CN107556219A

CN107556219A - A kind of preparation method of sulfone

Info

Publication number: CN107556219A
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: 2018-01-09
Anticipated expiration: 2036-06-30
Also published as: CN107556219B

Abstract

The invention discloses a kind of preparation method of sulfone, this method includes making a kind of reactant mixture and HTS haptoreaction in the reactor, obtain the product mixtures containing sulfone, the reactant mixture contains thioether, oxidant and optional solvent, wherein, when desirable oxidation selectivity of product is less than desired value, this method also includes the content for improving 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 HTS as catalyst, extend the single trip use life-span of HTS, reduce the regeneration frequency of HTS, 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 method of sulfone.

Background technology

Sulfone class material is important sulfur-containing compound, if dimethyl sulfone is 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 sulphur by strong oxidizer 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 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 medicine.Dimethyl sulfone has the ability that enhancing human body produces insulin, simultaneously as a kind of organic sulfur compound Metabolism to carbohydrate also has facilitation, is the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound to be cured Close, vitamin B, vitamin C, the synthesis of biotin and the activation needed for metabolism and neurological health can also be worked, 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 medicine of health care.It is external to be widely applied using dimethyl sulfone as with vitamin nutriment of equal importance, China Application study to dimethyl sulfone is not yet carried out very well, and product is mainly used in 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, market potential is big, and benefit protrudes, and has wide Wealthy production and application and development prospect.

At present, the product that dimethyl sulfone further aoxidizes as dimethyl sulfoxide (DMSO), for the main pair of dimethyl sulfoxide (DMSO) production Product.

The content of the invention

When directly prepared by sulfide oxidation into sulfone using oxidant (particularly peroxide), if using HTS As catalyst, it is possible to increase the conversion ratio of oxidant and the selectivity of desirable oxidation product.But with the extension in reaction time, The catalytic activity of HTS can be on a declining curve, causes oxidant conversion ratio and desirable oxidation selectivity of product substantially to drop It is low.When reaction is carried out in fixed bed reactors, because titanium molecular sieve catalysis activity is reduced, it is necessary to which HTS is existed Regenerated in reactor or outside reactor, cause reactor down-time, so as to influence production efficiency and improve the operation of device into This.

It is an object of the invention to provide a kind of preparation method of sulfone, this method can effectively extend as catalyst The single trip use life-span of HTS, during continuous run in long period can by desirable oxidation selectivity of product it is stable compared with High level.

The invention provides a kind of preparation method of sulfone, this method includes making a kind of raw mixture with HTS 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 also includes at least carrying out set-up procedure once, in the condition 1 of satisfaction The set-up procedure is carried out, to improve desirable oxidation selectivity of product until meeting to stop the set-up procedure during condition 2,

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.

According to the preparation method of the sulfone of the present invention, it can effectively delay the inactivation speed of HTS as catalyst Degree, extend the single trip use life-span of HTS, reduce the regeneration frequency of HTS, so as to improve the production of device effect Rate, reduce operating cost.

The method of the present invention is easy to operate, easy to implement.

Embodiment

The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment 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 includes making a kind of raw mixture with HTS 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 " represents one or more kinds of；It is " optional " represent with or without.

The method according to the invention, HTS are a kind of boilings of a part of silicon atom in titanium atom substitution lattice framework The general name of stone, chemical formula xTiO can be used₂·SiO₂Represent.Content no spy of the present invention for titanium atom in HTS Do not limit, can be the conventional selection of this area.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, more excellent Elect 0.015-0.025 as.

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

Preferably, the HTS be the HTS selected from MFI structure, MEL structures HTS, It is more than one or both of the HTS of BEA structures and the HTS of hexagonal structure.It is highly preferred that the titanium silicon Molecular sieve is the HTS of MFI structure, such as titanium-silicon molecular sieve TS-1 and/or hollow HTS.The hollow titanium silicon Molecular sieve is the HTS of MFI structure, and the crystal grain of the HTS is hollow-core construction, the chamber portion of the hollow-core construction Radical length be 5-300 nanometers, and the HTS 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 HTS Hysteresis loop between line be present.The hollow HTS, which is commercially available, (such as to be built feldspathization share commercially available from Hunan and has The trade mark of limit company is HTS molecular sieve), it can also be prepared according to the method disclosed in CN1132699C.

The method according to the invention, when the HTS uses template in preparation process, the titanium silicon molecule Sieve can be the HTS that experienced the process (such as roasting process) for removed template method, or do not undergo and be used for The HTS of the process (such as roasting process) of removed template method, can also be both mixtures.

The method according to the invention, at least part HTS are titanium-silicon molecular sieve TS-1, the HTS TS- 1 surface silicon titanium ratio is not less than body phase silicon titanium ratio, can so obtain the catalytic performance further improved, further extends titanium silicon point The single trip use life-span of son sieve.Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2.It is more excellent Selection of land, 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 ratio With the body phase silicon titanium than ratio be 1.5-4.5 (such as 2.2-4.5).It is further preferred that the surface silicon titanium ratio and institute State body phase silicon titanium than ratio be 2-3, such as 2.2-2.8.

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

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

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

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

(III) dispersion liquid that the dispersion liquid or step (II) obtained step (I) obtains order in reactor is sealed Experience stage (1), stage (2) and stage (3) carry out crystallization, and the stage (1) is in 80-150 DEG C of crystallization 6-72 hour (h), 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 more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine.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 (such as Alkyl) compound that is formed after substitution, the aliphatic hydramine can be various NH₃In at least one hydrogen by the fat of hydroxyl The compound formed after fat race group (such as alkyl) substitution.

Specifically, the alkali source template can be quaternary ammonium base, the aliphatic amine and formula of Formula II expression represented selected from Formulas I 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-C₄Branched alkane Base, R₁、R₂、R₃And R₄Instantiation can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, 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-C₆ Branched alkyl, its instantiation can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different Butyl, the tert-butyl group, 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, its instantiation 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, its instantiation can include but is not limited to methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1st, 2 or 3.

The instantiation of the alkali source template can include but is not limited to：TMAH, tetraethyl hydroxide Ammonium, TPAOH (include 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 and Four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine With it is more than one or both of triethanolamine.Preferably, the alkali source template is tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen Change more than one or both of ammonium and TBAH.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 both of more than；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 Ludox, preferably silica gel.SiO in the Ludox₂Quality hundred It can be more than 10% to divide content, preferably more than 15%, more preferably more than 20%.Preparing according to the preferred embodiment HTS when, without using organic silicon source, such as organosilan and organosiloxane.

