CN107235869A - A kind of preparation method of sulfone - Google Patents

A kind of preparation method of sulfone Download PDF

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Publication number
CN107235869A
CN107235869A CN201610186637.3A CN201610186637A CN107235869A CN 107235869 A CN107235869 A CN 107235869A CN 201610186637 A CN201610186637 A CN 201610186637A CN 107235869 A CN107235869 A CN 107235869A
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hts
titanium
stage
temperature
ratio
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CN107235869B (en
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林民
史春风
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)

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 oxidant conversion ratio is less than desired value, this method also includes the temperature for improving the liquid mixture, until oxidant conversion ratio gos 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, production cost be reduced, while the operational efficiency of device can also be improved.

Description

A kind of preparation method of sulfone
Technical field
The present invention relates to a kind of preparation method of sulfone.
Background technology
Sulfone class material is important sulfur-containing compound, such as dimethyl sulfone be white crystalline powder, soluble in water, ethanol, benzene, Methanol and acetone, are slightly soluble in ether.Potassium permanganate can not be made to change colour under normal temperature, dimethyl sulfone can be oxidized to first by strong oxidizer Sulfonic acid.The dimethyl sulfone aqueous solution is in neutrality.In 25 DEG C of microsublimations, accelerate to 60 DEG C of rate of sublimation, thus dimethyl sulfone Product is preferably dried under cryogenic vacuum.
Dimethyl sulfone is used as organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, food in the industry Product additive and medicine.Dimethyl sulfone produces the ability of insulin with enhancing human body as a kind of organic sulfur compound, The metabolism to carbohydrate also has facilitation simultaneously, is the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote Wound healing, to the vitamin B needed for metabolism and neurological health, vitamin C, the synthesis of biotin and can also swash Work is worked, and is referred to as " beautifying carbonizable substance naturally ".Skin, hair, nail, bone, muscle and each organ of human body In all contain dimethyl sulfone, dimethyl sulfone is primarily present in Yu Haiyang and soil in nature, the conduct in plant growth Nutriment is absorbed, and the mankind can absorb from the foods such as veterinary antibiotics, fish, meat, egg, milk, once lacking Health disorders can be caused or occur disease, be the main matter that human body maintains biological element sulphur balance, have to human body diseases Therapeutic value and healthcare function, are human survival and the indispensable medicine of health care.It is external to give birth to dimethyl sulfone as with dimension Element nutriment of equal importance is widely applied, and application study of the China to dimethyl sulfone is not yet carried out very well, current product master It is used to export.Therefore, dimethyl sulfone is not only a kind of new high-tech product, is also a kind of fine chemistry industry of high added value Product.Product is new, market potential is big, and benefit is protruded, with wide production and application and development prospect.
At present, the product that dimethyl sulfone is further aoxidized as dimethyl sulfoxide (DMSO), is the main by-product of dimethyl sulfoxide (DMSO) production Product.
The content of the invention
When directly prepared by sulfide oxidation into sulfone using oxidant (particularly peroxide), if using HTS It is used as catalyst, it is possible to increase the conversion ratio of oxidant and the selectivity of desirable oxidation product.But prolonging with the reaction time Long, the catalytic activity of HTS can be on a declining curve, causes oxidant conversion ratio and desirable oxidation selectivity of product bright Aobvious reduction.When reaction is carried out in fixed bed reactors, because titanium molecular sieve catalysis activity reduction is, it is necessary to by titanium silicon Molecular sieve is regenerated in reactor or outside reactor, causes reactor down-time, so as to influence production efficiency and improve dress The operating cost put.
It is an object of the invention to provide a kind of preparation method of sulfone, this method can effectively extend the single trip use of catalyst In the life-span, reduce regeneration frequency.
The invention provides a kind of preparation method of sulfone, this method includes making a kind of reactant mixture with HTS anti- Haptoreaction in device is answered, the product mixtures containing sulfone are obtained, the reactant mixture contains thioether, at least one oxidation Agent and optional at least one solvent, wherein, this method also includes at least carrying out set-up procedure once, is meeting bar The set-up procedure is carried out during part 1, to improve oxidant conversion ratio until stopping the set-up procedure when meeting condition 2,
Oxidant conversion ratio C under condition 1, sometime ttWith initial oxidant conversion ratio C0Ratio Ct/C0For 0.8≤Ct/C0＜ 1；
Condition 2, oxidant conversion ratio C ' and initial oxidant conversion ratio C0Ratio C '/C0For 0.85≤C '/C0≤1；
The set-up procedure is to improve the temperature of the reactant mixture.
According to the preparation method of the sulfone of the present invention, it can effectively delay the inactivation speed as the HTS of catalyst Degree, extends the single trip use life-span of HTS, the regeneration frequency of HTS is reduced, so as to improve the life of device Efficiency is produced, operating cost is reduced.
The method of the present invention is easy to operate, it is easy to implement.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that specific reality described herein The mode of applying is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of preparation method of sulfone, this method includes making a kind of reactant mixture with HTS anti- Haptoreaction in device is answered, the product mixtures containing sulfone are obtained, the reactant mixture contains thioether, at least one oxidation Agent 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 is a class zeolite of a part of silicon atom in titanium atom substitution lattice framework General name, 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 preferably 0.015-0.025.
The HTS can be the common HTS with various topological structures, for example：The titanium silicon point Son sieve can for the HTS (such as TS-1) selected from MFI structure, the HTS (such as TS-2) of MEL structures, The HTS (such as Ti-Beta) of BEA structures, the HTS (such as Ti-MCM-22) of MWW structures, six sides The HTS (such as Ti-MCM-41, Ti-SBA-15) of structure, the HTS (such as Ti-MOR) of MOR structures, One in the HTS (such as Ti-TUN) of TUN structures and the HTS (such as Ti-ZSM-48) of other structures Plant or two or more.
Preferably, the HTS be the HTS selected from MFI structure, the HTS of MEL structures, It is more than one or both of the HTS of BEA structures and the HTS of hexagonal structure.It is highly preferred that described HTS is the HTS of MFI structure, such as titanium-silicon molecular sieve TS-1 and/or hollow HTS.It is described Hollow HTS is the HTS of MFI structure, and the crystal grain of the HTS is hollow-core construction, the hollow knot The radical length of the chamber portion of structure is 5-300 nanometers, and the HTS is in 25 DEG C, P/P0=0.10, adsorption time It is at least 70 milligrams per grams, the suction of the nitrogen absorption under low temperature of the HTS for the benzene adsorbance that is measured under conditions of 1 hour There is hysteresis loop between attached thermoisopleth and desorption isotherm.The hollow HTS is commercially available (such as commercially available The molecular sieve for being HTS from the trade mark of Hunan Jianchang Petrochemical Co., Ltd), can also be according to public in CN1132699C The method opened is prepared.
The method according to the invention, when the HTS uses template in preparation process, the HTS Can be the HTS that experienced the process (such as roasting process) for removed template method, or do not undergo use Can also be both mixtures in the HTS of the process (such as roasting process) of removed template method.
The method according to the invention, at least part HTS is titanium-silicon molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 Surface silicon titanium ratio be not less than body phase silicon titanium ratio, can so obtain the catalytic performance further improved, further extension titanium silicon The single trip use life-span of molecular sieve.Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2. It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5.It is further preferred that the surface Silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5 (such as 2.2-4.5).It is further preferred that the surface silicon titanium Than with the body phase silicon titanium than ratio be 2-3, such as 2.2-2.8.
In the present invention, mol ratio of the silicon titanium than referring to silica and titanium oxide, surface silicon titanium ratio uses x-ray photoelectron energy Spectrometry is determined, and body phase silicon titanium ratio uses x-ray fluorescence spectrometry.
The method according to the invention, from the further catalytic performance for improving HTS and further extends the single trip use longevity The angle of life is set out, and at least part HTS is titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1, which is used, to be included It is prepared by the method for following steps：
(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively supplements water, obtained In dispersion liquid, the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：(0.5-8)：(5-30)： (100-2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N Meter is (in alkali source template Nitrogen element, in terms of N；In alkali source template not Nitrogen element, with OH-Meter)；
(II) alternatively, the dispersion liquid is stood into 6-24h at 15-60 DEG C；
(III) dispersion liquid that the dispersion liquid or step (II) obtained step (I) is obtained order in sealing reactor Experience stage (1), stage (2) and stage (3) carry out crystallization, and the stage (1) was in 80-150 DEG C of crystallization 6-72 hours (h), the stage (2) is cooled to after not higher than 70 DEG C and residence time at least 0.5h, and the stage (3) is warming up to 120-200 DEG C again crystallization 6-96h.
