CN106631931B - A kind of sulfide oxidation method - Google Patents

A kind of sulfide oxidation method Download PDF

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CN106631931B
CN106631931B CN201510725869.7A CN201510725869A CN106631931B CN 106631931 B CN106631931 B CN 106631931B CN 201510725869 A CN201510725869 A CN 201510725869A CN 106631931 B CN106631931 B CN 106631931B
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titanium
molecular sieve
sieve
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modification
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CN106631931A (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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Abstract

The invention discloses a kind of sulfide oxidation methods, comprising: step (1-1), the content of ethylbenzene hydroperoxide is 1 weight % or more in the reaction mixture for haptoreaction being obtained ethylbenzene and oxygen haptoreaction, catalytic condition；Optional step (1-2), the reaction mixture that step (1-1) obtains is mixed with inorganic acid；Step (2), under conditions of being enough sulfide oxidation, by the raw mixture and Titanium Sieve Molecular Sieve haptoreaction of the reaction mixture and thioether that are obtained containing step (1-1), or the raw mixture and Titanium Sieve Molecular Sieve haptoreaction that mixture and thioether that step (1-2) is obtained will be contained.This method is conducive to the device effective treating capacity improved, and can obtain higher thioether rate and desirable oxidation selectivity of product.This method directly installs sulfide oxidation reaction unit additional at the material outlet end of existing ethylbenzene oxidation device, easy to implement.

Description

A kind of sulfide oxidation method
Technical field
The present invention relates to a kind of sulfide oxidation methods.
Background technique
Sulfoxides are important sulfur-containing compound, if dimethyl sulfoxide (DMSO) is a kind of organic compounds containing sulfur, It is colourless transparent liquid under room temperature, there are the characteristics such as highly polar, high-hygroscopicity, flammable and higher boiling be non-proton.Dimethyl sulfoxide It is dissolved in water, ethyl alcohol, acetone, ether and chloroform, is the strong atent solvent of polarity, is widely used as solvent and reaction reagent.Also, two Methyl sulfoxide has very high selective extraction method ability, can be used as the Extraction solvent that alkane is separated with aromatic hydrocarbon, such as: dimethyl Sulfoxide can be used for the extracting of aromatic hydrocarbons or butadiene, as process solvent and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as poly- The synthetic of urethane and the solvent that reels off raw silk from cocoons, the synthetic as polyamide, fluoroaluminate glasses, polyimides and polysulfones.Meanwhile In medical industry, dimethyl sulfoxide not only can be directly as the raw material and carrier of some drugs, but also can also play anti-inflammatory and stop Bitterly, it the effects of diuresis, calmness, therefore is made an addition in drug frequently as the active component of analgesic drug product.In addition, dimethyl sulfoxide It can be used as capacitor dielectric, antifreezing agent, brake fluid, rare metal extracting agent etc..
Sulfoxide type generally uses sulfide oxidation method to prepare, according to the difference of used oxidant and mode of oxidizing, usually Including nitric acid oxidation method, peroxide oxidation method, Ozonation, anodizing and nitrogen dioxide oxidizing process.Nitric acid oxidation Deficiency existing for method is that reaction is not easy to control, equipment seriously corroded, while environmental pollution is heavier.There are two for ozone oxidation rule The low problem of Dimethyl sulfide conversion ratio.Anodizing is unsuitable for implementing on a large scale.There are environment dirts for nitrogen dioxide oxidation rule The problem of dye.The reaction condition of peroxide oxidation method is mild, and equipment and process route are simple, and product does not need in alkali progress With, and it is substantially pollution-free to environment.But as most common oxidant in peroxide oxidation method, hydrogen peroxide is usual It is provided in the form of hydrogen peroxide, commodity concentration is generally between 20-50 weight %, so in the reaction system inevitably A large amount of water are introduced, although water can play the role of solvent, the meltage of the thioether as reactant in water still has Limit, in order to improve the meltage of thioether, the dosage of water is larger or needs with the use of organic solvent, this is unavoidably reduced The effective treating capacity of device.
Summary of the invention
The purpose of the present invention is to provide a kind of method of oxidizing sulfur ether, the device that this method is conducive to improve is effectively treated Amount；This method can also obtain higher thioether rate and desirable oxidation selectivity of product simultaneously.
The present invention provides a kind of sulfide oxidation methods, and the method comprising the steps of (1-1), step (2) and optional step Suddenly (1-2):
In step (1-1), by ethylbenzene and oxygen haptoreaction, the catalytic condition obtains haptoreaction The content of ethylbenzene hydroperoxide is 1 weight % or more in reaction mixture；
In step (1-2), the reaction mixture that step (1-1) obtains is mixed with inorganic acid；
In step (2), under conditions of being enough sulfide oxidation, the reaction mixture that will obtain containing step (1-1) and The raw mixture and Titanium Sieve Molecular Sieve haptoreaction of thioether, or the mixture and thioether that step (1-2) is obtained will be contained Raw mixture and Titanium Sieve Molecular Sieve haptoreaction.
According to the method for the present invention, the amount for additionally introducing solvent is low or even can not introduce, and the device for being conducive to improve has Imitate treating capacity.Also, higher thioether rate can be obtained according to the method for the present invention.Meanwhile according to the method for the present invention also Higher desirable oxidation selectivity of product can be obtained.According to the method for the present invention, what ethylbenzene oxidation was formed contains ethylbenzene peroxidating The reaction mixture of hydrogen can be used to step (2) without isolating ethylbenzene hydroperoxide therein, on the one hand reduces and separated Loss of material caused by journey, on the other hand simplifies process flow.When using method of the invention by sulfide oxidation, directly existing The material outlet end of some ethylbenzene oxidation devices installs sulfide oxidation reaction unit additional, easy to implement.
Specific embodiment
The present invention provides a kind of sulfide oxidation methods, and the method comprising the steps of (1-1), step (2) and optional step Suddenly (1-2):
In step (1-1), by ethylbenzene and oxygen haptoreaction, the reaction that the catalytic condition makes is mixed The content of ethylbenzene hydroperoxide is 1 weight % or more in object；
In step (1-2), the reaction mixture that step (1-1) obtains is mixed with inorganic acid；
In step (2), under conditions of being enough sulfide oxidation, the reaction mixture that will obtain containing step (1-1) and The raw mixture and Titanium Sieve Molecular Sieve haptoreaction of thioether, or the mixture and thioether that step (1-2) is obtained will be contained Raw mixture and Titanium Sieve Molecular Sieve haptoreaction.
In the present invention, " optional " and " optionally " indicates inessential, it can be understood as " with or without ", " including or not Including ".
In step (1-1), by ethylbenzene and oxygen haptoreaction, ethylbenzene oxidation is obtained into the reaction containing ethylbenzene hydroperoxide Mixture, the reaction mixture are not necessarily to separate and can use directly as the oxidant of sulfide oxidation reaction, and can Obtain high thioether rate and desirable oxidation selectivity of product；Unreacted ethylbenzene is either to sulphur in simultaneous reactions mixture Ether still all has certain dissolubility to desirable oxidation product, to slacken the demand or even nothing for additional solvent Additional solvent is needed, the effective treating capacity for improving device is conducive to.
According to the method for the present invention, in step (1-1), the reaction that the catalytic condition generally makes is mixed The content of ethylbenzene hydroperoxide is 1 weight % or more in object, and such as 2-95 weight %, the content of ethylbenzene is 99 weight % hereinafter, such as 5-98 weight %.From the angle for further increasing reaction effect, step (1-1), the catalytic condition makes The content of ethylbenzene hydroperoxide is preferably 3-60 weight %, more preferably 4-30 weight % in obtained reaction mixture, into one Step is preferably 8-20 weight %, and the content of ethylbenzene is preferably 40-97 weight %, more preferably 70-96 weight %, further preferably For 80-92 weight %.
Ethylbenzene hydroperoxide can be obtained by adjusting ratio between ethylbenzene and oxygen and catalytic condition Content meet the reaction mixtures of above-mentioned requirements.Specifically, the molar ratio of ethylbenzene and oxygen can be 1:0.1-20, preferably 1:0.2-10 more preferably 1:0.5-5, such as 1:0.8-2.The haptoreaction can 50-180 DEG C, preferably 80-160 DEG C, more It is preferred that being carried out at a temperature of 90-140 DEG C.Carry out pressure in the catalytic reactor can in the range of 0-5MPa, It is preferred that the pressure is in terms of gauge pressure in the range of 0-3MPa.In the present invention, statement " ×-× in the range of " it include two Endpoint value.
In step (1-1), the oxygen of pure state is can be used in oxygen, and oxygen-containing gas also can be used.The oxygen-containing gas one As contain oxygen and carrier gas, the carrier gas for example can be nitrogen and/or group 0 element gas (such as argon gas).The oxygen-containing gas The dosage of middle oxygen generally can be 0.1-99 volume %, preferably 10-90 volume %, more preferably 15-80 volume %, into one Step is preferably 15-30 volume %.The oxygen-containing gas can be the gaseous mixture by the way that pure oxygen and carrier gas to be obtained by mixing, Air can also directly be used.
In step (1-1), contact of the ethylbenzene with oxygen is preferably carried out in the presence of at least one peroxide, the mistake Oxide plays the role of promotor, can further increase reaction efficiency, improves the selectivity of ethylbenzene hydroperoxide.The mistake The molar ratio of oxide and ethylbenzene can be 0.0001-0.1:1, preferably 0.0005-0.05:1, such as 0.001-0.01:1.Institute State peroxide refer in molecular structure contain-O-O- key compound, can be hydrogen peroxide and/or organic peroxide, The organic peroxide refers to that one or both of hydrogen peroxide molecule structure hydrogen atom is replaced by organic group and is formed Substance.The specific example of the peroxide can include but is not limited to: hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene peroxide Change hydrogen, cumyl hydroperoxide, Peracetic acid, Perpropionic Acid, cumyl peroxide, di-t-butyl peroxide, peroxidating two Benzoyl and dilauroyl peroxide.In the present invention, the organic peroxide is preferably R1-O-O-R2, R1And R2It is identical or not It together, respectively can be H, C4-C12Linear or branched alkyl group orR3For C4-C12Linear or branched alkyl group, R1With R2It is not simultaneously H.