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

The dispersion liquid that step (I) 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) 6-24h stood at a temperature of 15-60 DEG C.Enter between step (I) and step (III) Row step (II) can significantly improve the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 finally prepared so that the titanium silicon point finally prepared The surface silicon titanium ratio of son sieve is not less than body phase silicon titanium ratio, can so significantly improve the catalytic of the HTS finally prepared Can, extend its single trip use life-span.Usually, the setting steps (II) between step (I) and step (III), final system are passed through The surface silicon titanium of standby HTS than with body phase silicon titanium than 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 Put and carried out more preferably at a temperature of 20-50 DEG C, 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) is carried out in sealing container, can so be avoided during standing into dispersion liquid It is introduced into foreign matter or causes moieties volatilization in dispersion liquid to be lost in.

After the completion of step (II) described standing, directly the dispersion liquid through standing can be sent into reactor and carry out crystallization, Crystallization can also be carried out by being sent into after the dispersion liquid of standing carries out redisperse in reactor, be sent into instead after preferably carrying out redisperse Answer in kettle, so can further improve the dispersing uniformity for the dispersion liquid for carrying out crystallization.The method of the redisperse can be normal Combination more than rule method, such as one or both of stirring, supersound process and vibration.The duration of the redisperse with The dispersion liquid through standing can be made to form uniform dispersion liquid to be defined, typically 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, temperature is increased 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) The rate of temperature fall of temperature to stage (2) temperature can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 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 2-40 DEG C/min, more Preferably 5-20 DEG C/min.

In step (III), the crystallization temperature in stage (1) is preferably 110-140 DEG C, more preferably 120-140 DEG C, 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 less than the crystallization in stage (3) Temperature, it so can further improve the catalytic performance of the HTS of preparation.Preferably, the crystallization temperature in stage (1) compares rank The crystallization temperature of section (3) is low 10-50 DEG C.It is highly preferred that the crystallization temperature in stage (1) is lower 20-40 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 in stage (3) Between, it so can further improve the catalytic performance of the HTS finally prepared.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 shorter 6- than the crystallization time in stage (3) 12h, such as short 6-8h.In step (III), both preferred embodiments 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 Ask.

In step (III), in another preferred embodiment, the temperature in stage (2) is not higher than 50 DEG C, and is stopped Time is at least 0.5h, such as 0.5-6h, so can further improve the catalytic performance of the HTS finally prepared.It is preferred that Ground, the residence time in stage (2) is at least 1h, such as 1-5h.The preferred embodiment can be with foregoing two kinds preferable implementations Mode is used separately, and can also be applied in combination, preferred compositions use, i.e., the crystallization temperature and crystallization in stage (1) and stage (3) when Between and the temperature in stage (2) and residence time meet the requirements of above-mentioned three kinds of preferred embodiments simultaneously.

It can use in the mixture that is obtained from step (III) crystallization of conventional method and reclaim HTS.Specifically, may be used After alternatively being filtered and washed with the mixture for obtaining step (III) 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 with 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 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 the mode dried is selected, and is not particularly limited.For example, when the drying is carried out under ambient pressure, temperature is excellent Elect 80-150 DEG C, more preferably 100-120 DEG C as, the dry duration is preferably 0.5-5h, more preferably 1-3h.The roasting Burning can be carried out at a temperature of 300-800 DEG C, be carried out preferably at a temperature of 500-700 DEG C, more preferably at 550-650 DEG C At a temperature of carry out, carried out further preferably at a temperature of 550-600 DEG C.The duration of the roasting can be according to roasting Temperature is selected, and typically can be 2-12h, preferably 2-5h.The roasting is carried out preferably in air atmosphere.

The method according to the invention, at least part HTS are preferably modified HTS, the modification HTS undergoes modification, so can more effectively lift the catalytic performance of HTS, further extend titanium In the single trip use life-span of si molecular sieves, further reduce the regeneration frequency of HTS.The modification includes following step Suddenly：Using as the HTS of raw material and containing nitric acid (that is, HNO₃) and at least one peroxide modification liquid contact.Institute The HTS that raw material HTS refers to the raw material as modification is stated, can be without going through the modification HTS, or live through the modification but need to carry out the titanium silicon molecule of the modification again Sieve.The HTS that above-mentioned modification is lived through in the present invention is referred to as modified HTS, does not live through above-mentioned change Property processing HTS be referred to as unmodified HTS.Can whole HTSs live through it is above-mentioned modification at Reason, or modified HTS and the mixture of unmodified HTS.Preferably, with the titanium silicon molecule On the basis of the total amount of sieve, the HTS at least more than 50 weight % lives through the modification, more preferably at least 60 weights Amount more than % HTS lives through the modification, changes as described in living through 50-90 weight % HTS Property processing.

In the modification, peroxide can be selected from hydrogen peroxide, hydroperoxides and peracid.At the modification In reason, the instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, ethylbenzene hydroperoxide, 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 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 dosage of the nitric acid can be according to the use of the peroxide Amount 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 1：0.3-5, 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 can be each 0.1-50 weight %.Improved from further The angle of the catalytic performance of the HTS of the modification finally prepared is set out, preferably 0.5-25 weight %.It is highly preferred that institute State 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 weights % (such as 2-8 weight %) is measured, 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 is water.

In the modification, HTS and modification liquid as raw material can enter at a temperature of 10-350 DEG C Row 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.It is further excellent Selection of land, the contact are carried out at a temperature of 60-200 DEG C, such as contacted at a temperature of 70-170 DEG C.At the modification In reason, the pressure in container that will be contacted as the HTS of raw material with the modification liquid can be according to Contact Temperature Selected, can be environmental pressure, or pressurization.Usually, using as the HTS of raw material and the modification The pressure in container that liquid is contacted can be 0-5MPa (gauge pressure).Preferably, under pressure using as raw material HTS contacts with the modification liquid.It is highly preferred that using as the titanium silicon of raw material under self-generated pressure in closed container Molecular sieve contacts with the modification liquid.The duration that HTS as raw material is contacted with the modification liquid can be with For 0.5-10h, preferably 2-5h.