The alkali source template can be various templates usually used during synthesis of titanium silicon molecular sieve, for example：Institute It can be more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine to state alkali source template.The quaternary ammonium base Can be various organic level Four ammonium alkali, the aliphatic amine can be various NH3In at least one hydrogen by aliphatic alkyl The compound formed after (such as alkyl) substitution, the aliphatic hydramine can be various NH3In at least one hydrogen by containing The compound formed after aliphatic group (such as alkyl) substitution of hydroxyl.
Specifically, the alkali source template can represent for the quaternary ammonium base that is represented selected from Formulas I, Formula II aliphatic amine and formula It is more than one or both of aliphatic hydramine that III is represented.
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4's Branched alkyl, R1、R2、R3And R4Instantiation can include but is not limited to methyl, ethyl, n-propyl, isopropyl, Normal-butyl, sec-butyl, isobutyl group or the tert-butyl group.
R5(NH2)n(Formula II)
In Formula II, n is 1 or 2 integer.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl And C3-C6Branched alkyl, its instantiation can include but is not limited to methyl, ethyl, n-propyl, isopropyl, positive fourth Base, sec-butyl, isobutyl group, 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 be with Including but 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 it is sub- just Butyl；M is 1,2 or 3.
The instantiation of the alkali source template can include but is not limited to：TMAH, tetraethyl ammonium hydroxide, TPAOH (includes the various isomers of TPAOH, such as four n-propyl ammonium hydroxide and tetra isopropyl Ammonium hydroxide), TBAH (include the various isomers of TBAH, such as 4-n-butyl ammonium hydroxide With four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, It is more than one or both of diethanol amine and triethanolamine.Preferably, the alkali source template be tetraethyl ammonium hydroxide, It is more than one or both of TPAOH and TBAH.It is highly preferred that the alkali source template is TPAOH.
The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can be with For TiCl4、Ti(SO4)2And TiOCl2One or both of more than；The organic titanate can be general formula R7 4TiO4 The compound of expression, wherein, R7For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom, Such as butyl titanate.
The inorganic silicon source can be silica gel and/or Ludox, preferably silica gel.SiO in the Ludox2Quality hundred It can be more than 10%, preferably more than 15%, more preferably more than 20% to divide content.It is preferable to carry out preparing according to this During the HTS of mode, without using organic silicon source, such as organosilan and organosiloxane.
In the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is preferably 100：(1-6)：(8-25)： (200-1500), more preferably 100：(2-5)：(10-20)：(400-1000).
The dispersion liquid that step (I) is obtained, which can be sent directly into step (III), carries out crystallization.Preferably, by step (I) 6-24h is stood at a temperature of 15-60 DEG C in obtained dispersion liquid feeding step (II).In step (I) and step (III) Between carry out step (II) the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 finally prepared can be significantly improved so that final system The surface silicon titanium ratio of standby HTS is not less than body phase silicon titanium ratio, can so significantly improve the titanium silicon molecule finally prepared The catalytic performance of sieve, extends its single trip use life-span.Usually, by being set between step (I) and step (III) Step (II), the surface silicon titanium of the HTS finally prepared than with body phase silicon titanium than ratio can 1.2-5 scope It is interior, preferably in the range of 1.5-4.5 (such as in the range of 2.2-4.5), more preferably (such as in 2.2-2.8 in the range of 2-3 In the range of).The standing is carried out more preferably at a temperature of 20-50 DEG C, is carried out at a temperature of such as 25-45 DEG C.
In step (II), when being stood, dispersion liquid can be placed in sealing container, unlimited appearance can also be placed in Stood in device.Preferably, step (II) is carried out in sealing container, can so avoid during standing to point Foreign matter is introduced into dispersion liquid or causes moieties volatilization in dispersion liquid to be lost in.
After the completion of step (II) described standing, directly the dispersion liquid through standing can be sent into reactor and carry out crystallization, Crystallization is carried out in feeding reactor after dispersion liquid through standing can also being carried out into redisperse, preferably carries out sending into after redisperse In reactor, the dispersing uniformity for the dispersion liquid for carrying out crystallization so can be further improved.The method of the redisperse can be with For conventional method, such as combination of one or both of stirring, ultrasonically treated and vibration above.The redisperse is held The continuous time is defined so that the dispersion liquid through standing can be made to form uniform dispersion liquid, typically can be 0.1-12h, such as 0.5-2h. The redisperse can be carried out at ambient temperature, be carried out at a temperature of such as 15-40 DEG C.
In step (III), temperature is adjusted can be according to specific use to the heating rate of each phase temperature and rate of temperature fall The type of crystallization device selected, be not particularly limited.In general, temperature is increased into stage (1) crystallization The heating rate of temperature can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By the stage (1) temperature to stage (2) temperature rate of temperature fall can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably For 5-10 DEG C/min.Can be 1-50 DEG C/min by the heating rate of stage (2) temperature to stage (3) temperature, preferably For 2-40 DEG C/min, more preferably 5-20 DEG C/min.
In step (III), the crystallization temperature in stage (1) is preferably 110-140 DEG C, more preferably 120-140 DEG C, is entered One step is preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.Stage (2) Temperature be preferably not higher than 50 DEG C.The residence time in stage (2) is preferably at least 1h, more preferably 1-5h.Stage (3) crystallization temperature is preferably 140-180 DEG C, more preferably 160-170 DEG C.The stage crystallization time of (3) is preferably 12-20h, more preferably 12-16h.
In step (III), in a preferred embodiment, the crystallization temperature in stage (1) is less than the stage (3) Crystallization temperature, so can further improve the catalytic performance of the HTS of preparation.Preferably, the crystallization in stage (1) Temperature is lower 10-50 DEG C than the crystallization temperature in stage (3).It is highly preferred that the crystallization temperature in stage (1) is than stage (3) Crystallization temperature it is low 20-40 DEG C.In step (III), in another preferred embodiment, the crystallization in stage (1) Time is less than the crystallization time in stage (3), so can further improve the catalytic performance of the HTS finally prepared. Preferably, crystallization time short 5-24h of the crystallization time in stage (1) than the stage (3).It is highly preferred that the stage (1) Crystallization time than the stage (3) the short 6-12h of crystallization time, such as short 6-8h.In step (III), both are preferred Embodiment be may be used alone, can also be used in combination, and preferred compositions are used, i.e. stage (1) and stage (3) Crystallization temperature and crystallization time meet the requirement of both preferred embodiments simultaneously.
In step (III), another preferred embodiment in, the temperature in stage (2) is not higher than 50 DEG C, and Residence time is at least 0.5h, such as 0.5-6h, so can further improve the catalytic performance of the HTS finally prepared. Preferably, the residence time in stage (2) is at least 1h, such as 1-5h.This preferred embodiment can be with foregoing two kinds Preferred embodiment it is used separately, can also be applied in combination, preferred compositions are used, be i.e. stage (1) and stage (3) Crystallization temperature and the temperature and residence time in crystallization time and stage (2) simultaneously meet above-mentioned three kinds of preferred embodiments Requirement.
HTS is reclaimed in the mixture that can be obtained using conventional method from step (III) crystallization.Specifically, may be used After alternatively being filtered and washed with the mixture for obtaining step (III) crystallization, solid matter is dried and roasted Burn, so as to obtain HTS.The drying and the roasting can be carried out under normal conditions.Usually, it is described Drying can be in environment temperature (such as 15 DEG C) to carrying out at a temperature of 200 DEG C.The drying can be in environmental pressure (one As be 1 standard atmospheric pressure) under carry out, can also carry out at reduced pressure.The duration of the drying can root Selected, be not particularly limited according to the mode of dry temperature and pressure and drying.For example, in the drying in ring When being carried out under the pressure of border, temperature is preferably 80-150 DEG C, more preferably 100-120 DEG C, and the dry duration is preferably 0.5-5h, more preferably 1-3h.The roasting can be carried out at a temperature of 300-800 DEG C, preferably at 500-700 DEG C At a temperature of carry out, carry out, carried out further preferably at a temperature of 550-600 DEG C more preferably at a temperature of 550-650 DEG C. The duration of the roasting can select according to the temperature being calcined, and typically can be 2-12h, preferably 2-5h.Institute Roasting is stated to carry out preferably in air atmosphere.
The method according to the invention, at least part HTS is preferably modified HTS, the titanium of the modification Si molecular sieves undergo modification, so can more effectively lift the catalytic performance of HTS, further extend titanium The regeneration frequency in the single trip use life-span of si molecular sieves, further reduction HTS.The modification includes following Step：Using as the HTS of raw material with containing nitric acid (that is, HNO3) and at least one peroxide modification liquid Contact.The raw material HTS refers to the HTS of the raw material as modification, can be for without going through State the HTS of modification, or live through the modification but need to carry out again at the modification The HTS of reason.The HTS that above-mentioned modification is lived through in the present invention is referred to as modified HTS, The HTS for not living through above-mentioned modification is referred to as unmodified HTS.Can whole HTSs it is equal Live through above-mentioned modification, or modified HTS and the mixture of unmodified HTS.It is excellent Selection of land, on the basis of the total amount of the HTS, at least more than 50 weight % HTS lives through described change Property processing, more preferably at least more than 60 weight % HTS lives through the modification, such as 50-90 weight % HTS live through the modification.
