CN108794359A - A method of dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide - Google Patents

A method of dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide Download PDF

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Publication number
CN108794359A
CN108794359A CN201710292099.0A CN201710292099A CN108794359A CN 108794359 A CN108794359 A CN 108794359A CN 201710292099 A CN201710292099 A CN 201710292099A CN 108794359 A CN108794359 A CN 108794359A
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titanium
molecular sieve
sieve
silicon
stage
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CN108794359B (en
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史春风
林民
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides

Abstract

The invention discloses a kind of methods producing dimethyl sulfoxide (DMSO) by hydrogen sulfide, including：(1) hydrogen sulfide is contacted with methanol, obtains the mixture containing dimethyl sulfide；(2) mixture is subjected to gas-liquid separation, obtains gaseous stream and the liquid phase stream containing dimethyl sulfide, optionally gaseous stream is recycled and is sent into step (1)；(3) under oxidation reaction condition, liquid phase stream is contacted with oxidant and Titanium Sieve Molecular Sieve, obtains the mixture containing dimethyl sulfoxide (DMSO)；Optionally, (4) detach the mixture containing dimethyl sulfoxide (DMSO), obtain dimethyl sulfide；Optionally, the dimethyl sulfide cycle that (5) isolate step (4) is sent into step (3).This method can obtain higher dimethyl sulfide conversion ratio, especially suitable for the occasion mass produced using hydrogen sulfide as raw material continuous production dimethyl sulfoxide (DMSO).

Description

A method of dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide
Technical field
The present invention relates to a kind of methods producing dimethyl sulfoxide (DMSO) by hydrogen sulfide.
Background technology
Dimethyl sulfoxide (DMSO) (DMSO) is a kind of organic compounds containing sulfur, is colourless transparent liquid under room temperature, have it is highly polar, The characteristics such as high-hygroscopicity, flammable and higher boiling be non-proton.Dimethyl sulfoxide (DMSO) is dissolved in water, ethyl alcohol, acetone, ether and chloroform, is pole The strong atent solvent of property, is widely used as solvent and reaction reagent.Also, dimethyl sulfoxide (DMSO) has very high selective extraction method energy Power can be used as the Extraction solvent that alkane is detached with aromatic hydrocarbon, such as：Dimethyl sulfoxide (DMSO) can be used for the extracting of aromatic hydrocarbons or butadiene, It is used as process solvent and reel off raw silk from cocoons solvent, the synthetic as polyurethane and the solvent that reels off raw silk from cocoons in acrylonitrile polymerization reaction, as The synthetic of polyamide, fluoroaluminate glasses, polyimides and polysulfones.Meanwhile in medical industry, dimethyl sulfoxide (DMSO) not only can be with Directly as the raw material and carrier of some drugs, and the effects that anti-inflammatory analgetic, diuresis, calmness can also be played, therefore frequently as The active component of analgesic drug product makes an addition in drug.In addition, dimethyl sulfoxide (DMSO) also can be used as capacitor dielectric, antifreezing agent, brake fluid, Rare metal extracting agent etc..
Currently, dimethyl sulfoxide (DMSO) generally uses dimethyl sulfide oxidizing process to be made by following several techniques.
1, methanol carbon disulfide method：Using methanol and carbon disulfide as raw material, with γ-Al2O3As catalyst, synthesize first Dimethyl sulfide, then obtain dimethyl sulfoxide (DMSO) with nitrogen dioxide (or nitric acid) oxidation.
2, nitrogen dioxide method：Using methanol and hydrogen sulfide as raw material, dimethyl sulfide is generated under gama-alumina effect；It will Sulfuric acid is reacted with sodium nitrite is made nitrogen dioxide；The dimethyl sulfide of generation carries out aoxidizing at 60-80 DEG C anti-with nitrogen dioxide Thick dimethyl sulfoxide (DMSO) should be generated, also has and is directly aoxidized with oxygen, similarly generates thick dimethyl sulfoxide (DMSO)；Thick dimethyl sulfoxide (DMSO) warp Vacuum distillation obtains refined dimethyl sulfoxide (DMSO).
3, dimethyl sulfate method：Dimethyl suflfate is reacted with vulcanized sodium, dimethyl sulfide is made；Sulfuric acid and sodium nitrite Reaction generates nitrogen dioxide；Dimethyl sulfide carries out oxidation reaction with nitrogen dioxide, obtains thick dimethyl sulfoxide (DMSO), neutralized place Reason obtains refined dimethyl sulfoxide (DMSO) after distillation.
In addition, using anodizing dimethyl sulfoxide (DMSO) can also be produced by dimethyl sulphide.
Invention content
The purpose of the present invention is to provide a kind of method of continuous production dimethyl sulfoxide (DMSO), this method can obtain higher Dimethyl sulfide conversion ratio
The present invention provides a kind of methods producing dimethyl sulfoxide (DMSO) by hydrogen sulfide, and this approach includes the following steps：
(1) hydrogen sulfide is contacted with methanol, obtains the mixture containing dimethyl sulfide；
(2) mixture containing dimethyl sulfide is subjected to gas-liquid separation, obtains gaseous stream and contains dimethyl disulfide The gaseous stream is optionally recycled and is sent into step (1) by the liquid phase stream of ether；
(3) under oxidation reaction condition, the liquid phase stream that step (2) obtains is contacted with oxidant and Titanium Sieve Molecular Sieve, Obtain the mixture containing dimethyl sulfoxide (DMSO)；
Optionally, (4) detach the mixture containing dimethyl sulfoxide (DMSO), obtain dimethyl sulfide and dimethyl disulfide The dimethyl sulfoxide (DMSO) that ether content reduces；
Optionally, the dimethyl sulfide cycle that (5) isolate step (4) is sent into step (3).
According to the method for the present invention, by the oxidation reaction process knot of the production process of dimethyl sulfide and dimethyl sulfide It closes, realizes using hydrogen sulfide as raw material continuous production dimethyl sulfoxide (DMSO), especially suitable for the occasion mass produced.This hair Bright method can obtain higher diformazan using Titanium Sieve Molecular Sieve in dimethyl sulfide oxidation reaction process as catalyst Base thioether rate.
Description of the drawings
Fig. 1 is used to illustrate a kind of preferred implementation of the production method according to the present invention that dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide Mode.
Reference sign
1：Hydrogen sulfide 2：Methanol 3：Mixture containing dimethyl sulfide
4：Gaseous stream 5：Liquid phase stream 6：Oxidant
7：Supplementing solvent 8：Product stream 9：Liquid product logistics
10：Unreacted dimethyl sulfide
A：Thioether reaction of formation device B：Gas-liquid separator C：Oxidation reactor
D：Flash column
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of methods producing dimethyl sulfoxide (DMSO) by hydrogen sulfide, and the method comprising the steps of (1)：It will vulcanization Hydrogen is contacted with methanol, obtains the mixture containing dimethyl sulfide.
For contacting hydrogen sulfide with methanol, the method for obtaining the mixture containing dimethyl sulfide does not have the method for the present invention It is particularly limited to, under conditions of being enough to generate dimethyl sulfide, can will vulcanize in the presence of catalyst commonly used in the art Hydrogen is contacted with methanol, to obtain the mixture containing dimethyl sulfide.
Specifically, the catalyst can be selected from type ZSM 5 molecular sieve, BETA types molecular sieve, Y type molecular sieve and γ- Al2O3One or more of, preferably γ-Al2O3.The dosage of catalyst is not particularly limited in the present invention, can be with It is made appropriate choice according to specific contact conditions and expected reaction speed.Usually, the quality of catalyst and methanol Than that can be 0.1-100：1, preferably 5-50：1；When being reacted in fixed bed reactors, the mass space velocity of methanol can be with For 1-50h-1, preferably 5-20h-1。
In step (1), the dosage of hydrogen sulfide and methanol is not particularly limited, and can be the conventional selection of this field.Generally The molar ratio of ground, hydrogen sulfide and methanol can be 0.1-100：1, preferably 0.2-10：1, more preferably 0.3-5：1, further Preferably 0.4-2：1.
In step (1), hydrogen sulfide is contacted with methanol, the condition to obtain dimethyl sulfide is not particularly limited. Specifically, hydrogen sulfide can be contacted with methanol and catalyst at a temperature of 200-400 DEG C, preferably by hydrogen sulfide and first Alcohol and catalyst are contacted at a temperature of 250-400 DEG C.The pressure in reactor contacted can be 0-5MPa, excellent It is selected as 0.1-3MPa, more preferably 0.1-0.5MPa, the pressure is gauge pressure.
In step (1), the type of the reactor for contacting hydrogen sulfide with methanol is not particularly limited, Ke Yi It carries out, can also be carried out in flow reactor in batch reactor, as carried out in fixed bed reactors.
In step (1), hydrogen sulfide can be the hydrogen sulfide in various sources.In a preferred embodiment, the sulphur It is the hydrogen sulfide isolated from acid waste gas to change hydrogen.The acid waste gas for example can be refinery containing hydrogen sulfide Exhaust gas.The hydrogen sulfide isolated from the acid waste gas of refinery usually contains NH3., the present inventor is in research process Middle discovery, using containing NH3Hydrogen sulfide as starting material, the selectivity of dimethyl sulfoxide (DMSO) can be further increased.Therefore, institute It states hydrogen sulfide and preferably contains NH3Hydrogen sulfide.It is highly preferred that NH in the hydrogen sulfide3Mass content be 0.1-6%.Into one It walks preferably, NH in the hydrogen sulfide3Mass content be 0.2-5%.It is further preferred that NH in the hydrogen sulfide3Matter Amount content is 0.5-3%.
