CN107235870A

CN107235870A - A kind of preparation method of sulfone

Info

Publication number: CN107235870A
Application number: CN201610186655.1A
Authority: CN
Inventors: 林民; 史春风; 朱斌
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-03-29
Filing date: 2016-03-29
Publication date: 2017-10-10
Anticipated expiration: 2036-03-29
Also published as: CN107235870B

Abstract

The invention discloses a kind of preparation method of sulfone, this method is included under oxidation reaction condition, at least one thioether and at least one oxidant are contacted with HTS, the oxidant is selected from peroxide, obtain the mixture containing sulfone, the HTS is modified HTS, or the HTS is modified HTS and unmodified HTS, the HTS experience modification of the modification, the unmodified HTS does not undergo modification, the modification includes to contact as the HTS of raw material with the modification liquid containing nitric acid and at least one peroxide.The method of the present invention can effectively lift the catalytic performance of HTS, extend the single trip use life-span of HTS, reduce the regeneration frequency of HTS.

Description

A kind of preparation method of sulfone

Technical field

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

Background technology

Sulfone class material is important sulfur-containing compound, such as dimethyl sulfone be white crystalline powder, soluble in water, ethanol, benzene, Methanol and acetone, are slightly soluble in ether.Potassium permanganate can not be made to change colour under normal temperature, dimethyl sulfone can be oxidized to first by strong oxidizer Sulfonic acid.The 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 preferably 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 medicine.Dimethyl sulfone produces the ability of insulin with enhancing human body as a kind of organic sulfur compound, The metabolism to carbohydrate also has facilitation simultaneously, is the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote Wound healing, to the vitamin B needed for metabolism and neurological health, vitamin C, the synthesis of biotin and can also swash Work is worked, and is referred to as " beautifying carbonizable substance naturally ".Skin, hair, nail, bone, muscle and each organ of human body In all contain dimethyl sulfone, dimethyl sulfone is primarily present in Yu Haiyang and soil in nature, the conduct in plant growth Nutriment is absorbed, and the mankind can absorb from the foods such as veterinary antibiotics, fish, meat, egg, milk, once lacking Health disorders can be caused or occur disease, be the main matter that human body maintains biological element sulphur balance, have to human body diseases Therapeutic value and healthcare function, are human survival and the indispensable medicine of health care.It is external to give birth to dimethyl sulfone as with dimension Element nutriment of equal importance is widely applied, and application study of the China to dimethyl sulfone is not yet carried out very well, current product master It is used to export.Therefore, dimethyl sulfone is not only a kind of new high-tech product, is also a kind of fine chemistry industry of high added value Product.Product is new, market potential is big, and benefit is protruded, with wide production and application and development prospect.

At present, the product that dimethyl sulfone is further aoxidized as dimethyl sulfoxide (DMSO), is the main by-product of dimethyl sulfoxide (DMSO) production Product.

The content of the invention

It is an object of the invention to provide a kind of preparation method using peroxide as the sulfone of oxidant, this method can have The lifting of effect ground extends the single trip use life-span of HTS as the catalytic performance of the HTS of catalyst.

The invention provides a kind of preparation method of sulfone, this method is included under oxidation reaction condition, by least one thioether Contacted with least one oxidant with HTS, obtain the mixture containing sulfone, the oxidant is selected from peroxide, The HTS is modified HTS, or the HTS is modified HTS and does not change Property HTS, the modification HTS experience modification, the unmodified HTS without Modification is gone through, the modification is included as the HTS of raw material and containing nitric acid and at least one peroxidating The modification liquid contact of thing.

The method according to the invention, using modified processing modification HTS as at least part catalyst, In the case of remaining condition identical, compared with only with unmodified HTS as catalyst, can effectively it be lifted The catalytic performance of HTS, extends the single trip use life-span of HTS, reduces the regeneration frequency of HTS.

Embodiment

The embodiment to the present invention is described in detail below.It should be appreciated that specific reality described herein The mode of applying is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The invention provides a kind of preparation method of sulfone, this method is included under oxidation reaction condition, by least one thioether Contacted with least one oxidant with HTS, obtain the mixture containing sulfone.

The method according to the invention, the HTS is for modified HTS, or the HTS Modified HTS and unmodified HTS, the HTS experience modification of the modification is described Unmodified HTS does not undergo modification.

The modification comprises the following steps：Using as the HTS of raw material with containing nitric acid (that is, HNO₃) Contacted with the modification liquid of at least one peroxide.Refer to the raw material as modification as the HTS of raw material HTS, can be the HTS without going through the modification, or live through at the modification Reason still needs to carry out the HTS of the modification again.

In the present invention, peroxide refer in molecular structure contain-O-O- keys compound, can selected from hydrogen peroxide, Hydroperoxides and peracid.The hydroperoxides refer to that a hydrogen atom in hydrogen peroxide molecule is replaced by organic group Obtained from material.The peracid refers to the organic oxacid for containing-O-O- keys in molecular structure.

In the modification, the instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, tertiary fourth Base hydrogen peroxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid. Preferably, the oxidant is hydrogen peroxide.The hydrogen peroxide can in a variety of manners exist to be commonly used in the art Hydrogen peroxide.

Can be 1 as the HTS of raw material and the mol ratio of the peroxide in the modification： 0.01-5, preferably 1：0.05-3, more preferably 1：0.1-2.The consumption of the nitric acid can be according to the peroxide Consumption is selected.Usually, the mol ratio of the peroxide and the nitric acid can be 1：0.01-50, preferably 1： 0.1-20, more preferably 1：0.2-10, more preferably 1：0.5-5, particularly preferably 1：0.6-3.5, such as 1：0.7-2.8, The HTS is in terms of silica.

In the modification liquid, the concentration of the peroxide and nitric acid can be each 0.1-50 weight %.From further carrying The angle of the catalytic performance of the HTS for the modification that height is finally prepared is set out, preferably 0.5-30 weight %.More preferably In ground, the modification liquid, the concentration of the peroxide and nitric acid is respectively 1-25 weight %, such as 5-20 weight %.