According to the method for the present invention, step (1-2) is optional step, it may be assumed that can be mixed the reaction that step (1-1) is obtained Object is sent directly into step (2) and thioether and Titanium Sieve Molecular Sieve haptoreaction；The reaction that step (1-1) is obtained can also be mixed Object is sent into step (1-2) mix with inorganic acid after, then in mixture feeding step (2) that step (1-2) is obtained and thioether With Titanium Sieve Molecular Sieve haptoreaction.The reaction mixture that step (1-1) obtains is sent directly into step (2), this can be improved The operation terseness of inventive method；The reaction mixture that step (1-1) is obtained is sent into step (1-2), then by step (1- 2) reaction mixture obtained is sent into step (2), can be further improved the conversion ratio and desirable oxidation of thioether in step (2) The selectivity of product.It should be noted that regardless of whether progress step (1-2) as the case may be can be to step (1- 1) reaction mixture obtained is concentrated or is diluted, to meet the requirement of step (2).
In step (1-2), the dosage of inorganic acid can be according to ethylbenzene peroxide in the reaction mixture that step (1-1) is obtained The content for changing hydrogen is selected.Generally, ethylbenzene hydroperoxide rubs in the reaction mixture that inorganic acid is obtained with step (1-1) You than can be 0.00001-0.1:1, preferably 0.0001-0.05:1, more preferably 0.001-0.01:1, further preferably 0.001-0.005:1.
From the angle for further increasing thioether rate and desirable oxidation selectivity of product in step (2), step (1- 1) mixing of the reaction mixture and inorganic acid that obtain preferably 20-100 DEG C, more preferably 20-80 DEG C, further preferably exist It is carried out at a temperature of 20-60 DEG C (such as 30-40 DEG C).When the reaction mixture for obtaining step (1-1) is mixed with inorganic acid, into Pressure in the mixed reactor of row can be 0-2MPa, and preferably 0-0.5MPa, the pressure is in terms of gauge pressure.The mixing Time generally can be 0.1 hour or more, preferably 0.1-5 hours, more preferably 0.5-4 hours (such as 2-4 hours).
The inorganic acid can be common various inorganic acids, as one or both of halogen acids, sulfuric acid and phosphoric acid with On.Preferably, the inorganic acid is halogen acids, can be obtained in step (2) in this way the thioether rate that further increases and Desirable oxidation selectivity of product.It is highly preferred that the inorganic acid is HCl and/or HBr.
The inorganic acid can provide in form of an aqueous solutions, and the content of inorganic acid can be conventional choosing in the aqueous solution It selects, generally can be 20-40 weight %.
In step (2), Titanium Sieve Molecular Sieve is the total of a kind of zeolite of a part of silicon atom in titanium atom substitution lattice framework Claim, chemical formula xTiO can be used2·SiO2It indicates.The content of titanium atom in Titanium Sieve Molecular Sieve is not particularly limited in the present invention, It can be the conventional selection of this field.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, more preferably 0.015-0.025。
The Titanium Sieve Molecular Sieve can be the common Titanium Sieve Molecular Sieve with various topological structures, such as: the titanium silicon Molecular sieve can be the Titanium Sieve Molecular Sieve (such as TS-1) selected from MFI structure, the Titanium Sieve Molecular Sieve (such as TS-2) of MEL structure, BEA knot The Titanium Sieve Molecular Sieve (such as Ti-Beta) of structure, the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, hexagonal structure titanium silicon molecule Sieve (such as Ti-MCM-41, Ti-SBA-15), the Titanium Sieve Molecular Sieve (such as Ti-MOR) of MOR structure, the Titanium Sieve Molecular Sieve of TUN structure One or more of Titanium Sieve Molecular Sieve (such as Ti-ZSM-48) of (such as Ti-TUN) and other structures.
Preferably, the Titanium Sieve Molecular Sieve be Titanium Sieve Molecular Sieve selected from MFI structure, the Titanium Sieve Molecular Sieve of MEL structure, One or more of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve of hexagonal structure of BEA structure.It is highly preferred that the titanium silicon Molecular sieve is the Titanium Sieve Molecular Sieve of MFI structure, such as titanium-silicon molecular sieve TS-1 and/or hollow Titanium Sieve Molecular Sieve.The hollow titanium silicon Molecular sieve is the Titanium Sieve Molecular Sieve of MFI structure, and the crystal grain of the Titanium Sieve Molecular Sieve is hollow structure, the chamber portion of the hollow structure Radical length be 5-300 nanometers, and the Titanium Sieve Molecular Sieve is in 25 DEG C, P/P0=0.10, adsorption time is under conditions of 1 hour The benzene adsorbance measured is at least 70 milligrams per grams, the adsorption isotherm and desorption isothermal of the nitrogen absorption under low temperature of the Titanium Sieve Molecular Sieve There are hysteresis loops between line.The hollow Titanium Sieve Molecular Sieve, which is commercially available, (such as to be commercially available from Hunan and builds feldspathization share and have The trade mark of limit company be HTS molecular sieve), can also the method according to disclosed in CN1132699C be prepared.
According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the Titanium Sieve Molecular Sieve TS- 1 urface silicon titanium is not less than body phase silicon titanium ratio, can obtain the catalytic performance further increased in this way, further extends titanium silicon point The single trip use service life of son sieve.Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2 or more.It is more excellent The ratio of selection of land, the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5.It is further preferred that the urface silicon titanium Ratio with the body phase silicon titanium ratio is 1.5-4.5 (such as 2.5-4.5).It is further preferred that the urface silicon titanium and institute The ratio for stating body phase silicon titanium ratio is 2-3.
In the present invention, molar ratio of the silicon titanium than referring to silica and titanium oxide, urface silicon titanium uses x-ray photoelectron energy Spectrometry measurement, body phase silicon titanium ratio use x-ray fluorescence spectrometry.
According to the method for the present invention, from the catalytic performance for further increasing Titanium Sieve Molecular Sieve and further extend single trip use The angle in service life is set out, and at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1, which uses, includes It is prepared by the method for following steps:
(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and optionally supplements water, obtained Dispersion liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:(0.5-8): (5-30): (100- 2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N meter is (in alkali source mould When plate agent Nitrogen element, in terms of N；In alkali source template not Nitrogen element, with OH-Meter)；
(II) optionally, by the dispersion liquid in 15-60 DEG C of standing 6-24h；
(III) by the dispersion liquid that step (I) obtains or the dispersion liquid that step (II) obtains in sealing reaction kettle sequence Experience stage (1), stage (2) and stage (3) carry out crystallization, and the stage (1) is in 80-150 DEG C of crystallization 6-72 hours (h), stage (2) After being cooled to not higher than 70 DEG C and residence time at least 0.5h, the stage (3) is warming up to 120-200 DEG C of crystallization 6-96h again.
The alkali source template can be usually used various templates during synthesis of titanium silicon molecular sieve, such as: The alkali source template can be one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine.The quaternary ammonium base It can be various organic level Four ammonium alkali, the aliphatic amine can be various NH3In at least one hydrogen by aliphatic alkyl (such as Alkyl) replace after the compound that is formed, the aliphatic hydramine can be various NH3In at least one hydrogen by the rouge of hydroxyl The compound that fat race group (such as alkyl) is formed after replacing.
Specifically, the alkali source template can be the aliphatic amine and formula of the quaternary ammonium base, Formula II expression that indicate selected from Formulas I One or more of the aliphatic hydramine that III is indicated.
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane Base, R1、R2、R3And R4Specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group or tert-butyl.
R5(NH2)n(Formula II)
In Formula II, n is an integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6 Branched alkyl, specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different Butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6Branched alkylidene, specific example can include but is not limited to methylene, ethylidene, Sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3- C4Branched alkylidene, specific example can include but is not limited to methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.
The specific example of the alkali source template can include but is not limited to: tetramethylammonium hydroxide, tetraethyl hydroxide Ammonium, tetrapropylammonium hydroxide (the various isomers including tetrapropylammonium hydroxide, such as four n-propyl ammonium hydroxide and tetra isopropyl Ammonium hydroxide), tetrabutylammonium hydroxide (the various isomers including tetrabutylammonium hydroxide, such as 4-n-butyl ammonium hydroxide and Four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine One or more of with triethanolamine.Preferably, the alkali source template is tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen Change one or more of ammonium and tetrabutylammonium hydroxide.It is highly preferred that the alkali source template is tetrapropyl hydroxide Ammonium.
The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can Think TiCl4、Ti(SO4)2And TiOCl2One or more of；The organic titanate can be general formula R7 4TiO4Table The compound shown, wherein R7For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom.
The inorganic silicon source can be silica gel and/or silica solution, preferably silica gel.SiO in the silica solution2Quality hundred Dividing content can be 10% or more, preferably 15% or more, more preferably 20% or more.In preparation according to the preferred embodiment Titanium Sieve Molecular Sieve when, do not use organic silicon source, such as organosilan and organosiloxane.
In the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is preferably 100:(1-6): (8-25): (200-1500), more preferably 100:(2-5): (10-20): (400-1000).