The method according to the present invention that dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide, including step (2)：Dimethyl sulfide will be contained Mixture carry out gas-liquid separation, gaseous stream and the liquid phase stream containing dimethyl sulfide are obtained, optionally by the gas Phase logistics cycle is sent into step (1).It is " optional " to indicate with or without including or do not include in the present invention.
In step (2), common various gas-liquid separating methods may be used, by the mixture containing dimethyl sulfide into Row separation, to obtain the gaseous stream and the liquid phase stream.As an example, the method that condensation may be used will Mixture containing dimethyl sulfide is detached, and dimethyl sulfide and methanol that may be present are retained in the liquid phase, together When hydrogen sulfide that may be present in the mixture containing dimethyl sulfide is retained in the gas phase.
Methanol in the liquid phase stream can not be detached further, but as next step reaction (that is, step (3)) reaction dissolvent.
It, can be with discharge system for the gaseous stream isolated in step (2)；Contain in the gaseous stream unreacted When hydrogen sulfide, at least partly gaseous stream cycle can be sent into step (1), be used to prepare dimethyl sulfide.
The method according to the present invention that dimethyl sulfoxide (DMSO) is produced by hydrogen sulfide, including in step (3), in oxidation reaction condition Under, the liquid phase stream that step (2) obtains is contacted with oxidant and Titanium Sieve Molecular Sieve, obtains the mixing containing dimethyl sulfoxide (DMSO) Object.
In step (3), the oxidant can be the common various substances that can aoxidize dimethyl sulfide.The present invention Occasion of the method especially suitable for carrying out cacodyl oxide base thioether using peroxide as oxidant.The peroxide refers to point Contain the compound of-O-O- keys in minor structure, can be one kind or two in hydrogen peroxide, organic peroxide and peracid Kind or more.The organic peroxide refers to that one or two of hydrogen peroxide molecule hydrogen atom is replaced and obtained by organic group The substance arrived.The peracid refers to the organic oxacid for containing-O-O- keys in molecular structure.In the present invention, the oxidant Specific example can include but is not limited to：Hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, One or more of cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is peroxidating Hydrogen can further decrease separation costs in this way.
The peroxide can be peroxide existing in a variety of manners commonly used in the art.From further increasing root It sets out according to the angle of the safety of the method for the present invention, it is preferable to use existing peroxidating in the form of a solution according to the method for the present invention Object.According to the method for the present invention, when the peroxide provides in the form of a solution, the concentration of the aqueous solution can be ability The normal concentration in domain, such as：10-80 weight %, preferably 20-50 weight %.
In step (3), the dosage of oxidant can be selected according to the specific requirement of technique.Specifically, dimethyl disulfide The molar ratio of ether and the oxidant can be 1：0.1-2, preferably 1：0.1-1.5.In the preferred implementation of one kind of the present invention In mode, the molar ratio of dimethyl sulfide and the oxidant is not less than 1：1, such as can be 1：0.1-1 can be obtained in this way Higher dimethyl sulfoxide (DMSO) selectivity is obtained, operating cost is further decreased.It is further preferred that dimethyl sulfide and the oxidation The molar ratio of agent is 1：0.2-0.95, such as 1：0.5-0.9.
In step (3), dimethyl sulfoxide (DMSO) is prepared as dimethyl sulfide and oxidant haptoreaction using Titanium Sieve Molecular Sieve Catalyst.The Titanium Sieve Molecular Sieve is the general name of a kind of zeolite of a part of silicon atom in titanium atom substitution lattice framework.This The content of titanium atom in Titanium Sieve Molecular Sieve is not particularly limited in invention, can be the conventional selection of this field.Usually, institute The content for stating titanium atom in Titanium Sieve Molecular Sieve (in terms of titanium oxide) can be 2-6 weight %, preferably 2.5-4.5 weight %.
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 structures, BEA knots The titanium silicon molecule of the Titanium Sieve Molecular Sieve (such as Ti-Beta) of structure, the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structures, hexagonal structure Sieve (such as Ti-MCM-41, Ti-SBA-15), the Titanium Sieve Molecular Sieve (such as Ti-MOR) of MOR structures, the Titanium Sieve Molecular Sieve of TUN structures 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 structures, One or more of the Titanium Sieve Molecular Sieve of BEA structures and the Titanium Sieve Molecular Sieve of hexagonal 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-core construction, the chamber portion of the hollow-core construction Radical length be 5-300 nanometers, and the Titanium Sieve Molecular Sieve is in 25 DEG C, P/P0=0.10, adsorption time is the item of 1 hour (h) The benzene adsorbance measured under part is at least 70 milligrams per grams, the adsorption isotherm and desorption of the nitrogen absorption under low temperature of the Titanium Sieve Molecular Sieve There are hysteresis loops between thermoisopleth.The hollow Titanium Sieve Molecular Sieve is commercially available (such as builds feldspathization stock commercially available from Hunan The molecular sieve that the trade mark of part Co., Ltd is HTS), it can also be prepared according to method disclosed in CN1132699C.
When the Titanium Sieve Molecular Sieve uses template in preparation process, the Titanium Sieve Molecular Sieve can be that experienced to be used for The Titanium Sieve Molecular Sieve of the process (such as roasting process) of removed template method, or do not undergo the process for removed template method The Titanium Sieve Molecular Sieve of (such as roasting process) can also be the mixture of the two.
In step (3), at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the surface of the titanium-silicon molecular sieve TS-1 Silicon titanium ratio is not less than body phase silicon titanium ratio, can obtain the catalytic performance further increased in this way, further extends Titanium Sieve Molecular Sieve The single trip use service life.Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2 or more.It is highly preferred that institute The ratio for stating urface silicon titanium and the body phase silicon titanium ratio is 1.2-5.It is further preferred that the urface silicon titanium and the body Phase silicon titanium than ratio be 1.5-4.5 (such as 2.2-4.5).It is further preferred that the urface silicon titanium and the body phase silicon Titanium than ratio be 2-3, such as 2.2-2.8.
In the present invention, silicon titanium ratio refers to the molar ratio of silica and titanium oxide, and urface silicon titanium uses x-ray photoelectron energy Spectrometry measures, and body phase silicon titanium ratio uses x-ray fluorescence spectrometry.
In step (3), extend from the catalytic performance for further increasing Titanium Sieve Molecular Sieve and further the single trip use service life Angle is set out, and at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, and it includes following step that the titanium-silicon molecular sieve TS-1, which uses, It is prepared by rapid method：
(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 meters are (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, the dispersion liquid is stood to 6-24h at 15-60 DEG C；
(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 cooled in 80-150 DEG C of crystallization 6-72h, stage (2) Not higher than 70 DEG C and after 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 Can be various organic level Four ammonium alkali, the aliphatic amine can be various NH3At least one of hydrogen by aliphatic alkyl (such as Alkyl) compound that is formed after substitution, the aliphatic hydramine can be various NH3At least one of hydrogen by the fat of hydroxyl The compound formed after fat race group (such as alkyl) substitution.
Specifically, the alkali source template can be the aliphatic amine and formula of the quaternary ammonium base, Formula II expression that are indicated 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 tertiary 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, tertiary butyl, n-pentyl, neopentyl, isopentyl, tertiary pentyl or 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 or 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 (include the various isomers of tetrapropylammonium hydroxide, such as four n-propyl ammonium hydroxide and tetra isopropyl Ammonium hydroxide), tetrabutylammonium hydroxide (include the various isomers of tetrabutylammonium hydroxide, such as 4-n-butyl ammonium hydroxide and Four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine One or more of with triethanolamine.Preferably, the alkali source template is tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen Change one or more of ammonium and tetrabutylammonium hydroxide.It is highly preferred that the alkali source template is tetrapropyl hydroxide Ammonium.
The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can Think TiCl4、Ti(SO4)2And TiOCl2One or more of；The organic titanate can be general formula R7 4TiO4Table The compound shown, wherein R7For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom, such as metatitanic acid Four butyl esters.
The inorganic silicon source can be silica gel and/or Ludox, preferably silica gel.SiO in the Ludox2Quality hundred It can be 10% or more to divide content, preferably 15% or more, more preferably 20% or more.It is preparing 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) and stand 6-24h at a temperature of 15-60 DEG C.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.Usually, final to make by the setting steps (II) between step (I) and step (III) The urface silicon titanium of standby Titanium Sieve Molecular Sieve and the ratio of body phase silicon titanium ratio can be in the range of 1.2-5, preferably in 1.5-4.5 In the range of (such as in the range of 2.2-4.5), more preferably in the range of 2-3 (such as in the range of 2.2-2.8).It is described quiet It sets and is more preferably carried out at a temperature of 20-50 DEG C, as carried out at a temperature of 25-45 DEG C.
In step (II), when being stood, dispersion liquid can be placed in sealing container, open container can also be placed in In stood.Preferably, step (II) 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 in.
After the completion of step (II) described standing, directly the dispersion liquid through standing can be sent into reaction kettle and carry out crystallization, Crystallization can also be carried out by being sent into reaction kettle after the dispersion liquid of standing carries out redisperse, be sent into instead after preferably carrying out redisperse It answers in kettle, the dispersing uniformity for the dispersion liquid for carrying out crystallization can be further increased in this way.The method of the redisperse can be normal The combination of one or more of rule method, such as stirring, supersound process 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, more preferably 120-140 DEG C, further Preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.The stage temperature of (2) is preferably Not higher than 50 DEG C.The residence time in stage (2) is preferably at least 1h, more preferably 1-5h.The stage crystallization temperature of (3) is preferably 140-180 DEG C, more preferably 160-170 DEG C.The crystallization time in stage (3) is preferably 12-20h, more preferably 12-16h.