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

In the modification, it can be carried out as the HTS and modification liquid of raw material at a temperature of 10-350 DEG C Contact.From the angle of the catalytic performance for the HTS for further improving the modification finally prepared, the contact is excellent Contacted at a temperature of being selected in 20-300 DEG C.It is highly preferred that the contact is carried out at a temperature of 50-250 DEG C.Enter one Preferably, the contact is carried out step at a temperature of 60-200 DEG C.It is further preferred that the contact is at 70-170 DEG C At a temperature of carry out.The time of the contact can be 0.5-10 hours, preferably 1-8 hours, more preferably 2-5 hours. In the modification, the pressure in container that will be contacted as the HTS of raw material with the modification liquid can It can be environmental pressure to be selected according to Contact Temperature, or pressurization.Usually, the titanium of raw material will be used as The pressure in container that si molecular sieves are contacted with the modification liquid can be 0-5MPa, and the pressure is gauge pressure.It is preferred that Ground, will be contacted as the HTS of raw material with the modification liquid under pressure.It is highly preferred that holding closed In will be contacted under self-generated pressure as the HTS of raw material with the modification liquid in device.

In the modification, as the HTS of raw material and the exposure level of the modification liquid preferably so that, with On the basis of the HTS of raw material, in ultraviolet-visible spectrum, modified HTS 230-310nm it Between absworption peak peak area reduction by more than 2%, the pore volume of modified HTS reduces more than 1%.Modified titanium silicon The peak area of absworption peak of the molecular sieve between 230-310nm preferably reduces 2-30%, more preferably reduces 2.5-15%, enters one The preferred reduction 3-10% of step, still more preferably reduces 3-8%, for example, reduces 3-6%.The pore volume of modified HTS It is preferred that reducing 1-20%, 1.5-10% is more preferably reduced, 2-6% is further preferably reduced, for example, reduces 2-5%.The hole Hold using static determination of nitrogen adsorption.

The method according to the invention, progress oxidation reaction is contacted with thioether and oxidant to obtain the mixture containing sulfone HTS can be the HTS of the modification, or the HTS of the modification and unmodified HTS.

In one embodiment of the invention, from the angle of operation terseness, progress is contacted with thioether and oxidant Oxidation reaction is so that the HTS for obtaining the mixture containing sulfone is the HTS of the modification.

In another embodiment of the invention, progress oxidation reaction is contacted with thioether and oxidant to obtain containing sulfone Mixture HTS be the modification HTS and unmodified HTS.According to the embodiment party Formula, modified HTS is applied in combination that catalytic performance can be regulated and controled with unmodified HTS, together When can also reduce to HTS be modified processing and produce running cost.In this embodiment, with the titanium On the basis of the total amount of si molecular sieves, the content of the HTS of the modification can be 5-95 weight %, described unmodified The content of HTS can be 5-95 weight %.On the premise of the running cost of modification is taken into account, from entering one The angle that step improves catalytic performance is set out, on the basis of the total amount of the HTS, the HTS of the modification Content be preferably 20-90 weight %, the content of the unmodified HTS is preferably 10-80 weight %.It is more excellent Selection of land, on the basis of the total amount of the HTS, the content of the HTS of the modification is 40-80 weight %, The content of the unmodified HTS is 20-60 weight %.

In the various commercial plants using HTS as catalyst, such as Ammoximation reaction device, hydroxylating In device and epoxidation reaction device, generally plant running for a period of time after, the catalytic activity of catalyst declines, and needs Carry out in device or ex-situ regeneration, even if when carrying out regeneration and also being difficult to obtain satisfied activity, it is necessary to by catalyst from dress Drawn off in putting (that is, more catalyst changeout), and the current processing side of the catalyst (that is, drawing off agent or dead catalyst) drawn off Method is typically that accumulation is buried, and on the one hand occupies the land resource and inventory space of preciousness, the life of another aspect HTS Produce cost higher, directly pass into disuse and also result in great waste.These are drawn off into agent (that is, the titanium silicon molecule drawn off Sieve) regenerated after contacted with thioether and oxidant under oxidation reaction condition, remain able to obtain preferable catalytic performance, Higher oxidant effective rate of utilization can particularly be obtained.Therefore, the method according to the invention, at least partly described titanium silicon Molecular sieve is preferably the reaction unit using HTS as catalyst through regeneration (in addition to thioether oxidation reaction apparatus) Draw off agent.It is described that to draw off agent can be unloading of being drawn off from the various reaction units for using HTS as catalyst Go out agent, for example, can draw off agent for what is drawn off from oxidation reaction apparatus.Specifically, it is described to draw off agent for Ammoximation reaction Device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off one or both of agent with On.More specifically, it is described draw off agent can for cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction dress That puts draws off the drawing off more than one or both of agent of agent and propylene ring oxidation reaction device.

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

The activity for drawing off agent through regeneration is different according to its source.Usually, the activity for drawing off agent through regeneration can Think the 5-95% of activity (that is, the activity of fresh HTS) of the HTS when fresh.Preferably, The active 10-90% that the activity for drawing off agent through regeneration can be the HTS when fresh, more preferably exists Active 30-50% when fresh, is still more preferably the active 35-45% when fresh.The fresh titanium silicon point The activity of son sieve is generally more than 90%, and usually more than 95%.

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

The method according to the invention, it is described draw off agent can for modified HTS raw material, can also be as not changing The HTS of property is used.Preferably, in the modification, the HTS at least partly as raw material is institute State and draw off agent, so can further extend the single trip use life-span, and with it is non-modified draw off agent compared with, can substantially carry The selectivity and thioether rate of high sulfone.

The method according to the invention, the HTS is a class of a part of silicon atom in titanium atom substitution lattice framework The general name of zeolite, can use chemical formula xTiO₂·SiO₂Represent.The present invention does not have for the content of titanium atom in HTS It is particularly limited to, can is the conventional selection of this area.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, More preferably 0.015-0.025.

According to the preparation method of the sulfone of the present invention, the HTS can be the common titanium with various topological structures Si molecular sieves, for example：The HTS can be HTS (such as TS-1), MEL selected from MFI structure The HTS (such as TS-2) of structure, HTS (such as Ti-Beta), the titanium of MWW structures of BEA structures HTS (such as Ti-MCM-41, Ti-SBA-15), the MOR of si molecular sieves (such as Ti-MCM-22), hexagonal structure HTS (such as Ti-MOR), the HTS (such as Ti-TUN) of TUN structures and the other structures of structure It is more than one or both of HTS (such as Ti-ZSM-48).