In the modification, peroxide can be selected from hydrogen peroxide, hydroperoxides and peracid.At the modification In reason, the instantiation of the peroxide can include but is not limited to：Hydrogen peroxide, ethylbenzene hydroperoxide, the tert-butyl group Hydrogen peroxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxygen Agent is hydrogen peroxide.The hydrogen peroxide can be the hydrogen peroxide existed in a variety of manners commonly used in the art.
Can be 1 as the HTS of raw material and the mol ratio of the peroxide in the modification： 0.01-5, preferably 1：0.05-3, more preferably 1：0.1-2.The consumption of the nitric acid can be according to the peroxide Consumption is selected.Usually, the mol ratio of the peroxide and the nitric acid can be 1：0.01-50, preferably 1： 0.1-20, more preferably 1：0.2-10, more preferably 1：0.3-5, particularly preferably 1：0.5-3.5, such as 1：0.6-3, The HTS is in terms of silica.
In the modification liquid, the concentration of peroxide and nitric acid can be each 0.1-50 weight %.Improved most from further The angle of the catalytic performance of the HTS of the modification prepared eventually is set out, preferably 0.5-25 weight %.It is highly preferred that In the modification liquid, the concentration of peroxide and nitric acid is respectively 1-20 weight %.It is further preferred that the modification liquid In, the concentration of peroxide and nitric acid is respectively 2-15 weight %.In one embodiment, the concentration of peroxide is 2-10 weight % (such as 2-8 weight %), the concentration of nitric acid is 10-15 weight %.
The solvent of the modification liquid various can simultaneously dissolve the solvent of nitric acid and the peroxide to be common.It is preferred that Ground, the solvent of the modification liquid is water.
In the modification, it can be carried out as the HTS and modification liquid of raw material at a temperature of 10-350 DEG C Contact.From the angle of the catalytic performance for the HTS for further improving the modification finally prepared, the contact is excellent Contacted at a temperature of being selected in 20-300 DEG C.It is highly preferred that the contact is carried out at a temperature of 50-250 DEG C.Enter one Preferably, the contact is carried out step at a temperature of 60-200 DEG C, is such as contacted at a temperature of 70-170 DEG C.Institute State in modification, the pressure in container that will be contacted as the HTS of raw material with the modification liquid can root Selected according to Contact Temperature, can be environmental pressure, or pressurization.Usually, the titanium silicon point of raw material will be used as The pressure in container that son sieve is contacted with the modification liquid can be 0-5MPa.Preferably, under pressure will Contacted as the HTS of raw material with the modification liquid.It is highly preferred that in closed container under self-generated pressure will make Contacted for the HTS of raw material with the modification liquid.Contacted as the HTS of raw material with the modification liquid Duration can be 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, with On the basis of the HTS of raw material, in ultraviolet-visible spectrum, modified HTS 230-310nm it Between absworption peak peak area reduction by more than 2%, the pore volume of modified HTS reduces more than 1%.Modified titanium silicon The peak area of absworption peak of the molecular sieve between 230-310nm preferably reduces 2-30%, more preferably reduces 2.5-15%, enters one The preferred reduction 3-10% of step, still more preferably reduces 3-8%.The pore volume of modified HTS preferably reduces 1-20%, 2-10% is more preferably reduced, 2.5-5% is further preferably reduced.The pore volume is using static determination of nitrogen adsorption.
In the various commercial plants using HTS as catalyst, such as Ammoximation reaction device, hydroxylating In device and epoxidation reaction device, generally plant running for a period of time after, the catalytic activity of catalyst declines, and needs Carry out in device or ex-situ regeneration, even if when carrying out regeneration and also being difficult to obtain satisfied activity, it is necessary to by catalyst from dress Drawn off in putting (that is, more catalyst changeout), and the current processing side of the catalyst (that is, drawing off agent or dead catalyst) drawn off Method is typically that accumulation is buried, and on the one hand occupies the land resource and inventory space of preciousness, the life of another aspect HTS Produce cost higher, directly pass into disuse and also result in great waste.The present inventor has found in research process, If these are drawn off is used in step (2) after agent (that is, the HTS drawn off) is regenerated, remain able to obtain Preferable catalytic performance is obtained, while in continuous running for a long time, showing more preferable activity stability.Therefore, The method according to the invention, at least partly described HTS is preferably used as catalyst through regeneration using HTS Reaction unit (in addition to thioether oxidation unit) draw off agent.It is described that to draw off agent can be from various use HTSs As the agent that draws off drawn off in the reaction unit of catalyst, for example, it can draw off agent for what is drawn off from oxidation reaction apparatus. Specifically, it is described draw off agent for Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation is anti- Answer the one or more drawn off in agent of device.More specifically, described, to draw off agent can be cyclohexanone oxamidinating reaction unit Draw off agent, one kind drawn off in agent or many for drawing off agent and propylene ring oxidation reaction device of phenol hydroxylation reaction unit Kind.
The condition that agent regenerated will be drawn off to be not particularly limited, appropriate selection can be carried out according to the source for drawing off agent, For example：High-temperature roasting and/or solvent washing.
The activity for drawing off agent through regeneration is different according to its source.Usually, the activity for drawing off agent through regeneration can Think the 5-95% of activity (that is, the activity of fresh HTS) of the HTS when fresh.Preferably, The active 10-90% that the activity for drawing off agent through regeneration can be the HTS when fresh, more preferably exists Active 30-50% when fresh.It is that the HTS is active when fresh in the activity for drawing off agent through regeneration During 30-50%, in continuous running for a long time, more preferable activity stability is shown.Preferably, through regeneration Draw off the active 35-45% that the activity of agent is the HTS when fresh.The activity one of the fresh HTS As be more than 90%, usually more than 95%.
The activity is determined by the following method：Respectively agent and fresh HTS will be drawn off as cyclohexanone through regeneration The catalyst of Ammoximation reaction, the condition of the Ammoximation reaction is：HTS, 36 weight % ammoniacal liquor are (with NH3 Meter), 30 weight % hydrogen peroxide is (with H2O2Meter), the tert-butyl alcohol and cyclohexanone in mass ratio 1：7.5：10：7.5：10, At atmosheric pressure 2h is reacted in 80 DEG C.Calculate respectively using through regeneration when drawing off agent and fresh HTS as catalyst The conversion ratio of cyclohexanone, and using it as the activity for drawing off agent and fresh HTS through regeneration, wherein, ring Cyclohexanone that the conversion ratio of hexanone=[(mole of the mole of the cyclohexanone of addition-unreacted cyclohexanone)/is added rubs You measure] × 100%.
At least part HTS be the reaction unit through regeneration draw off agent when, using the total amount of the HTS as Benchmark, the content that the reaction unit through regeneration draws off agent is preferably more than 5 weight %.The method according to the invention, even if Whole HTSs are that the reaction unit through regeneration draws off agent (that is, the content for drawing off agent of the reaction unit through regeneration is 100 weight %) when, remain able to obtain preferable catalytic effect.
It is particularly preferably in the method according to the invention, the HTS of the modification as the HTS of raw material State and draw off agent through regeneration, the agent that draws off through regeneration is subjected to the modification, can further be improved through regeneration The single trip use life-span of agent is drawn off, and the desirable oxidation selectivity of product for drawing off agent through regeneration can be significantly improved.
The method according to the invention, the contact form of the HTS and the reactant mixture is not particularly limited, HTS can be seated in the beds of reactor, the reactant mixture is passed through the catalyst bed Layer, so as to realize in the presence of HTS, by thioether and oxidant haptoreaction；The reaction can also be mixed Thing is mixed to form slurry with HTS, so as to realize in the presence of HTS, thioether is contacted instead with oxidant Should.
When the reactant mixture and HTS are mixed to form into slurry, it can use various after the completion of haptoreaction Slurry is carried out solid-liquor separation by method, so as to obtain the liquid material containing desirable oxidation product.For example：Film can be passed through The liquid material is carried out solid-liquor separation by separator.
When the HTS is seated in beds, the quantity of the beds can for one or It is multiple.When the quantity of beds is multiple, it can be the different zones positioned at a reactor, can also be located at In multiple reactors.
The method according to the invention, the beds can only load HTS, can also contain titanium silicon molecule Sieve and inactive filler.Inactive filler is loaded in beds can be to the amount of HTS in beds It is adjusted, so that the speed to reaction is adjusted.Contain HTS in the beds and nonactive fill out During material, the content of inactive filler can be 5-95 weight % in beds.The inactive filler refers to oxidation Reaction without or the filler without catalytic activity substantially, its instantiation can include but is not limited to：Quartz sand, ceramic ring With the one or more in potsherd.