In step (III), in a preferred embodiment, the crystallization temperature in stage (1) is less than the crystallization in stage (3) Temperature can further increase 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 lower 20-40 than the crystallization temperature in stage (3) ℃.In step (III), in another preferred embodiment, when the crystallization time in stage (1) is less than the crystallization in stage (3) Between, the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared can be further increased 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 shorter 6- than the crystallization time in stage (3) 12h, such as short 6-8h.In step (III), both preferred embodiments may be used alone, can also be used in combination, preferably It is applied in combination, i.e., the crystallization temperature and crystallization time in stage (1) and stage (3) meet wanting for both preferred embodiments simultaneously It asks.
In step (III), in another preferred embodiment, the temperature in stage (2) is and to be stopped not higher than 50 DEG C Time is at least 0.5h, such as 0.5-6h, can further increase the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.It is preferred that The residence time on ground, stage (2) is 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.
Conventional method may be used and recycle Titanium Sieve Molecular Sieve from the mixture that step (III) crystallization obtains.Specifically, may be used After being optionally filtered and wash 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.Usually, the drying can be with It is carried out at a temperature of environment temperature (such as 15 DEG C) is to 200 DEG C.The drying can be in environmental pressure (generally 1 normal atmosphere Pressure) under carry out, can also carry out at reduced pressure.The duration of the drying can be according to dry temperature and pressure And dry mode is selected, and is not particularly limited.For example, when the drying carries out under ambient pressure, temperature is excellent 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 Burning can carry out at a temperature of 300-800 DEG C, 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 carried out at a temperature of 550-600 DEG C.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.
In step (3), at least partly Titanium Sieve Molecular Sieve is preferably modified Titanium Sieve Molecular Sieve, the titanium silicon molecule of the modification Sieve experience modification, can more effectively promote the catalytic performance of Titanium Sieve Molecular Sieve, further extend Titanium Sieve Molecular Sieve in this way The single trip use service life, further decrease the regeneration frequency of Titanium Sieve Molecular Sieve.The modification includes the following steps：By conduct The Titanium Sieve Molecular Sieve of raw material with containing nitric acid (that is, HNO3) and at least one peroxide modification liquid contact.The raw material titanium Si molecular sieves refer to the Titanium Sieve Molecular Sieve of the raw material as modification, can be without going through the titanium silicon of the modification point Son sieve, or live through the modification but need to carry out the Titanium Sieve Molecular Sieve of the modification again.This hair The Titanium Sieve Molecular Sieve that above-mentioned modification is lived through in bright is known as modified Titanium Sieve Molecular Sieve, does not live through above-mentioned modification Titanium Sieve Molecular Sieve is known as unmodified Titanium Sieve Molecular Sieve.Can whole Titanium Sieve Molecular Sieve live through above-mentioned modification, also may be used Think the mixture of modified Titanium Sieve Molecular Sieve and unmodified Titanium Sieve Molecular Sieve.Preferably, with the total of the Titanium Sieve Molecular Sieve On the basis of amount, the Titanium Sieve Molecular Sieve of at least 50 weight % or more lives through the modification, more preferably at least 60 weight % with On Titanium Sieve Molecular Sieve live through the modification, as the Titanium Sieve Molecular Sieve of 50-90 weight % lives through the modification.
In the modification, peroxide can be one kind in hydrogen peroxide, hydroperoxides and peracid or It is two or more.In the modification, the specific example of the peroxide can include but is not limited to：Hydrogen peroxide, second In benzene hydrogen peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid One or more.Preferably, the oxidant is hydrogen peroxide.The hydrogen peroxide can be it is commonly used in the art with Hydrogen peroxide existing for various forms.
Can be 1 as the Titanium Sieve Molecular Sieve of raw material and the molar ratio of the peroxide in the modification： 0.01-5, preferably 1：0.05-3, more preferably 1：0.1-2.The dosage of the nitric acid can be according to the use of the peroxide Amount is selected.Usually, the molar ratio of the peroxide and the nitric acid can be 1：0.01-50, preferably 1：0.1- 20, more preferably 1：0.2-10, further preferably 1：0.3-5, particularly preferably 1：0.5-3.5, such as 1：0.6-3, the titanium Si molecular sieves are in terms of silica.
In the modification liquid, the concentration of peroxide and nitric acid can be respectively 0.1-50 weight %.From further increasing The angle of the catalytic performance of the Titanium Sieve Molecular Sieve of the modification finally prepared is set out, preferably 0.5-25 weight %.It is highly preferred that institute It states in modification liquid, the concentration of peroxide and nitric acid is respectively 1-20 weight %.It is further preferred that in the modification liquid, mistake The concentration of oxide and nitric acid is respectively 2-15 weight %.In one embodiment, a concentration of 2-10 weights of peroxide Measure % (such as 2-8 weight %), a concentration of 10-15 weight % of nitric acid.
The solvent of the modification liquid can be the common various solvents that can dissolve nitric acid and the peroxide simultaneously.It is excellent The solvent of selection of land, the modification liquid is water.
In the modification, as raw material Titanium Sieve Molecular Sieve and modification liquid can at a temperature of 10-350 DEG C 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 the contact carries out at a temperature of 50-250 DEG C.It is further excellent Selection of land, the contact are carried out at a temperature of 60-200 DEG C, are such as contacted at a temperature of 70-170 DEG C.At the modification It, can be according to Contact Temperature by the pressure in the container contacted with the modification liquid as the Titanium Sieve Molecular Sieve of raw material in reason It is selected, can be environmental pressure, or pressurization.It usually, will be as the Titanium Sieve Molecular Sieve of raw material and the modification The pressure in container that liquid is contacted can be 0-5MPa.It preferably, under pressure will be as the titanium silicon of raw material point Son sieve is contacted with the modification liquid.It is highly preferred that by the Titanium Sieve Molecular Sieve as raw material under self-generated pressure in closed container It is contacted with the modification liquid.The duration that Titanium Sieve Molecular Sieve as raw material is contacted with the modification liquid can be 0.5- 10h, preferably 2-5h.
In the modification, as the Titanium Sieve Molecular Sieve of raw material and the exposure level of the modification liquid preferably so that, Using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, modified Titanium Sieve Molecular Sieve 230-310nm it Between the peak area of absorption peak reduce by 2% or more, the hole of modified Titanium Sieve Molecular Sieve, which holds, reduces 1% or more.Modified titanium silicon point The peak area of absorption peak of the son sieve between 230-310nm preferably reduces 2-30%, more preferably reduces 2.5-15%, further excellent Choosing reduces 3-10%, still more preferably reduces 3-8%, such as 3-6%.The hole of modified Titanium Sieve Molecular Sieve holds preferred reduction 1- 20%, 2-10% is more preferably reduced, 2.5-5%, such as 2.5-4.5% are further preferably reduced.The Kong Rong is inhaled using static nitrogen Attached method measures.
Using Titanium Sieve Molecular Sieve as in the various commercial plants of catalyst, as Ammoximation reaction device, hydroxylating are anti- It answers in device and epoxidation reaction device, usually after device runs a period of time, the catalytic activity of catalyst declines, and needs It carries out in device or even if ex-situ regeneration is needed catalyst when carrying out regenerating the activity for also being difficult to obtain satisfaction from device It draws off (that is, more catalyst changeout), and catalyst (that is, drawing off agent or dead catalyst) the current processing method drawn off is typically heap Product is buried, and on the one hand occupies valuable land resource and inventory space, another aspect Titanium Sieve Molecular Sieve production cost is higher, directly It connects to pass into disuse and also results in great waste.The present inventor has found in the course of the research, if these are drawn off agent (that is, the Titanium Sieve Molecular Sieve drawn off) is used for after being regenerated in step (3) oxidation reaction, remains able to obtain preferable catalytic Can, while during long-time continuous operation, showing better activity stability.Therefore, in step (3), at least partly The Titanium Sieve Molecular Sieve is preferably through regenerated reaction unit (the sulphur removal ether oxidation unit using Titanium Sieve Molecular Sieve as catalyst Outside) draw off agent.It is described draw off agent can be from various using Titanium Sieve Molecular Sieve as the reaction unit of catalyst in draw off Agent is drawn off, such as agent can be drawn off for what is drawn off from oxidation reaction apparatus.Specifically, described to draw off agent as Ammoximation reaction dress Set draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off one or more of agent. More specifically, it is described draw off agent can be cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit unloads Go out agent and propylene ring oxidation reaction device draws off one or more of agent.
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.Preferably, agent will be drawn off to carry out high-temperature roasting and regenerate.The high temperature Roasting can carry out under the conditions of conventional oxidizing roasting, be not particularly limited.Specifically, the high-temperature roasting can be in 400- 800 DEG C, preferably 450-700 DEG C, it is 500-650 DEG C more preferable, 550-600 DEG C further preferred at a temperature of carry out, the high temperature The duration of roasting can be 1-12h, preferably 1.5-8h, more preferably 3-6h.The high-temperature roasting is usually in air gas It is carried out in atmosphere.
It is different according to its source through the regenerated activity for drawing off agent.Usually, through the regenerated activity for drawing off agent 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 20-70%, be still more preferably active 25-60% when fresh, particularly preferably when fresh Active 30-50%.When being active 30-50% of Titanium Sieve Molecular Sieve when fresh through the regenerated activity for drawing off agent, During long-time continuous operation, better activity stability is shown.Preferably, it is being through the regenerated activity for drawing off agent Active 35-45% of Titanium Sieve Molecular Sieve when fresh.The activity of the fresh Titanium Sieve Molecular Sieve is generally 90% or more, leads to It is often 95% or more.
