CN107556219B

CN107556219B - A kind of preparation method of sulfone

Info

Publication number: CN107556219B
Application number: CN201610511420.5A
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: 2016-06-30
Filing date: 2016-06-30
Publication date: 2019-09-24
Anticipated expiration: 2036-06-30
Also published as: CN107556219A

Abstract

The invention discloses a kind of preparation methods of sulfone, this method includes making a kind of reaction mixture and Titanium Sieve Molecular Sieve haptoreaction in the reactor, obtain the product mixtures containing sulfone, the reaction mixture contains thioether, oxidant and optional solvent, wherein, when desirable oxidation selectivity of product is lower than desired value, this method further includes improving the content of oxidant in raw mixture, until desirable oxidation selectivity of product is gone up to more than desired value.This method can effectively delay the deactivation rate of the Titanium Sieve Molecular Sieve as catalyst, extend the single trip use service life of Titanium Sieve Molecular Sieve, reduce the regeneration frequency of Titanium Sieve Molecular Sieve, reduce production cost, while can also improve the operational efficiency of device.

Description

A kind of preparation method of sulfone

Technical field

The present invention relates to a kind of preparation methods of sulfone.

Background technique

Sulfone substance is important sulfur-containing compound, as dimethyl sulfone be white crystalline powder, soluble easily in water, ethyl alcohol, benzene, Methanol and acetone, are slightly soluble in ether.Potassium permanganate cannot be made to change colour under room temperature, dimethyl sulfone can be oxidized to methylsulphur by strong oxidizer Acid.Dimethyl sulfone aqueous solution is in neutrality.In 25 DEG C of microsublimations, accelerate to 60 DEG C of rate of sublimation, thus dimethyl sulfone product is suitable It is dried under cryogenic vacuum.

Dimethyl sulfone is used as organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, food in the industry Product additive and drug.Dimethyl sulfone is as a kind of organic sulfur compound, the ability that there is enhancing human body to generate insulin, simultaneously Also there is facilitation to the metabolism of carbohydrate, be the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound to be cured It closes, can also work to vitamin B, vitamin C, the synthesis of biotin and activation needed for metabolism and neurological health, quilt Referred to as " beautify carbonizable substance naturally ".All contain dimethyl sulfone in the skin of human body, hair, nail, bone, muscle and each organ, Dimethyl sulfone is primarily present in Yu Haiyang and soil in nature, is absorbed in plant growth as nutriment, the mankind It can be absorbed from the foods such as veterinary antibiotics, fish, meat, egg, milk, once health disorders will be caused or disease occurs by lacking, be Human body maintains the main matter of biological element sulphur balance, has therapeutic value and healthcare function to human body diseases, is human survival With the indispensable drug of health care.Foreign countries widely apply using dimethyl sulfone as with vitamin nutriment of equal importance, China The application study of dimethyl sulfone is not yet carried out very well, product is mainly used for exporting at present.Therefore, dimethyl sulfone is not only one kind New high-tech product and a kind of fine chemical product of high added value.Product is new, great market potential, and benefit is prominent, has wide Wealthy production and application and development prospect.

Currently, the product that dimethyl sulfone is further aoxidized as dimethyl sulfoxide, for the main pair of dimethyl sulfoxide production Product.

Summary of the invention

When sulfide oxidation is directly prepared sulfone using oxidant (especially peroxide), if using Titanium Sieve Molecular Sieve As catalyst, the conversion ratio of oxidant and the selectivity of desirable oxidation product can be improved.But with the extension in reaction time, The catalytic activity of Titanium Sieve Molecular Sieve can be on a declining curve, and oxidant conversion ratio and desirable oxidation selectivity of product is caused obviously to drop It is low.When reaction carries out in fixed bed reactors, since titanium molecular sieve catalysis activity reduces, need to exist Titanium Sieve Molecular Sieve Regenerated in reactor or outside reactor, lead to reactor down-time, thus influence production efficiency and improve the operation of device at This.

The purpose of the present invention is to provide a kind of preparation method of sulfone, this method can effectively extend as catalyst The single trip use service life of Titanium Sieve Molecular Sieve, during continuous run in long period can by desirable oxidation selectivity of product stablize compared with High level.

The present invention provides a kind of preparation method of sulfone, this method includes that a kind of raw mixture and Titanium Sieve Molecular Sieve is made to exist Haptoreaction in reactor, obtains the product mixtures containing sulfone, and the raw mixture contains thioether, at least one oxidant And optional at least one solvent, wherein this method further includes at least carrying out primary set-up procedure, in the condition 1 of satisfaction The set-up procedure is carried out, stops the set-up procedure when until meeting condition 2 to improve desirable oxidation selectivity of product,

Condition 1, sometime the desirable oxidation selectivity of product S under t_tWith initial target oxidation product selectivity S₀Ratio Value S_t/S₀For 0.8≤S_t/S₀<1；

Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation product selectivity S₀Ratio S '/S₀For 0.9≤ S’/S₀≤1；

The set-up procedure is to improve the content of oxidant in raw mixture.

The preparation method of sulfone according to the present invention can effectively delay the inactivation speed of the Titanium Sieve Molecular Sieve as catalyst Degree, extends the single trip use service life of Titanium Sieve Molecular Sieve, reduces the regeneration frequency of Titanium Sieve Molecular Sieve, to improve the production effect of device Rate reduces operating cost.

Method of the invention is easy to operate, easy to implement.

Specific embodiment

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

The present invention provides a kind of preparation method of sulfone, this method includes that a kind of raw mixture and Titanium Sieve Molecular Sieve is made to exist Haptoreaction in reactor, obtains the product mixtures containing sulfone, and the raw mixture contains thioether, at least one oxidant And optional at least one solvent.

In the present invention, "at least one" indicates one or more kinds of；It is " optional " indicate with or without.

According to the method for the present invention, Titanium Sieve Molecular Sieve is a kind of boiling that titanium atom replaces a part of silicon atom in lattice framework The general name of stone can use chemical formula xTiO₂·SiO₂It indicates.Present invention spy no for the content of titanium atom in Titanium Sieve Molecular Sieve It does not limit, can be the conventional selection of this field.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, it is more excellent It is selected as 0.015-0.025.

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

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

According to the method for the present invention, when the Titanium Sieve Molecular Sieve uses template during the preparation process, the titanium silicon molecule Sieve can be the Titanium Sieve Molecular Sieve that experienced the process (such as roasting process) for removed template method, or do not undergo and be used for The Titanium Sieve Molecular Sieve of the process (such as roasting process) of removed template method can also be the mixture of the two.

According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the Titanium Sieve Molecular Sieve TS- 1 urface silicon titanium is not less than body phase silicon titanium ratio, can obtain the catalytic performance further increased in this way, further extends titanium silicon point The single trip use service life of son sieve.Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2 or more.It is more excellent The ratio of selection of land, the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5.It is further preferred that the urface silicon titanium Ratio with the body phase silicon titanium ratio is 1.5-4.5 (such as 2.2-4.5).It is further preferred that the urface silicon titanium and institute The ratio for stating body phase silicon titanium ratio is 2-3, such as 2.2-2.8.

In the present invention, molar ratio of the silicon titanium than referring to silica and titanium oxide, urface silicon titanium uses x-ray photoelectron energy Spectrometry measurement, body phase silicon titanium ratio use x-ray fluorescence spectrometry.

According to the method for the present invention, from the catalytic performance for further increasing Titanium Sieve Molecular Sieve and further extend single trip use The angle in service life is set out, and at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1, which uses, includes 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 optionally supplements water, obtained Dispersion liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar 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 mould When plate agent Nitrogen element, in terms of N；In alkali source template not Nitrogen element, with OH^-Meter)；

(II) optionally, by the dispersion liquid in 15-60 DEG C of standing 6-24 hours (h)；

(III) by the dispersion liquid that step (I) obtains or the dispersion liquid that step (II) obtains in sealing reaction kettle sequence 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 hours (h), stage (2) After being cooled to not higher than 70 DEG C and residence time at least 0.5h, the stage (3) is warming up to 120-200 DEG C of crystallization 6-96h again.

The alkali source template can be usually used various templates during synthesis of titanium silicon molecular sieve, such as: The alkali source template can be one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine.The quaternary ammonium base It can be various organic level Four ammonium alkali, the aliphatic amine can be various NH₃In at least one hydrogen by aliphatic alkyl (such as Alkyl) replace after the compound that is formed, the aliphatic hydramine can be various NH₃In at least one hydrogen by the rouge of hydroxyl The compound that fat race group (such as alkyl) is formed after replacing.

Specifically, the alkali source template can be the aliphatic amine and formula of the quaternary ammonium base, Formula II expression that indicate selected from Formulas I One or more of the aliphatic hydramine that III is indicated.

In Formulas I, R₁、R₂、R₃And R₄Respectively C₁-C₄Alkyl, including C₁-C₄Straight chained alkyl and C₃-C₄Branched alkane Base, R₁、R₂、R₃And R₄Specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group or tert-butyl.

R⁵(NH₂)_n(Formula II)

In Formula II, n is an integer of 1 or 2.When n is 1, R⁵For C₁-C₆Alkyl, including C₁-C₆Straight chained alkyl and C₃-C₆ Branched alkyl, specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different Butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R⁵For C₁-C₆Alkylidene, including C₁-C₆Straight-chain alkyl-sub and C₃-C₆Branched alkylidene, specific example can include but is not limited to methylene, ethylidene, Sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.

(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, specific example can include but is not limited to methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.