The dispersion liquid that step (I) obtains, which can be sent directly into step (III), carries out crystallization.Preferably, step (I) is obtained To dispersion liquid be sent into step (II) in 15-60 DEG C at a temperature of stand 6-24h.Between step (I) and step (III) into Row step (II) can significantly improve the urface silicon titanium of the titanium-silicon molecular sieve TS-1 finally prepared, so that the titanium silicon finally prepared point The urface silicon titanium of son sieve is not less than body phase silicon titanium ratio, can significantly improve the catalytic of the Titanium Sieve Molecular Sieve finally prepared in this way Can, extend its single trip use service life.Generally, final to make by the setting steps (II) between step (I) and step (III) The urface silicon titanium of standby Titanium Sieve Molecular Sieve and the ratio of body phase silicon titanium ratio can be in the range of 1.2-5, preferably in 1.5-4.5 In the range of (such as in the range of 2.5-4.5), more preferably in the range of 2-3.The standing is more preferably in 20-50 DEG C of temperature Degree is lower to carry out, as carried out at a temperature of 25-45 DEG C.
In step (II), when being stood, dispersion liquid can be placed in sealing container, open container can also be placed in In stood.Preferably, step (II) carries out in a sealed container, in this way can to avoid during standing into dispersion liquid It is introduced into foreign matter or moieties volatilization in dispersion liquid is caused to be lost.
After the completion of step (II) described standing, directly the dispersion liquid through standing can be sent into reaction kettle and carry out crystallization, It is sent into reaction kettle after dispersion liquid through standing can also being carried out redisperse and carries out crystallization, be preferably sent into after progress redisperse anti- It answers in kettle, can be further improved the dispersing uniformity for carrying out the dispersion liquid of crystallization in this way.The method of the redisperse can be normal The combination of one or more of rule method, such as stirring, ultrasonic treatment and oscillation.The duration of the redisperse with The dispersion liquid through standing can be made to be formed subject to uniform dispersion liquid, generally can be 0.1-12h, such as 0.5-2h.The redisperse It can carry out at ambient temperature, as carried out at a temperature of 15-40 DEG C.
In step (III), temperature is adjusted can be according to specifically adopting to the heating rate of each phase temperature and rate of temperature fall The type of crystallization device is selected, and is not particularly limited.In general, raising the temperature to stage (1) crystallization temperature The heating rate of degree can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By stage (1) Temperature to stage (2) temperature rate of temperature fall can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5-10 DEG C/ min.By stage (2) temperature to stage (3) temperature heating rate can be 1-50 DEG C/min, preferably 2-40 DEG C/min, more Preferably 5-20 DEG C/min.
In step (III), the crystallization temperature in stage (1) is preferably 110-140 DEG C, and more preferably 120-140 DEG C, further Preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.The stage temperature of (2) is preferably Not higher than 50 DEG C.The residence time in stage (2) is preferably at least 1h, more preferably 1-5h.The stage crystallization temperature of (3) is preferably 140-180 DEG C, more preferably 160-170 DEG C.The crystallization time in stage (3) is preferably 12-20h.
In step (III), in a preferred embodiment, the crystallization temperature in stage (1) is lower than the crystallization of stage (3) Temperature can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve of preparation in this way.Preferably, the crystallization temperature in stage (1) compares rank The crystallization temperature of section (3) is 10-50 DEG C low.It is highly preferred that the crystallization temperature in stage (1) is 20-40 lower than the crystallization temperature in stage (3) ℃.In step (III), in another preferred embodiment, when the crystallization time in stage (1) is less than the crystallization of stage (3) Between, it can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.Preferably, the crystallization time ratio in stage (1) The short 5-24h of crystallization time in stage (3).It is highly preferred that the crystallization time in stage (1) is 6- shorter than the crystallization time in stage (3) 12h, such as short 6-8h.In step (III), both preferred embodiments be may be used alone, can also be used in combination, preferably It is applied in combination, i.e., the crystallization temperature and crystallization time in stage (1) and stage (3) meet wanting for both preferred embodiments simultaneously It asks.
In step (III), in another preferred embodiment, the temperature in stage (2) is and to stop not higher than 50 DEG C Time is at least 0.5h, such as 0.5-6h, can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.It is preferred that Ground, the residence time in stage (2) are at least 1h, such as 1-5h.The preferred embodiment can be with aforementioned two kinds preferred implementations Mode is used separately, and can also be applied in combination, is preferably applied in combination, i.e., the crystallization temperature and crystallization in stage (1) and stage (3) when Between and the stage (2) temperature and the residence time meet the requirements of above-mentioned three kinds of preferred embodiments simultaneously.
Titanium Sieve Molecular Sieve can be recycled from the mixture that step (III) crystallization obtains using conventional method.Specifically, may be used After being optionally filtered and washed with the mixture for obtaining step (III) crystallization, solid matter is dried and is roasted, To obtain Titanium Sieve Molecular Sieve.The drying and the roasting can carry out under normal conditions.Generally, the drying can be with Environment temperature (such as 15 DEG C) to 200 DEG C at a temperature of carry out.The drying can be in environmental pressure (generally 1 normal atmosphere Pressure) under carry out, can also carry out at reduced pressure.The duration of the drying can be according to dry temperature and pressure And dry mode is selected, and is not particularly limited.For example, temperature is excellent when the drying carries out under ambient pressure It is selected as 80-150 DEG C, more preferably 100-120 DEG C, the dry duration is preferably 0.5-5h, more preferably 1-3h.The roasting Burn can 300-800 DEG C at a temperature of carry out, preferably carry out at a temperature of 500-700 DEG C, more preferably at 550-650 DEG C At a temperature of carry out, further preferably 550-600 DEG C at a temperature of carry out.The duration of the roasting can be according to being roasted The temperature of burning selects, and generally can be 2-12h, preferably 2-5h.The roasting carries out preferably in air atmosphere.
According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is preferably modified processing before for step (2). The modification the following steps are included: by as the Titanium Sieve Molecular Sieve of raw material with containing nitric acid (that is, HNO3) and it is at least one The modification liquid of peroxide contacts.The raw material Titanium Sieve Molecular Sieve refers to the Titanium Sieve Molecular Sieve of the raw material as modification, can Think the Titanium Sieve Molecular Sieve for not living through the modification, or live through the modification but need again into The Titanium Sieve Molecular Sieve of the row modification.The Titanium Sieve Molecular Sieve that above-mentioned modification is lived through in the present invention is known as modified titanium Si molecular sieves, the Titanium Sieve Molecular Sieve for not living through above-mentioned modification are known as unmodified Titanium Sieve Molecular Sieve.It, can in step (2) Above-mentioned modification is lived through with whole Titanium Sieve Molecular Sieve, or modified Titanium Sieve Molecular Sieve and unmodified titanium silicon point The mixture of son sieve.Preferably, on the basis of the total amount of Titanium Sieve Molecular Sieve described in step (2), at least 50 weight % or more Titanium Sieve Molecular Sieve lives through the modification, and the Titanium Sieve Molecular Sieve of more preferably at least 60 weight % or more lives through the modification Processing, as the Titanium Sieve Molecular Sieve of 50-90 weight % lives through the modification.
In the modification, peroxide can be selected from hydrogen peroxide, hydroperoxides and peracid.At the modification In reason, the specific example of the peroxide be can include but is not limited to: hydrogen peroxide, ethylbenzene hydroperoxide, t-butyl peroxy Change hydrogen, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is peroxide Change hydrogen.The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.
Can be 1 as the Titanium Sieve Molecular Sieve of raw material and the molar ratio of the peroxide in the modification: 0.01-5, preferably 1:0.05-2, more preferably 1:0.1-1.The dosage of the nitric acid can be according to the use of the peroxide Amount is selected.Generally, the molar ratio of the peroxide and the nitric acid can be 1:0.01-50, preferably 1:0.1- 20, more preferably 1:0.2-10, further preferably 1:0.5-5, particularly preferably 1:0.6-3.5, such as 1:0.7-3, the titanium Si molecular sieves are in terms of silica.
In the modification liquid, the concentration of the peroxide and nitric acid respectively can be 0.1-50 weight %.From further The angle for improving the catalytic performance of the Titanium Sieve Molecular Sieve of the modification finally prepared is set out, preferably 0.5-25 weight %.More preferably Ground, in the modification liquid, the concentration of the peroxide and nitric acid is respectively 1-15 weight %.It is further preferred that described change In property liquid, the concentration of the peroxide and nitric acid is respectively 2-10 weight %.
The solvent of the modification liquid can be the common various solvents that can dissolve nitric acid and the peroxide simultaneously.It is excellent Selection of land, the solvent of the modification liquid are water.
In the modification, as raw material Titanium Sieve Molecular Sieve and modification liquid can 10-350 DEG C at a temperature of into Row contact.From the angle of the catalytic performance for the Titanium Sieve Molecular Sieve for further increasing the modification finally prepared, the contact is excellent It is contacted at a temperature of being selected in 20-300 DEG C.It is highly preferred that it is described contact 50-250 DEG C at a temperature of carry out.It is further excellent Selection of land, at a temperature of lower progress of the contact at 70-200 DEG C, such as 70-170 DEG C at a temperature of contacted.In the modification It, can be according to contact temperature by the pressure in the container contacted as the Titanium Sieve Molecular Sieve of raw material with the modification liquid in processing Degree is selected, and can be environmental pressure, or pressurization.Generally, will change as the Titanium Sieve Molecular Sieve of raw material with described The pressure in container that property liquid is contacted can be 0-5MPa.Preferably, under pressure by the titanium silicon as raw material Molecular sieve is contacted with the modification liquid.It is highly preferred that by the titanium silicon molecule as raw material under self-generated pressure in closed container Sieve is contacted with the modification liquid.
In the modification, as the Titanium Sieve Molecular Sieve of raw material and the exposure level of the modification liquid preferably so that, Using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, modified Titanium Sieve Molecular Sieve 230-310nm it Between the peak area of absorption peak reduce by 2% or more, the hole of modified Titanium Sieve Molecular Sieve, which holds, reduces 1% or more.Modified titanium silicon point The peak area of absorption peak of the son sieve between 230-310nm preferably reduces 2-30%, more preferably reduction 3-15%, further preferably Reduce 3.5-6%.The hole of modified Titanium Sieve Molecular Sieve holds preferred reduction 1-20%, more preferably reduction 2-10%, further preferably Reduce 2.5-5%.The Kong Rong is using static determination of nitrogen adsorption.
