure and embodiment 1 of gained sample 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, except for the difference that, 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 1 step of embodiment (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 List in table 1.

Embodiment 7

Dimethyl sulfide is aoxidized using method same as Example 3, except for the difference that, 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 1 step of embodiment (2) TS-1 is consistent for sieve, 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 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, except for the difference that, 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 1 step of embodiment (2) Sieve TS-1 is consistent for son, 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, except for the difference that, 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 1 step of embodiment (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, and in the HTS, 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, except for the difference that, in step (2), moisture dissipates Liquid does not stand 12h at room temperature, but crystallization is carried out in being sent directly into reactor.The XRD crystalline phases figure and reality of gained sample Apply that titanium-silicon molecular sieve TS-1 prepared by 1 step of example (2) is consistent, 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, except for the difference that, in step (2), titanium silicon point Son sieve TS-1 was modified process using following methods before as catalyst.

Using the titanium-silicon molecular sieve TS-1 of the preparation as raw material with contain HNO₃(HNO₃Mass concentration for 10%) and The aqueous solution of hydrogen peroxide (mass concentration of hydrogen peroxide is 7.5%), by the mixture for obtaining in hermetic container In 70 DEG C of stirring reactions 5h, the temperature of the reactant mixture for obtaining is filtered after being down to room temperature, by the solid matter for obtaining In 120 DEG C of dryings to constant weight, modified HTS is obtained.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂Meter, titanium silicon Molecular sieve is 1 with the mol ratio of hydrogen peroxide：0.1.Compared with raw material HTS, the modified titanium silicon molecule for obtaining The peak area of the 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

Using aoxidizing dimethyl sulfide with 11 identical method of embodiment, except for the difference that, in modification, as original What is expected is titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit of Jing regeneration Using preparing with embodiment 1 step (2) identical method, the titanium-silicon molecular sieve TS-1 for drawing off at a temperature of 570 DEG C in Roasting 5h in air atmosphere and regenerate, the activity after regeneration is 35%, and activity when fresh is for 96%).With raw material titanium silicon Molecular sieve is compared, the peak of the absworption peak in the UV-Vis spectrum of the modified HTS for obtaining between 230-310nm Area reduces 3.3%, reduces 2.8% by the pore volume of static determination of nitrogen adsorption.Titanium-silicon molecular sieve TS-1 the 1st time and the 75th Reaction result during secondary use is listed in table 1.

Embodiment 13

Using aoxidizing dimethyl sulfide with 12 identical method of embodiment, except for the difference that, directly will make in embodiment 11 The titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit regenerated for the Jing of raw material is used as catalyst, i.e., do 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

Using aoxidizing dimethyl sulfide with embodiment 1 step (2) identical method, except for the difference that, step is not carried out (1-1) and step (1-2), used in step (2) ethylbenzene hydroperoxide ethylbenzene solution (in the ethylbenzene solution, ethylbenzene The concentration of hydrogen peroxide is identical with the concentration of the ethylbenzene hydroperoxide in the reactant mixture that 1 step of embodiment (1) is obtained) The reactant mixture for replacing step (1-2) to obtain.Reaction knot when titanium-silicon molecular sieve TS-1 is used for the 1st time and the 30th time Fruit is listed in table 1.

Table 1

Embodiment 14

(1-1) by ethylbenzene and ethylbenzene hydroperoxide, (ethylbenzene hydroperoxide is 0.005 with the mol ratio of ethylbenzene：And oxygen 1) The haptoreaction under conditions of temperature is 90 DEG C and pressure is 2MPa, obtains the reactant mixture containing ethylbenzene hydroperoxide, The composition of the reactant mixture is analyzed with gas chromatogram, determines that the content of ethylbenzene hydroperoxide is 11 weight %.Its In, ethylbenzene is 1 with the mol ratio of oxygen：1, oxygen is provided in the form of oxygen-containing gas, and in oxygen-containing gas, oxygen contains Measure as 20 volumes %, the content of nitrogen is 80 volumes %.