The specific example of the alkali source template can include but is not limited to: tetramethylammonium hydroxide, tetraethyl hydroxide Ammonium, tetrapropylammonium hydroxide (the various isomers including tetrapropylammonium hydroxide, such as four n-propyl ammonium hydroxide and tetra isopropyl Ammonium hydroxide), tetrabutylammonium hydroxide (the various isomers including tetrabutylammonium hydroxide, such as 4-n-butyl ammonium hydroxide and Four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine One or more of with triethanolamine.Preferably, the alkali source template is tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen Change one or more of ammonium and tetrabutylammonium hydroxide.It is highly preferred that the alkali source template is tetrapropyl hydroxide Ammonium.

The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can Think TiCl₄、Ti(SO₄)₂And TiOCl₂One or more of；The organic titanate can be general formula R⁷ ₄TiO₄Table The compound shown, wherein R⁷For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom, such as metatitanic acid Four butyl esters.

The inorganic silicon source can be silica gel and/or silica solution, preferably silica gel.SiO in the silica solution₂Quality hundred Dividing content can be 10% or more, preferably 15% or more, more preferably 20% or more.In preparation according to the preferred embodiment Titanium Sieve Molecular Sieve when, do not use organic silicon source, such as organosilan and organosiloxane.

In the dispersion liquid, silicon source: titanium source: alkali source template: the molar 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) obtains, which can be sent directly into step (III), carries out crystallization.Preferably, step (I) is obtained To dispersion liquid be sent into step (II) in 15-60 DEG C at a temperature of stand 6-24h.Between step (I) and step (III) into Row step (II) can significantly improve the urface silicon titanium of the titanium-silicon molecular sieve TS-1 finally prepared, so that the titanium silicon finally prepared point The urface silicon titanium of son sieve is not less than body phase silicon titanium ratio, can significantly improve the catalytic of the Titanium Sieve Molecular Sieve finally prepared in this way Can, extend its single trip use service life.Generally, final to make by the setting steps (II) between step (I) and step (III) The urface silicon titanium of standby Titanium Sieve Molecular Sieve and the ratio of body phase silicon titanium ratio can be in the range of 1.2-5, preferably in 1.5-4.5 In the range of (such as in the range of 2.2-4.5), more preferably in the range of 2-3 (such as in the range of 2.2-2.8).It is described quiet Set more preferably 20-50 DEG C at a temperature of carry out, as carried out at a temperature of 25-45 DEG C.

In step (II), when being stood, dispersion liquid can be placed in sealing container, open container can also be placed in In stood.Preferably, step (II) carries out in a sealed container, in this way can to avoid during standing into dispersion liquid It is introduced into foreign matter or moieties volatilization in dispersion liquid is caused to be lost.

After the completion of step (II) described standing, directly the dispersion liquid through standing can be sent into reaction kettle and carry out crystallization, It is sent into reaction kettle after dispersion liquid through standing can also being carried out redisperse and carries out crystallization, be preferably sent into after progress redisperse anti- It answers in kettle, can be further improved the dispersing uniformity for carrying out the dispersion liquid of crystallization in this way.The method of the redisperse can be normal The combination of one or more of rule method, such as stirring, ultrasonic treatment and oscillation.The duration of the redisperse with The dispersion liquid through standing can be made to be formed subject to uniform dispersion liquid, generally can be 0.1-12h, such as 0.5-2h.The redisperse It can carry out at ambient temperature, as carried out at a temperature of 15-40 DEG C.

In step (III), temperature is adjusted can be according to specifically adopting to the heating rate of each phase temperature and rate of temperature fall The type of crystallization device is selected, and is not particularly limited.In general, raising the temperature to stage (1) crystallization temperature The heating rate of degree can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By 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 5-10 DEG C/ min.By stage (2) temperature to stage (3) temperature heating rate can be 1-50 DEG C/min, preferably 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, and more preferably 120-140 DEG C, further Preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.The stage temperature of (2) is preferably Not higher than 50 DEG C.The residence time in stage (2) is preferably at least 1h, more preferably 1-5h.The stage crystallization temperature of (3) is preferably 140-180 DEG C, more preferably 160-170 DEG C.The crystallization time in stage (3) is preferably 12-20h, more preferably 12-16h.

In step (III), in a preferred embodiment, the crystallization temperature in stage (1) is lower than the crystallization of stage (3) Temperature can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve of preparation in this way.Preferably, the crystallization temperature in stage (1) compares rank The crystallization temperature of section (3) is 10-50 DEG C low.It is highly preferred that the crystallization temperature in stage (1) is 20-40 lower than the crystallization temperature in stage (3) ℃.In step (III), in another preferred embodiment, when the crystallization time in stage (1) is less than the crystallization of stage (3) Between, it can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.Preferably, the crystallization time ratio in stage (1) The short 5-24h of crystallization time in stage (3).It is highly preferred that the crystallization time in stage (1) is 6- shorter than the crystallization time in stage (3) 12h, such as short 6-8h.In step (III), both preferred embodiments be may be used alone, can also be used in combination, preferably It is applied in combination, i.e., the crystallization temperature and crystallization time in stage (1) and stage (3) meet wanting for both preferred embodiments simultaneously It asks.

In step (III), in another preferred embodiment, the temperature in stage (2) is and to stop not higher than 50 DEG C Time is at least 0.5h, such as 0.5-6h, can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.It is preferred that Ground, the residence time in stage (2) are at least 1h, such as 1-5h.The preferred embodiment can be with aforementioned two kinds preferred implementations Mode is used separately, and can also be applied in combination, is preferably applied in combination, i.e., the crystallization temperature and crystallization in stage (1) and stage (3) when Between and the stage (2) temperature and the residence time meet the requirements of above-mentioned three kinds of preferred embodiments simultaneously.

Titanium Sieve Molecular Sieve can be recycled from the mixture that step (III) crystallization obtains using conventional method.Specifically, may be used After being optionally filtered and washed with the mixture for obtaining step (III) crystallization, solid matter is dried and is roasted, To obtain Titanium Sieve Molecular Sieve.The drying and the roasting can carry out under normal conditions.Generally, the drying can be with Environment temperature (such as 15 DEG C) to 200 DEG C at a temperature of carry out.The drying can be in environmental pressure (generally 1 normal atmosphere Pressure) under carry out, can also carry out at reduced pressure.The duration of the drying can be according to dry temperature and pressure And dry mode is selected, and is not particularly limited.For example, temperature is excellent when the drying carries out under ambient pressure It is selected as 80-150 DEG C, more preferably 100-120 DEG C, the dry duration is preferably 0.5-5h, more preferably 1-3h.The roasting Burn can 300-800 DEG C at a temperature of carry out, preferably carry out at a temperature of 500-700 DEG C, more preferably at 550-650 DEG C At a temperature of carry out, further preferably 550-600 DEG C at a temperature of carry out.The duration of the roasting can be according to roasting Temperature is selected, and generally can be 2-12h, preferably 2-5h.The roasting carries out preferably in air atmosphere.

According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is preferably modified Titanium Sieve Molecular Sieve, the modification Titanium Sieve Molecular Sieve undergoes modification, can more effectively promote the catalytic performance of Titanium Sieve Molecular Sieve in this way, further extend titanium In the single trip use service life of si molecular sieves, further decrease the regeneration frequency of Titanium Sieve Molecular Sieve.The modification includes following step It is rapid: by as the Titanium Sieve Molecular Sieve of raw material with containing nitric acid (that is, HNO₃) and at least one peroxide modification liquid contact.Institute The Titanium Sieve Molecular Sieve for the raw material that raw material Titanium Sieve Molecular Sieve refers to as modification is stated, it can be for without going through the modification Titanium Sieve Molecular Sieve, or live through the modification but need to carry out the titanium silicon molecule of the modification again Sieve.The Titanium Sieve Molecular Sieve that above-mentioned modification is lived through in the present invention is known as modified Titanium Sieve Molecular Sieve, does not live through above-mentioned change Property processing Titanium Sieve Molecular Sieve be known as unmodified Titanium Sieve Molecular Sieve.Can whole Titanium Sieve Molecular Sieve live through at above-mentioned modification Reason, or the mixture of modified Titanium Sieve Molecular Sieve and unmodified Titanium Sieve Molecular Sieve.Preferably, with the titanium silicon molecule On the basis of the total amount of sieve, the Titanium Sieve Molecular Sieve of at least 50 weight % or more lives through the modification, more preferably at least 60 weights The Titanium Sieve Molecular Sieve of amount % or more lives through the modification, changes as described in living through the Titanium Sieve Molecular Sieve of 50-90 weight % Property processing.

In the modification, peroxide can be selected from hydrogen peroxide, hydroperoxides and peracid.At the modification In reason, the specific example of the peroxide be can include but is not limited to: hydrogen peroxide, ethylbenzene hydroperoxide, t-butyl peroxy Change hydrogen, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is peroxide Change hydrogen.The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.

Can be 1 as the Titanium Sieve Molecular Sieve of raw material and the molar ratio of the peroxide in the modification: 0.01-5, preferably 1:0.05-3, more preferably 1:0.1-2.The dosage of the nitric acid can be according to the use of the peroxide Amount is selected.Generally, the molar 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, further preferably 1:0.3-5, particularly preferably 1:0.5-3.5, such as 1:0.6-3, the titanium Si molecular sieves are in terms of silica.

In the modification liquid, the concentration of peroxide and nitric acid respectively can be 0.1-50 weight %.From further increasing The angle of the catalytic performance of the Titanium Sieve Molecular Sieve of the modification finally prepared is set out, preferably 0.5-25 weight %.It is highly preferred that institute It states in modification liquid, the concentration of peroxide and nitric acid is respectively 1-20 weight %.It is further preferred that in the modification liquid, mistake The concentration of oxide and nitric acid is respectively 2-15 weight %.In one embodiment, the concentration of peroxide is 2-10 weight It measures % (such as 2-8 weight %), the concentration of nitric acid is 10-15 weight %.