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

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

The method according to the invention, at least part HTS is titanium-silicon molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 Surface silicon titanium ratio be not less than body phase silicon titanium ratio, so can further improve oxidant effective rate of utilization, and can be further Extend the single trip use life-span of HTS.Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2 more than.It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5.It is further preferred that The surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5 (such as 2.2-4.5).It is further preferred that described Surface silicon titanium than with the body phase silicon titanium than ratio be 2-3, such as 2.2-2.8.The silicon titanium ratio refers to silica and titanium oxide Mol ratio, the surface silicon titanium ratio determined using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses X-ray Fluorescence spectrum method for measuring.

The method according to the invention, extends from the further catalytic performance for improving HTS and further HTS The angle in single trip use life-span set out, at least part HTS is titanium-silicon molecular sieve TS-1, the HTS TS-1 is prepared using the method comprised the following steps：

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

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

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

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

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

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

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

R⁵(NH₂)_n(Formula II)

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

(HOR⁶)_mNH_(3-m)(formula III)

In formula III, m R⁶It is identical or different, respectively C₁-C₄Alkylidene, including C₁-C₄Straight-chain alkyl-sub And C₃-C₄Branched alkylidene, its instantiation can include but is not limited to methylene, ethylidene, sub- n-propyl and it is sub- just Butyl；M is 1,2 or 3.

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

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

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

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

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

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

In step (B), after the completion of the standing, directly the dispersion liquid through standing can be sent into and crystalline substance is carried out in reactor Change, carry out crystallization in feeding reactor after the dispersion liquid through standing can also being carried out into redisperse, preferably carry out after redisperse Send into reactor, so can further improve the dispersing uniformity for the dispersion liquid for carrying out crystallization.The method of the redisperse Can be conventional method, such as combination more than one or both of stirring, ultrasonically treated and vibration.The redisperse Duration be defined so that the dispersion liquid through standing can be made to form uniform dispersion liquid, typically can be 0.1-12h.It is described again It is scattered to carry out at ambient temperature, carried out at a temperature of such as 15-40 DEG C.

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

In step (C), the crystallization temperature in stage (1) is preferably 110-140 DEG C, more preferably 120-140 DEG C, enters one Step is preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.Stage (2) Temperature is preferably not higher than 50 DEG C.The crystallization temperature in stage (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 (C), in a preferred embodiment, the crystallization temperature in stage (1) is less than the stage (3) Crystallization temperature, so can further improve the catalytic performance of the HTS of preparation.Preferably, the crystallization in stage (1) Temperature it is lower 10-50 DEG C than the crystallization temperature in stage (3).It is highly preferred that the crystallization temperature in stage (1) is than stage (3) Crystallization temperature it is low 20-40 DEG C.In step (C), in another preferred embodiment, during the crystallization in stage (1) Between be less than the stage (3) crystallization time, so can further improve the catalytic performance of the HTS finally prepared.It is excellent Selection of land, the short 5-24h of crystallization time of the crystallization time in stage (1) than the stage (3).It is highly preferred that the stage (1) Crystallization time is than the short 6-12h of crystallization time in stage (3), such as short 6-8h.In step (C), both preferred realities The mode of applying be may be used alone, can also be used in combination, and preferred compositions are used, i.e. the crystalline substance in stage (1) and stage (3) Change temperature and crystallization time meets the requirement of both preferred embodiments simultaneously.

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

HTS is reclaimed in the mixture that can be obtained using conventional method from step (C) crystallization.Specifically, may be used After alternatively being filtered and washed with the mixture for obtaining step (C) crystallization, solid matter is dried and is calcined, So as to obtain HTS.The drying and the roasting can be carried out under normal conditions.Usually, the drying Can be in environment temperature (such as 15 DEG C) to carrying out at a temperature of 200 DEG C.The drying can be in environmental pressure (generally 1 Standard atmospheric pressure) under carry out, can also carry out at reduced pressure.The duration of the drying can be according to drying Temperature and pressure and the mode of drying selected, be not particularly limited.For example, the drying is under ambient pressure During progress, temperature is preferably 80-150 DEG C, more preferably 100-120 DEG C, and the dry duration is preferably 0.5-5h, more Preferably 1-3h.The roasting can be carried out at a temperature of 300-800 DEG C, be carried out preferably at a temperature of 500-700 DEG C, Carried out more preferably at a temperature of 550-650 DEG C.The duration of the roasting can be selected according to the temperature being calcined Select, typically can be 2-12h, preferably 2-5h.The roasting is carried out preferably in air atmosphere.

The method according to the invention, the preferred titanium-silicon molecular sieve TS-1 of above two can be used as unmodified titanium silicon molecule Sieve, can also as modification HTS raw material, can also be also served as both as unmodified HTS The raw material of modified HTS.

The topological structure of above-described HTS is not only suitable for modified HTS, is also applied for unmodified HTS.The HTS of the modification can be used with the unmodified HTS has phase homeomorphism The HTS of structure, it would however also be possible to employ the HTS with different topology structure.

The method according to the invention, HTS is as the catalyst of oxidation reaction, and its consumption is can realize catalysis work( It can be defined, can be catalytic amount.Furthermore it is also possible to be carried out according to the way of contact of thioether and oxidant and HTS Selection.For example, being seated in by HTS in the bed of fixed bed reactors, thioether and oxidant feeding are fixed When in bed reactor with HTS haptoreaction, the weight (hourly) space velocity (WHSV) of thioether can be 0.1-500h^-1, it is preferably 5-500h^-1, more preferably 10-150h^-1, such as 40-80h^-1.For another example being mixed by HTS with thioether and oxidant When conjunction forms slurry and contacted, the weight ratio of thioether and HTS can be 0.1-50：1, preferably 2-50：1.

According to the preparation method of the sulfone of the present invention, the oxidant is selected from peroxide.The instantiation of the oxidant can To include but is not limited to：Hydrogen peroxide, TBHP, ethylbenzene hydroperoxide, dicumyl peroxide, cyclohexyl Hydrogen peroxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide, so can further be dropped Low separation costs.The hydrogen peroxide can be the hydrogen peroxide existed in a variety of manners commonly used in the art.