In the modification, as the HTS of raw material and the exposure level of the modification liquid preferably so that, Using on the basis of the HTS as raw material, in ultraviolet-visible spectrum, modified HTS 230-310nm it Between the peak area of absworption peak reduce by more than 2%, the pore volume of modified HTS reduces more than 1%.Modified titanium silicon point The peak area of absworption peak of the son sieve between 230-310nm preferably reduces 2-30%, more preferably reduces 2.5-15%, further excellent Choosing reduces 3-10%, still more preferably reduces 3-8%.The pore volume of modified HTS preferably reduces 1-20%, more excellent Choosing reduces 2-10%, further preferably reduces 2.5-5%.The pore volume uses static determination of nitrogen adsorption.

Using HTS as in the various commercial plants of catalyst, as Ammoximation reaction device, hydroxylating are anti- Answer in device and epoxidation reaction device, generally plant running for a period of time after, the catalytic activity of catalyst decline, it is necessary to 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 device (that is, more catalyst changeout) is drawn off, and catalyst (that is, drawing off agent or dead catalyst) the current processing method drawn off is typically heap Product is buried, and on the one hand occupies the land resource and inventory space of preciousness, another aspect HTS production cost is higher, directly Connect to pass into disuse and also result in great waste.The present inventor has found in research process, if these are drawn off into agent (that is, the HTS drawn off) is used in step (2) after being regenerated, and remains able to obtain preferable catalytic performance, simultaneously In continuous running for a long time, more preferable activity stability is shown.Therefore, the method according to the invention, at least partly The HTS is preferably that the reaction unit using HTS as catalyst through regeneration (removes thioether oxidation unit Outside) draw off agent.It is described draw off agent can be from it is various using HTS as the reaction unit of catalyst in draw off Agent is drawn off, such as agent can be drawn off for what is drawn off from oxidation reaction apparatus.Specifically, it is described to draw off agent as Ammoximation reaction dress That puts draws off agent, the one or more drawn off in agent for drawing off agent and epoxidation reaction device of hydroxylating device.More Body, it is described draw off agent can be cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draws off agent With the one or more drawn off in agent of propylene ring oxidation reaction device.

The condition that agent regenerated will be drawn off to be not particularly limited, appropriate choosing can be carried out according to the source for drawing off agent Select, such as：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 be the 5-95% of activity (that is, the activity of fresh HTS) of the HTS when fresh, such as 5%, 6%, 7%th, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%th, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%th, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%th, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%th, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%th, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%.Preferably, through again The active 10-90% that the raw activity for drawing off agent can be the HTS when fresh.It is further preferred that through regeneration The activity for drawing off agent can be active 30-50% of the HTS when fresh.In the work for drawing off agent through regeneration Property be the HTS when fresh active 30-50% when, in continuous running for a long time, show preferably Activity stability.It is further preferred that it is activity of the HTS when fresh in the activity for drawing off agent through regeneration 35-45%.The activity of the fresh HTS is generally more than 90%, and usually more than 95%.

The activity determines by the following method：Respectively by through regeneration draw off agent and fresh HTS is used as hexamethylene The catalyst of ketone oxamidinating reaction, the condition of the Ammoximation reaction are：HTS, 36 weight % ammoniacal liquor are (with NH₃Meter), 30 weight % hydrogen peroxide is (with H₂O₂Meter), the tert-butyl alcohol and cyclohexanone in mass ratio 1：7.5：10：7.5：10, at atmosheric pressure 2h is reacted in 80 DEG C.Calculate respectively using the conversion of cyclohexanone when drawing off agent and fresh HTS as catalyst through regeneration Rate, and using it as the activity for drawing off agent and fresh HTS through regeneration, wherein, the conversion ratio of cyclohexanone= [mole of the cyclohexanone of (mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/addition] × 100%.

When at least part HTS is that the reaction unit through regeneration draws off agent, with the total amount of the HTS On the basis of, the content that the reaction unit through regeneration draws off agent is preferably more than 5 weight %.The method according to the invention, even if entirely Portion's HTS is that the reaction unit through regeneration draws off agent (that is, the content for drawing off agent of the reaction unit through regeneration is 100 weights Measure %) when, remain able to obtain preferable catalytic effect.

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

The method according to the invention, the contact form of the HTS and the raw mixture do not limit especially It is fixed, HTS can be seated in the beds of reactor, the raw mixture is passed through the catalyst Bed, so as to realize in the presence of HTS, by thioether and oxidant haptoreaction；Can also be by the raw mixture Slurry is mixed to form with HTS, so as to realize in the presence of HTS, by thioether and oxidant haptoreaction.

It can be used when the raw mixture and HTS are mixed to form into slurry, after the completion of haptoreaction each Slurry is carried out solid-liquor separation by kind method, so as 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 HTS is seated in beds, the quantity of the beds can be one It is or multiple.When the quantity of beds is multiple, it can be the different zones positioned at a reactor, can also be located at more In individual reactor.

The method according to the invention, the beds can only load HTS, can also contain titanium silicon point Son sieve and inactive filler.Loading inactive filler in beds can be to the amount of HTS in beds It is adjusted, so as to which the speed of reaction be adjusted.Contain HTS and inactive filler in the beds When, the content of inactive filler can be 5-95 weight % in beds.The inactive filler refers to oxidation reaction Without or the basic filler without catalytic activity, its instantiation can include but is not limited to：Quartz sand, ceramic ring and ceramics are broken One or more in piece.

The method according to the invention, the HTS can be HTS original powder, or shaping titanium silicon Molecular sieve, preferably it is molded HTS.Shaping HTS typically contain as active component HTS and As the carrier of binding agent, wherein, the content of HTS can be conventional selection.Usually, with the shaping titanium silicon point On the basis of the total amount of son sieve, the content of HTS can be 5-95 weight %, preferably 10-95 weight %, be more preferably 70-95 weight %, more preferably 80-90 weight %；The content of the carrier can be 5-95 weight %, preferably 5-90 Weight %, more preferably 5-30 weight %, more preferably 10-20 weight %.The carrier of the shaping HTS can Conventional selection is thought, such as aluminum oxide and/or silica.The method for preparing the shaping HTS is well known in the art , no longer it is described in detail herein.The granular size of the shaping HTS is also not particularly limited, and can be entered according to concrete shape The appropriate selection of row.Specifically, the average grain diameter of the shaping HTS can be 4-10000 microns, preferably 5- 5000 microns, more preferably 40-4000 microns, more preferably 50-1000 microns, such as 100-500 microns.The average grain Footpath is volume average particle size, laser particle analyzer can be used to determine.