The solvent of the modification liquid can be the common various solvents that can dissolve nitric acid and the peroxide simultaneously.It is excellent Selection of land, the solvent of the modification liquid are water.

In the modification, as raw material Titanium Sieve Molecular Sieve and modification liquid can 10-350 DEG C at a temperature of into Row contact.From the angle of the catalytic performance for the Titanium Sieve Molecular Sieve for further increasing the modification finally prepared, the contact is excellent It is contacted at a temperature of being selected in 20-300 DEG C.It is highly preferred that it is described contact 50-250 DEG C at a temperature of carry out.It is further excellent Selection of land, it is described contact 60-200 DEG C at a temperature of carry out, such as 70-170 DEG C at a temperature of contacted.At the modification It, can be according to Contact Temperature by the pressure in the container contacted as the Titanium Sieve Molecular Sieve of raw material with the modification liquid in reason It is selected, can be environmental pressure, or pressurization.It generally, will be as the Titanium Sieve Molecular Sieve of raw material and the modification The pressure in container that liquid is contacted can be 0-5MPa (gauge pressure).It preferably, under pressure will be as raw material Titanium Sieve Molecular Sieve is contacted with the modification liquid.It is highly preferred that by the titanium silicon as raw material under self-generated pressure in closed container Molecular sieve is contacted with the modification liquid.The duration that Titanium Sieve Molecular Sieve as raw material is contacted with the modification liquid can be with For 0.5-10h, preferably 2-5h.

In the modification, as the Titanium Sieve Molecular Sieve of raw material and the exposure level of the modification liquid preferably so that, Using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, modified Titanium Sieve Molecular Sieve 230-310nm it Between the peak area of absorption peak reduce by 2% or more, the hole of modified Titanium Sieve Molecular Sieve, which holds, reduces 1% or more.Modified titanium silicon point The peak area of absorption peak of the son sieve between 230-310nm preferably reduces 2-30%, more preferably reduction 2.5-15%, further excellent Choosing reduces 3-10%, still more preferably reduction 3-8%.The hole of modified Titanium Sieve Molecular Sieve holds preferred reduction 1-20%, more excellent Choosing reduces 2-10%, further preferably reduction 2.5-5%.The Kong Rong is using static determination of nitrogen adsorption.

In using various commercial plants of the Titanium Sieve Molecular Sieve as catalyst, as Ammoximation reaction device, hydroxylating are anti- It answers in device and epoxidation reaction device, usually after device runs a period of time, the catalytic activity of catalyst declines, and needs It carries out in device or ex-situ regeneration is needed catalyst from device when being difficult to obtain satisfied activity being regenerated It draws off (that is, more catalyst changeout), and catalyst (that is, drawing off agent or dead catalyst) the current processing method drawn off is usually heap Product is buried, and on the one hand occupies valuable land resource and inventory space, another aspect Titanium Sieve Molecular Sieve production cost is higher, directly It connects to pass into disuse and also results in great waste.The present inventor has found in the course of the research, if these are drawn off agent (that is, the Titanium Sieve Molecular Sieve drawn off) is used in step (2) after being regenerated, and still is able to obtain preferable catalytic performance, simultaneously During long-time continuous operation, better activity stability is shown.Therefore, according to the method for the present invention, at least partly The Titanium Sieve Molecular Sieve is preferably through regenerated reaction unit (the sulphur removal ether oxidation unit using Titanium Sieve Molecular Sieve as catalyst Outside) draw off agent.It is described draw off agent can be to use Titanium Sieve Molecular Sieve as drawing off in the reaction unit of catalyst from various Agent is drawn off, such as agent can be drawn off for what is drawn off from oxidation reaction apparatus.Specifically, described to draw off agent as Ammoximation reaction dress Set draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off one of agent or a variety of.More Body, it is described draw off agent can for cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draws off agent One of agent or a variety of is drawn off with propylene ring oxidation reaction device.

The regenerated condition of agent progress will be drawn off to be not particularly limited, choosing appropriate can be carried out according to the source for drawing off agent It selects, such as: high-temperature roasting and/or solvent washing.

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

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

When at least partly Titanium Sieve Molecular Sieve is to draw off agent through regenerated reaction unit, with the total amount of the Titanium Sieve Molecular Sieve On the basis of, the content for drawing off agent through regenerated reaction unit is preferably 5 weight % or more.According to the method for the present invention, even if entirely Portion's Titanium Sieve Molecular Sieve is to draw off agent (that is, the content for drawing off agent through regenerated reaction unit is 100 weights through regenerated reaction unit Measure %) when, it still is able to obtain preferable catalytic effect.

According to the method for the present invention, the Titanium Sieve Molecular Sieve in the Titanium Sieve Molecular Sieve of the modification as raw material is particularly preferably It is above-mentioned to draw off agent through regenerated, the agent progress modification is drawn off through regenerated by described, can be further improved through regenerated The single trip use service life of agent is drawn off, and can be significantly improved described through the regenerated desirable oxidation selectivity of product for drawing off agent.

According to the method for the present invention, the Titanium Sieve Molecular Sieve and the contact form of the raw mixture do not limit especially It is fixed, Titanium Sieve Molecular Sieve can be seated in the catalyst bed of reactor, the raw mixture is made to pass through the catalyst Bed, to realize in the presence of Titanium Sieve Molecular Sieve, by thioether and oxidant haptoreaction；It can also be by the raw mixture It is mixed to form slurry with Titanium Sieve Molecular Sieve, to realize in the presence of Titanium Sieve Molecular Sieve, by thioether and oxidant haptoreaction.

It, can be using each after the completion of haptoreaction when the raw mixture and Titanium Sieve Molecular Sieve are mixed to form slurry Slurry is carried out solid-liquor separation by kind method, to obtain the liquid material containing desirable oxidation product.Such as: film point can be passed through The liquid material is subjected to solid-liquor separation from device.

When the Titanium Sieve Molecular Sieve to be seated in catalyst bed, the quantity of the catalyst bed can be one Or it is multiple.When the quantity of catalyst bed is multiple, can also be located at more for positioned at the different zones of a reactor In a reactor.

According to the method for the present invention, the catalyst bed can only load Titanium Sieve Molecular Sieve, can also contain titanium silicon point Son sieve and inactive filler.Loading inactive filler in catalyst bed can be to the amount of Titanium Sieve Molecular Sieve in catalyst bed It is adjusted, so that the speed to reaction is adjusted.Contain Titanium Sieve Molecular Sieve and inactive filler in the catalyst bed When, the content of inactive filler can be 5-95 weight % in catalyst bed.The inactive filler refers to oxidation reaction Without or substantially the filler of catalytic activity, specific example not can include but is not limited to: quartz sand, ceramic ring and ceramics are broken One of piece is a variety of.

According to the method for the present invention, the Titanium Sieve Molecular Sieve can be Titanium Sieve Molecular Sieve original powder, or molding titanium silicon Molecular sieve, preferably molding Titanium Sieve Molecular Sieve.Molding Titanium Sieve Molecular Sieve typically contain as active constituent Titanium Sieve Molecular Sieve and Carrier as binder, wherein the content of Titanium Sieve Molecular Sieve can be conventional selection.Generally, with the molding titanium silicon point On the basis of the total amount of son sieve, the content of Titanium Sieve Molecular Sieve can be 5-95 weight %, preferably 10-95 weight %, more preferably 70-95 weight %, further preferably 80-90 weight %；The content of the carrier can be 5-95 weight %, preferably 5-90 Weight %, more preferably 5-30 weight %, further preferably 10-20 weight %.The carrier of the molding Titanium Sieve Molecular Sieve can Conventional selection is thought, such as aluminium oxide and/or silica.The method for preparing the molding Titanium Sieve Molecular Sieve is well known in the art , it is no longer described in detail herein.It is described molding Titanium Sieve Molecular Sieve granular size be also not particularly limited, can according to concrete shape into Row selection appropriate.Specifically, the average grain diameter of the molding Titanium Sieve Molecular Sieve can be 4-10000 microns, preferably 5- 5000 microns, more preferably 40-4000 microns, further preferably 50-1000 microns, such as 100-500 microns.The average grain Diameter is volume average particle size, can be measured using laser particle analyzer.

According to the method for the present invention, as catalyst, dosage is the Titanium Sieve Molecular Sieve can be realized catalysis Standard is not particularly limited.It can generally be selected according to Titanium Sieve Molecular Sieve and the contact form of the raw mixture.Example Such as, when Titanium Sieve Molecular Sieve and the raw mixture are mixed to form slurry, the weight of dimethyl sulfide and Titanium Sieve Molecular Sieve Than that can be 0.1-50:1, preferably 1-50:1, such as 1-25:1；When Titanium Sieve Molecular Sieve is seated in catalyst bed, institute The weight space velocity (in terms of thioether) for stating raw mixture can be 0.05-100h^-1, preferably 0.1-80h^-1, more preferably 15- 75h^-1.In the present invention, weight (hourly) space velocity (WHSV) is on the basis of the total amount of Titanium Sieve Molecular Sieve in whole catalyst beds.

According to the method for the present invention, the oxidant can be the common various objects that sulfide oxidation can be become to sulfone Matter.Method of the invention is particularly suitable for carry out oxidizing sulfur ether using peroxide as oxidant to prepare the occasion of sulfone, such energy Enough significantly improve the effective rate of utilization of peroxide.The peroxide refers to the compound for containing-O-O- key in molecular structure, Hydrogen peroxide, organic peroxide and peracid can be selected from.The organic peroxide refers to one in hydrogen peroxide molecule Or two hydrogen atoms replaced by organic group obtained from substance.The peracid refers to having containing-O-O- key in molecular structure Machine oxyacid.In the present invention, the specific example of the oxidant be can include but is not limited to: hydrogen peroxide, tert-butyl hydroperoxide Hydrogen, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is peroxidating Hydrogen can further decrease separation costs in this way.