From the angle of the further security for improving the method according to the invention, the method according to the invention is preferably used The hydrogen peroxide existed as an aqueous solution.The method according to the invention, is provided as an aqueous solution in the hydrogen peroxide When, the concentration of the aqueous hydrogen peroxide solution can be the normal concentration of this area, for example：20-80 weight %.Concentration expires The aqueous solution of the hydrogen peroxide of sufficient above-mentioned requirements can be prepared using conventional method, can also be commercially available, for example：Can be with For the hydrogen peroxide of the 30 weight % that can be commercially available hydrogen peroxide, 50 weight % hydrogen peroxide or 70 weight %.

The consumption of the oxidant can be conventional selection, be not particularly limited.Usually, mole of oxidant and thioether Than that can be 2：More than 1.The mol ratio of oxidant and thioether can be 20：Less than 1, such as 10：Less than 1, be preferably 5：Less than 1, more preferably 3：Less than 1, more preferably 2.5：Less than 1.Preferably, oxidant and thioether Mol ratio is 2-2.5：1.

The method according to the invention, mixability, enhanced dispersion from further raising reaction system between each reactant And more easily angle that the severe degree to reaction is adjusted is set out, preferably by thioether and oxidant and titanium silicon molecule Sieve is contacted in the presence of at least one solvent.I.e., by thioether and disperse oxidant in a solvent, reaction solution is formed, The reaction solution is contacted with HTS.The species of the solvent is not particularly limited.Usually, the solvent can With selected from water, C₁-C₆Alcohol, C₃-C₈Ketone and C₂-C₆Nitrile.The instantiation of the solvent can include but is not limited to： Water, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.It is used as solvent Water can be the water in various sources, be hydrogen peroxide in the oxidant, and hydrogen peroxide when providing as an aqueous solution, Water in aqueous hydrogen peroxide solution can be used as solvent.

The consumption of the solvent is not particularly limited, and can be conventional selection.Usually, the weight ratio of solvent and thioether can Think 0.1-1000：1, preferably 0.5-500：1, more preferably 1-200：1, more preferably 2-100：1, such as 2-20：1.

The method according to the invention, the oxidation reaction be enough by sulfide oxidation turn into sulfone under conditions of carry out.Usually, Temperature can be 0-200 DEG C, more preferably preferably 20-180 DEG C, 40-90 DEG C.In terms of gauge pressure, the oxidation reaction Pressure can be 0-3MPa, such as preferably 0.1-2.5MPa, 0.5-2.5MPa.

The method according to the invention, the thioether can be selected according to the species of expected sulfone.For example, preparing two During methyl sulfone, the thioether can be dimethyl sulfide；When preparing lauseto neu, the thioether can be thioanisole. The thioether can also be the mixture of two or more thioethers, the sulfone of two or more types can so be prepared simultaneously, for example： The thioether can be dimethyl sulfide and thioanisole, and dimethyl sulfone and thioanisole can be so prepared simultaneously.

The method according to the invention, the mixture containing sulfone that oxidation reaction is obtained can be separated using conventional method, So as to obtain target product sulfone, for example：Mixture containing sulfone can be distilled, so as to obtain target product sulfone. For excessive thioether, it can be recycled and use.

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

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

In following examples and comparative example, the content of each composition in obtained reaction solution is analyzed using gas chromatography, Below equation is respectively adopted on the basis of this and calculates thioether rate, oxidant effective rate of utilization and sulfone selectivity：

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

Oxidant effective rate of utilization=[mole/(mole-unreacted of the oxidant of addition of the sulfone of 2 × reaction generation Oxidant mole)] × 100%；

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

In following examples and comparative example, static nitrogen adsorption method is respectively adopted and solid ultraviolet-visible diffuses spectrometry to changing The pore volume and ultraviolet absorption peak of HTS before and after property are characterized.Wherein, solid ultraviolet-visible diffusing reflection spectrum (UV-Vis) analysis is carried out on SHIMADZU UV-3100 type ultraviolet-visible spectrometers；Static N2 adsorption exists Carried out on the static n2 absorption apparatus of the types of ASAP 2405 of Micromeritics companies.

It is related to drawing off in the embodiment and comparative example of agent through regeneration below, HTS (bag is determined using following methods Include regenerative agent and fresh dose) activity：

By HTS, 36 weight % ammoniacal liquor (with NH₃Meter), 30 weight % hydrogen peroxide is (with H₂O₂Meter), The tert-butyl alcohol and cyclohexanone are by weight=1：7.5：10：7.5：At atmosheric pressure in 80 DEG C of stirring reactions 2 after 10 mixing After hour, reactant is filtered, liquid phase analyzed with gas-chromatography, the conversion of cyclohexanone is calculated using below equation Rate and as the activity of HTS,

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

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

Embodiment 1-17 is used to illustrate the present invention.

Embodiment 1

(1) HTS used in the present embodiment is titanium-silicon molecular sieve TS-1, with reference to Zeolites, 1992, Vol.12 Prepared by the method described in the 943-950 pages, specific method is as follows.

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

(2) titanium-silicon molecular sieve TS-1 for preparing step (1) is with containing HNO₃(HNO₃Mass concentration for 10%) Mixed with the aqueous solution of hydrogen peroxide (mass concentration of hydrogen peroxide is 7.5%), by obtained mixture in closed container In in 70 DEG C of stirring reaction 5h, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid formation Matter is dried to constant weight at 120 DEG C, obtains modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂Meter, titanium The mol ratio of si molecular sieves and hydrogen peroxide is 1：0.1.Compared with raw material HTS, the titanium silicon point of obtained modification The peak area of absworption peak in the UV-Vis spectrum of son sieve between 230-310nm reduces 3.5%, by static nitrogen adsorption method The pore volume of measure reduces 2.6%.

(3) HTS for the modification for preparing step (2) is seated in isometrical fixed bed reactors, forms catalysis Agent bed, wherein, the quantity of beds is 1 layer.