The method according to the invention, the HTS can be the former powder of HTS, or shaping titanium silicon point Son sieve, is preferably 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 On the basis of the total amount of si molecular sieves, the content of HTS can be 5-95 weight %, preferably 10-95 weight %, 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 shaping titanium silicon The carrier of molecular sieve can be conventional selection, such as aluminum oxide and/or silica.The method for preparing the shaping HTS It is it is known in the art, being no longer described in detail herein.The granular size of the shaping HTS is also not particularly limited, Appropriate selection can be carried out according to concrete shape.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 diameter is volume average particle size, can be determined using laser particle analyzer.
The method according to the invention, the HTS as catalyst, its consumption can realize that catalysis is defined, It is not particularly limited.It can typically be selected according to the contact form of HTS and the reactant mixture.For example, When HTS and the reactant mixture are mixed to form into slurry, the weight ratio of dimethyl sulfide and HTS Can be 0.1-50：1, preferably 1-50：1, such as 1-25：1；When HTS is seated in beds, The weight space velocity (in terms of thioether) of the reactant mixture can be 0.05-100h-1, preferably 0.1-80h-1, more preferably For 5-60h-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 various can turn into sulfide oxidation the material of sulfone to be common. Method of the invention is particularly suitable for carrying out oxidizing sulfur ether using peroxide as oxidant to prepare the occasion of sulfone, so can 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 Material obtained from individual or two hydrogen atoms are replaced by organic group.The peracid refers to contain-O-O- keys in molecular structure Organic oxacid.In the present invention, the instantiation of the oxidant can include but is not limited to：Hydrogen peroxide, the tert-butyl group Hydrogen peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidation Agent is hydrogen peroxide, so can further reduce separation costs.
The hydrogen peroxide can be the hydrogen peroxide existed in a variety of manners commonly used in the art.Basis is improved from further The angle of the security of the method for the present invention is set out, and the method according to the invention preferably uses the mistake existed as an aqueous solution Hydrogen oxide.The method according to the invention, when the hydrogen peroxide is provided as an aqueous solution, the hydrogen peroxide is water-soluble The concentration of liquid can be the normal concentration of this area, for example：20-80 weight %.Concentration meets the hydrogen peroxide of above-mentioned requirements The aqueous solution can using conventional method prepare, can also be commercially available, for example：Can be 30 weights that can be commercially available Measure % hydrogen peroxide, 40 weight % hydrogen peroxide, 50 weight % hydrogen peroxide, 60 weight % hydrogen peroxide or 70 weight % Hydrogen peroxide.
The consumption of the oxidant can be conventional selection, be not particularly limited.Usually, the oxidant and thioether Mol ratio can be 2：More than 1.The mol ratio of the oxidant and thioether can be 20：Less than 1, such as 10：Less than 1, Preferably 5：Less than 1, more preferably 3：Less than 1, more preferably 2.5：Less than 1.Preferably, oxidant with The mol ratio of thioether is 2-2.5：1.
The method according to the invention, the reactant mixture preferably comprises solvent with or without solvent, so passes through regulation The content of solvent in reactant mixture, can be adjusted to the speed of reaction, make reaction more steady.The solvent can Think it is various can either dissolve thioether and oxidant or promote the two mix, the liquids of solubilized target oxidation product are capable of again Matter.Usually, the solvent can be selected from water, C1-C6Alcohol, C3-C8Ketone and C2-C6Nitrile.The tool of the solvent Body example can include but is not limited to：Water, methanol, ethanol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, Butanone and acetonitrile.
The consumption of the solvent can carry out appropriate selection according to the consumption of thioether and oxidant.Usually, the solvent Mol ratio with the thioether can be 0.1-100：1, preferably 0.2-80：1, such as 10-60：1.
The method according to the invention, the thioether can be the various compounds containing-S- keys, and preferably described thioether is selected from carbon Atomicity is 2-18 thioether, more preferably dimethyl sulfide or thioanisole.
The method according to the invention, this method also includes at least carrying out set-up procedure once, is carried out in the condition 1 of satisfaction The set-up procedure, to improve oxidant conversion ratio until stopping the set-up procedure when meeting condition 2,
Oxidant conversion ratio C under condition 1, sometime ttWith initial oxidant conversion ratio C0Ratio Ct/C0For 0.8≤Ct/C0＜ 1；
Condition 2, oxidant conversion ratio C ' and initial oxidant conversion ratio C0Ratio C '/C0For 0.85≤C '/C0≤1；
The set-up procedure is to improve the temperature of the reactant mixture.
The method according to the invention, in the condition 2 of satisfaction, stops set-up procedure, that is, stops improving the temperature of reactant mixture Numerical value when spending and temperature remaining to the condition 2 of satisfaction.
The method according to the invention, when oxidant conversion ratio declines, improves the temperature of the reactant mixture as liquid feedstock Degree, enables to the oxidant conversion ratio that downward trend is presented originally to go up, and go up in oxidant conversion ratio to meeting bar During part 2, reaction mixture temperature is kept.So oxidant conversion ratio with the long period can be maintained higher level, Delay the deactivation rate of the HTS as catalyst, extend the single trip use life-span of HTS.
In condition 1, it is preferable that 0.85≤Ct/C0.When condition 1 meets above-mentioned requirements, it can more effectively extend titanium The single trip use life-span of si molecular sieves.
From the angle of the complexity of reduction operation, condition 1, Ct/C0<0.95；Preferably, Ct/C0<0.92；More Preferably, Ct/C0<0.9。
From the further angle for improving oxidant conversion ratio, condition 2,0.9≤C '/C0。
In the present invention, oxidant conversion ratio=(participate in mole of the oxidant of molal quantity/addition of the oxidant of reaction Number) × 100%；
Wherein, the molal quantity=molal quantity of the oxidant of addition-of oxidant of reaction is participated in obtained reactant mixture Oxidant molal quantity.
The composition for the reactant mixture that can be exported by continuous monitoring during the course of the reaction from reactor determine oxidation Agent conversion ratio C0、CtAnd C '.When reactor is multiple reactors, on the basis of the flow direction of reactant mixture, by Oxidant conversion ratio C is determined positioned at the product mixtures of the reactor output of logistics end0、CtAnd C '.In the present invention, Initial oxidant conversion ratio C0After reactor stable operation, the composition of the first batch of reactant mixture exported from reactor is determined. For example, the reactant mixture that can obtain reactor stable operation within 0.5-10 hours is used as first batch of reactant mixture.
The composition of the reactant mixture exported from reactor, such as gas chromatography can be determined using conventional method.
Although in the condition 1 of satisfaction, the temperature of reactant mixture is improved, it is preferred that with 0.01-5 DEG C/day of amplitude The temperature of reactant mixture is improved, longer HTS single trip use life-span, the opposing party is so on the one hand resulted in Face can also enable reaction more smoothly carry out.It is highly preferred that improving reactant mixture with 0.02-2 DEG C/day of amplitude Temperature.
The method according to the invention, the initial temperature (that is, initial charge temperature) of the reactant mixture can be conventional Selection.Usually, the initial temperature of the reactant mixture can be in the range of 0-120 DEG C, preferably at 20-80 DEG C In the range of, more preferably in the range of 20-60 DEG C, further preferably in the range of 30-60 DEG C, such as in 40-60 DEG C of model In enclosing.The temperature elevation amplitude of the reactant mixture is not particularly limited.Due to raising the temperature of reactant mixture, Itself and the catalytic temperature of HTS can be improved, therefore the peak of the preferably temperature of the reactant mixture will not Make to be defined with the maximum temperature that the catalytic temperature of HTS exceedes oxidation reaction.The highest temperature of the oxidation reaction Degree typically can be not higher than 200 DEG C, preferably not higher than 180 DEG C, more preferably not above 120 DEG C, further preferably To be not higher than 90 DEG C, such as not higher than 80 DEG C.
The method according to the invention, in tandem reaction sequence, the elevation amplitude of the temperature of reactant mixture can with identical, Can also be different, typically early stage can raise the temperature of reactant mixture with relatively low amplitude in the reaction, after the reaction the phase The temperature of reactant mixture can be raised with higher amplitude.
The method according to the invention, the oxidation reaction be enough by sulfide oxidation turn into sulfone under conditions of carry out.With gauge pressure Meter, the pressure carried out in catalytic container can be 0-3MPa, such as preferably 0.1-2.5MPa, 1-2.5MPa. When the beds contain the first beds and the second beds, first beds and second The reaction condition of beds can be with identical, or different.From the angle of ease-to-operate, described first Reaction condition between beds and the second beds is identical.