The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.From further increasing root It sets out according to the angle of the safety of method of the invention, it is preferable to use existing mistakes as an aqueous solution according to the method for the present invention Hydrogen oxide.According to the method for the present invention, when the hydrogen peroxide provides as an aqueous solution, the aqueous hydrogen peroxide solution Concentration can be the normal concentration of this field, such as: 20-80 weight %.Concentration meets the water-soluble of the hydrogen peroxide of above-mentioned requirements Liquid can be prepared using conventional method, be also commercially available, such as: it can be the dioxygen for the 30 weight % that can be commercially available Water, the hydrogen peroxide of 40 weight %, the hydrogen peroxide of 50 weight %, the hydrogen peroxide of 60 weight % or 70 weight % hydrogen peroxide.

According to the method for the present invention, the raw mixture preferably comprises solvent with or without solvent, passes through adjusting in this way The content of solvent in raw mixture can be adjusted the speed of reaction, keep reaction more steady.The solvent can be It is various to dissolve thioether and oxidant or promote the two mixing, and it is capable of the liquid substance of solubilized target oxidation product.One As, the solvent can be selected from water, C₁-C₆Alcohol, C₃-C₈Ketone and C₂-C₆Nitrile.The specific example of the solvent can wrap It includes but is not limited to: water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.

The dosage of the solvent can make appropriate choice according to the dosage of thioether and oxidant.Generally, described molten The initial molar ratio of agent and the thioether can be 0.1-100:1, preferably 0.2-80:1, such as 5-60:1.

According to the method for the present invention, the thioether can be the various compounds containing-S- key, and the preferably described thioether is selected from Carbon atom number is the thioether of 2-18, more preferably dimethyl sulfide or thioanisole.

According to the method for the present invention, this method further includes at least carrying out primary set-up procedure, in the when progress of the condition 1 of satisfaction The set-up procedure stops the set-up procedure when until meeting condition 2 to improve desirable oxidation selectivity of product,

The set-up procedure is to improve the content of oxidant in raw mixture.

The content of oxidant can be in terms of mass content in the raw mixture.

According to the method for the present invention, in the condition 2 of satisfaction, stop set-up procedure, that is, stop improving oxygen in raw mixture The content of agent and the numerical value when content of oxidant to be remained to the condition 2 of satisfaction.

According to the method for the present invention when desirable oxidation selectivity of product drops to and meets above-mentioned condition 1, the original is improved The content for expecting oxidant in mixture can make the desirable oxidation selectivity of product that downward trend is presented originally go up, thus will Desirable oxidation selectivity of product maintains higher level for a long time, extends the single trip use longevity of the Titanium Sieve Molecular Sieve as catalyst Life, reduces the regeneration frequency of catalyst.

In condition 1, it is preferable that 0.85≤S_t/S₀.When condition 1 meets above-mentioned requirements, it can more effectively extend titanium silicon The single trip use service life of molecular sieve.

Under the premise of obtaining satisfactory device parallel-adder settle-out time, from when the further effective operation for extending device Between angle set out, in condition 1, S_t/S₀<0.95.Preferably, in condition 1, S_t/S₀< 0.92, such as S_t/S₀<0.9。

In the present invention, desirable oxidation selectivity of product is calculated by using the following formula.

The desirable oxidation selectivity of product=(molal quantity of desirable oxidation product/participation reaction in obtained reaction mixture Thioether molal quantity) × 100%；

Wherein, it participates in remaining in the obtained reaction mixture of molal quantity-of molal quantity=addition thioether of the thioether of reaction The molal quantity of remaining thioether.

Can by continuously monitor during the reaction the composition of the reaction mixture exported from fixed bed reactors come Determine desirable oxidation selectivity of product S_tAnd S '.

In the present invention, initial target oxidation product selectivity S₀It is anti-from fixed bed after fixed bed reactors stable operation The composition for the first batch of reaction mixture for answering device to export determines.For example, can will be obtained within reactor stable operation 0.5-10 hours The reaction mixture arrived is as first batch of reaction mixture.

It can be using the composition for the reaction mixture that conventional method measurement is exported from fixed bed reactors, such as gas phase color Spectrometry.

According to the method for the present invention, although in the condition 1 of satisfaction, the content of oxidant is increased until desirable oxidation product selects Selecting property S ' meets condition 2, contains it is preferred that improving oxidant in raw mixture with 0.01-5 weight %/day amplitude On the one hand amount can obtain the longer Titanium Sieve Molecular Sieve single trip use service life in this way, on the other hand can also avoid catalyst bed There is temperature runaway phenomenon in layer, so that reaction can be carried out steadily.It is highly preferred that increasing raw material with 0.05-2 weight %/day amplitude The content of oxidant in mixture.

Method according to the invention it is possible to improve the content of oxidant in raw mixture using various methods.Such as: The additive amount of oxidant when preparing the raw mixture can be improved to improve the content of oxidant in raw mixture.In oxygen When agent is provided in the form of oxidizing agent solution, original can be improved to realize by improving the concentration of oxidant in oxidizing agent solution Expect the content of oxidant in mixture, the dosage of oxidizing agent solution can remain unchanged at this time, can also accordingly be adjusted (example Such as, the dosage of oxidizing agent solution is reduced, accordingly to keep the constant rate between thioether and oxidant), as long as can ensure that raw material The content of oxidant is to improve in mixture.This mode is especially suitable for using the peroxidating provided in the form of hydrogen peroxide The occasion of hydrogen can pass through the concentration of hydrogen peroxide in raising hydrogen peroxide at this time.According to the method for the present invention, in the reaction The content of oxidant in raw mixture can be improved with lower amplitude early period；It phase after the reaction, can be with higher amplitude Improve the content of oxidant in raw mixture.

According to the method for the present invention, the amount of other materials in raw mixture as the case may be, can remain unchanged, It can also accordingly be adjusted, be not particularly limited.

The initial content of the oxidant can be selected according to expected oxidation product, be not particularly limited.Generally The initial molar ratio of ground, oxidant and thioether can be 2-5:1, preferably 2-4:1, more preferably 2-3:1, further preferably 2-2.5:1.

The initial molar ratio refers to the molar ratio of oxidant and thioether when device realizes stable operation.

According to the method for the present invention, in the condition 2 of satisfaction, stop improving the content of oxidant and holding in raw mixture Oxygenate content is remained into the numerical value after increasing.

According to the method for the present invention, the oxidation reaction carries out under conditions of being enough becomes sulfone for sulfide oxidation.Generally Ground, the oxidation reaction condition includes: the temperature of catalyst bed can be for 20-160 DEG C, and preferably 30-140 DEG C, more preferably It is 40-120 DEG C, is still more preferably 50-100 DEG C, particularly preferably 50-75 DEG C.Contain first in the catalyst bed When catalyst bed and the second catalyst bed, the reaction condition of first catalyst bed and the second catalyst bed can be with It is identical, or different.From the angle of ease-to-operate, first catalyst bed and the second catalyst bed it Between reaction condition it is identical.The oxidation reaction can carry out under the pressure of 0-3MPa, preferably in the pressure of 0.1-1.5MPa Lower progress, more preferably carries out under the pressure of 0.2-1MPa, and the pressure is gauge pressure.

Method according to the invention it is possible to implement in conventional reactor, carried out preferably in fixed bed reactors.

It according to the method for the present invention can also include that the reaction mixture that will be exported from reactor separates, to obtain Desirable oxidation product (such as sulfone) and unreacted reactant.The method that reaction mixture is separated can be this field Conventional selection is not particularly limited.The unreacted reactant isolated can be recycled.

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

In following embodiment and comparative example, used reagent is commercially available reagent, and pressure is gauge pressure.

In following embodiment and comparative example, each ingredient contains in the product mixtures analyzed using gas-chromatography Following formula is respectively adopted on this basis to calculate thioether rate and sulfone selectivity in amount:

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

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

In following embodiment and comparative example, static nitrogen adsorption method and solid ultraviolet-visible diffuse reflectance spectrum method is respectively adopted The Kong Rong and ultraviolet absorption peak of Titanium Sieve Molecular Sieve after before modified are characterized.Wherein, solid ultraviolet-visible diffuse reflectance spectrum (UV-Vis) analysis carries out on SHIMADZU UV-3100 type ultraviolet-visible spectrometer；Static nitrogen is adsorbed on It is carried out on the 2405 type static state n2 absorption apparatus of ASAP of Micromeritics company.

It is related to below through determining Titanium Sieve Molecular Sieve using following methods in the regenerated embodiment and comparative example for drawing off agent The activity of (including regenerative agent and fresh dose):

By Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH₃Meter), the hydrogen peroxide of 30 weight % is (with H₂O₂Meter), the tert-butyl alcohol With cyclohexanone by weight after=1:7.5:10:7.5:10 mixing at atmosheric pressure after 80 DEG C are stirred to react 2 hours, will be anti- It answers object to filter, liquid phase is analyzed with gas-chromatography, be calculated using the following equation the conversion ratio of cyclohexanone and as titanium The activity of si molecular sieves,

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

In the embodiment and comparative example of the step of preparation Titanium Sieve Molecular Sieve included below, X-ray diffraction analysis exists It is carried out on Siemens D5005 type X-ray diffractometer, with sample and authentic specimen, the five fingers spread out between 2 θ is 22.5 ° -25.0 ° The crystallinity for penetrating the ratio of the sum of diffracted intensity (peak height) of characteristic peak to indicate sample relative to authentic specimen；Fourier transform Infrared spectrum analysis carries out on 8210 type Fourier transformation infrared spectrometer of Nicolet；Silicon titanium ratio refers to silica and oxidation The molar ratio of titanium, urface silicon titanium use the ESCALab250 type x-ray photoelectron spectroscopy of Thermo Scientific company Measurement, body phase silicon titanium ratio are measured using Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer.