Dimethyl sulfide, hydrogen peroxide (being provided in the form of 30 weight % hydrogen peroxide) and methanol are mixed, liquid is formed Body mixture.Then, by the liquid mixture send into fixed bed reactors in modified HTS haptoreaction. Wherein, in liquid mixture, the mol ratio of dimethyl sulfide and hydrogen peroxide is 1：2, the weight of dimethyl sulfide and methanol Amount is than being 1：1, the weight (hourly) space velocity (WHSV) of liquid mixture is 60h^-1.Temperature in beds is 45 DEG C, and fixed bed is anti- It is 0.6MPa to answer the pressure in device.

Reaction is carried out continuously, the reactant mixture exported from fixed bed reactors is monitored with gas-chromatography during the course of the reaction Composition, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.Listed by table 1 Reaction time under reactor export reactant mixture determine result listed in table 1.

Embodiment 2

Dimethyl sulfone is prepared using method same as Example 1, unlike, in step (3), beds Middle filling is titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (1) and modification prepared by the step of embodiment 1 (2) HTS mixture, on the basis of the total amount of the mixture, the content of modified HTS is 50 weight %.The result that the reactant mixture that reactor is exported under the reaction time listed by table 1 is determined is listed in table 1.

Embodiment 3

(1) modified HTS is prepared using with the step of embodiment 1 (2) identical method, unlike, make For raw material HTS be being drawn off from phenol hydroxylation reaction unit through regeneration titanium-silicon molecular sieve TS-1 (titanium Silicalite TS-1 is used to be prepared with the step of embodiment 1 (1) identical method, and the HTS drawn off is at 570 DEG C At a temperature of be calcined 5h in air atmosphere and regenerate, the activity after regeneration is 35%, and 96%) activity when fresh is.With Raw material HTS is compared, the suction in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm The peak area for receiving peak reduces 3.3%, and 2.8% is reduced by the pore volume of static determination of nitrogen adsorption.

(2) use and prepare dimethyl sulfone with the step of embodiment 1 (3) identical method, unlike, beds Middle filling be the step of embodiment 3 (1) prepare modification HTS.

The result that the reactant mixture that reactor is exported under the reaction time listed by table 1 is determined is listed in table 1.

Comparative example 1

Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (3), beds Middle filling is used with being unloaded in the step of embodiment 3 (1) as raw material through regeneration from phenol hydroxylation reaction unit The titanium-silicon molecular sieve TS-1 gone out.The result that the reactant mixture that reactor is exported under the reaction time listed by table 1 is determined exists Listed in table 1.

Comparative example 2

Dimethyl sulfone is prepared using method same as Example 3, unlike, it is modified place in step (1) During reason, using only nitric acid (that is, the aqueous solution is free of hydrogen peroxide).Reactor is exported under the reaction time listed by table 1 The result that reactant mixture is determined is listed in table 1.

Comparative example 3

Dimethyl sulfone is prepared using method same as Example 3, unlike, it is modified place in step (1) During reason, using only hydrogen peroxide (that is, the aqueous solution is free of nitric acid).Reactor is exported under the reaction time listed by table 1 The result that reactant mixture is determined is listed in table 1.

Comparative example 4

Dimethyl sulfone is prepared using method same as Example 3, unlike, it is modified place in step (1) During reason, nitric acid with etc. the HCl of quality replace (that is, the aqueous solution contains hydrogen peroxide and HCl).The reaction listed by table 1 The result that the reactant mixture that reactor is exported under time is determined is listed in table 1.

Table 1

Embodiment 4

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

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

(2) HTS for the modification for preparing step (1) is seated in isometrical fixed bed reactors, forms catalysis Agent bed, wherein, the quantity of beds is 1 layer.

Dimethyl sulfide, hydrogen peroxide (being provided in the form of 40 weight % hydrogen peroxide) and water are mixed, liquid is formed Mixture.Then, the liquid mixture is sent into fixed bed reactors and the beds containing HTS Haptoreaction.Wherein, in liquid mixture, the mol ratio of dimethyl sulfide and hydrogen peroxide is 1：2.2, dimethyl disulfide The weight ratio of ether and water (not including the water in hydrogen peroxide) is 1：2, the weight (hourly) space velocity (WHSV) of liquid mixture is 80h^-1.Catalysis Temperature in agent bed is 60 DEG C, and the pressure in fixed bed reactors is 1.2MPa.

Reaction is carried out continuously, the reactant mixture exported from fixed bed reactors is monitored with gas-chromatography during the course of the reaction Composition, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.Listed by table 2 Reaction time under reactor export reactant mixture determine result listed in table 2.

Embodiment 5

Dimethyl sulfone is prepared using method same as Example 4, unlike, in step (2), beds Middle filling is prepared as the hollow HTS and the step of embodiment 4 (2) of raw material in the step of embodiment 4 (1) Modification HTS mixture, wherein, on the basis of the total amount of the mixture, modified HTS Content is 80 weight %.The result that the reactant mixture that reactor is exported under the reaction time listed by table 2 is determined is in table 2 In list.

Embodiment 6

(1) modified HTS is prepared using with the step of embodiment 4 (1) identical method, unlike, system The raw material used during for modified HTS is the hollow titanium drawn off from cyclohexanone oxamidinating reaction unit through regeneration Si molecular sieves (the hollow HTS and source phase of the step of embodiment 4 (1) as the hollow HTS of raw material Together, the hollow HTS drawn off is calcined 6h in air atmosphere at a temperature of 550 DEG C and regenerated, the work after regeneration Property be 40%, 97%) activity when fresh is.Compared with raw material HTS, the HTS of obtained modification The peak area of absworption peak in UV-Vis spectrum between 230-310nm reduces 4.8%, by the hole of static determination of nitrogen adsorption Hold and reduce 3.5%.

(2) use and prepare dimethyl sulfone with the step of embodiment 4 (2) identical method, unlike, beds Middle filling be the step of embodiment 6 (1) prepare modification HTS.

The result that the reactant mixture that reactor is exported under the reaction time listed by table 2 is determined is listed in table 2.

Comparative example 5

Dimethyl sulfone is prepared using method same as Example 4, unlike, in step (2), beds Middle filling is hollow HTS of the step of embodiment 4 (1) as raw material.It is anti-under the reaction time listed by table 2 The result that the reactant mixture for answering device to export is determined is listed in table 2.

Table 2

Embodiment 7

(1) prepared in the present embodiment as the HTS of raw material using following methods.