The method according to the invention, the HTS as catalyst, its dosage using can realize catalysis as Standard, it is not particularly limited.It can typically be selected according to the contact form of HTS and the raw mixture.Example Such as, when HTS and the raw mixture are mixed to form into slurry, the weight of dimethyl sulfide and HTS Than that can be 0.1-50：1, preferably 1-50：1, such as 1-25：1；When HTS is seated in beds, 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 HTS in whole beds.

The method according to the invention, the oxidant can be the common various things that sulfide oxidation can be turned into 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- keys 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 substituted by organic group obtained from material.The peracid refers to having containing-O-O- keys in molecular structure Machine oxyacid.In the present invention, the instantiation of the oxidant 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, it so can further reduce separation costs.

The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.Root is improved from further Set out according to the angle of the security of the method for the present invention, the method according to the invention is preferably using existing mistake as an aqueous solution Hydrogen oxide.The method according to the invention, when the hydrogen peroxide provides as an aqueous solution, the aqueous hydrogen peroxide solution Concentration can be the normal concentration of this area, such as：20-80 weight %.Concentration meets the water-soluble of the hydrogen peroxide of above-mentioned requirements Liquid can use conventional method to prepare, and can also be commercially available, such as：It can be the dioxygen for the 30 weight % that can be commercially available Water, 40 weight % hydrogen peroxide, 50 weight % hydrogen peroxide, 60 weight % hydrogen peroxide or 70 weight % hydrogen peroxide.

The method according to the invention, the raw mixture preferably comprise solvent, so pass through regulation with or without solvent The content of solvent in raw mixture, the speed of reaction can be adjusted, make reaction more steady.The solvent can be It is various to dissolve thioether and oxidant or promote the two to mix, the liquid substance of the enough solubilized target oxidation products of and can.One As, the solvent can be selected from water, C₁-C₆Alcohol, C₃-C₈Ketone and C₂-C₆Nitrile.The instantiation of the solvent can wrap Include but be not limited to：Water, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.

The dosage of the solvent can carry out appropriate selection according to the dosage of thioether and oxidant.Usually, it is described molten Agent and the initial molar ratio of the thioether can be 0.1-100：1, preferably 0.2-80：1, such as 5-60：1.

The method according to the invention, the thioether can be the various compounds containing-S- keys, and preferably described thioether is selected from Carbon number is 2-18 thioether, more preferably dimethyl sulfide or thioanisole.

The method according to the invention, this method also include at least carrying out set-up procedure once, carried out in the condition 1 of satisfaction The set-up procedure, to improve desirable oxidation selectivity of product until meeting to stop the set-up procedure during condition 2,

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.

The method according to the invention, in the condition 2 of satisfaction, stops set-up procedure, that is, stops 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.

The method according to the invention desirable oxidation selectivity of product drop to meet above-mentioned condition 1 when, improve the original Expect the content of oxidant in mixture, the desirable oxidation selectivity of product that can make downward trend is presented originally is gone up, so that will Desirable oxidation selectivity of product maintains higher level for a long time, extends the single trip use longevity of the HTS as catalyst Life, reduce 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 life-span of molecular sieve.

On the premise of gratifying device parallel-adder settle-out time is obtained, from during effective operation of further extension fixture 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 using below equation.

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

Wherein, the molal quantity=molal quantity of the thioether of addition-for participating in the thioether of reaction remains in obtained reactant mixture The molal quantity of remaining thioether.

The composition for the reactant mixture that can be exported by continuous monitoring during the course of the reaction 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 of the first batch of reactant mixture of device output is answered to determine.For example, it will can be obtained within reactor stable operation 0.5-10 hours The reactant mixture arrived is as first batch of reactant mixture.

Conventional method can be used to determine the composition of the reactant mixture exported from fixed bed reactors, such as gas phase color Spectrometry.

The method according to the invention, although in the condition 1 of satisfaction, the content of oxidant is raised until desirable oxidation product selects Selecting property S ' meets condition 2, it is preferred that improving containing for oxidant in raw mixture with the amplitude in 0.01-5 weight %/day Amount, the longer HTS single trip use life-span on the one hand so can be obtained, 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 raw material is raised with the amplitude in 0.05-2 weight %/day The content of oxidant in mixture.

Method according to the invention it is possible to the content of oxidant in raw mixture is improved using various methods.Such as： The addition that oxidant when preparing the raw mixture can be improved improves the content of oxidant in raw mixture.In oxygen When agent is provided in the form of oxidizing agent solution, original can be improved by improving the concentration of oxidant in oxidizing agent solution to realize Expect the content of oxidant in mixture, now the dosage of oxidizing agent solution can be kept constant, can also accordingly be adjusted (example Such as, the dosage of oxidizing agent solution is accordingly reduced, to keep the constant rate between thioether and oxidant), as long as can ensure that raw material The content of oxidant is raising in mixture.This mode is especially suitable for using the peroxidating provided in the form of hydrogen peroxide The occasion of hydrogen, now can be by improving the concentration of hydrogen peroxide in hydrogen peroxide.The method according to the invention, in the reaction Early stage, the content of oxidant in raw mixture can be improved with relatively low amplitude；Phase after the reaction, can be with higher amplitude Improve the content of oxidant in raw mixture.

The method according to the invention, the amount of other materials in raw mixture can keep constant as the case may be, 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.Typically The initial molar ratio of ground, oxidant and thioether can be 2-5：1, preferably 2-4：1, more preferably 2-3：1, more preferably 2-2.5：1.

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

The method according to the 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 rise.

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

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

The method according to the invention can also include being separated the reactant mixture exported from reactor, to obtain Desirable oxidation product (such as sulfone) and unreacted reactant.The method that reactant mixture is separated can be this area Conventional selection, it is not particularly limited.The unreacted reactant isolated can recycle.

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, containing for each composition in obtained product mixtures is analyzed using gas-chromatography Amount, below equation is respectively adopted on this basis to calculate thioether rate and sulfone selectivity：

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

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

In following examples and comparative example, static nitrogen adsorption method and solid ultraviolet-visible is respectively adopted and diffuses spectrometry The pore volume and ultraviolet absorption peak of HTS after before modified 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 type static state n2 absorption apparatus of ASAP 2405 of Micromeritics companies.