(1-2) reactant mixture for obtaining step (1-1) and hydrobromic acid (HBr concentration is 30 weight %) are in high pressure Mix in reactor, wherein, in the reactant mixture that step (1-1) is obtained, ethylbenzene hydroperoxide with the mol ratio of HBr is 1：0.001, by the temperature control in autoclave be 30 DEG C, by the Stress control in autoclave be normal pressure (i.e., 1 normal atmosphere), incorporation time is 3h.

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

By hollow HTS with contain HNO₃(HNO₃Mass concentration 10%) and hydrogen peroxide (peroxidating for The mass concentration of hydrogen is aqueous solution 5%), by the mixture for obtaining in hermetic container under 120 DEG C of pressure itselfs Stirring reaction 4h, the temperature of the reactant mixture for obtaining are filtered after being down to room temperature, by the solid matter for obtaining 120 DEG C drying obtains modified HTS to constant weight.Wherein, hollow HTS is with SiO₂Meter, HTS Mol ratio with hydrogen peroxide is 1：0.4.Compared with raw material HTS, the modified HTS for obtaining The peak area of the 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%.Will be the mixture of modified hollow HTS and non-modified hollow HTS (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 sends into reactor from the entrance positioned at reactor bottom In, flow through beds.Wherein, the ethylbenzene hydroperoxide and dimethyl disulfide in the reactant mixture that step (1) is obtained The mol ratio of ether is 1.1：1, it is 50 DEG C by the temperature control in beds, by the Stress control in reactor is 1.2MPa, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 15h^-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 550h and lists in table 2.

Embodiment 15

Using with 14 identical method cacodyl oxide base thioether of embodiment, except for the difference that, 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 380h and lists in table 2.

Embodiment 16

Using with 15 identical method cacodyl oxide base thioether of embodiment, except for the difference that, prepare modified HTS When the raw material that uses be Jing regeneration the hollow HTS (hollow titanium drawn off from cyclohexanone oxamidinating reaction unit Si molecular sieves and 14 step of embodiment (2) identical, the hollow titanium for drawing off as the source of the hollow HTS of raw material Si molecular sieves at a temperature of 550 DEG C in air atmosphere roasting 6h and regenerate, the activity after regeneration be 40%, when fresh Activity for 97%).Compared with raw material HTS, in the UV-Vis spectrum of the modified HTS for obtaining The peak area of the absworption peak between 230-310nm reduces 4.8%, reduces 3.5% 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 660h and lists in table 2.

Embodiment 17

(1-1) haptoreaction under conditions of temperature is 140 DEG C and pressure is 2.5MPa by ethylbenzene and oxygen, is contained There is the reactant mixture of ethylbenzene hydroperoxide, the composition of the reactant mixture is analyzed with gas chromatogram, determines ethylbenzene The content of hydrogen peroxide is 8 weight %.Wherein, ethylbenzene and the mol ratio of oxygen are 1：0.8；Oxygen is with oxygen-containing gas Form is provided, and in oxygen-containing gas, the content of oxygen is 25 volumes %, and the content of nitrogen is 75 volumes %.

(1-2) reactant mixture for obtaining step (1-1) is anti-in high pressure with hydrochloric acid (HCl concentration is 25 weight %) Mix in answering kettle, wherein, in the reactant mixture that step (1-1) is obtained, ethylbenzene hydroperoxide and the mol ratio of HCl are 1： 0.01, by 35 DEG C of temperature control in autoclave, it is normal pressure (that is, 1 standard by the Stress control in autoclave Atmospheric pressure), incorporation time is 3h.

