CN107235870B - A kind of preparation method of sulfone - Google Patents

A kind of preparation method of sulfone Download PDF

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Publication number
CN107235870B
CN107235870B CN201610186655.1A CN201610186655A CN107235870B CN 107235870 B CN107235870 B CN 107235870B CN 201610186655 A CN201610186655 A CN 201610186655A CN 107235870 B CN107235870 B CN 107235870B
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titanium
molecular sieve
sieve
modification
stage
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CN107235870A (en
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林民
史春风
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment

Abstract

The invention discloses a kind of preparation methods of sulfone, this method is included under oxidation reaction condition, at least one thioether and at least one oxidant are contacted with Titanium Sieve Molecular Sieve, the oxidant is selected from peroxide, obtain the mixture containing sulfone, the Titanium Sieve Molecular Sieve is modified Titanium Sieve Molecular Sieve, or the Titanium Sieve Molecular Sieve is modified Titanium Sieve Molecular Sieve and unmodified Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve of the modification undergoes modification, the unmodified Titanium Sieve Molecular Sieve does not undergo modification, the modification includes that will contact as the Titanium Sieve Molecular Sieve of raw material with the modification liquid containing nitric acid and at least one peroxide.Method of the invention can effectively promote the catalytic performance of Titanium Sieve Molecular Sieve, extend the single trip use service life of Titanium Sieve Molecular Sieve, reduce the regeneration frequency of Titanium Sieve Molecular Sieve.