In using various commercial plants of the Titanium Sieve Molecular Sieve as catalyst, as Ammoximation reaction, hydroxylating and In epoxidation reaction device, usually after device runs a period of time, the catalytic activity of catalyst declines, and needs to carry out in device Or ex-situ regeneration, when being difficult to obtain satisfied activity being regenerated, need to draw off catalyst from device (that is, More catalyst changeout), and the current processing method of the catalyst (that is, drawing off agent or dead catalyst) that draws off is usually to accumulate to bury, On the one hand valuable land resource and inventory space are occupied, another aspect Titanium Sieve Molecular Sieve production cost is higher, directly discarded Without also resulting in great waste.The present inventor has found in the course of the research, if these are drawn off agent (that is, unloading Titanium Sieve Molecular Sieve out) regenerated after for still being able to obtain preferable catalytic performance, while when long in step (2) Between during continuous operation, show better activity stability.Therefore, according to the method for the present invention, at least partly described titanium Si molecular sieves are preferably unloading through regenerated reaction unit (outside sulphur removal ether oxidation unit) using Titanium Sieve Molecular Sieve as catalyst Agent out.It is described draw off agent can to use Titanium Sieve Molecular Sieve to draw off agent as what is drawn off in the reaction unit of catalyst from various, Such as agent can be drawn off for what is drawn off from oxidation reaction apparatus.Specifically, described to draw off agent unloading for Ammoximation reaction device Out agent, hydroxylating device draw off agent and epoxidation reaction device draw off one of agent or a variety of.More specifically, institute State draw off agent can for cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draws off agent and propylene ring Oxidation reaction apparatus draws off one of agent or a variety of.
The regenerated condition of agent progress will be drawn off to be not particularly limited, choosing appropriate can be carried out according to the source for drawing off agent It selects, such as: high-temperature roasting and/or solvent washing.
It is different according to its source through the regenerated activity for drawing off agent.Generally, through the regenerated activity for drawing off agent It can be the 5-95% of activity (that is, activity of fresh Titanium Sieve Molecular Sieve) of Titanium Sieve Molecular Sieve when fresh.Preferably, through again The raw activity for drawing off agent can be active 10-90% of Titanium Sieve Molecular Sieve when fresh, further preferably fresh When active 30-50%.It is being active 30-50% of Titanium Sieve Molecular Sieve when fresh through the regenerated activity for drawing off agent When, during long-time continuous operation, show better activity stability.Preferably, through the regenerated work for drawing off agent Property be active 35-45% of Titanium Sieve Molecular Sieve when fresh.The activity of the fresh Titanium Sieve Molecular Sieve be generally 90% with On, usually 95% or more.
The activity measures by the following method: respectively will be through regenerated agent and the fresh Titanium Sieve Molecular Sieve of drawing off as hexamethylene Ketone oxamidinating reaction catalyst, the condition of the Ammoximation reaction are as follows: Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH3Meter), The hydrogen peroxide of 30 weight % is (with H2O2Meter), the tert-butyl alcohol and cyclohexanone 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure In 80 DEG C of reaction 2h.Calculate separately using through it is regenerated draw off agent and fresh Titanium Sieve Molecular Sieve as catalyst when cyclohexanone conversion Rate, and using it as through the regenerated activity for drawing off agent and fresh Titanium Sieve Molecular Sieve, wherein the conversion ratio of cyclohexanone= [mole of the cyclohexanone of (mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/addition] × 100%.
When at least partly Titanium Sieve Molecular Sieve is to draw off agent through regenerated reaction unit, with the total amount of the Titanium Sieve Molecular Sieve On the basis of, the content for drawing off agent through regenerated reaction unit is preferably 5 weight % or more.According to the method for the present invention, even if entirely Portion's Titanium Sieve Molecular Sieve is to draw off agent (that is, the content for drawing off agent through regenerated reaction unit is 100 weights through regenerated reaction unit Measure %) when, it still is able to obtain preferable catalytic effect.
According to the method for the present invention, the Titanium Sieve Molecular Sieve in the Titanium Sieve Molecular Sieve of the modification as raw material is particularly preferably It is above-mentioned to draw off agent through regenerated, the agent progress modification is drawn off through regenerated by described, can be further improved through regenerated The single trip use service life of agent is drawn off, and can be significantly improved described through the regenerated desirable oxidation selectivity of product for drawing off agent.
It according to the method for the present invention, can be by reaction mixture or step (1- that step (1-1) is obtained in step (2) 2) mixture and thioether and Titanium Sieve Molecular Sieve obtained is mixed to form slurry, to carry out haptoreaction；It can also be by titanium silicon molecule Sieve is seated in the catalyst bed of fixed bed reactors, so that liquid material is flowed through catalyst bed, to carry out haptoreaction.
In step (2), the Titanium Sieve Molecular Sieve can be Titanium Sieve Molecular Sieve original powder, or molding Titanium Sieve Molecular Sieve, Preferably form Titanium Sieve Molecular Sieve.The molding Titanium Sieve Molecular Sieve typically contains Titanium Sieve Molecular Sieve and conduct as active constituent The carrier of binder, wherein the content of Titanium Sieve Molecular Sieve can be conventional selection.Generally, with the molding Titanium Sieve Molecular Sieve Total amount on the basis of, the content of Titanium Sieve Molecular Sieve can be 5-95 weight %, preferably 10-95 weight %, more preferably 70-90 Weight %；The content of the carrier can be 5-95 weight %, preferably 5-90 weight %, more preferably 10-30 weight %.Institute The carrier for stating molding Titanium Sieve Molecular Sieve can be conventional selection, such as aluminium oxide and/or silica.Prepare the molding titanium silicon molecule The method of sieve is it is known in the art, being no longer described in detail herein.The granular size of the molding Titanium Sieve Molecular Sieve is also without special It limits, can be made appropriate choice according to concrete shape.Generally, the average grain diameter of the molding Titanium Sieve Molecular Sieve can be 4-10000 microns, preferably 5-5000 microns, more preferably 40-4000 microns, such as 100-2000 microns.The average grain diameter For volume average particle size, can be measured using laser particle analyzer.
In step (2), for the Titanium Sieve Molecular Sieve as catalyst, dosage, which is subject to, can be realized catalysis, can be with Catalytic concrete mode is carried out with the liquid material according to Titanium Sieve Molecular Sieve to be selected.Such as: by titanium silicon molecule Sieve is mixed to form slurry with the liquid material, thus when carrying out haptoreaction, the weight ratio of thioether and Titanium Sieve Molecular Sieve can be with For 0.01-100:1, preferably 1-100:1, more preferably 10-50:1, such as 15-30:1；In Titanium Sieve Molecular Sieve and the liquids When the contact of material carries out in fixed bed reactors, the weight (hourly) space velocity (WHSV) of thioether can be 0.1-100h-1, preferably 1-80h-1, such as 15-50h-1.In the present invention, weight (hourly) space velocity (WHSV) is on the basis of whole Titanium Sieve Molecular Sieve in catalyst bed.
According to the method for the present invention, catalyst bed can only load Titanium Sieve Molecular Sieve, can also contain Titanium Sieve Molecular Sieve And inactive filler.Inactive filler is loaded in catalyst bed can be to the amount progress of Titanium Sieve Molecular Sieve in catalyst bed Adjustment, so that the speed to reaction is adjusted.When catalyst bed contains Titanium Sieve Molecular Sieve and inactive filler, catalyst The content of inactive filler can be 5-95 weight % in bed.The inactive filler refers to no to oxidation reaction or basic There is no the filler of catalytic activity, specific example can include but is not limited to: one of quartz sand, ceramic ring and potsherd Or it is a variety of.
In step (2), the dosage of thioether can according to ethylbenzene hydroperoxide in the reaction mixture that step (1-1) is obtained or The content of ethylbenzene hydroperoxide selects in the reaction mixture that person's step (1-2) obtains.Generally, thioether and ethylbenzene peroxide The molar ratio for changing hydrogen can be 1:0.1-10.Furthermore it is also possible to according to the set goal oxidation product to thioether and ethylbenzene peroxide The molar ratio for changing hydrogen optimizes.For example, when desirable oxidation product is sulfoxide (such as dimethyl sulfoxide), thioether and ethylbenzene peroxide The molar ratio for changing hydrogen is preferably 1:0.1-2, more preferably 1:0.3-1.5.
According to the method for the present invention, the thioether can be the various compounds containing-S- key, and the thioether is preferably selected from Carbon atom number is the thioether of 2-18, such as dimethyl sulfide and/or thioanisole.
In step (2), mixture that the reaction mixture or step (1-2) that step (1-1) obtains obtain and thioether and The contact of Titanium Sieve Molecular Sieve carries out under conditions of being enough sulfide oxidation.It generally, can be at 0-120 DEG C, preferably 20-80 DEG C, it is 40-50 DEG C more preferable at a temperature of by the reaction mixture that step (1-1) obtains or the mixture that step (1-2) obtains With thioether and Titanium Sieve Molecular Sieve haptoreaction.The pressure in reactor contacted can be in the range of 0-5MPa, preferably In the range of 0.1-3.5MPa, such as in the range of 0.5-2MPa, the pressure is in terms of gauge pressure.
According to the method for the present invention, the desirable oxidation that the reaction mixture that step (2) obtains contains sulfide oxidation formation produces Object (such as sulfoxide) can separate it using conventional method, to obtain desirable oxidation product (such as sulfoxide), isolate Unreacted reactant can be recycled.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, agents useful for same is commercial reagent, and pressure is gauge pressure.