Embodiment 1-22 is for illustrating method of the invention.

Embodiment 1

Titanium-silicon molecular sieve TS-1 used in the present embodiment is referring to Zeolites, 1992, Vol.12 institutes in the 943-950 pages Prepared by the method for description, the specific method is as follows.

(20 DEG C) at room temperature mix 22.5g tetraethyl orthosilicate with 7.0g as the tetrapropylammonium hydroxide of template It closes, and 59.8g distilled water is added, it is molten in normal pressure and 60 DEG C of hydrolysis 1.0h, the hydrolysis for obtaining tetraethyl orthosilicate after being stirred Liquid.With vigorous stirring, it is slowly added into Xiang Suoshu hydrating solution by 1.1g butyl titanate and 5.0g anhydrous isopropyl alcohol institute The solution of composition obtains clear colloid by gained mixture in 75 DEG C of stirring 3h.It is anti-that this colloid is placed in stainless steel sealing It answers in kettle, places 36h in 170 DEG C of at a temperature of constant temperature, obtain the mixture of crystallization product.Obtained mixture is filtered, is received After collecting obtained solid matter water used wash, in 110 DEG C of dry 1h, then in 500 DEG C of roasting 6h, to obtain Titanium Sieve Molecular Sieve TS-1, titanium oxide content are 2.8 weight %.

The titanium-silicon molecular sieve TS-1 of preparation is formed using following methods, to obtain the catalyst that the present embodiment uses.

Titanium-silicon molecular sieve TS-1 is uniformly mixed with silica solution (silica content is 30 weight %) and water, wherein titanium silicon The weight ratio of molecular sieve TS-1, the silica solution in terms of silica and water is 1:0.2:1.5.Obtained mixture is made through spin Grain, and by obtained wet grain in 550 DEG C of roasting 5h, to obtain the catalyst that volume average particle size is 200 μm.Wherein, it is catalyzed In agent, the content of titanium-silicon molecular sieve TS-1 is 80 weight %.

By Catalyst packing in fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed is 1 Layer, the ratio of height to diameter of catalyst bed are 10.By dimethyl sulfide, as oxidant hydrogen peroxide (with the dioxygen of 30 weight % The form of water provides) and water as solvent be mixed to form raw mixture, by raw mixture from the bottom of fixed bed reactors Portion is sent into and flows through catalyst bed.Wherein, the initial molar ratio of dimethyl sulfide and hydrogen peroxide is 1:2.2, dimethyl disulfide The initial molar ratio of ether and water (including the water in hydrogen peroxide) is 1:40, and the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 70h^-1.Catalyst Temperature in bed is 55 DEG C, and the pressure in fixed bed reactors is 0.5MPa.

The composition that the raw mixture exported from reactor is continuously monitored in reaction process, in dimethyl sulfone selectivity S_t With initial while proceeding to 0.5 hour (react sampling and measuring) dimethyl sulfone selectivity S₀Ratio S_t/S₀For 0.8≤S_t/S₀<0.9 When, with 0.05-2 weight %/day amplitude improve raw mixture in oxidant concentration (in raw mixture hydrogen peroxide with The ratio of dimethyl sulfide remains unchanged, and improves the concentration of hydrogen peroxide in hydrogen peroxide), up to dimethyl sulfone selectivity S ' and just Beginning dimethyl sulfone selectivity S₀Ratio S '/S₀For 0.9≤S '/S₀When≤1, stops improving oxygenate content and contain oxidant Amount remains the numerical value after increasing.

When reaction proceeds to 620h, the concentration of hydrogen peroxide is 48 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 620h to obtain is listed in table 1.

Comparative example 1

Using method cacodyl oxide base sulfone same as Example 1, the difference is that, feed change does not mix in reaction process The concentration of oxidant in object.The result that reaction 0.5h and 400h is obtained is listed in table 1.

Embodiment 2

Dimethyl sulfone is prepared using method same as Example 1, unlike, the titanium-silicon molecular sieve TS-1 of preparation into It is modified using following methods (that is, the Titanium Sieve Molecular Sieve that will be prepared using method same as Example 1 before row molding TS-1 is modified processing as raw material), and the titanium-silicon molecular sieve TS-1 of obtained modification is used into side same as Example 1 Method is formed, to obtain the catalyst that the present embodiment uses.

Titanium-silicon molecular sieve TS-1 and contain HNO₃(HNO₃Mass concentration 10%) and the hydrogen peroxide (matter of hydrogen peroxide be Measuring concentration is aqueous solution mixing 7.5%), and obtained mixture is stirred to react 5h at 70 DEG C in closed container, is obtained The temperature of reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to constant weight at 120 DEG C, is modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂The molar ratio of meter, Titanium Sieve Molecular Sieve and hydrogen peroxide is 1:0.1. Suction compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification between 230-310nm The peak area for receiving peak reduces 3.5%, is held by the hole of static determination of nitrogen adsorption and reduces 2.6%.

When reaction proceeds to 800h, the concentration of hydrogen peroxide is 47 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 800h to obtain is listed in table 1.

Embodiment 3

Dimethyl sulfone is prepared using method same as Example 1, unlike, titanium silicon molecule is prepared using following methods Sieve TS-1.

First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar 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.Above-mentioned dispersion liquid is sealed in beaker using sealed membrane It is stood for 24 hours after mouthful room temperature (being 25 DEG C, similarly hereinafter), is stirred 2h at 35 DEG C followed by magnetic agitation, is allowed to disperse again. Again the dispersion liquid after dispersing is transferred in sealing reaction kettle, in 140 DEG C of experience first stage crystallization 6h, then by mixture Be cooled to after 30 DEG C of experience second stage stop 2h, continue in sealing reaction kettle in 170 DEG C at a temperature of undergo the phase III Crystallization 12h (is wherein, 2 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first stage crystallization temperature The rate of temperature fall for spending second stage treatment temperature is 5 DEG C/min, by second stage treatment temperature to phase III crystallization temperature Heating rate be 10 DEG C/min), will gained crystallization product take out after without filtering and washing step, directly in 110 DEG C dry Then 2h roasts 3h at 550 DEG C, obtain molecular sieve.The titanium of XRD crystalline phase figure and 1 step of embodiment (2) preparation of gained sample Silicalite TS-1 is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier Transform Infrared Spectroscopy figure In, in 960cm^-1Nearby there is absorption peak, show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, titanium oxide content is 3.5 weight %, urface silicon titanium/body phase silicon titanium ratio be 2.58 (embodiment 1 prepare Titanium Sieve Molecular Sieve in, urface silicon titanium/body 1.05) phase silicon titanium ratio is.

When reaction proceeds to 960h, the concentration of hydrogen peroxide is 48 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 960h to obtain is listed in table 1.

Embodiment 4

Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), preparing titanium silicon molecule When sieving TS-1, the crystallization temperature of phase III is also 140 DEG C.It is prepared by the XRD crystalline phase figure and 1 step of embodiment (2) of gained sample Titanium-silicon molecular sieve TS-1 it is consistent, what is illustrated is the TS-1 molecular sieve with MFI structure；In fourier-transform infrared spectrogram In 960cm^-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase Silicon titanium ratio is 4.21, and titanium oxide content is 3.1 weight %.

When reaction proceeds to 850h, the concentration of hydrogen peroxide is 50 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 850h to obtain is listed in table 1.

Embodiment 5

Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), preparing titanium silicon molecule When sieving TS-1, the crystallization temperature of first stage is 110 DEG C.XRD crystalline phase figure and 1 step of embodiment (2) preparation of gained sample Titanium-silicon molecular sieve TS-1 is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；In fourier-transform infrared spectrogram 960cm^-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon Titanium ratio is 2.37, and titanium oxide content is 3.2 weight %.

When reaction proceeds to 900h, the concentration of hydrogen peroxide is 49 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 900h to obtain is listed in table 1.

Embodiment 6

Dimethyl sulfone is prepared using method same as Example 3, unlike, the crystallization time of first stage is 12h. The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (2), and what is illustrated is to have The TS-1 molecular sieve of MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absorption peak, shows that titanium has entered and divide Sub- sieve skeleton frame, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 3.78, and titanium oxide content is 3.4 weight %.

When reaction proceeds to 820h, the concentration of hydrogen peroxide is 48 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 820h to obtain is listed in table 1.

Embodiment 7

Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), second stage is cooling To 70 DEG C of stop 2h.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (2), explanation What is obtained is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absorption peak, table Bright titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.75, and titanium oxide content is 3.1 weight %.

Embodiment 8

Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), second stage is cooling To 30 DEG C of stop 0.2h.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (2), says It is bright that obtain is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absorption peak, Show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.14, titanium oxide content For 2.4 weight %.

When reaction proceeds to 740h, the concentration of hydrogen peroxide is 53 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 740h to obtain is listed in table 1.

Embodiment 9

Dimethyl sulfone is prepared using method same as Example 3, unlike, when preparing titanium-silicon molecular sieve TS-1, In step (2), without second stage.The Titanium Sieve Molecular Sieve of XRD crystalline phase figure and 1 step of embodiment (2) preparation of gained sample TS-1 is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Near There is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.08, Titanium oxide content is 2.5 weight %.

When reaction proceeds to 700h, the concentration of hydrogen peroxide is 52 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 700h to obtain is listed in table 1.

Embodiment 10

Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), aqueous dispersions are not in room Temperature is lower to be stood for 24 hours, but is sent directly into reaction kettle and is carried out crystallization.The XRD crystalline phase figure and 1 step of embodiment (2) of gained sample The titanium-silicon molecular sieve TS-1 of preparation is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；Fourier-transform infrared spectrum In 960cm in figure^-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, urface silicon titanium/body phase silicon titanium ratio is 1.18, in the Titanium Sieve Molecular Sieve, titanium oxide content is 3.5 weight %.