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

By HTS, 36 weight % ammoniacal liquor (with NH₃Meter), 30 weight % hydrogen peroxide is (with H₂O₂Meter), the tert-butyl alcohol With cyclohexanone by weight=1：7.5：10：7.5：, will be anti-after 10 mixing at atmosheric pressure after 80 DEG C of stirring reactions 2 hours Answer thing to filter, liquid phase is analyzed with gas-chromatography, the conversion ratio of cyclohexanone is calculated and as titanium using below equation The activity of si molecular sieves,

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

In the embodiment and comparative example of the step of preparing HTS included below, X-ray diffraction analysis exists Carried out on Siemens D5005 type X-ray diffractometers, using sample and authentic specimen, the five fingers spread out between 2 θ is 22.5 ° -25.0 ° The ratio of diffracted intensity (peak height) sum of characteristic peak is penetrated to represent crystallinity of the sample relative to authentic specimen；Fourier transform Infrared spectrum analysis is carried out on the type Fourier transformation infrared spectrometers of Nicolet 8210；Silicon titanium ratio refers to silica and oxidation The mol ratio of titanium, surface silicon titanium is than the ESCALab250 type x-ray photoelectron spectroscopies using Thermo Scientific companies Measure, body phase silicon titanium ratio are determined using Rigaku Electric Co., Ltd 3271E types Xray fluorescence spectrometer.

Embodiment 1-22 is used for the method for illustrating the present invention.

Embodiment 1

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

(20 DEG C) at room temperature, 22.5g tetraethyl orthosilicates are mixed with 7.0g as the TPAOH of template Close, and add 59.8g distilled water, be stirred molten after normal pressure and 60 DEG C of hydrolysis 1.0h, the hydrolysis for obtaining tetraethyl orthosilicate Liquid.With vigorous stirring, it is slowly added into the hydrating solution by 1.1g butyl titanates and 5.0g anhydrous isopropyl alcohols institute The solution of composition, gained mixture is stirred into 3h at 75 DEG C, obtains clear colloid.It is anti-that this colloid is placed in stainless steel sealing Answer in kettle, constant temperature places 36h at a temperature of 170 DEG C, obtains the mixture of crystallization product.Obtained mixture is filtered, received After collecting obtained solid matter water used wash, in 110 DEG C of dry 1h, 6h then is calcined at 500 DEG C, so as to obtain HTS TS-1, its titanium oxide content are 2.8 weight %.

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

Titanium-silicon molecular sieve TS-1 is well mixed with Ludox (silica content is 30 weight %) and water, wherein, titanium silicon The weight ratio of molecular sieve TS-1, the Ludox counted using silica and water is 1：0.2：1.5.Obtained mixture is made through spin Grain, and obtained wet grain is calcined 5h at 550 DEG C, so as 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, beds are formed, wherein, the quantity of beds is 1 Layer, the ratio of height to diameter of beds is 10.Using dimethyl sulfide, as the hydrogen peroxide of oxidant (with 30 weight % dioxygen The form of water provides) and as the water of solvent raw mixture is mixed to form, by raw mixture from the bottom of fixed bed reactors Portion is sent into and flows through beds.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 water in hydrogen peroxide) is 1：40, 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 for the raw mixture that continuous monitoring exports from reactor in course of reaction, in dimethyl sulfone selectivity S_t With initial (reaction is measured by sampling when proceeding to 0.5 hour) dimethyl sulfone selectivity S₀Ratio S_t/S₀For 0.8≤S_t/S₀<0.9 When, with the amplitude in 0.05-2 weight %/day improve oxidant in raw mixture concentration (in raw mixture hydrogen peroxide with The ratio of dimethyl sulfide keeps constant, 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, stop improving oxygenate content and contain oxidant Amount remains the numerical value after rise.

When reaction proceeds to 620h, the concentration of hydrogen peroxide is 48 weight % in hydrogen peroxide.It is right in tandem reaction sequence Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 620h are obtained is answered to be 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 course of reaction The concentration of oxidant in thing.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 is entering Before row shaping (that is, the HTS that will be prepared using method same as Example 1 is modified using following methods 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 molded, so as to obtain the catalyst that the present embodiment uses.

Titanium-silicon molecular sieve TS-1 is with containing HNO₃(HNO₃Mass concentration 10%) and the hydrogen peroxide (matter of hydrogen peroxide for Measure concentration for 7.5%) the aqueous solution mixing, by obtained mixture in closed container in 70 DEG C of stirring reaction 5h, obtain The temperature of reactant mixture is filtered after being down to room temperature, and obtained solid matter is dried to constant weight at 120 DEG C, is modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂The mol ratio of meter, HTS and hydrogen peroxide is 1：0.1. Compared with raw material HTS, the suction in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm The peak area for receiving peak reduces 3.5%, and 2.6% is reduced by the pore volume of static determination of nitrogen adsorption.

When reaction proceeds to 800h, the concentration of hydrogen peroxide is 47 weight % in hydrogen peroxide.It is right in tandem reaction sequence Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 800h are obtained is answered to be listed in table 1.

Embodiment 3

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

First butyl titanate is dissolved in the alkali source template TPAOH aqueous 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 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.Above-mentioned dispersion liquid is sealed in beaker using sealed membrane 24h is stood in room temperature (for 25 DEG C, similarly hereinafter) after mouthful, 2h is stirred at 35 DEG C followed by magnetic agitation, is allowed to disperse again. Again the dispersion liquid after disperseing is transferred in sealing reactor, first stage crystallization 6h is undergone at 140 DEG C, then by mixture After being cooled to 30 DEG C of experience second stage stop 2h, continue to undergo the phase III at a temperature of 170 DEG C in reactor is sealed 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 drying 2h, 3h is then calcined at 550 DEG C, obtains molecular sieve.The titanium that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) Silicalite TS-1 is consistent, and illustrate to obtain is the titanium-silicon molecular sieve TS-1 with MFI structure；FFIR figure In, in 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, titanium oxide content is 3.5 weight %, surface silicon titanium ratio/body phase silicon titanium ratio be 2.58 (embodiment 1 prepare HTS in, surface silicon titanium ratio/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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 960h are obtained is answered to be 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.The XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) Titanium-silicon molecular sieve TS-1 it is consistent, 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 %.

When reaction proceeds to 850h, the concentration of hydrogen peroxide is 50 weight % in hydrogen peroxide.It is right in tandem reaction sequence Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 850h are obtained is answered to be 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.The XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) Titanium-silicon molecular 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 %.