In following embodiment and comparative example, the content of each ingredient in the reaction solution analyzed using gas-chromatography, Following formula is respectively adopted on the basis of this to calculate thioether rate and sulfoxide selectivity.
XThioether=[(mo Thioether- mThioether)/mo Thioether] × 100%
Wherein, XThioetherIndicate thioether rate；
mo ThioetherIndicate the mole for the thioether being added；
mThioetherIndicate the mole of unreacted thioether.
nSulfoxideIndicate the mole for the sulfoxide that reaction generates.
SSulfoxide=[nSulfoxide/(no Thioether- nThioether)] × 100%
Wherein, SSulfoxideIndicate sulfoxide selectivity；
no ThioetherIndicate the mole for the thioether being added；
nThioetherIndicate the mole of unreacted thioether；
nSulfoxideIndicate the mole for the sulfoxide that reaction generates.
In following embodiment and comparative example, static nitrogen adsorption method and solid ultraviolet-visible diffuse reflectance spectrum method is respectively adopted The Kong Rong and ultraviolet absorption peak of Titanium Sieve Molecular Sieve after before modified are characterized.Wherein, solid ultraviolet-visible diffuse reflectance spectrum (UV-Vis) analysis carries out on SHIMADZU UV-3100 type ultraviolet-visible spectrometer；Static nitrogen adsorption analysis exists It is carried out on the 2405 type static state n2 absorption apparatus of ASAP of Micromeritics company.
It is related to below through determining Titanium Sieve Molecular Sieve using following methods in the regenerated embodiment and comparative example for drawing off agent The activity of (including regenerative agent and fresh dose): by Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH3Meter), 30 weight % it is double Oxygen water is (with H2O2Meter), the tert-butyl alcohol and cyclohexanone by weight after=1:7.5:10:7.5:10 mixing at atmosheric pressure in 80 DEG C After being stirred to react 2 hours, reactant is filtered, liquid phase is analyzed with gas-chromatography, is calculated using the following equation cyclohexanone Conversion ratio and activity as Titanium Sieve Molecular Sieve,
The conversion ratio of cyclohexanone=[(the unreacted cyclohexanone mole of the mole-of the cyclohexanone of addition)/it is added The mole of cyclohexanone] × 100%.
In the embodiment and comparative example of the step of preparation Titanium Sieve Molecular Sieve included below, X-ray diffraction analysis exists It is carried out on Siemens D5005 type X-ray diffractometer, with sample and authentic specimen, the five fingers spread out between 2 θ is 22.5 ° -25.0 ° The crystallinity for penetrating the ratio of the sum of diffracted intensity (peak height) of characteristic peak to indicate sample relative to authentic specimen；Fourier transform Infrared spectrum analysis carries out on 8210 type Fourier infrared spectrograph of Nicolet；Silicon titanium is than referring to silica and titanium oxide Molar ratio, urface silicon titanium are surveyed using the ESCALab250 type x-ray photoelectron spectroscopy of Thermo Scientific company Fixed, body phase silicon titanium ratio is measured using Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer.
Embodiment 1-20 is for illustrating method of the invention.
Embodiment 1
(1-1) haptoreaction under conditions of temperature is 120 DEG C and pressure is 1MPa by ethylbenzene and oxygen, obtains containing second The reaction mixture of benzene hydrogen peroxide is analyzed with composition of the gas-chromatography to the reaction mixture, determines ethylbenzene peroxidating The content of hydrogen is 15 weight %.Wherein, the molar ratio of ethylbenzene and oxygen is 1:2；Oxygen is provided in the form of oxygen-containing gas, oxygen-containing In gas, the content of oxygen is 21 volume %, and the content of nitrogen is 79 volume %.
The reaction mixture and hydrochloric acid (HCl concentration is 36.5 weight %) that (1-2) obtains step (1-1) are in reaction under high pressure It being mixed in kettle, wherein the molar ratio of ethylbenzene hydroperoxide and HCl are 1:0.005 in the reaction mixture that step (1-1) obtains, It is 40 DEG C by the temperature control in autoclave, the pressure in autoclave is controlled as normal pressure (that is, 1 normal atmosphere Pressure), incorporation time 2h.
(2) titanium-silicon molecular sieve TS-1 is referring to Zeolites, 1992, Vol.12 method systems described in the 943-950 pages Standby, the specific method is as follows.
(20 DEG C) at room temperature mix 22.5g tetraethyl orthosilicate with 7.0g as the tetrapropylammonium hydroxide of template It closes, and 59.8g distilled water is added, it is molten in normal pressure and 60 DEG C of hydrolysis 1.0h, the hydrolysis for obtaining tetraethyl orthosilicate after being stirred Liquid.With vigorous stirring, it is slowly added into Xiang Suoshu hydrating solution by 1.1g butyl titanate and 5.0g anhydrous isopropyl alcohol institute The solution of composition obtains clear colloid by gained mixture in 75 DEG C of stirring 3h.It is anti-that this colloid is placed in stainless steel sealing It answers in kettle, places 36h in 170 DEG C of at a temperature of constant temperature, obtain the mixture of crystallization product.Obtained mixture is filtered, is received After collecting obtained solid matter water used wash, in 110 DEG C of dry 1h, then in 500 DEG C of roasting 6h, to obtain Titanium Sieve Molecular Sieve TS-1, titanium oxide content are 2.8 weight %.
Reaction mixture and dimethyl sulfide and titanium-silicon molecular sieve TS-1 that step (1-2) obtains are placed in autoclave In, it is stirred to react.Wherein, the weight ratio of dimethyl sulfide and Titanium Sieve Molecular Sieve is 15:1, the reaction that step (1-2) obtains The molar ratio of ethylbenzene hydroperoxide and dimethyl sulfide in mixture is 1:1, is 45 by the temperature control in autoclave DEG C, pressure is controlled as 0.5MPa.After reacting 2h, stops reaction, the reaction mixture in autoclave is filtered, is obtained To the Titanium Sieve Molecular Sieve of liquid material and recycling, the composition for the liquid material analyzed, calculate dimethyl sulfide conversion ratio and Dimethyl sulfoxide selectivity, the Titanium Sieve Molecular Sieve of recycling is re-fed into step (2) and is recycled.Titanium-silicon molecular sieve TS-1 Reaction result when 1 time and the 30th time use is listed in table 1.
Embodiment 2
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, without step (1-2), step The reaction mixture that (1-1) is obtained is sent directly into step (2).It is anti-when titanium-silicon molecular sieve TS-1 the 1st time and the 25th time use Result is answered to list in table 1.
Embodiment 3
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, in step (2), Titanium Sieve Molecular Sieve TS-1 is prepared using following methods.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:4:12: 400, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is sealed in beaker using sealed membrane It is stood for 24 hours after mouthful room temperature (being 25 DEG C, similarly hereinafter), is stirred 2h at 35 DEG C followed by magnetic agitation, is allowed to disperse again. Again the dispersion liquid after dispersing is transferred in sealing reaction kettle, in 140 DEG C of experience first stage crystallization 6h, then by mixture Be cooled to after 30 DEG C of experience second stage stop 2h, continue in sealing reaction kettle in 170 DEG C at a temperature of undergo the phase III Crystallization 12h (is wherein, 2 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first stage crystallization temperature The rate of temperature fall for spending second segment treatment temperature is 5 DEG C/min, by second stage treatment temperature to phase III crystallization temperature Heating rate is 10 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly in 110 DEG C of drying 2h, Then 3h is roasted at 550 DEG C, obtains molecular sieve.The titanium silicon of XRD crystalline phase figure and 1 step of embodiment (2) preparation of gained sample Molecular sieve TS-1 is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier Transform Infrared Spectroscopy figure In, in 960cm-1Nearby there is absorption peak, show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, titanium oxide content is 3.5 weight %, urface silicon titanium/body phase silicon titanium ratio be 2.58 (embodiment 1 prepare Titanium Sieve Molecular Sieve in, urface silicon titanium/body 1.05) phase silicon titanium ratio is.Reaction result when titanium-silicon molecular sieve TS-1 the 1st time and the 60th time use is listed in table 1.
Embodiment 4
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), preparing titanium silicon When molecular sieve TS-1, the crystallization temperature of phase III is also 140 DEG C.The XRD crystalline phase figure and 1 step of embodiment (2) of gained sample The titanium-silicon molecular sieve TS-1 of preparation is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；Fourier-transform infrared spectrum In 960cm in figure-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/ Body phase silicon titanium ratio is 4.21, and titanium oxide content is 3.1 weight %.It is anti-when titanium-silicon molecular sieve TS-1 the 1st time and the 45th time use Result is answered to list in table 1.
Embodiment 5
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), preparing titanium silicon When molecular sieve TS-1, the crystallization temperature of first stage is 110 DEG C.The XRD crystalline phase figure and 1 step of embodiment (2) of gained sample are made Standby titanium-silicon molecular sieve TS-1 is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；Fourier-transform infrared spectrogram In in 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body Phase silicon titanium ratio is 2.37, and titanium oxide content is 3.2 weight %.Reaction when titanium-silicon molecular sieve TS-1 the 1st time and the 50th time use As a result it is listed in table 1.
Embodiment 6
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), the first stage Crystallization time is 12h.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (2), says It is bright that obtain is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absorption peak, Show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 3.78, titanium oxide content For 3.4 weight %.Reaction result when titanium-silicon molecular sieve TS-1 the 1st time and the 45th time use is listed in table 1.
Embodiment 7
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), second stage is It is cooled to 70 DEG C of stop 2h.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (2), What is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby absorb Peak shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.75, and titanium oxide contains Amount is 3.1 weight %.Reaction result when titanium-silicon molecular sieve TS-1 the 1st time and the 50th time use is listed in table 1.