The method according to the invention can also include being separated the reactant mixture exported from reactor, to obtain mesh Mark oxidation product (such as sulfone) and unreacted reactant.The method that reactant mixture is separated can be this area Conventional selection, be not particularly limited.The unreacted reactant isolated can be recycled.
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, used reagent is commercially available reagent, and pressure is gauge pressure.
In following examples and comparative example, the content of each composition in obtained product mixtures is analyzed using gas-chromatography, Below equation is respectively adopted on this basis to calculate oxidant conversion ratio, oxidant effective rate of utilization and sulfone selectivity：
Oxidant conversion ratio=(molal quantity for participating in the oxidant of molal quantity/addition of the oxidant of reaction) × 100%；
Oxidant effective rate of utilization (%)=[mole of the sulfone of 2 × reaction generation/(mole of the oxidant of addition- The mole of unreacted oxidant)] × 100%；
Sulfone selectivity (%)=[mole/(mole of the thioether of addition-unreacted thioether of the sulfone of reaction generation Mole)] × 100%,
Wherein, the molal quantity=molal quantity of the oxidant of addition-of oxidant of reaction is participated in obtained product mixtures The molal quantity of remaining oxidant,
The molal quantity=molal quantity of the thioether of addition-of the thioether of participation reaction remaining thioether in obtained product mixtures Molal quantity.
In following examples and comparative example, static nitrogen adsorption method is respectively adopted and solid ultraviolet-visible diffuses spectrometry to changing The pore volume and ultraviolet absorption peak of HTS before and after property are characterized.Wherein, solid ultraviolet-visible diffusing reflection spectrum (UV-Vis) analysis is carried out on SHIMADZU UV-3100 type ultraviolet-visible spectrometers；Static N2 adsorption exists Carried out on the static n2 absorption apparatus of the types of ASAP 2405 of Micromeritics companies.
It is related to drawing off in the embodiment and comparative example of agent through regeneration below, HTS (bag is determined using following methods Include regenerative agent and fresh dose) activity：
By HTS, 36 weight % ammoniacal liquor (with NH3Meter), 30 weight % hydrogen peroxide is (with H2O2Meter), The tert-butyl alcohol and cyclohexanone are by weight=1：7.5：10：7.5：At atmosheric pressure in 80 DEG C of stirring reactions 2 after 10 mixing After hour, reactant is filtered, liquid phase analyzed with gas-chromatography, the conversion of cyclohexanone is calculated using below equation Rate and as the activity of HTS,
The conversion ratio of cyclohexanone=[(mole of the cyclohexanone of addition-unreacted cyclohexanone mole)/ring added The mole of hexanone] × 100%.
In embodiment and comparative example included below the step of prepare HTS, X-ray diffraction is analyzed in Siemens On D5005 type X-ray diffractometers carry out, using sample and authentic specimen between 2 θ is 22.5 ° -25.0 ° the five fingers diffractive features The ratio of diffracted intensity (peak height) sum at peak represents crystallinity of the sample relative to authentic specimen；Fourier transform is red External spectrum analysis is carried out on the type Fourier transformation infrared spectrometers of Nicolet 8210；Silicon titanium ratio refers to silica and titanium oxide Mol ratio, surface silicon titanium is than the ESCALab250 type x-ray photoelectron power spectrums using Thermo Scientific companies Instrument is determined, and body phase silicon titanium ratio is determined using Rigaku Electric Co., Ltd 3271E types Xray fluorescence spectrometer.
Embodiment 1-21 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), the TPAOH of 22.5g tetraethyl orthosilicates and 7.0g as template is mixed at room temperature Close, and add 59.8g distilled water, stirring mixing obtains the water of tetraethyl orthosilicate after normal pressure and 60 DEG C of hydrolysis 1.0h Solve solution.With vigorous stirring, it is slowly added into the hydrating solution anhydrous different with 5.0g by 1.1g butyl titanates The solution that propyl alcohol is constituted, stirs 3h at 75 DEG C by gained mixture, obtains clear colloid.This colloid is placed in not Become rusty in steel sealing reactor, constant temperature places 36h at a temperature of 170 DEG C, obtains the mixture of crystallization product.By what is obtained Mixture is filtered, and is collected after obtained solid matter water used wash, in 110 DEG C of dry 1h, is then calcined 6h at 500 DEG C, So as to obtain titanium-silicon molecular sieve TS-1, its titanium oxide content is 2.8 weight %.
The titanium-silicon molecular sieve TS-1 of preparation is molded using following methods, so as to obtain the catalyst that the present embodiment is used.
Titanium-silicon molecular sieve TS-1 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 1：0.2：1.5.By obtained mixture through rolling Ball is granulated, and obtained wet grain is calcined into 5h at 550 DEG C, so as to obtain the catalyst that volume average particle size is 200 μm. Wherein, in catalyst, 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 oxidant hydrogen peroxide (with 30 weight %'s The form of hydrogen peroxide is provided) and as the water of solvent reactant mixture is mixed to form, by reactant mixture from fixed bed reaction The bottom of device is sent into and flows through beds.Wherein, the mol ratio of dimethyl sulfide and hydrogen peroxide is 1：2.2, two The mol ratio of Dimethyl sulfide and water (including water in hydrogen peroxide) is 1：40, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 60h-1。 The initial charge temperature of reactant mixture is 50 DEG C, is added beds by the heater strip being arranged in beds Heat to temperature is 50 DEG C, in course of reaction, and the heating condition of heater strip keeps constant, by fixed bed reaction in course of reaction Stress control in device is 1.5MPa.
The composition for the product mixtures that continuous monitoring is exported from reactor in course of reaction, in oxidant conversion ratio CtWith it is first Beginning oxidant conversion ratio C0The ratio C of (reaction is measured by sampling when proceeding to 0.5h)t/C0For 0.87≤Ct/C0<When 0.92, The feeding temperature of reactant mixture is improved with 0.02-2 DEG C/day of amplitude, until oxidant conversion ratio C ' turns with initial oxidant Rate C0Ratio C '/C0For 0.92≤C '/C0When≤1, stop improving the temperature of reactant mixture and keep reactant mixture Temperature.
When reaction proceeds to 650h, the temperature of reactant mixture is 70 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 650h is obtained is listed in table 1.
Comparative example 1
Using method cacodyl oxide base sulfone same as Example 1, unlike, do not change reaction mixing in course of reaction The feeding temperature of 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 exists Before being molded (that is, the titanium silicon point that will be prepared using method same as Example 1 is modified using following methods Son sieve TS-1 is modified processing as raw material), and the titanium-silicon molecular sieve TS-1 of obtained modification is used and embodiment 1 Identical method is molded, so as to obtain the catalyst that the present embodiment is used.
Titanium-silicon molecular sieve TS-1 is with containing HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (hydrogen peroxide for Mass concentration for 7.5%) the aqueous solution mixing, by obtained mixture in closed container in 70 DEG C of stirring reaction 5h, The temperature of obtained reactant mixture is down to after room temperature and filtered, and obtained solid matter is dried to constant weight at 120 DEG C, Obtain modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS and hydrogen peroxide Mol ratio is 1：0.1.Compared with raw material HTS, in the UV-Vis spectrum of the HTS of obtained modification The peak area of absworption peak between 230-310nm reduces 3.5%, and 2.6% is reduced by the pore volume of static determination of nitrogen adsorption.
When reaction proceeds to 760h, the temperature of reactant mixture is 68 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 760h is obtained is listed in table 1.
Embodiment 3
Dimethyl sulfone is prepared using method same as Example 2, 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 (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：4： 12：400, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker 24h is stood in room temperature (being 25 DEG C, similarly hereinafter) after being sealed using sealed membrane, is stirred followed by magnetic agitation at 35 DEG C 2h is mixed, is allowed to disperse again.Again the dispersion liquid after disperseing is transferred in sealing reactor, first is undergone at 140 DEG C Stage crystallization 6h, is then cooled to 30 DEG C of experience second stage by mixture and stops after 2h, continue in sealing reactor Phase III crystallization 12h is undergone at a temperature of 170 DEG C (wherein, by the heating of room temperature to first stage crystallization temperature Speed is 2 DEG C/min, is 5 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by the Two-stage treatment temperature to phase III crystallization temperature heating rate be 10 DEG C/min), by gained crystallization product take out after not Through filtering and washing step, 2h directly is dried in 110 DEG C, 3h is then calcined at 550 DEG C, molecular sieve is obtained.Gained The XRD crystalline phases figure of sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), and illustrate to obtain is tool There is the titanium-silicon molecular sieve TS-1 of MFI structure；In FFIR figure, in 960cm-1Nearby there is absworption peak, Show that titanium has been enter into framework of molecular sieve, in the HTS, titanium oxide content is 3.5 weight %, surface silicon titanium ratio/body Phase silicon titanium ratio is that 2.58 (in HTS prepared by embodiment 1,1.05) surface silicon titanium ratio/body phase silicon titanium ratio is.