When reaction proceeds to 900h, the concentration of hydrogen peroxide is 49 weight % in hydrogen peroxide.It is right in tandem reaction sequence Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 900h are obtained is answered to be 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 phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), and illustrate to obtain is to have The TS-1 molecular sieves of MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absworption peak, show that titanium has been enter into point Sub- sieve skeleton frame, in the HTS, surface silicon titanium ratio/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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 820h are obtained is answered to be 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 phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), explanation What is obtained is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absworption peak, table Bright titanium has been enter into framework of molecular sieve, and in the HTS, surface silicon titanium ratio/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 phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), says It is bright that obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Nearby there is absworption peak, Show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 740h are obtained is answered to be 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 HTS that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram^-1Near 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 1.08, 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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 700h are obtained is answered to be 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 stand 24h, but is sent directly into reactor and carries out crystallization.The XRD crystalline phases figure of gained sample and the step of embodiment 1 (2) The titanium-silicon molecular sieve TS-1 of preparation is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；Fourier-transform infrared is composed In 960cm in figure^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, surface silicon titanium ratio/body phase silicon titanium ratio is 1.18, in the HTS, 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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 730h are obtained is answered to be listed in table 1.

Embodiment 11

Dimethyl sulfone is prepared using method same as Example 2, unlike, the titanium silicon as the raw material of modification Molecular sieve is that (titanium-silicon molecular sieve TS-1 is adopted for the titanium-silicon molecular sieve TS-1 of being drawn off from phenol hydroxylation reaction unit through regeneration Prepared with method same as Example 1, the HTS drawn off be calcined in air atmosphere 5h at a temperature of 570 DEG C and Regeneration, the activity after regeneration are 35%, 96%) activity when fresh is.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 N2 adsorption The pore volume of method measure 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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 960h are obtained is answered to be listed in table 1.

Embodiment 12

Dimethyl sulfone is prepared using with the identical method of embodiment 11, unlike, catalyst is directly by through regeneration The titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit is molded (with embodiment 11), so as to the catalysis prepared 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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 760h are obtained is answered to be listed in table 1.

Table 1

Embodiment 13

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

By hollow HTS and contain HNO₃(HNO₃Mass concentration for 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 reactant mixture is filtered after being down to room temperature, and obtained solid matter is dried to perseverance at 120 DEG C Weight, obtains modified HTS.Wherein, hollow HTS is with SiO₂Meter, HTS and hydrogen peroxide rub You are than being 1：0.4.Compared with raw material HTS, in 230- in the UV-Vis spectrum of the HTS of obtained modification The peak area of absworption peak between 310nm reduces 4.6%, and 3.8% is reduced by the pore volume of static determination of nitrogen adsorption.

The hollow HTS of the modification of preparation is molded using following methods, obtains the catalysis that the present embodiment uses Agent.

Modified HTS is well mixed with Ludox (silica content is 30 weight %) and water, wherein, titanium The weight ratio of silicalite TS-1, the Ludox counted using silica and water is 1：0.15：5.Obtained mixture is made through spin Grain, and obtained wet grain is calcined 5h at 550 DEG C, so as to obtain the catalyst that average grain diameter is 500 μm.Wherein, in catalyst, The content of hollow HTS is 85 weight %.

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

The composition for the raw mixture that continuous monitoring exports from reactor in course of reaction, in dimethyl sulfone selectivity S_t With initial (reaction is measured by sampling when proceeding to 0.5 hour) 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 the amplitude in 0.05-1.5 weight %/day The ratio for changing hydrogen and dimethyl sulfide keeps constant, 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 rise.

When reaction proceeds to 850h, the concentration of hydrogen peroxide is 52 weight % in hydrogen peroxide.It is right in tandem reaction sequence Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 850h are obtained is answered to be listed in table 2.

Embodiment 14

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

The hollow HTS of obtained modification is used and is molded with the identical method of embodiment 13, so as to 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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 960h are obtained is answered to be listed in table 2.

Embodiment 15

Dimethyl sulfone is prepared using with the identical method of embodiment 13, unlike, hollow HTS is without modification Processing, is directly molded, 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 Reactor output product mixtures composition be monitored and calculate dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, instead The result that 0.5h and 660h are obtained is answered to be 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 the alkali source template TPAOH aqueous 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 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.Utilize sealed membrane close in beaker above-mentioned dispersion liquid It is honored as a queen and stands 10h at 40 DEG C, 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 reactor, undergoes first stage crystallization 8h at 130 DEG C, mixture then is cooled into 50 DEG C After undergoing second stage stop 5h, continue the temperature in 170 DEG C in reactor is sealed 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, is to the heating rate of phase III crystallization temperature by second stage treatment temperature 20 DEG C/min), without filtering and washing step after gained crystallization product is taken out, 3h directly is dried in 120 DEG C, then 580 2h is calcined at DEG C, obtains molecular sieve.The titanium-silicon molecular sieve TS-1 that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (1) Unanimously, illustrate to obtain is the titanium-silicon molecular sieve TS-1 with MFI structure；In FFIR figure, in 960cm^-1 Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.25, titanium oxide content is 2.6 weight %.

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

Titanium-silicon molecular sieve TS-1 is well mixed with Ludox (silica content is 30 weight %) and water, wherein, titanium silicon The weight ratio of molecular sieve TS-1, the Ludox counted using silica and water is 1：0.1：8.Obtained mixture is granulated through spin, And obtained wet grain is calcined 5h at 550 DEG C, so as 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, beds are formed, wherein, the quantity of beds is 1 Layer, the ratio of height to diameter of beds is 10.Using dimethyl sulfide, as the TBHP of oxidant (with 22 weight % The form of acetonitrile solution provide) and as the acetonitrile of solvent be mixed to form reactant mixture, by reactant mixture from fixed bed The bottom of reactor is sent into and flows through beds.Wherein, the mol ratio of dimethyl sulfide and TBHP is 1： 2.1, the initial molar ratio of dimethyl sulfide and acetonitrile (including acetonitrile in the acetonitrile solution of TBHP) is 1：35, The weight (hourly) space velocity (WHSV) of dimethyl sulfide is 45h^-1.Temperature in beds is 72 DEG C, and the pressure in fixed bed reactors is 0.6MPa。

The composition for the raw mixture that continuous monitoring exports from reactor in course of reaction, in dimethyl sulfone selectivity S_t With initial (reaction is measured by sampling when proceeding to 0.5 hour) 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 the amplitude in 0.05-2 weight %/day The ratio for changing hydrogen and dimethyl sulfide keeps constant, improves the TBHP in the acetonitrile solution of TBHP 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 rise.