Embodiment 8
Dimethyl sulfide is aoxidized 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 titanium-silicon molecular sieve TS-1 one of XRD crystalline phase figure and 1 step of embodiment (2) preparation of gained sample It causes, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby inhale Peak is received, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.14, titanium oxide Content is 2.4 weight %.Reaction result when titanium-silicon molecular sieve TS-1 the 1st time and the 25th time use is listed in table 1.
Embodiment 9
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), without second Stage.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (2), and what is illustrated is TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absorption peak, show titanium into Enter framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.08, and titanium oxide content is 2.5 weights Measure %.Reaction result when titanium-silicon molecular sieve TS-1 the 1st time and the 25th time use is listed in table 1.
Embodiment 10
Dimethyl sulfide is aoxidized using method same as Example 3, unlike, in step (2), aqueous dispersions are not 12h is stood at room temperature, but is sent directly into reaction kettle and is carried out crystallization.The XRD crystalline phase figure and 1 step of embodiment of gained sample (2) titanium-silicon molecular sieve TS-1 prepared is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；Fourier transform is red In 960cm in outer spectrogram-1Nearby there is absorption peak, show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, titanium oxide contains Amount is 3.5 weight %, and urface silicon titanium/body phase silicon titanium ratio is 1.18.When titanium-silicon molecular sieve TS-1 the 1st time and the 40th time use Reaction result is listed in table 1.
Embodiment 11
Dimethyl sulfide is aoxidized using method same as Example 1, unlike, in step (2), Titanium Sieve Molecular Sieve TS-1 is modified processing using following methods before being used as catalyst.
It will be as the titanium-silicon molecular sieve TS-1 of the preparation of raw material and containing HNO3(HNO3Mass concentration 10%) and peroxide be The aqueous solution mixing for changing hydrogen (mass concentration of hydrogen peroxide is 7.5%), by obtained mixture at 70 DEG C in closed container It is stirred to react 5h, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry at 120 DEG C It is dry to constant weight, obtain modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and peroxidating The molar ratio of hydrogen is 1:0.1.Compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 230-310nm reduces 3.5%, is held by the hole of static determination of nitrogen adsorption and reduces 2.6%.Titanium silicon Reaction result when molecular sieve TS-1 the 1st time and the 65th time use is listed in table 1.
Embodiment 12
Dimethyl sulfide is aoxidized using method identical with embodiment 11, unlike, in modification, as raw material Be drawn off from phenol hydroxylation reaction unit through regenerated titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 use with 1 step of embodiment (2) identical method preparation, the titanium-silicon molecular sieve TS-1 drawn off 570 DEG C at a temperature of in air atmosphere It roasts 5h and regenerates, the activity after regeneration is 35%, 96%) activity when fresh is.Compared with raw material Titanium Sieve Molecular Sieve, obtain Modification Titanium Sieve Molecular Sieve UV-Vis spectrum in the peak area of absorption peak between 230-310nm reduce 3.3%, by quiet The hole of state determination of nitrogen adsorption, which holds, reduces 2.8%.Reaction result when titanium-silicon molecular sieve TS-1 the 1st time and the 75th time use is in table It is listed in 1.
Embodiment 13
Dimethyl sulfide is aoxidized using method identical with embodiment 12, unlike, it will directly make in embodiment 11 Be used as catalyst through the regenerated titanium-silicon molecular sieve TS-1 drawn off from phenol hydroxylation reaction unit for raw material, i.e., without Modification.Reaction result when titanium-silicon molecular sieve TS-1 the 1st time and the 60th time use is listed in table 1.
Comparative example 1
Dimethyl sulfide is aoxidized using method identical with 1 step of embodiment (2), unlike, without step (1- 1) and step (1-2), in step (2) using the ethylbenzene solution of ethylbenzene hydroperoxide (in the ethylbenzene solution, ethylbenzene hydroperoxide Concentration is identical as the concentration of ethylbenzene hydroperoxide in the reaction mixture that 1 step of embodiment (1) obtains) replace step (1-2) Obtained reaction mixture.Reaction result when titanium-silicon molecular sieve TS-1 the 1st time and the 30th time use is listed in table 1.
Table 1
Embodiment 14
(1-1) is by ethylbenzene and ethylbenzene hydroperoxide (molar ratio of ethylbenzene hydroperoxide and ethylbenzene is 0.005:1) and oxygen Haptoreaction under conditions of temperature is 90 DEG C and pressure is 2MPa obtains the reaction mixture containing ethylbenzene hydroperoxide, uses Gas-chromatography analyzes the composition of the reaction mixture, determines that the content of ethylbenzene hydroperoxide is 11 weight %.Wherein, second The molar ratio of benzene and oxygen is 1:1, and oxygen is provided in the form of oxygen-containing gas, and in oxygen-containing gas, the content of oxygen is 20 bodies Product %, the content of nitrogen are 80 volume %.
The reaction mixture and hydrobromic acid (HBr concentration is 30 weight %) that (1-2) obtains step (1-1) are in reaction under high pressure It being mixed in kettle, wherein the molar ratio of ethylbenzene hydroperoxide and HBr are 1:0.001 in the reaction mixture that step (1-1) obtains, It is 30 DEG C by the temperature control in autoclave, the pressure in autoclave is controlled as normal pressure (that is, 1 normal atmosphere Pressure), incorporation time 3h.
(2) sky for being HTS for the trade mark purchased from Hunan Jianchang Petrochemical Co., Ltd as the Titanium Sieve Molecular Sieve of raw material Heart Titanium Sieve Molecular Sieve, titanium oxide content are 2.5 weight %.
By hollow Titanium Sieve Molecular Sieve and contain HNO3(HNO3Mass concentration be 10%) and hydrogen peroxide (hydrogen peroxide Mass concentration is aqueous solution mixing 5%), obtained mixture is stirred under 120 DEG C of pressure itselfs in closed container anti- 4h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C Weight, obtains modified Titanium Sieve Molecular Sieve.Wherein, hollow Titanium Sieve Molecular Sieve is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub You are than being 1:0.4.Compared with raw material Titanium Sieve Molecular Sieve, in 230- in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 310nm reduces 4.6%, is held by the hole of static determination of nitrogen adsorption and reduces 3.8%.It will be modified The mixture of hollow Titanium Sieve Molecular Sieve and non-modified hollow Titanium Sieve Molecular Sieve is (modified on the basis of the total amount of the mixture Hollow Titanium Sieve Molecular Sieve content be 60 weight %) be seated in micro fixed-bed reactor, formed catalyst bed.
The reaction mixture and dimethyl sulfide that step (1-2) is obtained are sent into reaction from the entrance for being located at reactor bottom In device, catalyst bed is flowed through.Wherein, the ethylbenzene hydroperoxide and dimethyl sulfide in reaction mixture that step (1) obtains Molar ratio be 1.1:1, be 50 DEG C by the temperature control in catalyst bed, the pressure in reactor controlled as 1.2MPa, The weight (hourly) space velocity (WHSV) of dimethyl sulfide is 15h-1。
The composition of reaction mixture exported from reactor is monitored in reaction process, calculate dimethyl sulfide conversion ratio and Dimethyl sulfoxide selectivity, wherein the reaction result that reaction obtains when proceeding to 2h and 550h is listed in table 2.
Embodiment 15
Using method cacodyl oxide base thioether identical with embodiment 14, the difference is that, what is loaded in catalyst bed is Non-modified hollow Titanium Sieve Molecular Sieve.
The composition of reaction mixture exported from reactor is monitored in reaction process, calculate dimethyl sulfide conversion ratio and Dimethyl sulfoxide selectivity, wherein the reaction result that reaction obtains when proceeding to 2h and 380h is listed in table 2.
Embodiment 16
Using method cacodyl oxide base thioether identical with embodiment 15, the difference is that, prepare modified Titanium Sieve Molecular Sieve When the raw material that uses be hollow Titanium Sieve Molecular Sieve (the hollow titanium silicon drawn off from cyclohexanone oxamidinating reaction unit through regenerated Molecular sieve is identical as the source of hollow Titanium Sieve Molecular Sieve of raw material as 14 step of embodiment (2), the hollow titanium silicon molecule drawn off Sieve 550 DEG C at a temperature of roast 6h in air atmosphere and regenerate, the activity after regeneration is 40%, and activity when fresh is 97%).Compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification 230-310nm it Between absorption peak peak area reduce 4.8%, by static determination of nitrogen adsorption hole hold reduce 3.5%.
The composition of reaction mixture exported from reactor is monitored in reaction process, calculate dimethyl sulfide conversion ratio and Dimethyl sulfoxide selectivity, wherein the reaction result that reaction obtains when proceeding to 2h and 660h is listed in table 2.
Embodiment 17
(1-1) haptoreaction under conditions of temperature is 140 DEG C and pressure is 2.5MPa by ethylbenzene and oxygen, is contained The reaction mixture of ethylbenzene hydroperoxide is analyzed with composition of the gas-chromatography to the reaction mixture, determines ethylbenzene peroxide The content for changing hydrogen is 8 weight %.Wherein, the molar ratio of ethylbenzene and oxygen is 1:0.8；Oxygen is provided in the form of oxygen-containing gas, In oxygen-containing gas, the content of oxygen is 25 volume %, and the content of nitrogen is 75 volume %.
The reaction mixture and hydrochloric acid (HCl concentration is 25 weight %) that (1-2) obtains step (1-1) are in autoclave Middle mixing, wherein the molar ratio of ethylbenzene hydroperoxide and HCl are 1:0.01 in the reaction mixture that step (1-1) obtains, will be high It presses the temperature in reaction kettle to control 35 DEG C, the pressure in autoclave is controlled as normal pressure (that is, 1 standard atmospheric pressure), mixing Time is 3h.