When reaction proceeds to 730h, the concentration of hydrogen peroxide is 50 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 730h to obtain is listed in table 1.

Embodiment 11

Dimethyl sulfone is prepared using method same as Example 2, unlike, the titanium silicon of the raw material as modification Molecular sieve is that (titanium-silicon molecular sieve TS-1 is adopted through the regenerated titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit Prepared with method same as Example 1, the Titanium Sieve Molecular Sieve drawn off 570 DEG C at a temperature of roast in air atmosphere 5h and Regeneration, the activity after regeneration are 35%, 96%) activity when fresh is.Compared with raw material Titanium Sieve Molecular Sieve, obtained modification The peak area of absorption peak in the UV-Vis spectrum of Titanium Sieve Molecular Sieve between 230-310nm reduces 3.3%, by static N2 adsorption The hole of method measurement, which holds, reduces 2.8%.

When reaction proceeds to 960h, the concentration of hydrogen peroxide is 46 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 960h to obtain is listed in table 1.

Embodiment 12

Dimethyl sulfone is prepared using method identical with embodiment 11, unlike, catalyst is directly will be through regenerated The titanium-silicon molecular sieve TS-1 (with embodiment 11) drawn off from phenol hydroxylation reaction unit is formed, thus the catalysis of preparation Agent C3.

When reaction proceeds to 760h, the concentration of hydrogen peroxide is 48 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 760h to obtain is listed in table 1.

Table 1

Embodiment 13

It will be as the Titanium Sieve Molecular Sieve of the raw material (trade mark purchased from Hunan Jianchang Petrochemical Co., Ltd using following methods For the hollow Titanium Sieve Molecular Sieve of HTS, titanium oxide content is 2.5 weight %) it is modified processing.

By hollow Titanium Sieve Molecular Sieve and contain HNO₃(HNO₃Mass concentration be 10%) and hydrogen peroxide (hydrogen peroxide Mass concentration is aqueous solution mixing 5%), obtained mixture is stirred under 120 DEG C of pressure itselfs in closed container anti- 4h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C Weight, obtains modified Titanium Sieve Molecular Sieve.Wherein, hollow Titanium Sieve Molecular Sieve is with SiO₂Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub You are than being 1:0.4.Compared with raw material Titanium Sieve Molecular Sieve, in 230- in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 310nm reduces 4.6%, is held by the hole of static determination of nitrogen adsorption and reduces 3.8%.

The hollow Titanium Sieve Molecular Sieve of the modification of preparation is formed using following methods, obtains the catalysis that the present embodiment uses Agent.

Modified Titanium Sieve Molecular Sieve is uniformly mixed with silica solution (silica content is 30 weight %) and water, wherein titanium The weight ratio of silicalite TS-1, the silica solution in terms of silica and water is 1:0.15:5.Obtained mixture is made through spin Grain, and by obtained wet grain in 550 DEG C of roasting 5h, to obtain the catalyst that average grain diameter is 500 μm.Wherein, in catalyst, The content of hollow Titanium Sieve Molecular Sieve is 85 weight %.

By Catalyst packing in fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed is 1 Layer, the ratio of height to diameter of catalyst bed are 10.By dimethyl sulfide, as oxidant hydrogen peroxide (with the dioxygen of 25 weight % The form of water provides) and methanol as solvent be mixed to form reaction mixture, by reaction mixture from fixed bed reactors Bottom is sent into and flows through catalyst bed.Wherein, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1:2.5, dimethyl sulfide Molar ratio with methanol is 1:15, and the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 75h^-1.Temperature in catalyst bed is 70 DEG C, fixed Pressure in bed reactor is 0.8MPa.

The composition that the raw mixture exported from reactor is continuously monitored in reaction process, in dimethyl sulfone selectivity S_t With initial while proceeding to 0.5 hour (react sampling and measuring) dimethyl sulfone selectivity S₀Ratio S_t/S₀For 0.82≤S_t/S₀< When 0.92, the concentration (peroxide in raw mixture of oxidant in raw mixture is improved with 0.05-1.5 weight %/day amplitude The ratio for changing hydrogen and dimethyl sulfide remains unchanged, and improves the concentration of hydrogen peroxide in hydrogen peroxide), until dimethyl sulfone selectivity S ' and initial dimethyl sulfone selectivity S₀Ratio S '/S₀For 0.92≤S '/S₀When≤1, stop improving oxygenate content and by oxygen Agent content remains the numerical value after increasing.

When reaction proceeds to 850h, the concentration of hydrogen peroxide is 52 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 850h to obtain is listed in table 2.

Embodiment 14

Dimethyl sulfone is prepared using method identical with embodiment 13, unlike, as the sky of raw material in modification Heart Titanium Sieve Molecular Sieve is hollow Titanium Sieve Molecular Sieve (the hollow titanium silicon drawn off from cyclohexanone oxamidinating reaction unit through regenerated Molecular sieve is identical as the source of hollow Titanium Sieve Molecular Sieve of raw material of modification as embodiment 13, the hollow titanium silicon drawn off point Son sieve 550 DEG C at a temperature of roast 6h in air atmosphere and regenerate, the activity after regeneration is 40%, and activity when fresh is 97%).Compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification 230-310nm it Between absorption peak peak area reduce 4.8%, by static determination of nitrogen adsorption hole hold reduce 3.5%.

The hollow Titanium Sieve Molecular Sieve of obtained modification is formed using method identical with embodiment 13, thus this reality Apply the catalyst that example uses.

When reaction proceeds to 960h, the concentration of hydrogen peroxide is 50 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 960h to obtain is listed in table 2.

Embodiment 15

Dimethyl sulfone is prepared using method identical with embodiment 13, unlike, hollow Titanium Sieve Molecular Sieve is without modification Processing, is directly formed, to prepare catalyst.

When reaction proceeds to 660h, the concentration of hydrogen peroxide is 52 weight % in hydrogen peroxide.It is right in tandem reaction sequence The composition of the product mixtures of reactor output is monitored and calculates dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result for answering 0.5h and 660h to obtain is listed in table 2.

Table 2

Embodiment 16

The titanium-silicon molecular sieve TS-1 that the present embodiment uses is prepared using following methods.

First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar 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.Above-mentioned dispersion liquid is close using sealed membrane in beaker It is honored as a queen in 40 DEG C of standing 10h, is stirred 0.5h at 25 DEG C followed by magnetic agitation, is allowed to disperse again.It will disperse again Dispersion liquid afterwards is transferred in sealing reaction kettle, and in 130 DEG C of experience first stage crystallization 8h, mixture is then cooled to 50 DEG C After undergoing second stage to stop 5h, continues the temperature in sealing reaction kettle in 170 DEG C and undergo phase III crystallization 16h (wherein, It is 1 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first stage crystallization temperature to second stage The rate of temperature fall for the treatment of temperature is 10 DEG C/min, and the heating rate by second stage treatment temperature to phase III crystallization temperature is 20 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly in 120 DEG C of drying 3h, then 580 2h is roasted at DEG C, obtains molecular sieve.The titanium-silicon molecular sieve TS-1 of XRD crystalline phase figure and 1 step of embodiment (1) preparation of gained sample Unanimously, what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；In Fourier Transform Infrared Spectroscopy figure, in 960cm^-1 Nearby there is absorption peak, show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.25, titanium oxide content is 2.6 weight %.

The titanium-silicon molecular sieve TS-1 of preparation is formed using following methods, obtains the catalyst that the present embodiment uses.

Titanium-silicon molecular sieve TS-1 is uniformly mixed with silica solution (silica content is 30 weight %) and water, wherein titanium silicon The weight ratio of molecular sieve TS-1, the silica solution in terms of silica and water is 1:0.1:8.Obtained mixture is granulated through spin, And by obtained wet grain in 550 DEG C of roasting 5h, to obtain the catalyst that average grain diameter is 100 μm.Wherein, in catalyst, titanium The content of silicalite TS-1 is 90 weight %.

By Catalyst packing in fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed is 1 Layer, the ratio of height to diameter of catalyst bed are 10.By dimethyl sulfide, as oxidant tert-butyl hydroperoxide (with 22 weight % The form of acetonitrile solution provide) and acetonitrile as solvent be mixed to form reaction mixture, by reaction mixture from fixed bed The bottom of reactor is sent into and flows through catalyst bed.Wherein, the molar ratio of dimethyl sulfide and tert-butyl hydroperoxide is 1: 2.1, the initial molar ratio of dimethyl sulfide and acetonitrile (acetonitrile in the acetonitrile solution including tert-butyl hydroperoxide) is 1:35, The weight (hourly) space velocity (WHSV) of dimethyl sulfide is 45h^-1.Temperature in catalyst bed is 72 DEG C, and the pressure in fixed bed reactors is 0.6MPa。

The composition that the raw mixture exported from reactor is continuously monitored in reaction process, in dimethyl sulfone selectivity S_t With initial while proceeding to 0.5 hour (react sampling and measuring) dimethyl sulfone selectivity S₀Ratio S_t/S₀For 0.85≤S_t/S₀<0.9 When, the concentration (t-butyl peroxy in raw mixture of oxidant in raw mixture is improved with 0.05-2 weight %/day amplitude The ratio for changing hydrogen and dimethyl sulfide remains unchanged, and improves the tert-butyl hydroperoxide in the acetonitrile solution of tert-butyl hydroperoxide Concentration), until dimethyl sulfone selectivity S ' and initial dimethyl sulfone selectivity S₀Ratio S '/S₀For 0.9≤S '/S₀≤1 When, stop improving oxygenate content and oxygenate content is remained into the numerical value after increasing.