When reaction proceeds to 840h, the concentration of TBHP is 45 weights in the acetonitrile solution of TBHP 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

Prepare dimethyl sulfone using with the identical method of embodiment 16, unlike, titanium-silicon molecular sieve TS-1 carry out into Before type, processing is modified using following methods, and by the HTS of obtained modification using identical with embodiment 16 Method be molded, to prepare the catalyst that the present embodiment uses.

The titanium-silicon molecular sieve TS-1 of preparation is with containing HNO₃(HNO₃Mass concentration 15%) and hydrogen peroxide (peroxidating for The mass concentration of hydrogen for 8%) the aqueous solution mixing, by obtained mixture in closed container in 150 DEG C of stirring reaction 3h, obtain To reactant mixture temperature be down to room temperature after filtered, by obtained solid matter 120 DEG C dry to constant weight, obtain Modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂The mol ratio of meter, HTS and hydrogen peroxide is 1： 2.Through characterizing, compared with raw material HTS, in 230-310nm in the UV-Vis spectrum of the HTS of obtained modification Between absworption peak peak area reduce 5.5%, by static determination of nitrogen adsorption pore volume reduce 4.3%.

When reaction proceeds to 920h, the concentration of TBHP is 43 weights in the acetonitrile solution of TBHP 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 with the identical method of embodiment 17, unlike, the titanium in modification as raw material Si molecular sieves are titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1s of being drawn off from propylene ring oxidation reaction device through regeneration Prepared using with the identical method of embodiment 16, the HTS drawn off is calcined at a temperature of 580 DEG C in air atmosphere 3h and regenerate, the activity after regeneration is 40%, 95%) activity when fresh is.Compared with raw material HTS, what is obtained changes Property HTS UV-Vis spectrum in the peak area of absworption peak between 230-310nm reduce 5.3%, by static nitrogen The pore volume of determination of adsorption method reduces 4.8%.

The HTS of obtained modification is used and is molded with the identical method of embodiment 16, obtains the present embodiment The catalyst used.

When reaction proceeds to 1000h, the concentration of TBHP is 40 in the acetonitrile solution of TBHP 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

Prepare dimethyl sulfone using with the identical method of embodiment 18, unlike, by through regeneration from epoxidation of propylene The titanium-silicon molecular sieve TS-1 drawn off in reaction unit is directly molded, to prepare catalyst without modification.

When reaction proceeds to 780h, the concentration of TBHP is 41 weights in the acetonitrile solution of TBHP 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 the alkali source template TPAOH aqueous 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 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.Above-mentioned dispersion liquid is utilized into sealed membrane in beaker After sealing 8h is stood at 45 DEG C；Dispersion liquid through standing is transferred in sealing reactor, undergoes first stage crystallization at 140 DEG C 6h, after mixture then is cooled into 40 DEG C of experience second stage stop 1h, continue in reactor is sealed in 160 DEG C of temperature It is lower experience phase III crystallization 12h (be wherein, 5 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by First stage crystallization temperature to the rate of temperature fall of second stage treatment temperature be 5 DEG C/min, by second stage treatment temperature to The heating rate of three stage crystallization temperatures is 5 DEG C/min), by gained crystallization product take out after without filtering and washing step, directly 110 DEG C of drying 2h are connected to, 3h is then calcined at 550 DEG C, obtains molecular sieve.The XRD crystalline phases figure of gained sample and the step of embodiment 1 Suddenly the titanium-silicon molecular sieve TS-1 that prepared by (1) is consistent, and illustrate to obtain is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier In transform infrared spectroscopy figure, in 960cm^-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, the HTS In, surface silicon titanium ratio/body phase silicon titanium ratio is 2.71, and titanium oxide content is 4.3 weight %.

Titanium-silicon molecular sieve TS-1 is well mixed with Ludox (silica content is 30 weight %) and water, wherein, titanium silicon The weight ratio of molecular sieve TS-1, the Ludox counted using silica and water is 1：0.1：8.Obtained mixture is granulated through spin, And obtained wet grain is calcined 6h at 500 DEG C, so as 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, beds are formed, wherein, the quantity of beds is 1 Layer, the ratio of height to diameter of beds is 10.Using thioanisole, it is (molten with 25 weight % acetone as the Perpropionic Acid of oxidant The form of liquid provides) and as the acetone of solvent reactant mixture is mixed to form, by reactant mixture from fixed bed reactors Bottom is sent into and flows through beds.Wherein, the mol ratio of thioanisole and Perpropionic Acid is 1：2.2, thioanisole and third The initial molar ratio of ketone (including acetone in the acetone soln of Perpropionic Acid) is 1：45, the weight (hourly) space velocity (WHSV) of thioanisole is 15h^-1.Temperature in beds is 65 DEG C, and the pressure in fixed bed reactors is 0.5MPa.

The composition for the raw mixture that continuous monitoring exports from reactor in course of reaction, in lauseto neu selectivity S_tWith Initially (reaction is measured by sampling when proceeding to 0.5 hour) lauseto neu selectivity S₀Ratio S_t/S₀For 0.85≤S_t/S₀<When 0.9, Concentration (Perpropionic Acid and the benzene in compound of reaction of oxidant in raw mixture are improved with the amplitude in 0.05-2 weight %/day The ratio of methyl sulfide keeps constant, 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, stop improving oxygenate content and will aoxidize Agent content remains the numerical value after rise.

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 exported in course of reaction to reactor is monitored 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 with the identical method of embodiment 20, unlike, titanium-silicon molecular sieve TS-1 is being molded Before, it is modified using following methods, and the HTS of obtained modification is used and the identical method of embodiment 20 It is molded, obtains the catalyst that the present embodiment uses.

Titanium-silicon molecular sieve TS-1 is with containing HNO₃(HNO₃Mass concentration 10%) and the hydrogen peroxide (matter of hydrogen peroxide for Measure concentration for 2%) the aqueous solution mixing, by obtained mixture in closed container in 170 DEG C of stirring reaction 2.5h, obtain The temperature of reactant mixture is filtered after being down to room temperature, and obtained solid matter is dried to constant weight at 120 DEG C, is modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO₂The mol ratio of meter, HTS and hydrogen peroxide is 1：1.Through Characterize, compared with raw material HTS, in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm Absworption peak peak area reduce 5.7%, by static determination of nitrogen adsorption pore volume 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 exported in course of reaction to reactor is monitored 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 with the identical method of embodiment 21, unlike, the titanium silicon in modification as raw material Molecular sieve be as raw material be being drawn off from phenol hydroxylation reaction unit through regeneration titanium-silicon molecular sieve TS-1 (titanium silicon Molecular sieve TS-1 use with the identical method of embodiment 20 prepare, the titanium-silicon molecular sieve TS-1 drawn off at a temperature of 580 DEG C in 4h is calcined 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 absworption peak in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm subtracts Few 5.5%, reduce 4.3% by the pore volume of static determination of nitrogen adsorption.