The activity measures by the following method：It respectively will be through regenerated agent and the fresh Titanium Sieve Molecular Sieve of drawing off as hexamethylene The catalyst of ketone oxamidinating reaction, the condition of the Ammoximation reaction are：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 in mass ratio 1：7.5：10：7.5：10, at atmosheric pressure 2h is reacted in 80 DEG C.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 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 that agent is drawn off through regenerated reaction unit is preferably 5 weight % or more.In step (3), even if whole titanium silicon point When son sieves to draw off agent (that is, the content for drawing off agent through regenerated reaction unit is 100 weight %) through regenerated reaction unit, It remains able to obtain preferable catalytic effect.
In step (3), above-mentioned warp is particularly preferably as the Titanium Sieve Molecular Sieve of raw material in the Titanium Sieve Molecular Sieve of the modification It is regenerated to draw off agent.With will through it is regenerated draw off agent directly as catalyst compared with, by it is described through it is regenerated draw off agent carry out institute Modification is stated, can be further increased through the regenerated single trip use service life for drawing off agent, it is often more important that, it can significantly improve described Through the regenerated desirable oxidation selectivity of product for drawing off agent and feed stock conversion.
In step (3), the Titanium Sieve Molecular Sieve and the contact form of the reaction mixture are not particularly limited, and can incite somebody to action Titanium Sieve Molecular Sieve is seated in the catalyst bed of reactor, and the reaction mixture is made to pass through the catalyst bed, to It realizes in the presence of Titanium Sieve Molecular Sieve, by thioether and oxidant haptoreaction；It can also be by the reaction mixture and titanium silicon point Son sieve is mixed to form slurry, to realize in the presence of Titanium Sieve Molecular Sieve, by thioether and oxidant haptoreaction.
When the reaction mixture and Titanium Sieve Molecular Sieve are mixed to form slurry, may be used after the completion of haptoreaction each Slurry is carried out solid-liquor separation by kind method, to obtain the liquid material containing desirable oxidation product.Such as：Film point can be passed through The liquid material is subjected to solid-liquor separation from device.
When the Titanium Sieve Molecular Sieve to be seated in catalyst bed, the quantity of the catalyst bed can be one Or it is multiple.When the quantity of catalyst bed is multiple, it can be the different zones positioned at a reactor, can also be located at more In a reactor.
In step (3), the catalyst bed can only load Titanium Sieve Molecular Sieve, can also contain Titanium Sieve Molecular Sieve and non- Active filler.Inactive filler is loaded in catalyst bed to adjust the amount of Titanium Sieve Molecular Sieve in catalyst bed It is whole, to which the speed of reaction be adjusted.When the catalyst bed contains Titanium Sieve Molecular Sieve and inactive filler, catalysis The content of inactive filler can be 5-95 weight % in agent bed.The inactive filler refers to no to oxidation reaction or base Originally the filler of catalytic activity, specific example not can include but is not limited to：One in quartz sand, ceramic ring and potsherd Kind is two or more.
In step (3), the Titanium Sieve Molecular Sieve can be Titanium Sieve Molecular Sieve original powder, or molding Titanium Sieve Molecular Sieve, Preferably it is molded Titanium Sieve Molecular Sieve.Molding Titanium Sieve Molecular Sieve is typically contained as the Titanium Sieve Molecular Sieve of active constituent and as bonding The carrier of agent, wherein the content of Titanium Sieve Molecular Sieve can be conventional selection.Usually, with the total of the molding Titanium Sieve Molecular Sieve On the basis of amount, the content of Titanium Sieve Molecular Sieve can be 5-95 weight %, preferably 10-95 weight %, more preferably 70-95 weight Measure %, further preferably 75-90 weight %；The content of the carrier can be 5-95 weight %, preferably 5-90 weight %, More preferably 5-30 weight %, further preferably 10-25 weight %.The carrier of the molding Titanium Sieve Molecular Sieve can be conventional Selection, such as aluminium oxide and/or silica.The method for preparing the molding Titanium Sieve Molecular Sieve is it is known in the art, herein not It is described in detail again.The granular size of the molding Titanium Sieve Molecular Sieve is also not particularly limited, and can be carried out according to concrete shape appropriate Selection.Specifically, it is described molding Titanium Sieve Molecular Sieve average grain diameter can be 4-10000 microns, preferably 5-5000 microns, more Preferably 40-4000 microns, further preferably 50-1000 microns, such as 100-500 microns.The average grain diameter is flat for volume Laser particle analyzer measurement may be used in equal grain size.
In step (3), for the Titanium Sieve Molecular Sieve as catalyst, dosage, which is subject to, can realize catalysis, not have It is particularly limited to.It can generally be selected according to Titanium Sieve Molecular Sieve and the contact form of the reaction mixture.For example, by titanium When si molecular sieves are mixed to form slurry with the reaction mixture, the weight ratio of dimethyl sulfide and Titanium Sieve Molecular Sieve can be 0.1-50：1, preferably 1-50：1, such as 1-25：1；When Titanium Sieve Molecular Sieve is seated in catalyst bed, dimethyl sulfide Weight space velocity can be 1-200h-1, preferably 10-150h-1, more preferably 50-120h-1.In the present invention, weight space velocity with In whole catalyst beds on the basis of the total amount of Titanium Sieve Molecular Sieve.
In step (3), the liquid phase stream that step (2) obtains is contacted with oxidant with Titanium Sieve Molecular Sieve, step (2) obtains Liquid phase stream be also possible to while containing dimethyl sulfide containing unreacted methanol in step (1), this part methanol can Using the reaction dissolvent as step (3) oxidation reaction.In one embodiment, step (3) no longer additionally adds solvent.
In another embodiment, step (3) further includes that at least one supplement is added into the liquid phase that step (2) obtains Solvent in this way can be adjusted the speed of reaction, keep reaction more steady.That is, the liquid phase stream that step (2) is obtained and Supplementing solvent is contacted with oxidant and Titanium Sieve Molecular Sieve.The supplementing solvent can be it is various can either dissolve dimethyl sulfide and Oxidant promotes the two mixing, and can dissolve the liquid substance of dimethyl sulfoxide (DMSO).Usually, the supplementing solvent can be Selected from water, C1-C6Alcohol, C3-C8Ketone and C2-C6One or more of nitrile.The specific example of the supplementing solvent It can include but is not limited to：In water, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile It is one or more kinds of.
The dosage of the supplementing solvent can make appropriate choice according to the dosage of dimethyl sulfide and oxidant.Generally The molar ratio on ground, the supplementing solvent and the dimethyl sulfide can be 1-200：1, preferably 10-100：1.
In step (3), the temperature of the oxidation reaction can be 0-100 DEG C, preferably 20-80 DEG C, more preferably 30-60 ℃.In terms of gauge pressure, the pressure of the oxidation reaction can be 0-3MPa, preferably 0.1-2.5MPa, more preferably 0.1- 0.3MPa。
With the method for the invention it is preferred to further include step (4)：Mixture containing dimethyl sulfoxide (DMSO) is detached, Obtain the dimethyl sulfoxide (DMSO) that dimethyl sulfide and dimethyl disulfide ether content reduce.
Various methods may be used and isolate unreacted dimethyl sulfide from reaction mixture, such as：It can incite somebody to action To reaction mixture flashed, so that dimethyl sulfide therein be separated.
According to the method for the present invention, dimethyl disulfide ether content reduce dimethyl sulfoxide (DMSO) mainly contain dimethyl sulfoxide (DMSO) and Optional methanol and optional supplementing solvent, can further detach the dimethyl sulfoxide (DMSO) that dimethyl disulfide ether content reduces (for example, distillation), to isolate optional methanol and optional supplementing solvent.The methanol isolated can recycle feeding Step is used to prepare dimethyl sulfide in (1), can also be sent into the solvent as oxidation reaction in step (3)；The benefit isolated The middle solvent as oxidation reaction of step (3) can be sent by filling solvent.
With the method for the invention it is preferred to further include step (5)：The dimethyl sulfide cycle that step (4) is isolated is sent Enter in step (3).
According to the method for the present invention, the effective rate of utilization of peroxide is high and the selectivity of product is good, from reaction mixture In the purity of unreacted dimethyl sulfide isolated it is higher, can be sent directly into step (3) without further purifying It recycles, is not less than the occasion of 1 (as being higher than 1) particularly suitable for the molar ratio of dimethyl sulfide and peroxide.
Fig. 1 shows a kind of preferred embodiment according to the method for the present invention, below in conjunction with Fig. 1 to the preferred reality The mode of applying is described in detail.