(2) titanium-silicon molecular sieve TS-1 used in this step is prepared using following methods.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:2:10: 600, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is close using sealed membrane in beaker It is honored as a queen in 40 DEG C of standing 10h, is stirred 0.5h at 25 DEG C followed by magnetic agitation, is allowed to disperse again.It will disperse again Dispersion liquid afterwards is transferred in sealing reaction kettle, and in 130 DEG C of experience first stage crystallization 8h, mixture is then cooled to 50 DEG C After undergoing second stage to stop 5h, continues the temperature in sealing reaction kettle in 170 DEG C and undergo phase III crystallization 16h (wherein, It is 1 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first segment crystallization temperature to second segment processing The rate of temperature fall of temperature be 10 DEG C/min, by second segment treatment temperature to third section crystallization temperature heating rate for 20 DEG C/ Min), then roasted at 580 DEG C without filtering and washing step directly in 120 DEG C of drying 3h after gained crystallization product being taken out 2h is burnt, molecular sieve is obtained.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (2), What is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；In Fourier Transform Infrared Spectroscopy figure, in 960cm-1Nearby go out Existing absorption peak, shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.25, oxygen Change Ti content is 2.6 weight %.
The titanium-silicon molecular sieve TS-1 of preparation is seated in micro fixed-bed reactor, catalyst bed is formed.By step The reaction mixture and dimethyl sulfide that (1-2) is obtained are sent into reactor from the entrance for being located at reactor bottom, flow through catalysis Agent bed.Wherein, the molar ratio for the ethylbenzene hydroperoxide and dimethyl sulfide in reaction mixture that step (1-1) obtains is 1: 3, it is 50 DEG C by the temperature control in catalyst bed, the pressure in reactor is controlled as 0.5MPa, the weight of dimethyl sulfide When air speed be 50h-1。
The composition of reaction mixture exported from reactor is monitored in reaction process, calculate dimethyl sulfide conversion ratio and Dimethyl sulfoxide selectivity, wherein the reaction result that reaction obtains when proceeding to 2h and 520h is listed in table 2.
Table 2
Embodiment 18
(1-1) haptoreaction under conditions of temperature is 125 DEG C and pressure is 1.5MPa by ethylbenzene and oxygen, is contained The reaction mixture of ethylbenzene hydroperoxide is analyzed with composition of the gas-chromatography to the reaction mixture, determines ethylbenzene peroxide The content for changing hydrogen is 20 weight %.Wherein, the molar ratio of ethylbenzene and oxygen is 1:2；Oxygen is provided in the form of oxygen-containing gas, is contained In carrier of oxygen, the content of oxygen is 22 volume %, and the content of argon gas is 78 volume %.
The reaction mixture and hydrochloric acid (HCl concentration is 20 weight %) that (1-2) obtains step (1-1) are in autoclave Middle mixing, wherein the molar ratio of ethylbenzene hydroperoxide and HCl are 1:0.005 in the reaction mixture that step (1-1) obtains, will Temperature in autoclave controls 30 DEG C, and the pressure in autoclave control as normal pressure (that is, 1 standard atmospheric pressure), mixed The conjunction time is 4h.
(2) titanium-silicon molecular sieve TS-1 that this step uses is prepared using following methods.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:5:18: 1000, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is utilized into sealed membrane in beaker In 45 DEG C of standing 8h after sealing；Dispersion liquid through standing is transferred in sealing reaction kettle, it is brilliant in 140 DEG C of experience first stage Change 6h, after mixture is then cooled to 40 DEG C of experience second stage stop 1h, continues in sealing reaction kettle in 160 DEG C of temperature The lower experience phase III crystallization 12h of degree (it is wherein, 5 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, It is 5 DEG C/min by the rate of temperature fall of first segment crystallization temperature to second segment treatment temperature, by second segment treatment temperature to third section The heating rate of crystallization temperature is 5 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly in 110 DEG C drying 2h, then roasts 3h at 550 DEG C, obtains molecular sieve.The XRD crystalline phase figure and 1 step of embodiment (2) of gained sample are made Standby titanium-silicon molecular sieve TS-1 is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier-transform infrared In spectrogram, in 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, surface silicon Titanium ratio/body phase silicon titanium ratio is 2.71, and titanium oxide content is 4.3 weight %.
The titanium-silicon molecular sieve TS-1 of preparation is seated in micro fixed-bed reactor, catalyst bed is formed.By step The mixture and thioanisole that (1-2) is obtained are sent into reactor from the entrance for being located at reactor bottom, flow through catalyst bed. Wherein, the molar ratio for the ethylbenzene hydroperoxide and thioanisole in reaction mixture that step (1) obtains is 1.5:1, will be catalyzed Temperature control in agent bed is 85 DEG C, the pressure in reactor is controlled as 1.8MPa, the weight (hourly) space velocity (WHSV) of thioanisole is 15h-1。
The composition of the reaction mixture exported from reactor is monitored in reaction process, calculates thioanisole conversion ratio and benzene First sulfoxide selectivity, wherein the reaction result that reaction obtains when proceeding to 2h and 450h is listed in table 3.
Embodiment 19
Thioanisole is aoxidized using method identical with embodiment 18, unlike, the titanium-silicon molecular sieve TS-1 of preparation Before being used as catalyst, processing is modified using following methods.
By the titanium-silicon molecular sieve TS-1 of preparation and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (peroxide be Change the mass concentration of hydrogen as aqueous solution mixing 2%), obtained mixture is stirred to react in closed container at 170 DEG C 2.5h, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C Weight, obtains modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub You are than being 1:1.Through characterizing, compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 230-310nm reduces 5.7%, is held by the hole of static determination of nitrogen adsorption and reduces 4.1%.
The composition of the reaction mixture exported from reactor is monitored in reaction process, calculates thioanisole conversion ratio and benzene First sulfoxide selectivity, wherein the reaction result that reaction obtains when proceeding to 2h and 540h is listed in table 3.
Embodiment 20
Thioanisole is aoxidized using method identical with embodiment 19, unlike, what it is as raw material is through regenerating Slave phenol hydroxylation reaction unit in draw off titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1 use and 18 step of embodiment Suddenly (2) identical method preparation, the titanium-silicon molecular sieve TS-1 drawn off 580 DEG C at a temperature of roast in air atmosphere 4h and again Raw, the activity after regeneration is 40%, 95%) activity when fresh is.Compared with raw material Titanium Sieve Molecular Sieve, the titanium of obtained modification The peak area of absorption peak in the UV-Vis spectrum of si molecular sieves between 230-310nm reduces 5.5%, by static nitrogen adsorption method The hole of measurement, which holds, reduces 4.3%.
The composition of the reaction mixture exported from reactor is monitored in reaction process, calculates thioanisole conversion ratio and benzene First sulfoxide selectivity, wherein the reaction result that reaction obtains when proceeding to 2h and 640h is listed in table 3.
Table 3
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (71)

1. a kind of sulfide oxidation method, the method comprising the steps of (1-1), step (2) and optional step (1-2):
In step (1-1), by ethylbenzene and oxygen haptoreaction, the catalytic condition makes the reaction that haptoreaction obtains The content of ethylbenzene hydroperoxide is 1 weight % or more in mixture；
In step (1-2), the reaction mixture that step (1-1) obtains is mixed with inorganic acid；
In step (2), under conditions of being enough sulfide oxidation, the reaction mixture and thioether that step (1-1) is obtained will be contained Raw mixture and Titanium Sieve Molecular Sieve haptoreaction, or the raw material of mixture and thioether that will be obtained containing step (1-2) Mixture and Titanium Sieve Molecular Sieve haptoreaction, at least partly Titanium Sieve Molecular Sieve are to undergo the titanium silicon molecule of the modification of modification Sieve, the modification includes that will connect as the Titanium Sieve Molecular Sieve of raw material with the modification liquid being made of nitric acid, hydrogen peroxide and water Touching is 1:0.01-5 as the Titanium Sieve Molecular Sieve of raw material and the molar ratio of the hydrogen peroxide, and the Titanium Sieve Molecular Sieve is with dioxy The molar ratio of SiClx meter, the hydrogen peroxide and the nitric acid is 1:0.01-50, and the Titanium Sieve Molecular Sieve is Titanium Sieve Molecular Sieve TS-1 and/or hollow Titanium Sieve Molecular Sieve, the thioether are dimethyl sulfide and/or thioanisole.
2. according to the method described in claim 1, wherein, in step (1-1), the catalytic condition makes anti- The content for answering ethylbenzene hydroperoxide in mixture is 2-95 weight %；The content of ethylbenzene is 5-98 weight %.
3. according to the method described in claim 2, wherein, in step (1-1), the catalytic condition makes anti- The content for answering ethylbenzene hydroperoxide in mixture is 3-60 weight %；The content of ethylbenzene is 40-97 weight %.
4. according to the method described in claim 3, wherein, in step (1-1), the catalytic condition makes anti- The content for answering ethylbenzene hydroperoxide in mixture is 4-30 weight %；The content of ethylbenzene is 70-96 weight %.
5. according to the method described in claim 4, wherein, in step (1-1), the catalytic condition makes anti- The content for answering ethylbenzene hydroperoxide in mixture is 8-20 weight %；The content of ethylbenzene is 80-92 weight %.
6. method described in any one of -5 according to claim 1, wherein in step (1-1), the molar ratio of ethylbenzene and oxygen For 1:0.1-20, the haptoreaction is 50-180 DEG C in temperature, and pressure be 0-5MPa under conditions of carry out, the pressure with Gauge pressure meter.
7. according to the method described in claim 6, wherein, in step (1-1), the molar ratio of ethylbenzene and oxygen is 1:0.2-10.
8. according to the method described in claim 7, wherein, in step (1-1), the molar ratio of ethylbenzene and oxygen is 1:0.5-5.
9. according to the method described in claim 6, wherein, in step (1-1), the catalytic temperature is 80-160 DEG C.
10. according to the method described in claim 9, wherein, in step (1-1), the catalytic temperature is 90-140 DEG C.