The HTS of obtained modification is used and is molded with the identical method of 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 exported in course of reaction to reactor is monitored 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 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, a variety of simple variants can be carried out to technical scheme, this A little 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 lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy no longer separately illustrates.

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

Claims

1. a kind of preparation method of sulfone, this method includes making a kind of raw mixture contact in the reactor with HTS instead Should, obtain the product mixtures containing sulfone, the raw mixture contain thioether, at least one oxidant and it is optional at least A kind of solvent, wherein, this method also includes at least carrying out set-up procedure once, and the adjustment step is carried out in the condition 1 of satisfaction Suddenly, to improve desirable oxidation selectivity of product until meeting to stop the set-up procedure during 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. the method according to claim 11, 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 the width in 0.01-5 weight %/day Degree improves the content of oxidant in raw mixture.

4. according to the method described in any one in claim 1-3, wherein, at least part HTS is modified titanium silicon Molecular sieve, the HTS experience modification of the modification, the modification are included as the titanium silicon molecule of raw material Sieve contacts with the modification liquid containing nitric acid and at least one peroxide.

5. the method according to claim 11, wherein, in the modification, HTS and institute as raw material The mol ratio for stating peroxide is 1：0.01-5, preferably 1：0.05-3, more preferably 1：0.1-2, the peroxide and institute The mol ratio for stating nitric acid is 1：0.01-50, preferably 1：0.1-20, more preferably 1：0.2-10, more preferably 1：0.3- 5, particularly preferably 1：0.5-3.5, the HTS is in terms of silica.

6. the method according to claim 4 or 5, wherein, in the modification liquid, the concentration of peroxide and nitric acid is respectively 0.1-50 weight %, preferably 0.5-25 weight %, more preferably 1-20 weight %.

7. according to the method described in any one in claim 4-6, wherein, in the modification, the titanium as raw material Si molecular sieves and the modification liquid 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, it is further preferred 60-200 DEG C At a temperature of contacted, it is described contact pressure be 0-5MPa container in carry out, the pressure is gauge pressure；The contact Duration is 0.5-10 hours, preferably 2-5 hours.

8. according to the method described in any one in claim 4-7, wherein, in the modification, the titanium as raw material The exposure level of si molecular sieves and the modification liquid causes, using on the basis of the HTS as raw material, in ultraviolet-visible light In spectrum, the peak area of absworption peak of the modified HTS between 230-310nm reduces by more than 2%, preferably reduces 2- 30%, 2.5-15% is more preferably reduced, 3-10% is further preferably reduced, still more preferably reduces 3-8%；Modified titanium silicon The pore volume of molecular sieve reduces more than 1%, preferably reduces 1-20%, more preferably reduces 2-10%, further preferably reduce 2.5- 5%, the pore volume uses static determination of nitrogen adsorption.

9. according to the method described in any one in claim 1-8, wherein, at least part HTS derives from least one Kind of reaction unit draws off agent, it is described draw off agent for Ammoximation reaction device draw off agent, hydroxylating device draws off agent Agent is drawn off with epoxidation reaction device.

10. according to the method described in any one in claim 1-9, wherein, at least part HTS is titanium silicon molecule Sieve TS-1, the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 be not less than body phase silicon titanium ratio, the silicon titanium ratio refer to silica and The mol ratio of titanium oxide, the surface silicon titanium ratio are determined using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio is penetrated using X Line fluorescence spectrum method for measuring；

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.

11. according to the method described in any one in claim 1-10, wherein, at least part HTS is titanium silicon molecule TS-1 is sieved, the titanium-silicon molecular sieve TS-1 is prepared using the method comprised the following steps：

(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively supplements water, disperseed 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 meters；

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

(III) dispersion liquid that the dispersion liquid or step (II) obtained step (I) obtains sequentially undergoes in reactor is sealed Stage (1), stage (2) and stage (3) carry out crystallization, and the stage, (1) was at 80-150 DEG C, preferably 110-140 DEG C, more preferably 120- 140 DEG C, further preferred 130-140 DEG C of crystallization 6-72 hours, preferably 6-8 hours；Stage (2) is cooled to not higher than 70 DEG C and stopped Stay time at least 0.5h, be preferably 1-5 hours；Stage (3) is warming up to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160- 170 DEG C, then crystallization 6-96 hours, preferred 12-20 hours.

12. according to the method described in any one in claim 1-11, wherein, stage (1) and stage (3) meet following condition One of or both：

Condition 1：The crystallization temperature in stage (1) is less than the crystallization temperature in stage (3), it is preferable that the crystallization temperature in stage (1) compares rank The crystallization temperature of section (3) is low 10-50 DEG C, 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 crystallization time in stage (1) compares rank The crystallization time short 5-24 hours of section (3), preferably short 6-12 hours.

13. according to the method described in any one in claim 1-12, wherein, the stage (2) is cooled to not higher than 50 DEG C, and is stopped The time is stayed to be at least 1 hour.

14. according to the method described in any one in claim 1-13, wherein, the titanium source is inorganic titanium salt and/or organic Titanate esters；The alkali source template is more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine, preferably season Ammonium alkali, 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；Organic metatitanic acid Ester is selected from general formula R⁷ ₄TiO₄The compound of expression, R⁷Selected from the alkyl with 2-4 carbon atom.

15. according to the method described in any one in claim 1-14, wherein, the initial molar ratio of oxidant and thioether is 2- 5：1, preferably 2-4：1, more preferably 2-3：1, more preferably 2-2.5：1.

16. according to the method described in any one in claim 1-15, wherein, as oxidant peroxide and described change Property processing in the peroxide that uses it is identical or different, each be selected from hydrogen peroxide, TBHP, ethylbenzene peroxidating Hydrogen, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid；

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

17. according to the method described in any one in claim 1-16, wherein, the thioether is dimethyl sulfide and/or benzene Methyl sulfide.

18. according to the method described in any one in claim 1-17, wherein, raw mixture is with HTS in 20- Contacted at a temperature of 160 DEG C, preferably 30-140 DEG C, more preferably 40-120 DEG C, raw mixture and HTS Contacted under conditions of pressure is 0-3MP, the pressure is gauge pressure.