It reacts, is obtained containing diformazan as shown in Figure 1, hydrogen sulfide 1 and methanol 2 are sent into thioether reaction of formation device A The mixture 3 of base thioether；The mixture 3 for containing dimethyl sulfide is sent into gas-liquid separator B, gaseous stream is separated into 4, and the liquid phase stream 5 containing dimethyl sulfide.When gaseous stream 4 contains unreacted hydrogen sulfide, as shown in Figure 1, excellent Choosing will at least partly gaseous stream 4 be re-fed into thioether reaction of formation device A, be used to prepare dimethyl sulfide.By liquid phase stream 5 It is sent into oxidation reactor C and is contacted with the catalyst containing Titanium Sieve Molecular Sieve with oxidant 6 and optional supplementing solvent 7, with Dimethyl sulfoxide (DMSO) is obtained, and the obtained product stream 8 containing dimethyl sulfoxide (DMSO) is sent into flash column D and is flashed, is obtained The liquid product logistics 9 and unreacted dimethyl sulfide 10 containing dimethyl sulfoxide (DMSO) that dimethyl disulfide ether content reduces.It will The cycle of unreacted dimethyl sulfide 10 is sent into oxidation reactor C, dimethyl disulfide ether content is reduced sub- containing dimethyl The liquid product logistics 9 of sulfone, which is sent into subsequent separation process, further to be detached, and dimethyl sulfoxide (DMSO) and optional is obtained Methanol and optional supplementing solvent, the methanol can be sent into thioether reaction of formation device A, and oxidation reactor C can also be sent into In, the supplementing solvent, which can recycle, to be sent into oxidation reactor C.
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 commercially available analytical reagents, and pressure is in terms of gauge pressure.
In following embodiment and comparative example, each ingredient contains in the product mixtures analyzed using gas-chromatography Following formula is respectively adopted to calculate dimethyl sulfide conversion ratio and dimethyl sulfoxide (DMSO) selectivity in amount on this basis：
XThioether=[(mo Thioether-mThioether)/mo Thioether] × 100% (IV)
In formula IV, XThioetherIndicate the conversion ratio of dimethyl sulfide；
mo ThioetherIndicate the quality for the dimethyl sulfide being added；
mThioetherIndicate the quality of unreacted dimethyl sulfide.
SSulfoxide=[nSulfoxide/(no Thioether-nThioether)] × 100% (V)
In Formula V, SSulfoxideIndicate the selectivity of dimethyl sulfoxide (DMSO)；
no ThioetherIndicate the mole for the dimethyl sulfide being added；
nThioetherIndicate the mole of unreacted dimethyl sulfide；
nSulfoxideIndicate the mole of obtained dimethyl sulfoxide (DMSO).
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 spectrometers；Static nitrogen is adsorbed on It is carried out on the 2405 type static state n2 absorption apparatus of ASAP of Micromeritics companies.
It is related to below through in the regenerated embodiment and comparative example for drawing off agent, Titanium Sieve Molecular Sieve is determined using following methods The activity of (including regenerative agent and fresh dose)：
By Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH3Meter), the hydrogen peroxide of 30 weight % is (with H2O2Meter), the tert-butyl alcohol With cyclohexanone by weight=1：7.5：10：7.5：It will be reacted after 80 DEG C are stirred to react 2h at atmosheric pressure after 10 mixing Object filters, and is analyzed liquid phase with gas-chromatography, calculates the conversion ratio of cyclohexanone using following formula and as titanium silicon The activity of molecular sieve,
The conversion ratio of cyclohexanone=[(the unreacted cyclohexanone mole of mole-of the cyclohexanone of addition)/it is added The mole of cyclohexanone] × 100%.
In the embodiment and comparative example of the step of preparing Titanium Sieve Molecular Sieve included below, X-ray diffraction analysis exists It is carried out on Siemens D5005 type X-ray diffractometers, the five fingers spread out between being 22.5 ° -25.0 ° in 2 θ with sample and authentic specimen The crystallinity for penetrating the ratio of the sum of diffracted intensity (peak height) of characteristic peak to indicate sample relative to authentic specimen；Fourier transform Infrared spectrum analysis carries out on 8210 type Fourier transformation infrared spectrometers of Nicolet；Silicon titanium ratio refers to silica and oxidation The molar ratio of titanium, urface silicon titanium use the ESCALab250 type x-ray photoelectron spectroscopies of Thermo Scientific companies It measures, body phase silicon titanium ratio is measured using Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometers.
Embodiment 1-26 is for illustrating the present invention.
Embodiment 1
(1) dimethyl sulfide is prepared
It is 1 by molar ratio under 380 DEG C and 0.5MPa：1 hydrogen sulfide (NH3Mass content be 1.2%) and methanol and γ-Al as catalyst2O3Hybrid reaction obtains the mixture containing dimethyl sulfide, wherein the weight of catalyst and methanol Amount is than being 15：1.
(2) gas-liquid separation
The mixture containing dimethyl sulfide that step (1) obtains is condensed, gaseous stream and liquid phase stream are obtained, Gaseous stream cycle is used to prepare dimethyl sulfide.
(3) oxidation reaction
The titanium-silicon molecular sieve TS-1 that is used in step (3) is with reference to Zeolites, 1992, Vol.12 institutes in the 943-950 pages Prepared by the method for description, the specific method is as follows.
(20 DEG C) at room temperature mix 22.5g tetraethyl orthosilicates 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 the hydrating solution by 1.1g butyl titanates and 5.0g anhydrous isopropyl alcohols institute Gained mixture is stirred 3h at 75 DEG C, obtains clear colloid by the solution of composition.It is anti-that this colloid is placed in stainless steel sealing It answers in kettle, constant temperature places 36h at a temperature of 170 DEG C, obtains 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, 6h is then roasted at 500 DEG C, to obtain Titanium Sieve Molecular Sieve TS-1, titanium oxide content are 2.8 weight %.
The titanium-silicon molecular sieve TS-1 of preparation is molded using following methods, to obtain the catalyst that step (3) uses.
Titanium-silicon molecular sieve TS-1 is uniformly mixed with Ludox (silica content is 30 weight %) and water, wherein titanium silicon The weight ratio of molecular sieve TS-1, the Ludox in terms of silica and water is 1：0.2：1.5.Obtained mixture is made through spin Grain, and obtained wet grain is roasted into 8h at 590 DEG C, to obtain the catalyst that volume average particle size is 320 μm.In catalyst, The content of titanium-silicon molecular sieve TS-1 is 80 weight %.
By Catalyst packing in fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed is 1 The ratio of height to diameter of layer, catalyst bed is 10.
By the isolated liquid phase stream of step (2) with the hydrogen peroxide as oxidant (with concentration of hydrogen peroxide for 30 The form of the hydrogen peroxide of weight % provides) and methanol as supplementing solvent be sent into together from the bottom of fixed bed reactors, Flow up with the catalyst haptoreaction that is seated in fixed bed reactors, obtain the reaction mixing containing dimethyl sulfoxide (DMSO) Object.Wherein, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1：0.5, the molar ratio of dimethyl sulfide and supplementing solvent is 1： 15, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 80h-1；Reaction temperature is 35 DEG C, and the pressure in reactor is 0.1MPa.Reaction process In, it is monitored and calculates thioether rate to the composition of the reaction mixture of fixed bed reactors output and dimethyl sulfoxide (DMSO) selects Selecting property, the result obtained at differential responses time point are listed in table 1.
(4) product detaches
The reaction mixture that step (3) obtains is flashed, unreacted dimethyl sulfide is obtained and contains diformazan Unreacted dimethyl sulfide is recycled and is sent into step (3) by the product stream of base sulfoxide.
Embodiment 2
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 1, unlike, the titanium-silicon molecular sieve TS-1 of preparation exists It is modified (that is, the Titanium Sieve Molecular Sieve that will be prepared using method same as Example 1 using following methods before being molded TS-1 is modified processing as raw material), and the titanium-silicon molecular sieve TS-1 of obtained modification is used into side same as Example 1 Method is molded, to obtain the catalyst that the present embodiment uses.
By the titanium-silicon molecular sieve TS-1 of preparation and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (peroxide be The mass concentration for changing hydrogen is aqueous solution mixing 7.5%), and obtained mixture is stirred to react in closed container at 70 DEG C 5h, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dried at 120 DEG C to perseverance 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 1：0.1.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 3.5%, is held by the hole of static determination of nitrogen adsorption and reduces 2.6%.Step (3) Reaction process in, the result obtained at differential responses time point is listed in table 1.