When reaction proceeds to 840h, the concentration of tert-butyl hydroperoxide is 45 weights in the acetonitrile solution of tert-butyl hydroperoxide Measure %.The composition of the product mixtures of reactor output is monitored in tandem reaction sequence and calculates dimethyl sulfide and is turned Rate and dimethyl sulfone selectivity, the result that reaction 0.5h and 840h is obtained are listed in table 3.

Embodiment 17

Dimethyl sulfone is prepared using method identical with embodiment 16, unlike, titanium-silicon molecular sieve TS-1 carry out at Before type, it is modified processing using following methods, and by the Titanium Sieve Molecular Sieve of obtained modification using identical as embodiment 16 Method formed, to prepare the catalyst that the present embodiment uses.

The titanium-silicon molecular sieve TS-1 of preparation and contain HNO₃(HNO₃Mass concentration 15%) and hydrogen peroxide (peroxidating be The mass concentration of hydrogen is aqueous solution mixing 8%), and obtained mixture is stirred to react 3h at 150 DEG C in closed container, is obtained To the temperature of reaction mixture be cooled to room temperature and be filtered, obtained solid matter is dry to constant weight at 120 DEG C, obtain Modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂The molar ratio of meter, Titanium Sieve Molecular Sieve and hydrogen peroxide is 1: 2.Through characterizing, compared with raw material Titanium Sieve Molecular Sieve, in 230-310nm in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification Between absorption peak peak area reduce 5.5%, by static determination of nitrogen adsorption hole hold reduce 4.3%.

When reaction proceeds to 920h, the concentration of tert-butyl hydroperoxide is 43 weights in the acetonitrile solution of tert-butyl hydroperoxide Measure %.The composition of the product mixtures of reactor output is monitored in tandem reaction sequence and calculates dimethyl sulfide and is turned Rate and dimethyl sulfone selectivity, the result that reaction 0.5h and 920h is obtained are listed in table 3.

Embodiment 18

Dimethyl sulfone is prepared using method identical with embodiment 17, unlike, as the titanium of raw material in modification Si molecular sieves are through regenerated titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 drawn off from propylene ring oxidation reaction device Prepared using method identical with embodiment 16, the Titanium Sieve Molecular Sieve drawn off 580 DEG C at a temperature of roast in air atmosphere 3h and regenerate, the activity after regeneration is 40%, 95%) activity when fresh is.Compared with raw material Titanium Sieve Molecular Sieve, what is obtained changes Property Titanium Sieve Molecular Sieve UV-Vis spectrum in the peak area of absorption peak between 230-310nm reduce 5.3%, by static nitrogen The hole of determination of adsorption method, which holds, reduces 4.8%.

The Titanium Sieve Molecular Sieve of obtained modification is formed using method identical with embodiment 16, obtains the present embodiment The catalyst used.

When reaction proceeds to 1000h, the concentration of tert-butyl hydroperoxide is 40 in the acetonitrile solution of tert-butyl hydroperoxide Weight %.The composition of the product mixtures of reactor output is monitored in tandem reaction sequence and calculates dimethyl sulfide Conversion ratio and dimethyl sulfone selectivity, the result that reaction 0.5h and 1000h is obtained are listed in table 3.

Embodiment 19

Dimethyl sulfone is prepared using method identical with embodiment 18, unlike, it will be through regenerated from epoxidation of propylene The titanium-silicon molecular sieve TS-1 drawn off in reaction unit is directly formed without modification, to prepare catalyst.

When reaction proceeds to 780h, the concentration of tert-butyl hydroperoxide is 41 weights in the acetonitrile solution of tert-butyl hydroperoxide Measure %.The composition of the product mixtures of reactor output is monitored in tandem reaction sequence and calculates dimethyl sulfide and is turned Rate and dimethyl sulfone selectivity, the result that reaction 0.5h and 780h is obtained are listed in table 3.

Table 3

Embodiment 20

First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar 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.Above-mentioned dispersion liquid is utilized into sealed membrane in beaker In 45 DEG C of standing 8h after sealing；Dispersion liquid through standing is transferred in sealing reaction kettle, in 140 DEG C of experience first stage crystallization 6h continues in sealing reaction kettle after mixture is then cooled to 40 DEG C of experience second stage stop 1h in 160 DEG C of temperature Lower experience phase III crystallization 12h (it is wherein, 5 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by The rate of temperature fall of first stage crystallization temperature to second stage treatment temperature is 5 DEG C/min, by second stage treatment temperature to the The heating rate of three stage crystallization temperatures is 5 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly 110 DEG C of drying 2h are connected to, 3h is then roasted at 550 DEG C, obtain molecular sieve.The XRD crystalline phase figure and 1 step of embodiment of gained sample Suddenly the titanium-silicon molecular sieve TS-1 of (1) preparation is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier In transform infrared spectroscopy figure, in 960cm^-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, the Titanium Sieve Molecular Sieve In, urface silicon titanium/body phase silicon titanium ratio is 2.71, and titanium oxide content is 4.3 weight %.

Titanium-silicon molecular sieve TS-1 is uniformly mixed with silica solution (silica content is 30 weight %) and water, wherein titanium silicon The weight ratio of molecular sieve TS-1, the silica solution in terms of silica and water is 1:0.1:8.Obtained mixture is granulated through spin, And by obtained wet grain in 500 DEG C of roasting 6h, to obtain the catalyst that average grain diameter is 300 μm.Wherein, in catalyst, titanium The content of si molecular sieves is 90 weight %.

By Catalyst packing in fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed is 1 Layer, the ratio of height to diameter of catalyst bed are 10.By thioanisole, it is (molten with the acetone of 25 weight % as the Perpropionic Acid of oxidant The form of liquid provides) and acetone as solvent be mixed to form reaction mixture, by reaction mixture from fixed bed reactors Bottom is sent into and flows through catalyst bed.Wherein, the molar ratio of thioanisole and Perpropionic Acid is 1:2.2, thioanisole and third The initial molar ratio of ketone (acetone in the acetone soln including Perpropionic Acid) is 1:45, and the weight (hourly) space velocity (WHSV) of thioanisole is 15h^-1.Temperature in catalyst bed is 65 DEG C, and the pressure in fixed bed reactors is 0.5MPa.

The composition that the raw mixture exported from reactor is continuously monitored in reaction process, in lauseto neu selectivity S_tWith Initially (sampling and measuring when reaction proceeds to 0.5 hour) lauseto neu selectivity S₀Ratio S_t/S₀For 0.85≤S_t/S₀When < 0.9, Concentration (Perpropionic Acid and the benzene in compound of reaction of oxidant in raw mixture are improved with 0.05-2 weight %/day amplitude The ratio of methyl sulfide remains unchanged, and improves the concentration of Perpropionic Acid in the acetone soln of Perpropionic Acid), until lauseto neu selectivity S ' and initial lauseto neu selectivity S₀Ratio S '/S₀For 0.9≤S '/S₀When≤1, stops improving oxygenate content and will aoxidize Agent content remains the numerical value after increasing.

When reaction proceeds to 750h, the concentration of Perpropionic Acid is 51 weight % in the acetone soln of Perpropionic Acid.Continuous The composition of the product mixtures of reactor output is monitored in reaction process and calculates thioanisole conversion ratio and lauseto neu Selectivity, the result that reaction 0.5h and 750h is obtained are listed in table 4.

Embodiment 21

Lauseto neu is prepared using method identical with embodiment 20, unlike, titanium-silicon molecular sieve TS-1 is being formed Before, it is modified using following methods, and the Titanium Sieve Molecular Sieve of obtained modification is used into method identical with embodiment 20 It is formed, obtains the catalyst that the present embodiment uses.

Titanium-silicon molecular sieve TS-1 and contain HNO₃(HNO₃Mass concentration 10%) and the hydrogen peroxide (matter of hydrogen peroxide be Measuring concentration is aqueous solution mixing 2%), and obtained mixture is stirred to react 2.5h at 170 DEG C in closed container, is obtained The temperature of reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to constant weight at 120 DEG C, is modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂The molar ratio of meter, Titanium Sieve Molecular Sieve and hydrogen peroxide is 1:1.Through Characterization, compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification between 230-310nm Absorption peak peak area reduce 5.7%, by static determination of nitrogen adsorption hole hold reduce 4.1%.

When reaction proceeds to 840h, the concentration of Perpropionic Acid is 50 weight % in the acetone soln of Perpropionic Acid.Continuous The composition of the product mixtures of reactor output is monitored in reaction process and calculates thioanisole conversion ratio and lauseto neu Selectivity, the result that reaction 0.5h and 840h is obtained are listed in table 4.

Embodiment 22

Lauseto neu is prepared using method identical with embodiment 21, unlike, as the titanium silicon of raw material in modification Molecular sieve be as raw material be through regenerated titanium-silicon molecular sieve TS-1 (titanium silicon drawn off from phenol hydroxylation reaction unit Molecular sieve TS-1 using method identical with embodiment 20 prepare, the titanium-silicon molecular sieve TS-1 drawn off 580 DEG C at a temperature of in 4h is roasted in air atmosphere and is regenerated, and the activity after regeneration is 40%, 95%) activity when fresh is.With raw material titanium silicon molecule Sieve is compared, and the peak area of the absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification between 230-310nm subtracts Few 5.5%, held by the hole of static determination of nitrogen adsorption and reduces 4.3%.

The Titanium Sieve Molecular Sieve of obtained modification is formed using method identical with embodiment 20, obtains the present embodiment The catalyst used.

When reaction proceeds to 950h, the concentration of Perpropionic Acid is 51 weight % in the acetone soln of Perpropionic Acid.Continuous The composition of the product mixtures of reactor output is monitored in reaction process and calculates thioanisole conversion ratio and lauseto neu Selectivity, the result that reaction 0.5h and 950h is obtained are listed in table 4.