When reaction proceeds to 1000h, the temperature of reactant mixture is 68 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 1000h is obtained is listed in table 1.
Embodiment 4
Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), preparing titanium silicon During molecular sieve TS-1, the crystallization temperature of phase III is also 140 DEG C.The XRD crystalline phases figure of gained sample and embodiment 1 Titanium-silicon molecular sieve TS-1 prepared by step (2) is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure； In 960cm in fourier-transform infrared spectrogram-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, the titanium silicon In molecular sieve, surface silicon titanium ratio/body phase silicon titanium ratio is 4.21, and titanium oxide content is 3.1 weight %.
When reaction proceeds to 880h, the temperature of reactant mixture is 71 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 880h is obtained is listed in table 1.
Embodiment 5
Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), preparing titanium silicon During molecular sieve TS-1, the crystallization temperature of first stage is 110 DEG C.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 (2) is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；Fu In 960cm in vertical leaf transformation infrared spectrum-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, the titanium silicon point In son sieve, 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 temperature of reactant mixture is 72 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 900h is obtained is listed in table 1.
Embodiment 6
Dimethyl sulfone is prepared using method same as Example 3, unlike, the crystallization time of first stage is 12h. The XRD crystalline phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (2), illustrates what is obtained It 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, in the HTS, and surface silicon titanium ratio/body phase silicon titanium ratio is 3.78, titanium oxide content For 3.4 weight %.
When reaction proceeds to 860h, the temperature of reactant mixture is 71 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 860h is obtained is listed in table 1.
Embodiment 7
Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), second stage is It is cooled to 70 DEG C of stop 2h.The HTS that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1 Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio For 2.75, titanium oxide content is 3.1 weight %.
When reaction proceeds to 880h, the temperature of reactant mixture is 73 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 880h is obtained is listed in table 1.
Embodiment 8
Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), second stage is It is cooled to 30 DEG C of stop 0.2h.The HTS that the XRD crystalline phases figure of gained sample is prepared with the step of embodiment 1 (2) TS-1 is consistent, and illustrate to obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1 Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium ratio/body phase silicon titanium ratio For 1.14, titanium oxide content is 2.4 weight %.
When reaction proceeds to 780h, the temperature of reactant mixture is 71 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 780h is obtained is listed in table 1.
Embodiment 9
Dimethyl sulfone is prepared using method same as Example 3, unlike, when preparing titanium-silicon molecular sieve TS-1, In step (2), without second stage.The titanium 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 TS-1 molecular sieves with MFI structure；Fourier-transform infrared spectrogram In in 960cm-1Nearby there is absworption peak, show that titanium has been enter into framework of molecular sieve, in the HTS, surface silicon titanium It is 1.08 than/body phase silicon titanium ratio, titanium oxide content is 2.5 weight %.
When reaction proceeds to 740h, the temperature of reactant mixture is 69 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 740h is obtained is listed in table 1.
Embodiment 10
Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (2), aqueous dispersions are not 24h is stood at room temperature, but is sent directly into reactor and is carried out crystallization.The XRD crystalline phases figure and embodiment of gained sample Titanium-silicon molecular sieve TS-1 prepared by 1 step (2) is consistent, and illustrate to obtain is the 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, surface silicon Titanium ratio/body phase silicon titanium ratio is 1.18, in the HTS, and titanium oxide content is 3.5 weight %.
When reaction proceeds to 760h, the temperature of reactant mixture is 70 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 760h is obtained is listed in table 1.
Embodiment 11
Dimethyl sulfone is prepared using method same as Example 2, unlike, it is used as the titanium silicon of the raw material of modification Molecular sieve is titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 of being drawn off from phenol hydroxylation reaction unit through regeneration Prepared using method same as Example 1, the HTS drawn off is calcined at a temperature of 570 DEG C in air atmosphere 5h and regenerate, the activity after regeneration is 35%, and 96%) activity when fresh is.Compared with raw material HTS, obtain To modification HTS UV-Vis spectrum in the peak area of absworption peak between 230-310nm reduce 3.3%, 2.8% is reduced by the pore volume of static determination of nitrogen adsorption.
When reaction proceeds to 920h, the temperature of reactant mixture is 69 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 920h is obtained is 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 (be the same as Example 11) drawn off from phenol hydroxylation reaction unit is molded, so that prepare Catalyst C3.
When reaction proceeds to 800h, the temperature of reactant mixture is 70 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 800h is obtained is listed in table 1.
Table 1
Embodiment 13
Use following methods using as the HTS of raw material (purchased from Hunan Jianchang Petrochemical Co., Ltd the trade mark for HTS hollow HTS, its titanium oxide content is 2.5 weight %) it is modified processing.
By hollow HTS with containing HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (peroxidating for The mass concentration of hydrogen for 5%) the aqueous solution mixing, by obtained mixture in closed container under 120 DEG C of pressure itselfs Stirring reaction 4h, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid matter 120 DEG C dry to constant weight, obtain modified HTS.Wherein, hollow HTS is with SiO2Meter, HTS Mol ratio with hydrogen peroxide is 1：0.4.Compared with raw material HTS, the HTS of obtained modification The peak area of absworption peak in UV-Vis spectrum between 230-310nm reduces 4.6%, by the hole of static determination of nitrogen adsorption Hold and reduce 3.8%.
The hollow HTS of the modification of preparation is molded using following methods, the catalyst that the present embodiment is used is obtained.
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.By obtained mixture through rolling Ball is granulated, and obtained wet grain is calcined into 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 oxidant hydrogen peroxide (with 40 weight %'s The form of hydrogen peroxide is provided) and as the methanol of solvent reactant mixture is mixed to form, reactant mixture is anti-from fixed bed Answer the bottom of device to send into and flow through beds.Wherein, the mol ratio of dimethyl sulfide and hydrogen peroxide is 1：2, two The mol ratio of Dimethyl sulfide and methanol is 1：15, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 40h-1.Reactant mixture it is initial Feeding temperature is 45 DEG C, and it is 45 DEG C that beds are heated into temperature by the heater strip being arranged in beds, In course of reaction, the heating condition of heater strip keeps constant, is by the Stress control in fixed bed reactors in course of reaction 1.2MPa。
The composition for the product mixtures that continuous monitoring is exported from reactor in course of reaction, in oxidant conversion ratio CtWith it is first Beginning oxidant conversion ratio C0The ratio C of (reaction is measured by sampling when proceeding to 0.5h)t/C0For 0.85≤Ct/C0<When 0.9, The feeding temperature of reactant mixture is improved with 0.02-2 DEG C/day of amplitude, until oxidant conversion ratio C ' turns with initial oxidant Rate C0Ratio C '/C0For 0.9≤C '/C0When≤1, stop improving the temperature of reactant mixture and keep reactant mixture Temperature.
When reaction proceeds to 800h, the temperature of reactant mixture is 54 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 800h is obtained is listed in table 2.
Embodiment 14
Dimethyl sulfone is prepared using with the identical method of embodiment 13, unlike, the sky of raw material is used as in modification Heart HTS is hollow HTS (hollow titanium of being drawn off from cyclohexanone oxamidinating reaction unit through regeneration Si molecular sieves and embodiment 13 identical, the hollow titanium drawn off as the source of the hollow HTS of the raw material of modification Si molecular sieves are calcined 6h in air atmosphere at a temperature of 550 DEG C and regenerated, and the activity after regeneration is 40%, when fresh Activity for 97%).Compared with raw material HTS, in the UV-Vis spectrum of the HTS of obtained modification The peak area of absworption peak between 230-310nm reduces 4.8%, and 3.5% is reduced by the pore volume of static determination of nitrogen adsorption.
By the hollow HTS of obtained modification using being molded with the identical method of embodiment 13, so that this reality Apply the catalyst that example is used.
When reaction proceeds to 960h, the temperature of reactant mixture is 53 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 960h is obtained is 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 680h, the temperature of reactant mixture is 54 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 680h is obtained is listed in table 2.
Table 2
Embodiment 16
The titanium-silicon molecular sieve TS-1 that the present embodiment is used is prepared using following methods.