Embodiment 3
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 2, unlike, prepare titanium silicon point using following methods Son sieve TS-1.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source：Titanium source：Alkali source template：The molar ratio of water is 100：4：12： 400, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is sealed in beaker using sealed membrane It is stood for 24 hours in room temperature (being 25 DEG C, similarly hereinafter) after mouthful, is stirred 2h at 35 DEG C followed by magnetic agitation, is allowed to disperse again. Again the dispersion liquid after disperseing is transferred in sealing reaction kettle, first stage crystallization 6h is undergone at 140 DEG C, then by mixture After being cooled to 30 DEG C of experience second stage stop 2h, continuation undergoes the phase III at a temperature of in sealing reaction kettle in 170 DEG C Crystallization 12h (is wherein, 2 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first stage crystallization temperature The rate of temperature fall for spending second stage treatment temperature is 5 DEG C/min, by second stage treatment temperature to phase III crystallization temperature Heating rate be 10 DEG C/min), will gained crystallization product take out after without filtering and washing step, directly in 110 DEG C drying Then 2h roasts 3h at 550 DEG C, obtain molecular sieve.The titanium that the XRD crystalline phase figures of gained sample are prepared with 1 step of embodiment (3) Silicalite TS-1 is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier Transform Infrared Spectroscopy figure In, in 960cm-1Nearby there is absorption peak, show that titanium has been enter into 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.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 4
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 3, unlike, in step (2), preparing titanium silicon point When son sieve TS-1, the crystallization temperature of phase III is also 140 DEG C.The XRD crystalline phase figures of gained sample are made with 1 step of embodiment (3) Standby titanium-silicon molecular sieve TS-1 is consistent, and what is illustrated is the TS-1 molecular sieves with MFI structure；Fourier-transform infrared spectrogram In in 960cm-1Nearby there is absorption peak, shows that titanium has been enter into 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 %.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 5
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 3, unlike, in step (2), preparing titanium silicon point When son sieve TS-1, the crystallization temperature of first stage is 110 DEG C.The XRD crystalline phase figures of gained sample are prepared with 1 step of embodiment (3) Titanium-silicon molecular sieve TS-1 it is consistent, what is illustrated is the TS-1 molecular sieves with MFI structure；In fourier-transform infrared spectrogram In 960cm-1Nearby there is absorption peak, shows that titanium has been enter into 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 %.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 6
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 3, unlike, the crystallization time of first stage is 12h.The XRD crystalline phase figures of gained sample are consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (3), and what is illustrated is TS-1 molecular sieves 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 3.78, and titanium oxide content is 3.4 weights Measure %.In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 7
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 3, unlike, in step (2), second stage is drop Temperature to 70 DEG C stop 2h.The XRD crystalline phase figures of gained sample are consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (3), say It is bright that obtain is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absorption peak, Show that titanium has been enter into framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.75, titanium oxide content For 3.1 weight %.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 8
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 3, unlike, in step (2), second stage is drop Temperature to 30 DEG C stop 0.2h.The XRD crystalline phase figures of gained sample are consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (3), What is illustrated is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby absorb Peak shows that titanium has been enter into framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.14, and titanium oxide contains Amount is 2.4 weight %.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 9
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 3, unlike, preparing titanium-silicon molecular sieve TS-1 When, in step (2), without second stage.The titanium silicon molecule that the XRD crystalline phase figures of gained sample are prepared with 1 step of embodiment (3) Sieve TS-1 is consistent, and what is illustrated is the TS-1 molecular sieves with MFI structure；In 960cm in fourier-transform infrared spectrogram-1It is attached Closely there is absorption peak, show that titanium has been enter into framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.08, titanium oxide content is 2.5 weight %.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 10
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 3, unlike, in step (2), aqueous dispersions do not exist It stands at room temperature for 24 hours, but is sent directly into reaction kettle and carries out crystallization.The XRD crystalline phase figures of gained sample and 1 step of embodiment (3) titanium-silicon molecular sieve TS-1 prepared is consistent, and what is illustrated is the TS-1 molecular sieves with MFI structure；Fourier transform is red In 960cm in outer spectrogram-1Nearby there is absorption peak, shows that titanium has been enter into framework of molecular sieve, urface silicon titanium/body phase silicon titanium ratio is 1.18, in the Titanium Sieve Molecular Sieve, titanium oxide content is 3.5 weight %.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 11
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 2, unlike, the titanium of the raw material as modification Si molecular sieves are titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1s through being drawn off in the regenerated reaction unit from phenol hydroxylation It is prepared using method same as Example 1, the Titanium Sieve Molecular Sieve drawn off roasts 5h at a temperature of 570 DEG C in air atmosphere And regenerate, the activity after regeneration is 35%, 96%) activity when fresh is.Compared with raw material Titanium Sieve Molecular Sieve, obtained modification Titanium Sieve Molecular Sieve UV-Vis spectrum in the peak area of absorption peak between 230-310nm reduce 3.3%, inhaled by static nitrogen The hole that attached method measures, which holds, reduces 2.8%.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 12
Dimethyl sulfoxide (DMSO) is prepared using method identical with embodiment 11, unlike, catalyst is directly will be through regeneration Slave phenol hydroxylation reaction unit in the titanium-silicon molecular sieve TS-1 that draws off be molded (with embodiment 11).
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 1.
Embodiment 13
Dimethyl sulfoxide (DMSO) is prepared using method same as Example 1, unlike, the hydrogen sulfide of use in step (1) Middle NH3Mass content be 50ppm.In the reaction process of step (3), the result obtained at differential responses time point is in table 1 In list.
Table 1
Embodiment 14
(1) dimethyl sulfide is prepared
It is 2 by molar ratio under 320 DEG C and 0.3MPa：1 hydrogen sulfide (NH3Mass content be 2.6%) and methanol and γ-Al as catalyst2O3Hybrid reaction obtains the mixture containing dimethyl sulfide, wherein the weight of catalyst and methanol Amount is than being 20：1.
(2) gas-liquid separation
The mixture containing dimethyl sulfide that step (1) obtains is condensed, gaseous stream and liquid phase stream are obtained, Gaseous stream cycle is used to prepare dimethyl sulfide.
(3) oxidation reaction
(trade mark of Hunan Jianchang Petrochemical Co., Ltd will be purchased from as the Titanium Sieve Molecular Sieve of raw material using following methods For the hollow Titanium Sieve Molecular Sieve of HTS, titanium oxide content is 2.5 weight %) it is modified processing.
By hollow Titanium Sieve Molecular Sieve and contain HNO3(HNO3Mass concentration be 10%) and hydrogen peroxide (hydrogen peroxide Mass concentration is aqueous solution mixing 5%), and obtained mixture is stirred instead in closed container under 120 DEG C of pressure itselfs 4h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dried at 120 DEG C to perseverance Weight, obtains modified Titanium Sieve Molecular Sieve.Wherein, hollow Titanium Sieve Molecular Sieve is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub You are than being 1：0.4.Compared with raw material Titanium Sieve Molecular Sieve, in 230- in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 310nm reduces 4.6%, is held by the hole of static determination of nitrogen adsorption and reduces 3.8%.
The hollow Titanium Sieve Molecular Sieve of the modification of preparation is molded using following methods, obtains the catalysis that the present embodiment uses Agent.
Modified Titanium Sieve Molecular Sieve is uniformly mixed with Ludox (silica content is 30 weight %) and water, wherein titanium The weight ratio of silicalite TS-1, the Ludox in terms of silica and water is 1：0.1：8.Obtained mixture is made through spin Grain, and obtained wet grain is roasted into 8h at 460 DEG C, to obtain the catalyst that average grain diameter is 100 μm.Wherein, in catalyst, The content of hollow Titanium Sieve Molecular Sieve is 90 weight %.
By Catalyst packing in fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed is 1 The ratio of height to diameter of layer, catalyst bed is 10.
By the isolated liquid phase stream of step (2) with the hydrogen peroxide as oxidant (with concentration of hydrogen peroxide for 40 The form of the hydrogen peroxide of weight % provides) and acetone as supplementing solvent be sent into together from the bottom of fixed bed reactors, Flow up with the catalyst haptoreaction that is seated in fixed bed reactors, obtain the reaction mixing containing dimethyl sulfoxide (DMSO) Object.Wherein, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1：0.8, the molar ratio of dimethyl sulfide and supplementing solvent is 1： 20, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 120h-1；Reaction temperature is 30 DEG C, and the pressure in reactor is 0.15MPa.It reacted Cheng Zhong is monitored the composition of the reaction mixture of fixed bed reactors output and calculates thioether rate and dimethyl sulfoxide (DMSO) Selectively, the result obtained when differential responses time point is listed in table 2.
(4) product detaches
The reaction mixture that step (3) obtains is flashed, unreacted dimethyl sulfide is obtained and contains diformazan Unreacted dimethyl sulfide is recycled and is sent into step (3) by the product stream of base sulfoxide.
Embodiment 15
Dimethyl sulfone is prepared using method identical with embodiment 14, unlike, as the sky of raw material in modification Heart Titanium Sieve Molecular Sieve is hollow Titanium Sieve Molecular Sieve (hollow titanium silicon through being drawn off in the regenerated reaction unit from cyclohexanone oxamidinating Molecular sieve is identical as the source of hollow Titanium Sieve Molecular Sieve of raw material of modification as embodiment 14, the hollow titanium silicon drawn off point Son sieve roasts 6h in air atmosphere at a temperature of 550 DEG C and regenerates, and the activity after regeneration is 40%, and activity when fresh is 97%).Compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification 230-310nm it Between absorption peak peak area reduce 4.8%, by static determination of nitrogen adsorption hole hold reduce 3.5%.
The hollow Titanium Sieve Molecular Sieve of obtained modification is molded using method identical with embodiment 14, to this reality Apply the catalyst that example uses.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 2.
Embodiment 16
Dimethyl sulfone is prepared using method identical with embodiment 14, unlike, through regenerated from cyclohexanone oxamidinating The hollow Titanium Sieve Molecular Sieve drawn off in reaction unit is directly molded without modification, to prepare catalyst.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 2.
Table 2
Embodiment 17
(1) dimethyl sulfide is prepared
It is 1.5 by molar ratio under 280 DEG C and 0.2MPa：1 hydrogen sulfide (NH3Mass content 1.8%) and methanol be With the γ-Al as catalyst2O3Hybrid reaction obtains the mixture containing dimethyl sulfide, wherein catalyst and methanol Weight ratio is 10：1.
(2) gas-liquid separation
The mixture containing dimethyl sulfide that step (1) obtains is condensed, gaseous stream and liquid phase stream are obtained, Gaseous stream cycle is used to prepare dimethyl sulfide.