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

First butyl titanate is dissolved in alkali source template TPAOH aqueous solution, silica gel is subsequently adding (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 Using 10h being stood at 40 DEG C after sealing film phonograph seal, be stirred 0.5h at 25 DEG C followed by magnetic agitation, be allowed to again Dispersion.Again the dispersion liquid after disperseing is transferred in sealed reactor, first stage crystallization 8h is experienced at 130 DEG C, is connect And mixture is cooled to after 50 DEG C of experience second stage stop 5h, continue in sealed reactor in 170 DEG C of temperature Jing Go through phase III crystallization 16h (wherein, by room temperature to first stage crystallization temperature heating rate be 1 DEG C/min, by The rate of temperature fall of first paragraph crystallization temperature to second segment treatment temperature is 10 DEG C/min, by second segment treatment temperature to the 3rd section The heating rate of crystallization temperature be 20 DEG C/min), by gained crystallization product take out after without filter and washing step, directly in 120 DEG C of drying 3h, then the roasting 2h at 580 DEG C, obtains molecular sieve.The XRD crystalline phases figure and embodiment of gained sample Titanium-silicon molecular sieve TS-1 prepared by 1 step (2) is consistent, and illustrate to obtain is the titanium-silicon molecular sieve TS-1 with MFI structure； In Fourier transform infrared spectroscopy figure, in 960cm^-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 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 (1-2) reactant mixture and dimethyl sulfide for obtaining is sent in reactor from the entrance positioned at reactor bottom, flows through and urges Agent bed.Wherein, ethylbenzene hydroperoxide in the reactant mixture that step (1-1) is obtained and dimethyl sulfide mole Than for 1：3, by the temperature control in beds be 50 DEG C, by the Stress control in reactor be 0.5MPa, two The weight (hourly) space velocity (WHSV) of Dimethyl sulfide is 50h^-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 lists in table 2.

Table 2

Embodiment 18

(1-1) haptoreaction under conditions of temperature is 125 DEG C and pressure is 1.5MPa by ethylbenzene and oxygen, is contained There is the reactant mixture of ethylbenzene hydroperoxide, the composition of the reactant mixture is analyzed with gas chromatogram, determines ethylbenzene The content of hydrogen peroxide is 20 weight %.Wherein, ethylbenzene and the mol ratio of oxygen are 1：2；Oxygen is with the shape of oxygen-containing gas Formula is provided, and in oxygen-containing gas, the content of oxygen is 22 volumes %, and the content of argon is 78 volumes %.

(1-2) reactant mixture for obtaining step (1-1) is anti-in high pressure with hydrochloric acid (HCl concentration is 20 weight %) Mix in answering kettle, wherein, in the reactant mixture that step (1-1) is obtained, ethylbenzene hydroperoxide and the mol ratio of HCl are 1： 0.005, by 30 DEG C of temperature control in autoclave, it is normal pressure (that is, 1 mark by the Stress control in autoclave Quasi- atmospheric pressure), incorporation time is 4h.

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

First butyl titanate is dissolved in alkali source template TPAOH aqueous solution, silica gel is subsequently adding (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 8h is being stood at 45 DEG C after the middle film phonograph seal using sealing；The dispersion liquid that Jing stands is transferred in sealed reactor, at 140 DEG C Mixture is then cooled to 40 DEG C of experience second stage and is stopped after 1h, continued in sealing by experience first stage crystallization 6h Phase III crystallization 12h is experienced (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 5 DEG C/min by the rate of temperature fall of first paragraph crystallization temperature to second segment treatment temperature, It is 5 DEG C/min by the heating rate of second segment treatment temperature to the 3rd section of crystallization temperature), after gained crystallization product is taken out not Jing is filtered and washing step, directly dries 2h in 110 DEG C, then the roasting 3h at 550 DEG C, obtains molecular sieve.Gained The titanium-silicon molecular sieve TS-1 that the XRD crystalline phases figure of sample is prepared with 1 step of embodiment (2) is consistent, and illustrate to obtain is tool There is the titanium-silicon molecular sieve TS-1 of MFI structure；In Fourier transform infrared spectroscopy figure, in 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 2.71, and titanium oxide contains Measure as 4.3 weight %.