First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：4： 12：400, silicon source is with SiO₂Meter, titanium source is with TiO₂Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker 24h is stood in room temperature (being 25 DEG C, similarly hereinafter) after being sealed using sealed membrane, 2h is stirred at 35 DEG C followed by magnetic agitation, It is allowed to disperse again.Again the dispersion liquid after disperseing is transferred in sealing reactor, first stage crystallization is undergone at 140 DEG C 6h, is then cooled to 30 DEG C of experience second stage by mixture and stops after 2h, continue in sealing reactor in 170 DEG C At a temperature of experience phase III crystallization 12h (wherein, be by the heating rate of room temperature to first stage crystallization temperature 2 DEG C/min, be 5 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by second stage Treatment temperature to phase III crystallization temperature heating rate be 10 DEG C/min), by gained crystallization product take out after without filtering And washing step, 2h directly is dried in 110 DEG C, then 3h is calcined at 550 DEG C, molecular sieve is obtained.The XRD of gained sample Crystalline phase figure is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (1), and illustrate to obtain is with MFI structure Titanium-silicon molecular sieve TS-1；In FFIR figure, in 960cm^-1Nearby there is absworption peak, show titanium Into framework of molecular sieve, in the HTS, titanium oxide content is 3.5 weight %, surface silicon titanium ratio/body phase silicon titanium ratio For 2.58, (in HTS prepared by the step of embodiment 1 (1), 1.05) surface silicon titanium ratio/body phase silicon titanium ratio is.

(2) modified HTS is prepared using with the step of embodiment 1 (2) identical method, unlike, it is former Expect the titanium-silicon molecular sieve TS-1 prepared for the step of embodiment 7 (1).Compared with raw material HTS, obtained modification The peak area of absworption peak in the UV-Vis spectrum of HTS between 230-310nm reduces 3.4%, by static nitrogen The pore volume of determination of adsorption method reduces 2.7%.

(3) use and prepare dimethyl sulfone with the step of embodiment 1 (3) identical method, unlike, beds Middle filling be the step of embodiment 7 (2) prepare modification HTS.

The result that the reactant mixture that reactor is exported under the reaction time listed by table 3 is determined is listed in table 3.

Embodiment 8

(1) use and prepare titanium-silicon molecular sieve TS-1 with the step of embodiment 7 (1) identical method, unlike, the 3rd The crystallization temperature in stage is also 140 DEG C.The titanium silicon that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (1) Molecular sieve TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram In 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/ Body phase silicon titanium ratio is 4.21, and titanium oxide content is 3.1 weight %.

(2) modified HTS is prepared using with the step of embodiment 7 (2) identical method, unlike, it is former Expect the titanium-silicon molecular sieve TS-1 prepared for the step of embodiment 8 (1).Compared with raw material HTS, obtained modification The peak area of absworption peak in the UV-Vis spectrum of HTS between 230-310nm reduces 3.3%, by static nitrogen The pore volume of determination of adsorption method reduces 2.5%.

(3) use and prepare dimethyl sulfone with the step of embodiment 7 (3) identical method, unlike, beds Middle filling be the step of embodiment 8 (2) prepare modification HTS.

Embodiment 9

(1) use and prepare titanium-silicon molecular sieve TS-1 with the step of embodiment 7 (1) identical method, unlike, first The crystallization temperature in stage is 110 DEG C.The titanium silicon point that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (1) Son sieve TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body Phase silicon titanium ratio is 2.37, and titanium oxide content is 3.2 weight %.

(2) modified HTS is prepared using with the step of embodiment 7 (2) identical method, unlike, it is former Expect the titanium-silicon molecular sieve TS-1 prepared for the step of embodiment 9 (1).Compared with raw material HTS, obtained modification The peak area of absworption peak in the UV-Vis spectrum of HTS between 230-310nm reduces 3.4%, by static nitrogen The pore volume of determination of adsorption method reduces 2.4%.

(3) use and prepare dimethyl sulfone with the step of embodiment 7 (3) identical method, unlike, beds Middle filling be the step of embodiment 9 (2) prepare modification HTS.

Embodiment 10

(1) use and prepare titanium-silicon molecular sieve TS-1 with the step of embodiment 7 (1) identical method, unlike, first The crystallization time in stage is 12h.The titanium silicon molecule that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (1) Sieve that TS-1 is consistent, illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body Phase silicon titanium ratio is 3.78, and titanium oxide content is 3.4 weight %.

(2) modified HTS is prepared using with the step of embodiment 7 (2) identical method, unlike, it is former Expect the titanium-silicon molecular sieve TS-1 prepared for the step of embodiment 10 (1).Compared with raw material HTS, obtained modification HTS UV-Vis spectrum in the peak area of absworption peak between 230-310nm reduce 3.2%, by static state The pore volume of determination of nitrogen adsorption reduces 2.5%.

(3) use and prepare dimethyl sulfone with the step of embodiment 7 (3) identical method, unlike, beds Middle filling be the step of embodiment 10 (2) prepare modification HTS.

Embodiment 11

(1) use and prepare titanium-silicon molecular sieve TS-1 with the step of embodiment 7 (1) identical method, unlike, second Stage is to be cooled to 70 DEG C of stop 2h.The titanium silicon point that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (1) Son sieve TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body Phase silicon titanium ratio is 2.75, and titanium oxide content is 3.1 weight %.

(2) modified HTS is prepared using with the step of embodiment 7 (2) identical method, unlike, it is former Expect the titanium-silicon molecular sieve TS-1 prepared for the step of embodiment 11 (1).Compared with raw material HTS, obtained modification HTS UV-Vis spectrum in the peak area of absworption peak between 230-310nm reduce 3.3%, by static state The pore volume of determination of nitrogen adsorption reduces 2.4%.

(3) use and prepare dimethyl sulfone with the step of embodiment 7 (3) identical method, unlike, beds Middle filling be the step of embodiment 11 (2) prepare modification HTS.

Embodiment 12

(1) use and prepare titanium-silicon molecular sieve TS-1 with the step of embodiment 7 (1) identical method, unlike, second Stage is to be cooled to 30 DEG C of stop 0.2h.The titanium silicon that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (1) Molecular sieve TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram In 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/ Body phase silicon titanium ratio is 1.14, and titanium oxide content is 3.1 weight %.