(3) oxidation reaction
Titanium-silicon 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 100：2：10： 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 and stands 10h at 40 DEG C, be stirred 0.5h at 25 DEG C followed by magnetic agitation, be allowed to disperse again.It will disperse again Dispersion liquid afterwards is transferred in sealing reaction kettle, and first stage crystallization 8h is undergone at 130 DEG C, mixture is then cooled to 50 DEG C After undergoing second stage stop 5h, continues the temperature in 170 DEG C in sealing reaction kettle and undergo phase III crystallization 16h (wherein, It is 1 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first stage crystallization temperature to second stage The rate of temperature fall for the treatment of temperature is 10 DEG C/min, and the heating rate by second stage treatment temperature to phase III crystallization temperature is 20 DEG C/min), without filtering and washing step after gained crystallization product is taken out, 3h directly is dried in 120 DEG C, then 580 DEG C roasting 2h, obtain molecular sieve.The titanium-silicon molecular sieve TS-1 one that the XRD crystalline phase figures of gained sample are prepared with 1 step of embodiment (3) It causes, what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；In Fourier Transform Infrared Spectroscopy figure, in 960cm-1It is attached Closely there is absorption peak, show that titanium has been enter into framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.25, titanium oxide content is 2.6 weight %.
The titanium-silicon molecular sieve TS-1 of preparation is molded using following methods, obtains the catalyst that the present embodiment uses.
The titanium-silicon molecular sieve TS-1 of preparation is uniformly mixed with Ludox (silica content is 30 weight %) and water, In, the weight ratio of hollow Titanium Sieve Molecular Sieve, the Ludox in terms of silica and water is 1：0.25：20.Obtained mixture is passed through Spin is granulated, and obtained wet grain is roasted 7h at 580 DEG C, to obtain the catalyst that average grain diameter is 480 μm.Wherein, it urges In agent, the content of titanium-silicon molecular sieve TS-1 is 75 weight %.
By Catalyst packing in fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed is 1 The ratio of height to diameter of layer, catalyst bed is 10.
By the isolated liquid phase stream of step (2) with the tert-butyl hydroperoxide as oxidant (with t-butyl peroxy Change hydrogen concentration to provide for the form of the acetonitrile solution of 30 weight %) and acetonitrile as supplementing solvent together from fixed bed reaction The bottom of device is sent into, flow up with the catalyst haptoreaction that is seated in fixed bed reactors, obtain containing dimethyl The reaction mixture of sulfoxide.Wherein, the molar ratio of dimethyl sulfide and tert-butyl hydroperoxide is 1：0.9, dimethyl sulfide with The molar ratio of supplementing solvent is 1：18, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 50h-1；Reaction temperature is 45 DEG C, the pressure in reactor Power is 0.2MPa.In reaction process, the composition of the reaction mixture of fixed bed reactors output is monitored and calculates thioether Conversion ratio and dimethyl sulfoxide (DMSO) selectivity, the result that when differential responses time point obtains are listed in table 3.
(4) product detaches
The reaction mixture that step (3) obtains is flashed, unreacted dimethyl sulfide is obtained and contains diformazan Unreacted dimethyl sulfide is recycled and is sent into step (3) by the product stream of base sulfoxide.
Embodiment 18
Dimethyl sulfone is prepared using method identical with embodiment 17, unlike, titanium-silicon molecular sieve TS-1 carry out at Before type, it is modified processing using following methods, and by the Titanium Sieve Molecular Sieve of obtained modification using identical as embodiment 17 Method be molded, to prepare the catalyst that the present embodiment uses.
By the titanium-silicon molecular sieve TS-1 of preparation and contain HNO3(HNO3Mass concentration 15%) and hydrogen peroxide (peroxide be The mass concentration for changing hydrogen is aqueous solution mixing 8%), and obtained mixture is stirred to react 3h in closed container at 150 DEG C, The temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dried at 120 DEG C to constant weight, is obtained To modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2It counts, the molar ratio of Titanium Sieve Molecular Sieve and hydrogen peroxide is 1：2.Through characterization, 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 5.5%, is held by the hole of static determination of nitrogen adsorption and reduces 4.3%.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 3.
Embodiment 19
Dimethyl sulfone is prepared using method identical with embodiment 18, unlike, as the titanium of raw material in modification Si molecular sieves are titanium-silicon molecular sieve TS-1 (titanium-silicon molecular sieve TS-1s through being drawn off in the regenerated device from propylene ring oxidation reaction It is prepared using method identical with embodiment 17, the Titanium Sieve Molecular Sieve drawn off roasts at a temperature of 580 DEG C in air atmosphere 3h and regenerate, the activity after regeneration is 40%, 95%) activity when fresh is.Compared with raw material Titanium Sieve Molecular Sieve, what is obtained changes Property Titanium Sieve Molecular Sieve UV-Vis spectrum in the peak area of absorption peak between 230-310nm reduce 5.3%, by static nitrogen The hole of determination of adsorption method, which holds, reduces 4.8%.
The Titanium Sieve Molecular Sieve of obtained modification is molded using method identical with embodiment 17, obtains the present embodiment The catalyst used.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 3.
Embodiment 20
Dimethyl sulfoxide (DMSO) is prepared using method identical with embodiment 19, unlike, through regenerated from epoxidation of propylene The titanium-silicon molecular sieve TS-1 drawn off in reaction unit is without modification, but be directly used in that preparation process (3) uses urges Agent.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 3.
Table 3
Embodiment 21
(1) dimethyl sulfide is prepared
It is 1 by molar ratio under 260 DEG C and 0.1MPa：2.2 hydrogen sulfide (NH3Mass content 0.9%) and methanol be With the γ-Al as catalyst2O3Hybrid reaction obtains the mixture containing dimethyl sulfide, wherein catalyst and methanol Weight ratio is 15：1.
(2) gas-liquid separation
The mixture containing dimethyl sulfide that step (1) obtains is condensed, gaseous stream and liquid phase stream are obtained, By gaseous stream discharge system.
(3) oxidation reaction
Step (3) prepares titanium-silicon molecular sieve TS-1 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 8h is stood after sealing at 45 DEG C；Dispersion liquid through standing is transferred in sealing reaction kettle, first stage crystallization is undergone at 140 DEG C 6h continues in sealing reaction kettle after mixture is then cooled to 40 DEG C of experience second stage stop 1h in 160 DEG C of temperature Lower experience phase III crystallization 12h (it is wherein, 5 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by The rate of temperature fall of first stage crystallization temperature to second stage treatment temperature is 5 DEG C/min, by second stage treatment temperature to the The heating rate of three stage crystallization temperatures is 5 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly 110 DEG C of drying 2h are connected to, 3h is then roasted at 550 DEG C, obtains molecular sieve.The XRD crystalline phase figures of gained sample and 1 step of embodiment (3) titanium-silicon molecular sieve TS-1 prepared is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier becomes It changes in infrared spectrogram, in 960cm-1Nearby there is absorption peak, shows that titanium has been enter into framework of molecular sieve, in the Titanium Sieve Molecular Sieve, Urface silicon titanium/body phase silicon titanium ratio is 2.71, and titanium oxide content is 4.3 weight %.
Titanium-silicon molecular sieve TS-1 is uniformly mixed with Ludox (silica content is 30 weight %) and water, wherein titanium silicon The weight ratio of molecular sieve TS-1, the Ludox in terms of silica and water is 1：0.12：15.Obtained mixture is made through spin Grain, and obtained wet grain is roasted into 6h at 560 DEG C, to obtain the catalyst that average grain diameter is 120 μm.In catalyst, titanium silicon The content of molecular sieve is 88 weight %.
By Catalyst packing in fixed bed reactors, catalyst bed is formed, wherein the quantity of catalyst bed is 1 The ratio of height to diameter of layer, catalyst bed is 10.
By the isolated liquid phase stream of step (2) with the Peracetic acid as oxidant (with peroxyacetic acid concentration for 30 The form of the aqueous solution of weight % provides) and water as supplementing solvent be sent into together from the bottom of fixed bed reactors, to Upper flowing with the catalyst haptoreaction that is seated in fixed bed reactors, obtain the reaction mixing containing dimethyl sulfoxide (DMSO) Object.Wherein, the molar ratio of dimethyl sulfide and Peracetic acid is 1：0.7, the molar ratio of dimethyl sulfide and supplementing solvent is 1： 20, the weight (hourly) space velocity (WHSV) of dimethyl sulfide is 130h-1；Reaction temperature is 55 DEG C, and the pressure in reactor is 0.15MPa.It reacted Cheng Zhong is monitored the composition of the reaction mixture of fixed bed reactors output and calculates thioether rate and dimethyl sulfoxide (DMSO) Selectively, the result obtained when differential responses time point is listed in table 4.
(4) product detaches
The reaction mixture that step (3) obtains is flashed, unreacted dimethyl sulfide is obtained and contains diformazan Unreacted dimethyl sulfide is recycled and is sent into step (3) by the product stream of base sulfoxide.
Embodiment 22
Dimethyl sulfoxide (DMSO) is prepared using method identical with embodiment 21, unlike, titanium-silicon molecular sieve TS-1 is carrying out It before molding, is modified using following methods, and by the Titanium Sieve Molecular Sieve of obtained modification using identical with embodiment 21 Method is molded, and the catalyst that the present embodiment step (3) uses is obtained.
By the titanium-silicon molecular sieve TS-1 of preparation and contain HNO3(HNO3Mass concentration 10%) and hydrogen peroxide (peroxide be The mass concentration for changing hydrogen is aqueous solution mixing 2%), and 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 dried at 120 DEG C to perseverance 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 characterization, 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%.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 4.
Embodiment 23
Dimethyl sulfoxide (DMSO) is prepared using method identical with embodiment 22, unlike, as raw material in modification Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1 (Titanium Sieve Molecular Sieve through being drawn off in the regenerated reaction unit from phenol hydroxylation TS-1 is prepared using method identical with embodiment 21, and the titanium-silicon molecular sieve TS-1 drawn off is at a temperature of 580 DEG C in air gas 4h is roasted in atmosphere and is regenerated, and the activity after regeneration is 40%, 95%) activity when fresh is.Compared with raw material Titanium Sieve Molecular Sieve, The peak area of absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification between 230-310nm reduces 5.5%, Held by the hole of static determination of nitrogen adsorption and reduces 4.3%.