The titanium-silicon molecular sieve TS-1 of preparation is seated in micro fixed-bed reactor, beds are formed.By step (1-2) mixture and thioanisole for obtaining is sent in reactor from the entrance positioned at reactor bottom, flows through catalyst bed Layer.Wherein, the ethylbenzene hydroperoxide in the reactant mixture that step (1) is obtained is 1.5 with the mol ratio of thioanisole：1, By the temperature control in beds be 85 DEG C, by the Stress control in reactor be 1.8MPa, thioanisole it is heavy when Air speed is 15h^-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 lists in table 3.

Embodiment 19

Using aoxidizing thioanisole with 18 identical method of embodiment, except for the difference that, the titanium-silicon molecular sieve TS-1 of preparation Before as catalyst, process is modified using following methods.

By the titanium-silicon molecular sieve TS-1 of preparation with contain HNO₃(HNO₃Mass concentration 10%) and hydrogen peroxide (mistake for The mass concentration of hydrogen oxide is aqueous solution 2%), and the mixture for obtaining is anti-in 170 DEG C of stirrings in hermetic container 2.5h is answered, the temperature of the reactant mixture for obtaining is filtered after being down to room temperature, by the solid matter for obtaining 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.Jing is characterized, compared with raw material HTS, the modified HTS for obtaining The peak area of the 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 540h and lists in table 3.

Embodiment 20

Using aoxidizing thioanisole with 19 identical method of embodiment, except for the difference that, as raw material be Jing regeneration The titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit (titanium-silicon molecular sieve TS-1 is adopted and embodiment Prepared by 18 steps (2) identical method, the titanium-silicon molecular sieve TS-1 for drawing off is at a temperature of 580 DEG C in air atmosphere Roasting 4h and regenerate, the activity after regeneration is 40%, and activity when fresh is for 95%).Compared with raw material HTS, The peak area of the absworption peak in the UV-Vis spectrum of the modified HTS for obtaining between 230-310nm is reduced 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 640h and lists in table 3.

Table 3

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment Detail, in the range of the technology design of the present invention, can carry out various 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 specific embodiment, in not contradiction In the case of, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is to various Possible compound mode is no longer separately illustrated.

Additionally, combination in any between a variety of embodiments of the present invention, can also be carried out, as long as which is without prejudice to this The thought of invention, which 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. method according to claim 1, wherein, in step (1-1), the catalytic condition is caused In the reactant mixture for obtaining, the content of ethylbenzene hydroperoxide is 2-95 weight %, preferably 3-60 weight %, more preferably 4-30 weight %, more preferably 8-20 weight %；The content of ethylbenzene is 5-98 weight %, preferably 40-97 weight %, more preferably 70-96 weight %, more preferably 80-92 weight %.

3. method according to claim 1 and 2, wherein, in step (1-1), the mol ratio of ethylbenzene and oxygen For 1：0.1-20, preferably 1：0.2-10, more preferably 1：0.5-5, the haptoreaction temperature be 50-180 DEG C, Preferably 80-160 DEG C, more preferably 90-140 DEG C, and pressure be 0-5MPa, be preferably 0-3MPa under conditions of carry out, The pressure is in terms of gauge pressure.

4. the method according to any one in claim 1-3, wherein, in step (1-2), mineral acid and second The mol ratio of benzene hydrogen peroxide 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 in step (1-2), described to be blended in Temperature is 20-100 DEG C, is preferably 20-80 DEG C, more preferably 20-60 DEG C, and pressure is to enter under conditions of 0-2MPa OK, the pressure is in terms of gauge pressure；The time of the mixing is 0.1-5 hours, preferably 0.5-4 hours, more preferably 2-4 Hour.