(2) modified HTS is prepared using with the step of embodiment 7 (2) identical method, unlike, it is former Expect the titanium-silicon molecular sieve TS-1 prepared for the step of embodiment 12 (1).Compared with raw material HTS, obtained modification HTS UV-Vis spectrum in the peak area of absworption peak between 230-310nm reduce 3.5%, by static state The pore volume of determination of nitrogen adsorption reduces 2.5%.

(3) use and prepare dimethyl sulfone with the step of embodiment 7 (3) identical method, unlike, beds Middle filling be the step of embodiment 12 (2) prepare modification HTS.

Embodiment 13

(1) use and prepare titanium-silicon molecular sieve TS-1 with the step of embodiment 7 (1) identical method, unlike, without Cross second stage.The XRD crystalline phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (1), Illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Nearby occur Absworption peak, shows that titanium has been enter into framework of molecular sieve, in the HTS, and surface silicon titanium ratio/body phase silicon titanium ratio is 1.08, Titanium oxide content is 2.5 weight %.

(2) modified HTS is prepared using with the step of embodiment 7 (2) identical method, unlike, it is former Expect the titanium-silicon molecular sieve TS-1 prepared for the step of embodiment 13 (1).Compared with raw material HTS, obtained modification HTS UV-Vis spectrum in the peak area of absworption peak between 230-310nm reduce 3.4%, by static state The pore volume of determination of nitrogen adsorption reduces 2.6%.

(3) use and prepare dimethyl sulfone with the step of embodiment 7 (3) identical method, unlike, beds Middle filling be the step of embodiment 13 (2) prepare modification HTS.

Embodiment 14

(1) use and prepare titanium-silicon molecular sieve TS-1 with the step of embodiment 7 (1) identical method, unlike, moisture Dispersion liquid does not stand 24h at room temperature, but is sent directly into reactor and carries out crystallization.The XRD crystalline phases figure of gained sample with Titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (1) is consistent, and illustrate to obtain is that the titanium silicon with MFI structure divides Son sieve TS-1；In FFIR figure, in 960cm^-1Nearby there is absworption peak, show that titanium has been enter into molecule In sieve skeleton frame, the HTS, titanium oxide content is 3.5 weight %, and surface silicon titanium ratio/body phase silicon titanium ratio is 1.18.

(2) modified HTS is prepared using with the step of embodiment 7 (2) identical method, unlike, it is former Expect the titanium-silicon molecular sieve TS-1 prepared for the step of embodiment 14 (1).Compared with raw material HTS, obtained modification HTS UV-Vis spectrum in the peak area of absworption peak between 230-310nm reduce 3.5%, by static state The pore volume of determination of nitrogen adsorption reduces 2.2%.

(3) use and prepare dimethyl sulfone with the step of embodiment 7 (3) identical method, unlike, beds Middle filling be the step of embodiment 14 (2) prepare modification HTS.

Comparative example 6

Dimethyl sulfone is prepared using with the step of embodiment 7 (3) identical method, unlike, filled in beds What is filled out is the titanium-silicon molecular sieve TS-1 prepared using the step of embodiment 7 (1) identical method.

Table 3

Embodiment 15

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

(2) titanium-silicon molecular sieve TS-1 for preparing step (1) is with containing HNO₃(HNO₃Mass concentration for 15%) Mixed with the aqueous solution of hydrogen peroxide (mass concentration of hydrogen peroxide is 8%), by obtained mixture in closed container In 150 DEG C of stirring reaction 3h, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid formation Matter is dried to constant weight at 120 DEG C, obtains modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂Meter, titanium The mol ratio of si molecular sieves and hydrogen peroxide is 1：2.Through characterizing, compared with raw material HTS, obtained modification The peak area of absworption peak in the UV-Vis spectrum of HTS between 230-310nm reduces 5.5%, by static nitrogen The pore volume of determination of adsorption method reduces 4.3%.

(3) HTS for the modification for preparing step (2) is seated in fixed bed reactors, forms catalyst bed Layer, wherein, the quantity of beds is 1 layer.

Dimethyl sulfide, TBHP and acetonitrile are mixed, liquid mixture is formed.Then, by the liquid With the beds haptoreaction containing HTS in mixture feeding fixed bed reactors.Wherein, liquid is mixed In thing, the mol ratio of dimethyl sulfide and TBHP is 1：2.5, the weight ratio of dimethyl sulfide and acetonitrile is 1： 5, the weight (hourly) space velocity (WHSV) of liquid mixture is 80h^-1.Temperature in beds is 80 DEG C, the pressure in fixed bed reactors Power is 2.5MPa.

Reaction is carried out continuously, the reactant mixture exported from fixed bed reactors is monitored with gas-chromatography during the course of the reaction Composition, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.Listed by table 4 Reaction time under reactor export reactant mixture determine result listed in table 4.

Embodiment 16

(1) modified HTS is prepared using with the step of embodiment 15 (2) identical method, unlike, (should as the titanium-silicon molecular sieve TS-1 that the HTS of raw material is being drawn off from propylene ring oxidation reaction device through regeneration Titanium-silicon molecular sieve TS-1 is used to be prepared with the step of embodiment 15 (1) identical method, and the HTS drawn off is 580 3h being calcined in air atmosphere at a temperature of DEG C and being regenerated, the activity after regeneration is 40%, 95%) activity when fresh is. Compared with raw material HTS, in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm The peak area of absworption peak reduces 5.3%, and 4.8% is reduced by the pore volume of static determination of nitrogen adsorption.

(2) use and prepare dimethyl sulfone with the step of embodiment 15 (3) identical method, unlike, catalyst bed What is loaded in layer is the HTS of modification prepared by the step of embodiment 16 (1).

The result that the reactant mixture that reactor is exported under the reaction time listed by table 4 is determined is listed in table 4.

Embodiment 17

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

(2) titanium-silicon molecular sieve TS-1 for preparing step (1) is with containing HNO₃(HNO₃Mass concentration for 10%) Mixed with the aqueous solution of hydrogen peroxide (mass concentration of hydrogen peroxide is 2%), by obtained mixture in closed container In 170 DEG C of stirring reaction 2.5h, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid formation Matter is dried to constant weight at 120 DEG C, obtains modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂Meter, titanium The mol ratio of si molecular sieves and hydrogen peroxide is 1：1.Through characterizing, compared with raw material HTS, obtained modification The peak area of absworption peak in the UV-Vis spectrum of HTS between 230-310nm reduces 5.7%, by static nitrogen The pore volume of determination of adsorption method reduces 4.1%.