Table 4

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

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

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

Claims

1. a kind of preparation method of sulfone, this method includes making a kind of raw mixture and Titanium Sieve Molecular Sieve in fixed bed reactors Haptoreaction, obtains the product mixtures containing sulfone, and the raw mixture contains thioether, at least one oxidant and optional At least one solvent, the oxidant be peroxide, the thioether be dimethyl sulfide and/or thioanisole, wherein should Method further includes at least carrying out primary set-up procedure, and the set-up procedure is carried out in the condition 1 of satisfaction, to improve desirable oxidation Selectivity of product stops the set-up procedure when until meeting condition 2,

Condition 1, sometime the desirable oxidation selectivity of product S under t_tWith initial target oxidation product selectivity S₀Ratio S_t/ S₀For 0.8≤S_t/S₀<1；

Condition 2, desirable oxidation selectivity of product S ' and initial target oxidation product selectivity S₀Ratio S '/S₀For 0.9≤S '/ S₀≤1；

The set-up procedure is to improve the content of oxidant in raw mixture.

2. according to the method described in claim 1, wherein, in condition 1,0.85≤S_t/S₀；In condition 1, S_t/S₀<0.95。

3. method according to claim 1 or 2, wherein in the raw mixture, with 0.01-5 weight %/day width Degree improves the content of oxidant in raw mixture.

4. according to the method described in claim 1, wherein, at least partly Titanium Sieve Molecular Sieve is modified Titanium Sieve Molecular Sieve, described Modified Titanium Sieve Molecular Sieve undergoes modification, the modification include by as the Titanium Sieve Molecular Sieve of raw material with contain nitric acid It is contacted with the modification liquid of at least one peroxide.

5. according to the method described in claim 4, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The molar ratio of peroxide is stated as 1:0.01-5, the molar ratio of the peroxide and the nitric acid is 1:0.01-50, the titanium Si molecular sieves are in terms of silica.

6. according to the method described in claim 5, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The molar ratio of peroxide is stated as 1:0.05-3, the molar ratio of the peroxide and the nitric acid is 1:0.1-20, the titanium Si molecular sieves are in terms of silica.

7. according to the method described in claim 6, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The molar ratio of peroxide is stated as 1:0.1-2, the molar ratio of the peroxide and the nitric acid is 1:0.2-10, the titanium silicon Molecular sieve is in terms of silica.

8. according to the method described in claim 7, wherein, in the modification, the peroxide and the nitric acid Molar ratio is 1:0.3-5.

9. according to the method described in claim 8, wherein, in the modification, the peroxide and the nitric acid Molar ratio is 1:0.5-3.5.

10. according to the method described in claim 4, wherein, in the modification liquid, the concentration of peroxide and nitric acid is respectively 0.1-50 weight %.

11. according to the method described in claim 10, wherein, in the modification liquid, the concentration of peroxide and nitric acid is respectively 0.5-25 weight %.

12. according to the method for claim 11, wherein in the modification liquid, the concentration of peroxide and nitric acid is respectively 1-20 weight %.

13. the method according to any one of claim 4-12, wherein in the modification, as raw material Titanium Sieve Molecular Sieve and the modification liquid 10-350 DEG C at a temperature of contacted, the contact is in the container that pressure is 0-5MPa Interior progress, the pressure are gauge pressure；The duration of the contact is 0.5-10 hours.

14. according to the method for claim 13, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 20-300 DEG C at a temperature of contacted, duration of the contact is 2-5 hours.

15. according to the method for claim 14, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 50-250 DEG C at a temperature of contacted.

16. according to the method for claim 15, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 60-200 DEG C at a temperature of contacted.

17. the method according to any one of claim 4-12, wherein in the modification, as raw material Titanium Sieve Molecular Sieve and the exposure level of the modification liquid make, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible In spectrum, the peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces by 2% or more；Modified titanium silicon The hole of molecular sieve, which holds, reduces 1% or more, and the Kong Rong is using static determination of nitrogen adsorption.

18. according to the method for claim 17, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 2-30%；The Kong Rong of modified Titanium Sieve Molecular Sieve 1-20% is reduced, the Kong Rong is using static determination of nitrogen adsorption.

19. according to the method for claim 18, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 2.5-15%；The hole of modified Titanium Sieve Molecular Sieve Hold and reduce 2-10%, the Kong Rong is using static determination of nitrogen adsorption.

20. according to the method for claim 19, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 3-10%；The Kong Rong of modified Titanium Sieve Molecular Sieve 2.5-5% is reduced, the Kong Rong is using static determination of nitrogen adsorption.

21. according to the method for claim 20, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 3-8%.

22. according to the method described in claim 1, wherein, at least partly Titanium Sieve Molecular Sieve derives from least one reaction unit Draw off agent, it is described draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation is anti- That answers device draws off agent.

23. according to the method described in claim 1, wherein, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the titanium The urface silicon titanium of silicalite TS-1 is not less than body phase silicon titanium ratio, mole of the silicon titanium than referring to silica and titanium oxide Than the urface silicon titanium is measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses x ray fluorescence spectrometry Measurement.

24. according to the method for claim 23, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is More than 1.2.

25. according to the method for claim 24, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5。

26. according to the method for claim 25, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5。

27. according to the method for claim 26, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 2- 3。

28. according to claim 1-2, method described in any one of 4-12 and 22-27, wherein at least partly titanium silicon molecule Sieve is titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1 is prepared using method comprising the following steps:

(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and optionally supplements water, dispersed Liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar 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) optionally, by the dispersion liquid 15-60 DEG C standing 6-24 hours；

(III) dispersion liquid that step (I) obtains or the dispersion liquid that step (II) obtains sequentially are undergone in sealing reaction kettle Stage (1), stage (2) and stage (3) carry out crystallization, the stage (1) 80-150 DEG C crystallization 6-72 hours；Stage (2) is cooled to Not higher than 70 DEG C and residence time at least 0.5h；Stage (3) is warming up to 120-200 DEG C, then crystallization 6-96 hours.

29. according to the method for claim 28, wherein the stage (1) 110-140 DEG C crystallization 6-8 hours.

30. according to the method for claim 29, wherein the stage, (1) was in 120-140 DEG C of crystallization.

31. according to the method for claim 30, wherein the stage, (1) was in 130-140 DEG C of crystallization.

32. according to the method for claim 28, wherein in the stage (2), the residence time is 1-5 hours.

33. according to the method for claim 28, wherein the stage (3) is warming up to 140-180 DEG C, then crystallization 12-20 hours.

34. according to the method for claim 33, wherein the stage (3) is warming up to 160-170 DEG C of crystallization again.

35. according to the method for claim 28, wherein stage (1) and stage (3) meet one of the following conditions or The two:

Condition 1: the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3)；

Condition 2: the crystallization time in stage (1) is less than the crystallization time of stage (3).

36. according to the method for claim 35, wherein the crystallization temperature in stage (1) is lower than the crystallization temperature in stage (3) 10-50℃。

37. according to the method for claim 36, wherein the crystallization temperature in stage (1) is lower than the crystallization temperature in stage (3) 20-40℃。

38. according to the method for claim 35, wherein the crystallization time in stage (1) is 5- shorter than the crystallization time in stage (3) 24 hours.

39. according to the method for claim 38, wherein the crystallization time in stage (1) is 6- shorter than the crystallization time in stage (3) 12 hours.

40. according to the method for claim 28, wherein the stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.

41. according to the method for claim 28, wherein the titanium source is inorganic titanium salt and/or organic titanate；The alkali Source template is one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine；The inorganic silicon source be silica gel and/ Or silica solution.

42. according to the method for claim 41, wherein the alkali source template is quaternary ammonium base.

43. according to the method for claim 42, wherein the alkali source template is tetrapropylammonium hydroxide.

44. according to the method for claim 41, wherein the inorganic titanium salt is TiCl₄、Ti(SO₄)₂And TiOCl₂In one Kind is two or more；The organic titanate is selected from general formula R⁷ ₄TiO₄The compound of expression, R⁷Selected from 2-4 carbon atom Alkyl.

45. according to claim 1-2, method described in any one of 4-12 and 22-27, wherein oxidant and thioether just Beginning molar ratio is 2-5:1.

46. according to the method for claim 45, wherein the initial molar ratio of oxidant and thioether is 2-4:1.

47. according to the method for claim 46, wherein the initial molar ratio of oxidant and thioether is 2-3:1.

48. according to the method for claim 47, wherein the initial molar ratio of oxidant and thioether is 2-2.5:1.

49. according to claim 1-2, method described in any one of 4-12 and 22-27, wherein the peroxide as oxidant Compound is selected from hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, mistake Fluoroacetic acid and Perpropionic Acid.

50. according to the method for claim 49, wherein the peroxide as oxidant is hydrogen peroxide.

51. the method according to any one of claim 4-12, wherein as oxidant peroxide and described change Property processing used in peroxide it is identical or different, peroxide used in the modification be selected from hydrogen peroxide, uncle Butylhydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.

52. according to the method for claim 49, wherein peroxide used in the modification is hydrogen peroxide.

53. according to claim 1-2, method described in any one of 4-12 and 22-27, wherein raw mixture and titanium silicon Molecular sieve 20-160 DEG C at a temperature of contacted, raw mixture and Titanium Sieve Molecular Sieve are under conditions of pressure is 0-3MP It is contacted, the pressure is gauge pressure.

54. method according to claim 53, wherein raw mixture and Titanium Sieve Molecular Sieve 30-140 DEG C at a temperature of It is contacted.

55. method according to claim 54, wherein raw mixture and Titanium Sieve Molecular Sieve 40-120 DEG C at a temperature of It is contacted.