11. according to the method described in claim 6, wherein, in step (1-1), pressure 0-3MPa, the pressure is with gauge pressure Meter.
12. according to the method described in claim 1, wherein, in step (1-2), the molar ratio of inorganic acid and ethylbenzene hydroperoxide For 0.00001-0.1:1.
13. according to the method for claim 12, wherein in step (1-2), the molar ratio of inorganic acid and ethylbenzene hydroperoxide For 0.0001-0.05:1.
14. according to the method for claim 13, wherein in step (1-2), the molar ratio of inorganic acid and ethylbenzene hydroperoxide For 0.001-0.01:1.
15. according to the method for claim 14, wherein in step (1-2), the molar ratio of inorganic acid and ethylbenzene hydroperoxide For 0.001-0.005:1.
16. in step (1-2), the temperature that is blended in is 20-100 DEG C according to the method described in claim 1, wherein, and Pressure carries out under conditions of being 0-2MPa, and the pressure is in terms of gauge pressure；The mixed time is 0.1-5 hours.
17. according to the method for claim 16, wherein in step (1-2), temperature is 20-80 DEG C.
18. according to the method for claim 17, wherein in step (1-2), temperature is 20-60 DEG C.
19. according to the method for claim 16, wherein in step (1-2), the mixed time is 0.5-4 hours.
20. according to the method for claim 19, wherein in step (1-2), the mixed time is 2-4 hours.
21. according to the method described in claim 1, wherein, in step (1-2), the inorganic acid is HCl and/or HBr.
22. according to the method described in claim 1, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The molar ratio of hydrogen peroxide is stated as 1:0.05-2, the molar ratio of the hydrogen peroxide and the nitric acid is 1:0.1-20, the titanium Si molecular sieves are in terms of silica.
23. according to the method for claim 22, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The molar ratio of the hydrogen peroxide is 1:0.1-1, and the Titanium Sieve Molecular Sieve is in terms of silica.
24. according to the method for claim 22, wherein in the modification, the hydrogen peroxide and the nitric acid Molar ratio be 1:0.2-10.
25. according to the method for claim 24, wherein in the modification, the hydrogen peroxide and the nitric acid Molar ratio be 1:0.5-5.
26. according to claim 1 with the method described in any one of 22-25, wherein in the modification liquid, the peroxidating The concentration of hydrogen and nitric acid is respectively 0.1-50 weight %.
27. according to the method for claim 26, wherein in the modification liquid, the concentration of the hydrogen peroxide and nitric acid is each From for 0.5-25 weight %.
28. according to the method for claim 27, wherein in the modification liquid, the concentration of the hydrogen peroxide and nitric acid is each From for 1-15 weight %.
29. according to the method for claim 28, wherein in the modification liquid, the concentration of the hydrogen peroxide and nitric acid is each From for 2-10 weight %.
30. according to claim 1 with the method described in any one of 22-25, wherein in the modification, as original The Titanium Sieve Molecular Sieve of material and the modification liquid 10-350 DEG C at a temperature of contacted, the contact is 0-5MPa's in pressure It is carried out in container, the pressure is gauge pressure.
31. according to the method for claim 30, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 20-300 DEG C at a temperature of contacted.
32. according to the method for claim 31, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 50-250 DEG C at a temperature of contacted.
33. according to the method for claim 32, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 70-200 DEG C at a temperature of contacted.
34. according to claim 1 with the method described in any one of 22-25, wherein in the modification, as original The Titanium Sieve Molecular Sieve of material and the exposure level of the modification liquid make, using on the basis of the Titanium Sieve Molecular Sieve as raw material, it is ultraviolet- In visible spectrum, the peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces by 2% or more, is modified The hole of Titanium Sieve Molecular Sieve, which holds, reduces 1% or more, and the Kong Rong is using static determination of nitrogen adsorption.
35. according to the method for claim 34, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 2-30%.
36. according to the method for claim 25, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 3-15%.
37. according to the method for claim 36, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 3.5-6%.
38. according to the method for claim 34, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, using on the basis of the Titanium Sieve Molecular Sieve as raw material, the Kong Rong of modified Titanium Sieve Molecular Sieve 1-20% is reduced, the Kong Rong is using static determination of nitrogen adsorption.
39. according to the method for claim 38, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, using on the basis of the Titanium Sieve Molecular Sieve as raw material, the Kong Rong of modified Titanium Sieve Molecular Sieve 2-10% is reduced, the Kong Rong is using static determination of nitrogen adsorption.
40. according to the method for claim 39, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, using on the basis of the Titanium Sieve Molecular Sieve as raw material, the Kong Rong of modified Titanium Sieve Molecular Sieve 2.5-5% is reduced, the Kong Rong is using static determination of nitrogen adsorption.
41. according to claim 1 with the method described in any one of 22-25, wherein the total amount with the Titanium Sieve Molecular Sieve is Benchmark, the content of the Titanium Sieve Molecular Sieve of the modification are 50 weight % or more.
42. according to claim 1 with the method described in any one of 22-25, wherein in step (2), at least partly titanium silicon point Son sieve is titanium-silicon molecular sieve TS-1, and the urface silicon titanium of the titanium-silicon molecular sieve TS-1 is not less than body phase silicon titanium ratio, the silicon titanium Than the molar ratio for referring to silica and titanium oxide, the urface silicon titanium is measured using X-ray photoelectron spectroscopy, the body phase Silicon titanium ratio uses x-ray fluorescence spectrometry.
43. according to the method for claim 42, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is More than 1.2.
44. according to the method for claim 43, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5。
45. according to the method for claim 44, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5。
46. according to claim 1 with the method described in any one of 22-25, wherein in step (2), at least partly titanium silicon point Son sieve is titanium-silicon molecular sieve TS-1, and the titanium-silicon molecular sieve TS-1 is prepared using method comprising the following steps:
(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and optionally supplements water, dispersed Liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:(0.5-8): (5-30): (100- 2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N meter；
(II) optionally, by the dispersion liquid 15-60 DEG C standing 6-24 hours；
(III) dispersion liquid that step (I) obtains or the dispersion liquid that step (II) obtains sequentially are undergone in sealing reaction kettle Stage (1), stage (2) and stage (3) to carry out crystallization, the stage (1) 80-150 DEG C crystallization 6-72 hours；Stage (2) cooling It is extremely not higher than 70 DEG C and the residence time is at least 0.5 hour；Stage (3) is warming up to 120-200 DEG C, then crystallization 6-96 hours.
47. according to the method for claim 46, wherein the stage, (1) was in 110-140 DEG C of crystallization.
48. according to the method for claim 47, wherein the stage, (1) was in 120-140 DEG C of crystallization.
49. according to the method for claim 48, wherein the stage, (1) was in 130-140 DEG C of crystallization.
50. according to the method for claim 46, wherein crystallization 6-8 hours stage (1).
51. according to the method for claim 46, wherein the residence time in stage (2) is at least 1-5 hours.
52. according to the method for claim 46, wherein the stage (3) is warming up to 140-180 DEG C.
53. method according to claim 52, wherein the stage (3) is warming up to 160-170 DEG C.
54. according to the method for claim 46, wherein the stage (3) crystallization 12-20 hours again.
55. according to the method for claim 46, wherein stage (1) and stage (3) meet one of the following conditions or two Person:
Condition 1: the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3)；
Condition 2: the crystallization time in stage (1) is less than the crystallization time of stage (3).
56. method according to claim 55, wherein condition 1: crystallization temperature of the crystallization temperature in stage (1) than the stage (3) Spend low 10-50 DEG C.
57. method according to claim 56, wherein condition 1: crystallization temperature of the crystallization temperature in stage (1) than the stage (3) Spend low 20-40 DEG C.
58. method according to claim 55, wherein condition 2: the crystallization time in stage (1) than the stage (3) crystallization when Between it is 5-24 hours short.
59. method according to claim 58, wherein condition 2: the crystallization time in stage (1) than the stage (3) crystallization when Between it is 6-12 hours short.
60. according to the method for claim 46, wherein the stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
61. according to the method for claim 46, wherein the titanium source is inorganic titanium salt and/or organic titanate；The alkali Source template is one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine；The inorganic silicon source be silica gel and/ Or silica solution.
62. method according to claim 61, wherein the alkali source template is quaternary ammonium base.
63. method according to claim 62, wherein the alkali source template is tetrapropylammonium hydroxide.
64. method according to claim 61, wherein the inorganic titanium salt is TiCl4、Ti(SO4)2And TiOCl2In one Kind is two or more；The organic titanate is selected from general formula R7 4TiO4The compound of expression, R7Selected from 2-4 carbon atom Alkyl.
65. method described in any one of -5 and 12-25 according to claim 1, wherein at least partly Titanium Sieve Molecular Sieve source In the agent that draws off of at least one reaction unit, described to draw off agent be that Ammoximation reaction device draws off agent, hydroxylating device Draw off agent and epoxidation reaction device draw off agent.
66. method described in any one of -5 and 12-25 according to claim 1, wherein in step (2), step (1-1) To reaction mixture in ethylbenzene hydroperoxide and thioether molar ratio be 0.1-10:1.
67. method according to claim 66, wherein in step (2), in the reaction mixture that step (1-1) obtains The molar ratio of ethylbenzene hydroperoxide and thioether is 1:0.1-2.
68. method described in any one of -5 and 12-25 according to claim 1, wherein in step (2), the haptoreaction It is 0-120 DEG C in temperature, and pressure is carries out under conditions of 0-5MPa, the pressure is in terms of gauge pressure.
69. method according to claim 68, wherein in step (2), the catalytic temperature is 20-80 DEG C.
70. method according to claim 69, wherein in step (2), the catalytic temperature is 40-50 DEG C.
71. method according to claim 68, wherein in step (2), pressure 0.1-3.5MPa, the pressure is with table Pressure meter.
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