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

7. the method according to any one in claim 1-6, wherein, in step (2), at least part of titanium silicon Molecular sieve is the modified HTS for experiencing modification, and the modification includes the titanium silicon molecule as 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, as the titanium silicon molecule of raw material Sieve is 1 with the mol ratio of the peroxide：0.01-5, preferably 1：0.05-2, more preferably 1：0.1-1, the mistake Oxide is 1 with the mol ratio of the nitric acid：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 silicon dioxide.

9. the method according to claim 7 or 8, wherein, in the modification liquid, the peroxide and nitric acid Concentration be respectively 0.1-50 weight %, preferably 0.5-25 weight %, more preferably 1-15 weight %, further preferably For 2-10 weight %.

10. the method according to any one in claim 7-9, wherein, in the modification, as original The HTS of material and the modification liquid 10-350 DEG C, preferred 20-300 DEG C, more preferably 50-250 DEG C, it is further excellent Select, the contact is carried out in container of the pressure for 0-5MPa, and the pressure is Gauge pressure.

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

12. methods according to any one in claim 7-11, wherein, in the modification, as original The HTS of material is caused with the exposure level of the modification liquid, using on the basis of the HTS as raw material, in purple In outward-visible spectrum, the peak area of the absworption peak of modified HTS between 230-310nm reduces by more than 2%, It is preferred that reducing 2-30%, 3-15% is more preferably reduced, further preferably reduce 3.5-6%, 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. methods according to any one in claim 7-12, wherein, the total amount with the HTS is Benchmark, the content of the modified HTS is more than 50 weight %.

14. methods according to any one in claim 1-13, wherein, in step (2), at least part of 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 Silicon titanium is stated than referring to the mol ratio of silicon oxide and titanium oxide, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, The body phase silicon titanium ratio adopts x-ray fluorescence spectrometry；

Preferably, the surface silicon titanium ratio and the ratio of the body phase silicon titanium ratio are more than 1.2；

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

It is further preferred that the surface silicon titanium ratio is 1.5-4.5 with the ratio of the body phase silicon titanium ratio.

15. methods according to any one in claim 1-14, wherein, in step (2), at least part of titanium Si molecular sieves are titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1 is prepared using the method for comprising 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 Dispersion liquid, in 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 into 6-24 hours at 15-60 DEG C；

(III) dispersion liquid that the dispersion liquid or step (II) for obtaining step (I) is obtained order in sealed 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 hour, preferred 6-8 hours；Stage (2) It is cooled to not higher than 70 DEG C and at least 0.5 hour time of staying, preferably 1-5 hours；Stage (3) is warming up to 120-200 DEG C, preferred 140-180 DEG C, more preferably 160-170 DEG C, then crystallization 6-96 hour, preferred 12-20 hours.

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

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

17. methods according to any one in claim 15-16, wherein, the stage (2) is cooled to not higher than 50 DEG C, and at least 1 hour time of staying.

18. methods according to any one in claim 15-17, wherein, the titanium source be inorganic titanium salt and/ Or organic titanate；The alkali source template be quaternary ammonium base, aliphatic amine and aliphatic hydramine in one or more, 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 TiOCl₂In one or more；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. methods according to any one in claim 1-18, wherein, at least part of HTS is derived from At least one reaction unit draws off agent, it is described draw off agent for Ammoximation reaction device draw off agent, hydroxylating device Draw off agent and epoxidation reaction device draw off agent.

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

21. methods according to any one in claim 1-20, wherein, in step (2), step (1-1) Ethylbenzene hydroperoxide in the reactant mixture for obtaining is 0.1-10 with the mol ratio of thioether：1, preferably 1：0.1-2.

22. methods according to any one in claim 1-21, wherein, in step (2), the contact is anti- Should be 0-120 DEG C in temperature, be preferably 20-80 DEG C, be more preferably 40-50 DEG C, and pressure is 0-5MPa, is preferably Carry out under conditions of 0.1-3.5MPa, the pressure is in terms of gauge pressure.