Thioanisole, Perpropionic Acid and acetone are mixed, liquid mixture is formed.Then, the liquid mixture is sent Enter in fixed bed reactors and the beds haptoreaction containing HTS.Wherein, in liquid mixture, benzene The mol ratio of methyl sulfide and Perpropionic Acid is 1：2.5, the weight ratio of thioanisole and acetone is 1：15, liquid mixture Weight (hourly) space velocity (WHSV) is 40h^-1.Temperature in beds is 90 DEG C, and the pressure in fixed bed reactors is 3MPa.

Reaction is carried out continuously, the reactant mixture exported from fixed bed reactors is monitored with gas-chromatography during the course of the reaction Composition, and calculate thioether rate, oxidant effective rate of utilization and lauseto neu selectivity.During the reaction listed by table 4 Between the result that determines of reactant mixture of lower reactor output listed in table 4.

Table 4

Embodiment 1-17's as a result, it was confirmed that the method according to the invention can effectively lift the HTS as catalyst Catalytic performance, extend HTS the single trip use life-span, reduce HTS regeneration frequency.

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

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

In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to this hair Bright thought, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of preparation method of sulfone, this method is included under oxidation reaction condition, by least one thioether and at least one Plant oxidant to contact with HTS, obtain the mixture containing sulfone, the oxidant is selected from peroxide, the titanium Si molecular sieves are modified HTS, or the HTS is modified HTS and unmodified titanium Si molecular sieves, the HTS experience modification of the modification, the unmodified HTS does not undergo modification Processing, the modification includes that the HTS of raw material and changing containing nitric acid and at least one peroxide will be used as Property liquid contact.

2. according to the method described in claim 1, wherein, in the modification, be used as the titanium silicon molecule of raw material The mol ratio of sieve and the peroxide is 1：0.01-5, preferably 1：0.05-3, more preferably 1：0.1-2, the mistake The mol ratio of oxide and the nitric acid is 1：0.01-50, preferably 1：0.1-20, more preferably 1：0.2-10, enters one Step is preferably 1：0.5-5, particularly preferably 1：0.6-3.5, the HTS is in terms of silica.

3. method according to claim 1 or 2, wherein, in the modification liquid, peroxide and nitric acid it is dense Degree is respectively 0.1-50 weight %, more preferably preferably 0.5-30 weight %, 1-25 weight %.

4. the method according to any one in claim 1-3, wherein, in the modification, it is used as raw material HTS and the modification liquid 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, further preferably Contacted at a temperature of 60-200 DEG C, the contact in 0-5MPa container in pressure to carry out, and the pressure is gauge pressure； The duration of the contact is 0.5-10 hours, preferably 2-5 hours.

5. the method according to any one in claim 1-4, wherein, in the modification, it is used as raw material The exposure level of HTS and the modification liquid cause, using on the basis of the HTS as raw material, it is ultraviolet- In visible spectrum, the peak area reduction by more than 2% of the absworption peak of modified HTS between 230-310nm, preferably 2-30% is reduced, 2.5-15% is more preferably reduced, further preferably reduces 3-10%, still more preferably reduce 3-8%； The pore volume of modified HTS reduces more than 1%, preferably reduces 1-20%, more preferably reduces 1.5-10%, further It is preferred that reducing 2-6%, the pore volume is using static determination of nitrogen adsorption.

6. the method according to any one in claim 1-5, wherein, the catalyst is unmodified titanium silicon point Son sieve and modified HTS, on the basis of the total amount of the HTS, the HTS of the modification Content is 5-95 weight %, more preferably preferably 20-90 weight %, 40-80 weight %；The unmodified titanium silicon point The content of son sieve is 5-95 weight %, more preferably preferably 10-80 weight %, 20-60 weight %.

7. the method according to any one in claim 1-6, wherein, at least part HTS is from extremely A kind of few reaction unit draws off agent, described to draw off agent and draw off agent, hydroxylating device for Ammoximation reaction device Draw off agent and epoxidation reaction device draws off agent.

8. the method according to any one in claim 1-7, wherein, at least part HTS is titanium silicon point Son sieve TS-1, the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 is not less than body phase silicon titanium ratio, and the silicon titanium ratio refers to oxidation The mol ratio of silicon and titanium oxide, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, the body phase silicon titanium ratio Using x-ray fluorescence spectrometry；

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

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

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

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

9. the method according to any one in claim 1-8, wherein, at least part HTS is titanium silicon point Son sieve TS-1, the titanium-silicon molecular sieve TS-1 is prepared using the method comprised the following steps：

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

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

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

10. method according to claim 9, wherein, stage (1) and stage (3) are met in following condition One or both：

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

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

11. the method according to claim 9 or 10, wherein, the stage (2) is cooled to not higher than 50 DEG C, and stop The time is stayed to be at least 1 hour.

12. the method according to any one in claim 9-11, wherein, the titanium source be inorganic titanium salt and/or Organic titanate；The alkali source template is more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine, Preferably quaternary ammonium base, more preferably TPAOH；The inorganic silicon source is silica gel and/or Ludox；

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

13. the method according to any one in claim 1-12, wherein, the oxidant and the dimethyl disulfide The mol ratio of ether is 2-20：1, preferably 2-10：1, more preferably 2-5：1.

14. the method according to any one in claim 1-13, wherein, peroxide and institute as oxidant State that the peroxide used in modification is identical or difference, each be selected from hydrogen peroxide, TBHP, ethylbenzene Hydrogen peroxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid；

It is highly preferred that being hydrogen peroxide as the peroxide used in the peroxide of oxidant and the modification.

15. the method according to any one in claim 1-14, wherein, the thioether be dimethyl sulfide and/ Or thioanisole.

16. the method according to any one in claim 1-15, wherein, the oxidation reaction is 0-200 in temperature DEG C, preferably 20-180 DEG C, more preferably 40-90 DEG C；And pressure is progress under conditions of 0-3MP, the pressure is Gauge pressure.