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：2： 10：600, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker 10h is stood at 40 DEG C after being sealed using sealed membrane, 0.5h is stirred at 25 DEG C followed by magnetic agitation, is allowed to again It is scattered.Again the dispersion liquid after disperseing is transferred in sealing reactor, first stage crystallization 8h is undergone at 130 DEG C, connects And mixture is cooled to after 50 DEG C of experience second stage stop 5h, continue the temperature in 170 DEG C in sealing reactor and pass through Go through phase III crystallization 16h (wherein, by room temperature to first stage crystallization temperature heating rate be 1 DEG C/min, by First stage crystallization temperature to second stage treatment temperature rate of temperature fall be 10 DEG C/min, by second stage treatment temperature to The heating rate of phase III crystallization temperature is 20 DEG C/min), without filtering and purge step after gained crystallization product is taken out Suddenly, 3h directly is dried in 120 DEG C, 2h is then calcined at 580 DEG C, obtain molecular sieve.The XRD crystalline phases of gained sample Figure is consistent with the titanium-silicon molecular sieve TS-1 of the step of embodiment 1 (1) preparation, and illustrate to obtain is the titanium with MFI structure Silicalite TS-1；In FFIR figure, in 960cm-1Nearby there is absworption peak, show that titanium has been enter into In framework of molecular sieve, the HTS, surface silicon titanium ratio/body phase silicon titanium ratio is 2.25, and titanium oxide content is 2.6 weight %.
The titanium-silicon molecular sieve TS-1 of preparation is molded using following methods, the catalyst that the present embodiment is used is obtained.
Titanium-silicon molecular sieve TS-1 is well mixed with Ludox (silica content is 30 weight %) and water, wherein, it is empty The weight ratio of heart HTS, the Ludox counted using silica and water is 1：0.1：8.By obtained mixture through spin Granulation, 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, the content of titanium-silicon molecular sieve 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 oxidant TBHP (with 45 The form of weight % acetonitrile solution is provided) and as the acetonitrile of solvent reactant mixture is mixed to form, by reactant mixture Sent into from the bottom of fixed bed reactors and flow through beds.Wherein, dimethyl sulfide and TBHP Mol ratio is 1：2.5, dimethyl sulfide rubs with acetonitrile (including acetonitrile in the acetonitrile solution of TBHP) You are than being 1：30, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 10h-1.The initial charge temperature of reactant mixture is 55 DEG C, is led to Cross the heater strip being arranged in beds and beds are heated to temperature for 55 DEG C, in course of reaction, heater strip Heating condition keep it is constant, in course of reaction by the Stress control in fixed bed reactors be 2.5MPa.
The composition for the product mixtures that continuous monitoring is exported from reactor in course of reaction, in oxidant conversion ratio CtWith it is first Beginning oxidant conversion ratio C0The ratio C of (reaction is measured by sampling when proceeding to 0.5h)t/C0For 0.85≤Ct/C0<When 0.9, The feeding temperature of reactant mixture is improved with 0.02-2 DEG C/day of amplitude, until oxidant conversion ratio C ' turns with initial oxidant Rate C0Ratio C '/C0For 0.9≤C '/C0When≤1, stop improving the temperature of reactant mixture and keep reactant mixture Temperature.
When reaction proceeds to 800h, the temperature of reactant mixture is 66 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 800h is obtained is listed in table 3.
Embodiment 17
Dimethyl sulfone is prepared using with the identical method of embodiment 16, unlike, titanium-silicon molecular sieve TS-1 is being carried out into Before type, processing is modified using following methods, and the HTS of obtained modification is used and the phase of embodiment 16 Same method is molded, to prepare the catalyst that the present embodiment is used.
The titanium-silicon molecular sieve TS-1 of preparation is with containing HNO3(HNO3Mass concentration 15%) and hydrogen peroxide (mistake for The mass concentration of hydrogen oxide is aqueous solution mixing 8%), and obtained mixture is stirred into anti-at 150 DEG C in closed container 3h is answered, the temperature of obtained reactant mixture, which is down to after room temperature, to be filtered, by obtained solid matter in 120 DEG C of dryings To constant weight, modified HTS is obtained.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS and mistake The mol ratio of hydrogen oxide is 1：2.Through characterizing, compared with raw material HTS, the HTS of obtained modification The peak area of absworption peak in UV-Vis spectrum between 230-310nm reduces 5.5%, by the hole of static determination of nitrogen adsorption Hold and reduce 4.3%.
When reaction proceeds to 900h, the temperature of reactant mixture is 65 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 900h is obtained is listed in table 3.
Embodiment 18
Dimethyl sulfone is prepared using with the identical method of embodiment 17, unlike, the titanium of raw material is used as in modification Si molecular sieves are titanium-silicon molecular sieve TS-1 (HTSs of being drawn off from propylene ring oxidation reaction device through regeneration TS-1 is used to be prepared with the identical method of embodiment 16, and the HTS drawn off is at a temperature of 580 DEG C in air atmosphere Middle roasting 3h and regenerate, the activity after regeneration is 40%, and 95%) activity when fresh is.With raw material HTS phase Than the peak area of the absworption peak in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm is reduced 5.3%, reduce 4.8% by the pore volume of static determination of nitrogen adsorption.
By the HTS of obtained modification using being molded with the identical method of embodiment 16, the present embodiment is obtained The catalyst used.
When reaction proceeds to 980h, the temperature of reactant mixture is 64 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selection Property, the result that reaction 0.5h and 980h is obtained is listed in table 3.
Table 3
Embodiment 19
The titanium-silicon molecular sieve TS-1 that the present embodiment is used is prepared using following methods.
First butyl titanate is dissolved in the alkali source template TPAOH aqueous solution, silica gel is then added (purchased from green grass or young crops Island silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：5： 18：1000, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.By above-mentioned dispersion liquid in beaker After middle utilization sealed membrane sealing 8h is stood at 45 DEG C；Dispersion liquid through standing is transferred in sealing reactor, at 140 DEG C First stage crystallization 6h is undergone, mixture then is cooled into 40 DEG C of experience second stage stops after 1h, continues in sealing Phase III crystallization 12h is undergone (wherein, by room temperature to first stage crystallization temperature at a temperature of 160 DEG C in reactor The heating rate of degree is 5 DEG C/min, is 5 DEG C by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature / min, is 5 DEG C/min by the heating rate of second stage treatment temperature to phase III crystallization temperature), gained crystallization is produced Without filtering and washing step after thing taking-up, 2h directly are dried in 110 DEG C, then 3h is calcined at 550 DEG C, is divided Son sieve.The XRD crystalline phases figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by the step of embodiment 1 (1), explanation What is obtained is the titanium-silicon molecular sieve TS-1 with MFI structure；In FFIR figure, in 960cm-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 2.71, 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 The weight ratio of silicalite TS-1, the Ludox counted using silica and water is 1：0.1：8.By obtained mixture through spin Granulation, 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, the content of HTS 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, as oxidant Perpropionic Acid (with the third of 40 weight % The form of ketone solution is provided) and as the acetone of solvent reactant mixture is mixed to form, reactant mixture is anti-from fixed bed Answer the bottom of device to send into and flow through beds.Wherein, the mol ratio of thioanisole and Perpropionic Acid is 1：2.2, benzene The mol ratio of methyl sulfide and acetone (including acetone in the acetone soln of Perpropionic Acid) is 1：60, thioanisole it is heavy when Air speed is 5h-1.The initial charge temperature of reactant mixture is 60 DEG C, will by the heater strip being arranged in beds Beds are heated to temperature for 60 DEG C, in course of reaction, and the heating condition of heater strip keeps constant, in course of reaction It is 2.5MPa by the Stress control in fixed bed reactors.
The composition for the reactant mixture that continuous monitoring is exported from reactor in course of reaction, in oxidant conversion ratio CtWith it is first Beginning oxidant conversion ratio C0The ratio C of (reaction is measured by sampling when proceeding to 0.5h)t/C0For 0.85≤Ct/C0<When 0.9, The feeding temperature of reactant mixture is improved with 0.02-2 DEG C/day of amplitude, until oxidant conversion ratio C ' turns with initial oxidant Rate C0Ratio C '/C0For 0.9≤C '/C0When≤1, stop improving the temperature of reactant mixture and keep reactant mixture Temperature.
When reaction proceeds to 700h, the temperature of reactant mixture is 71 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and lauseto neu selectivity, The result that reaction 0.5h and 700h is obtained is listed in table 4.
Embodiment 20
Lauseto neu is prepared using with the identical method of embodiment 19, 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 side of embodiment 19 Method is molded, and obtains the catalyst that the present embodiment is used.
Titanium-silicon molecular sieve TS-1 is with containing HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (hydrogen peroxide for Mass concentration for 2%) the aqueous solution mixing, by obtained mixture in closed container in 170 DEG C of stirring reaction 2.5h, The temperature of obtained reactant mixture is down to after room temperature and filtered, and obtained solid matter is dried to constant weight at 120 DEG C, Obtain modified HTS.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, HTS and hydrogen peroxide Mol ratio is 1：1.Through characterizing, compared with raw material HTS, the UV-Vis of the HTS of obtained modification The peak area of absworption peak in spectrum between 230-310nm reduces 5.7%, is reduced by the pore volume of static determination of nitrogen adsorption 4.1%.
When reaction proceeds to 780h, the temperature of reactant mixture is 70 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and lauseto neu selectivity, The result that reaction 0.5h and 780h is obtained is listed in table 4.