The Titanium Sieve Molecular Sieve of obtained modification is molded using method identical with embodiment 21, obtains the present embodiment The catalyst that step (3) uses.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 4.
Embodiment 24
Dimethyl sulfoxide (DMSO) is prepared using method identical with embodiment 23, unlike, without modification, but will Titanium-silicon molecular sieve TS-1 through being drawn off in the regenerated reaction unit from phenol hydroxylation is directly used in molding and prepares catalyst.
In the reaction process of step (3), the result obtained at differential responses time point is listed in table 4.
Embodiment 25
Dimethyl sulfoxide (DMSO) is prepared using method identical with embodiment 23, unlike, it will be through regenerated from phenolic hydroxy Change when the titanium-silicon molecular sieve TS-1 drawn off in reaction unit is modified processing and do not use hydrogen peroxide, but HNO is used only3 (dosage is identical as embodiment 23), the result obtained when the reaction time is 0.5 hour are listed in table 4.
Embodiment 26
Dimethyl sulfoxide (DMSO) is prepared using method identical with embodiment 23, unlike, it will be through regenerated from phenolic hydroxy Change when the titanium-silicon molecular sieve TS-1 drawn off in reaction unit is modified processing and does not use HNO3, but hydrogen peroxide is used only (dosage is identical as embodiment 23), the result obtained at differential responses time point are listed in table 4.
Table 4
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to Protection scope of the present invention.

Claims (20)

1. a kind of method producing dimethyl sulfoxide (DMSO) by hydrogen sulfide, this approach includes the following steps：
(1) hydrogen sulfide is contacted with methanol, obtains the mixture containing dimethyl sulfide；
(2) mixture containing dimethyl sulfide is subjected to gas-liquid separation, obtains gaseous stream and containing dimethyl sulfide The gaseous stream is optionally recycled and is sent into step (1) by liquid phase stream；
(3) under oxidation reaction condition, the liquid phase stream that step (2) obtains is contacted with oxidant and Titanium Sieve Molecular Sieve, is obtained Mixture containing dimethyl sulfoxide (DMSO)；
Optionally, (4) detach the mixture containing dimethyl sulfoxide (DMSO), obtain dimethyl sulfide and dimethyl sulfide contains Measure the dimethyl sulfoxide (DMSO) reduced；
Optionally, the dimethyl sulfide cycle that (5) isolate step (4) is sent into step (3).
2. according to the method described in claim 1, wherein, the hydrogen sulfide is the hydrogen sulfide isolated from acid waste gas.
3. method according to claim 1 or 2, wherein the hydrogen sulfide is to contain NH3Hydrogen sulfide；Preferably, described NH in hydrogen sulfide3Mass content be 0.1-6%, preferably 0.5-3%.
4. according to the method described in any one of claim 1-3, wherein step (1) contact is catalyzed at least one It is carried out in the presence of agent, the catalyst is selected from type ZSM 5 molecular sieve, BETA types molecular sieve, Y type molecular sieve and γ-Al2O3 One or more of.
5. according to the method described in any one of claim 1-4, wherein temperature of step (1) contact at 200-400 DEG C Degree is lower to carry out.
6. according to the method described in claim 1, wherein, in step (3), at least partly Titanium Sieve Molecular Sieve is modified titanium silicon point The Titanium Sieve Molecular Sieve of son sieve, the modification undergoes modification, and the modification includes will be as the Titanium Sieve Molecular Sieve of raw material It is contacted with the modification liquid containing nitric acid and at least one peroxide.
7. according to the method described in claim 6, wherein, in the modification, the Titanium Sieve Molecular Sieve as raw material and institute The molar ratio for stating peroxide is 1：0.01-5, preferably 1：0.05-3, more preferably 1：0.1-2, the peroxide and institute The molar ratio for stating nitric acid is 1：0.01-50, preferably 1：0.1-20, more preferably 1：0.2-10, further preferably 1：0.3- 5, particularly preferably 1：0.5-3.5, the Titanium Sieve Molecular Sieve is in terms of silica.
8. the method described according to claim 6 or 7, wherein the peroxide is selected from hydrogen peroxide, tert-butyl hydroperoxide One kind in hydrogen, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid or two Kind or more, more preferably hydrogen peroxide.
9. according to the method described in any one of claim 6-8, wherein in the modification liquid, peroxide and nitric acid Concentration is respectively 0.1-50 weight %, preferably 0.5-25 weight %, more preferably 1-20 weight %.
10. according to the method described in any one of claim 6-9, wherein in the modification, the titanium as raw material Si molecular sieves and the modification liquid 10-350 DEG C, preferably 20-300 DEG C, it is 50-250 DEG C more preferable, 60-200 DEG C further preferred At a temperature of contacted, it is described contact pressure be 0-5MPa container in carry out, the pressure be gauge pressure；The contact Duration is 0.5-10h, preferably 2-5h.
11. according to the method described in any one of claim 6-10, wherein in the modification, as raw material Titanium Sieve Molecular Sieve and the exposure level of the modification liquid make, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible In spectrum, the peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces by 2% or more, preferably reduces 2- 30%, 2.5-15% is more preferably reduced, 3-10% is further preferably reduced, still more preferably reduces 3-8%；Modified titanium silicon The hole of molecular sieve, which holds, reduces 1% or more, preferably reduces 1-20%, more preferably reduces 2-10%, further preferably reduce 2.5- 5%, the Kong Rong are using static determination of nitrogen adsorption.
12. according to the method described in any one of claim 1-11, wherein at least partly Titanium Sieve Molecular Sieve is through regenerated Using Titanium Sieve Molecular Sieve as the agent that draws off of the reaction unit of catalyst, it is described draw off agent be Ammoximation reaction device draw off agent, Hydroxylating device draw off agent and epoxidation reaction device draw off one or more of agent；
Preferably, it is 25-60%, preferably 30-50% through the regenerated activity for drawing off agent.
13. according to the method described in any one of claim 1-12, wherein at least partly Titanium Sieve Molecular Sieve is titanium silicon molecule Sieve TS-1, the urface silicon titanium of the titanium-silicon molecular sieve TS-1 is not less than body phase silicon titanium ratio, the silicon titanium ratio refer to silica with The molar ratio of titanium oxide, the urface silicon titanium are measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio is penetrated using X Line fluorescence spectrum method for measuring；
Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2 or more；
It is highly preferred that the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5；
It is further preferred that the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5；
It is further preferred that the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 2-3.
14. according to the method described in any one of claim 1-13, wherein at least partly Titanium Sieve Molecular Sieve is titanium silicon molecule TS-1 is sieved, the titanium-silicon molecular sieve TS-1 is prepared using method comprising the following steps：
(A) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and optionally supplements water, disperseed 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 meters；
(B) optionally, the dispersion liquid is stood to 6-24h at 15-60 DEG C；
(C) dispersion liquid that step (A) obtains or the dispersion liquid that step (B) obtains sequentially are undergone into the stage in sealing reaction kettle (1), stage (2) and stage (3) carry out crystallization, the stage (1) 80-150 DEG C, preferably 110-140 DEG C, it is 120-140 DEG C more preferable, Further preferred 130-140 DEG C of crystallization 6-72h, preferably 6-8h；Stage (2) be cooled to not higher than 70 DEG C and the residence time at least 0.5h, preferably 1-5h；Stage (3) is warming up to 120-200 DEG C, preferably 140-180 DEG C, 160-170 DEG C more preferable, then crystallization 6- 96h, preferably 12-20h.
15. according to the method for claim 14, wherein stage (1) and stage (3) meet one of the following conditions or The two：
Condition 1：The crystallization temperature in stage (1) is less than the crystallization temperature in stage (3), it is preferable that the crystallization temperature in stage (1) compares rank The crystallization temperature of section (3) is 10-50 DEG C low, 20-40 DEG C preferably low；
Condition 2：The crystallization time in stage (1) is less than the crystallization time in stage (3), it is preferable that the crystallization time in stage (1) compares rank The crystallization time short 5-24h, preferably short 6-12h of section (3).
16. the method according to claims 14 or 15, wherein the stage (2) is cooled to not higher than 50 DEG C, and the residence time is extremely It is 1h less.
17. according to the method described in any one of claim 14-16, wherein the titanium source is inorganic titanium salt and/or organic Titanate esters；The alkali source template is one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine, preferably season Ammonium alkali, more preferably tetrapropylammonium hydroxide；The inorganic silicon source is silica gel and/or Ludox；
Preferably, the inorganic titanium salt is TiCl4、Ti(SO4)2And TiOCl2One or more of；Organic metatitanic acid Ester is selected from general formula R7 4TiO4The compound of expression, R7Selected from the alkyl with 2-4 carbon atom.
18. according to the method described in any one of claim 1-17, wherein the oxidant and the dimethyl sulfide Molar ratio is 0.1-2：1, preferably 0.1-1.5：1.
19. according to the method described in any one of claim 1-18, wherein the oxidant is selected from hydrogen peroxide, uncle In butylhydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid One or more, more preferably hydrogen peroxide.
20. according to the method described in any one of claim 1-19, wherein the oxidation reaction is 0-100 DEG C in temperature, Preferably 20-80 DEG C；And pressure is carries out under conditions of 0-3MP, the pressure is gauge pressure.
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