Embodiment 21
Lauseto neu is prepared using with the identical method of embodiment 20, unlike, the titanium silicon of raw material is used as in modification Molecular sieve be as raw material be being drawn off from phenol hydroxylation reaction unit through regeneration titanium-silicon molecular sieve TS-1 (should Titanium-silicon molecular sieve TS-1 is used to be prepared with the identical method of embodiment 19, and the titanium-silicon molecular sieve TS-1 drawn off is at 580 DEG C At a temperature of be calcined 4h in air atmosphere and regenerate, the activity after regeneration is 40%, and 95%) activity when fresh is.With Raw material HTS is compared, the suction in the UV-Vis spectrum of the HTS of obtained modification between 230-310nm The peak area for receiving peak reduces 5.5%, and 4.3% is reduced by the pore volume of static determination of nitrogen adsorption.
By the HTS of obtained modification using being molded with the identical method of embodiment 19, the present embodiment is obtained The catalyst used.
When reaction proceeds to 900h, the temperature of reactant mixture is 71 DEG C.Reactor is exported in tandem reaction sequence Product mixtures composition be monitored and calculate oxidant conversion ratio, oxidant effective rate of utilization and lauseto neu selectivity, The result that reaction 0.5h and 900h is obtained is 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, can carry out a variety of simple variants to technical scheme, These simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not contradiction In the case of, it can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention is to various Possible combination no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to this hair Bright thought, it should equally be considered as content disclosed in this invention.

Claims (18)

1. a kind of preparation method of sulfone, this method includes making a kind of reactant mixture connect in the reactor with HTS Reaction is touched, the product mixtures containing sulfone are obtained, the reactant mixture contains thioether, at least one oxidant and can At least one solvent of choosing, wherein, this method also includes at least carrying out set-up procedure once, enters in the condition 1 of satisfaction The row set-up procedure, to improve oxidant conversion ratio until stopping the set-up procedure when meeting condition 2,
Oxidant conversion ratio C under condition 1, sometime ttWith initial oxidant conversion ratio C0Ratio Ct/C0For 0.8≤Ct/C0＜ 1；
Condition 2, oxidant conversion ratio C ' and initial oxidant conversion ratio C0Ratio C '/C0For 0.85≤C '/C0≤1；
The set-up procedure is to improve the temperature of the reactant mixture.
2. according to the method described in claim 1, wherein, in condition 1, Ct/C0<0.95；In condition 2,0.9≤C '/C0。
3. method according to claim 1 or 2, wherein, the initial temperature of the reactant mixture is 0-120 DEG C, It is preferred that in the range of 20-80 DEG C, more preferably in the range of 20-60 DEG C, further preferably in the range of 30-60 DEG C, The temperature of reactant mixture is improved with 0.01-5 DEG C/day of amplitude.
4. the method according to any one in claim 1-3, wherein, at least part HTS is modified HTS, the HTS experience modification of the modification, the modification includes that the titanium of raw material will be used as Si molecular sieves are contacted with the modification liquid containing nitric acid and at least one peroxide.
5. method according to claim 4, wherein, in the modification, it is used as the titanium silicon molecule of raw material The mol ratio of sieve and the peroxide is 1：0.01-5, preferably 1：0.05-3, more preferably 1：0.1-2, the mistake The mol ratio of oxide and the nitric acid is 1：0.01-50, preferably 1：0.1-20, more preferably 1：0.2-10, enters one Step is preferably 1：0.3-5, 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, peroxide and nitric acid it is dense Degree is respectively 0.1-50 weight %, more preferably preferably 0.5-25 weight %, 1-20 weight %.
7. the method according to any one in claim 4-6, wherein, in the modification, it is used as raw material HTS and the modification liquid 10-350 DEG C, preferably 20-300 DEG C, more preferably 50-250 DEG C, further preferably Contacted at a temperature of 60-200 DEG C, the contact in 0-5MPa container in pressure to carry out, and the pressure is gauge pressure； The duration of the contact is 0.5-10 hours, preferably 2-5 hours.
8. the method according to any one in claim 4-7, wherein, in the modification, it is used as raw material The exposure level of HTS and the modification liquid cause, using on the basis of the HTS as raw material, it is ultraviolet- In visible spectrum, the peak area reduction by more than 2% of the absworption peak of modified HTS between 230-310nm, preferably 2-30% is reduced, 2.5-15% is more preferably reduced, further preferably reduces 3-10%, still more preferably reduce 3-8%； The pore volume of modified HTS reduces more than 1%, preferably reduces 1-20%, more preferably reduces 2-10%, further excellent Choosing reduces 2.5-5%, and the pore volume is using static determination of nitrogen adsorption.
9. the method according to any one in claim 1-8, wherein, at least part HTS is from extremely A kind of few reaction unit draws off agent, described to draw off agent and draw off agent, hydroxylating device for Ammoximation reaction device Draw off agent and epoxidation reaction device draws off agent.
10. the method according to any one in claim 1-9, wherein, at least part HTS is titanium silicon Molecular sieve TS-1, the surface silicon titanium ratio of the titanium-silicon molecular sieve TS-1 is not less than body phase silicon titanium ratio, and the silicon titanium ratio refers to oxygen The mol ratio of SiClx and titanium oxide, the surface silicon titanium ratio is determined using X-ray photoelectron spectroscopy, the body phase silicon titanium Than using x-ray fluorescence spectrometry；
Preferably, the surface silicon titanium than with the body phase silicon titanium than ratio be more than 1.2；
It is highly preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.2-5；
It is further preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 1.5-4.5；
It is further preferred that the surface silicon titanium than with the body phase silicon titanium than ratio be 2-3.
11. the method according to any one in claim 1-10, wherein, at least part HTS is titanium silicon Molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 is prepared using the method comprised the following steps：
(A) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and alternatively supplements water, obtained To dispersion liquid, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The mol ratio of water is 100：(0.5-8)：(5-30)： (100-2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N Meter；
(B) alternatively, the dispersion liquid is stood into 6-24h at 15-60 DEG C；
(C) dispersion liquid that the dispersion liquid or step (B) obtained step (A) is obtained order in sealing reactor Experience stage (1), stage (2) and stage (3) carry out crystallization, 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 6-72h, preferably 6-8h；Stage (2) is cooled to Not higher than 70 DEG C and residence time at least 0.5h, preferably 1-5 hours；Stage (3) be warming up to 120-200 DEG C, preferably 140-180 DEG C, more preferably 160-170 DEG C, then crystallization 6-96h, preferably 12-20h.
12. the method according to any one in claim 1-11, wherein, stage (1) and stage (3) meet One of following condition or both：
Condition 1：The crystallization temperature in stage (1) is less than the crystallization temperature in stage (3), it is preferable that the crystalline substance in stage (1) Change temperature lower 10-50 DEG C than the crystallization temperature in stage (3), it is preferably low 20-40 DEG C；
Condition 2：The crystallization time in stage (1) is less than the crystallization time in stage (3), it is preferable that the crystalline substance in stage (1) The change time is shorter 5-24 hours than the crystallization time in stage (3), preferably short 6-12 hours.
13. the method according to any one in claim 1-12, wherein, the stage (2) is cooled to not higher than 50 DEG C, and the residence time be at least 1 hour.
14. the method according to any one in claim 1-13, wherein, the titanium source be inorganic titanium salt and/or Organic titanate；The alkali source template is more than one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine, Preferably quaternary ammonium base, more preferably TPAOH；The inorganic silicon source is silica gel and/or Ludox；
Preferably, the inorganic titanium salt is TiCl4、Ti(SO4)2And TiOCl2One or both of more than；It is described organic Titanate esters are selected from general formula R7 4TiO4The compound of expression, R7Selected from the alkyl with 2-4 carbon atom.
15. the method according to any one in claim 1-14, wherein, the mol ratio of oxidant and thioether is 2-20：1, preferably 2-10：1, more preferably 2-5：1.
16. the method according to any one in claim 1-15, wherein, peroxide and institute as oxidant State that the peroxide used in modification is identical or difference, each be selected from hydrogen peroxide, TBHP, ethylbenzene Hydrogen peroxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid；
It is highly preferred that being hydrogen peroxide as the peroxide used in the peroxide of oxidant and the modification.
17. the method according to any one in claim 1-16, wherein, the thioether be dimethyl sulfide and/ Or thioanisole.
18. the method according to any one in claim 1-17, wherein, reactant mixture and HTS Haptoreaction temperature be not higher than 200 DEG C, preferably not higher than 180 DEG C, more preferably not above 120 DEG C, further Preferably not higher than 90 DEG C, haptoreaction progress under conditions of pressure is 0-3MP of reactant mixture and HTS, The pressure is gauge pressure.
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