Description

A kind of preparation method of sulfone
Technical field
The present invention relates to a kind of preparation methods of sulfone.
Background technique
Sulfone substance is important sulfur-containing compound, as dimethyl sulfone be white crystalline powder, soluble easily in water, ethyl alcohol, benzene, Methanol and acetone, are slightly soluble in ether.Potassium permanganate cannot be made to change colour under room temperature, dimethyl sulfone can be oxidized to methylsulphur by strong oxidizer Acid.Dimethyl sulfone aqueous solution is in neutrality.In 25 DEG C of microsublimations, accelerate to 60 DEG C of rate of sublimation, thus dimethyl sulfone product is suitable It is dried under cryogenic vacuum.
Dimethyl sulfone is used as organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, food in the industry Product additive and drug.Dimethyl sulfone is as a kind of organic sulfur compound, the ability that there is enhancing human body to generate insulin, simultaneously Also there is facilitation to the metabolism of carbohydrate, be the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound to be cured It closes, can also work to vitamin B, vitamin C, the synthesis of biotin and activation needed for metabolism and neurological health, quilt Referred to as " beautify carbonizable substance naturally ".All contain dimethyl sulfone in the skin of human body, hair, nail, bone, muscle and each organ, Dimethyl sulfone is primarily present in Yu Haiyang and soil in nature, is absorbed in plant growth as nutriment, the mankind It can be absorbed from the foods such as veterinary antibiotics, fish, meat, egg, milk, once health disorders will be caused or disease occurs by lacking, be Human body maintains the main matter of biological element sulphur balance, has therapeutic value and healthcare function to human body diseases, is human survival With the indispensable drug of health care.Foreign countries widely apply using dimethyl sulfone as with vitamin nutriment of equal importance, China The application study of dimethyl sulfone is not yet carried out very well, product is mainly used for exporting at present.Therefore, dimethyl sulfone is not only one kind New high-tech product and a kind of fine chemical product of high added value.Product is new, great market potential, and benefit is prominent, has wide Wealthy production and application and development prospect.
Currently, the product that dimethyl sulfone is further aoxidized as dimethyl sulfoxide, for the main pair of dimethyl sulfoxide production Product.
Summary of the invention
The preparation method for the sulfone that the purpose of the present invention is to provide a kind of using peroxide as oxidant, this method can The catalytic performance for effectively promoting the Titanium Sieve Molecular Sieve as catalyst, extends the single trip use service life of Titanium Sieve Molecular Sieve.
The present invention provides a kind of preparation method of sulfone, this method is included under oxidation reaction condition, by least one sulphur Ether and at least one oxidant are contacted with Titanium Sieve Molecular Sieve, obtain the mixture containing sulfone, and the oxidant is selected from peroxide, The Titanium Sieve Molecular Sieve is modified Titanium Sieve Molecular Sieve or the Titanium Sieve Molecular Sieve be the Titanium Sieve Molecular Sieve of modification and unmodified Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve of the modification undergoes modification, and the unmodified Titanium Sieve Molecular Sieve, which is not undergone, to be changed Property processing, the modification includes will be as the Titanium Sieve Molecular Sieve of raw material and changing containing nitric acid and at least one peroxide Property liquid contact.
According to the method for the present invention, at least partly catalyst is used as using the Titanium Sieve Molecular Sieve of the modification of modified processing, In the identical situation of remaining condition, with only with unmodified Titanium Sieve Molecular Sieve as catalyst compared with, can effectively be promoted The catalytic performance of Titanium Sieve Molecular Sieve extends the single trip use service life of Titanium Sieve Molecular Sieve, reduces the regeneration frequency of Titanium Sieve Molecular Sieve.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of preparation method of sulfone, this method is included under oxidation reaction condition, by least one sulphur Ether and at least one oxidant are contacted with Titanium Sieve Molecular Sieve, obtain the mixture containing sulfone.
According to the method for the present invention, the Titanium Sieve Molecular Sieve is modified Titanium Sieve Molecular Sieve or the Titanium Sieve Molecular Sieve For modified Titanium Sieve Molecular Sieve and unmodified Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve of the modification undergoes modification, described Unmodified Titanium Sieve Molecular Sieve does not undergo modification.
The modification the following steps are included: by as the Titanium Sieve Molecular Sieve of raw material with containing nitric acid (that is, HNO3) and The modification liquid of at least one peroxide contacts.Titanium Sieve Molecular Sieve as raw material refers to the titanium silicon of the raw material as modification Molecular sieve, can be for without the Titanium Sieve Molecular Sieve for going through the modification, or live through the modification still Need to carry out the Titanium Sieve Molecular Sieve of the modification again.
In the present invention, peroxide refer in molecular structure contain-O-O- key compound, can selected from hydrogen peroxide, Hydroperoxides and peracid.The hydroperoxides refer to a hydrogen atom in hydrogen peroxide molecule replaced by organic group and Obtained substance.The peracid refers to the organic oxacid for containing-O-O- key in molecular structure.
In the modification, the specific example of the peroxide be can include but is not limited to: hydrogen peroxide, tertiary fourth Base hydrogen peroxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid.It is preferred that Ground, the oxidant are hydrogen peroxide.The hydrogen peroxide can be peroxidating existing in a variety of manners commonly used in the art Hydrogen.
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.Generally, the molar ratio of the peroxide and the nitric acid can be 1:0.01-50, preferably 1:0.1- 20, more preferably 1:0.2-10, further preferably 1:0.5-5, particularly preferably 1:0.6-3.5, such as 1:0.7-2.8, it is described Titanium Sieve Molecular Sieve is in terms of silica.
In the modification liquid, the concentration of the peroxide and nitric acid respectively can be 0.1-50 weight %.From further The angle for improving the catalytic performance of the Titanium Sieve Molecular Sieve of the modification finally prepared is set out, preferably 0.5-30 weight %.More preferably Ground, in the modification liquid, the concentration of the peroxide and nitric acid is respectively 1-25 weight %, such as 5-20 weight %.
The solvent of the modification liquid can be the common various solvents that can dissolve nitric acid and the peroxide simultaneously.It is excellent Selection of land, the solvent of the modification liquid are water.
In the modification, as raw material Titanium Sieve Molecular Sieve and modification liquid can 10-350 DEG C at a temperature of into Row contact.From the angle of the catalytic performance for the Titanium Sieve Molecular Sieve for further increasing the modification finally prepared, the contact is excellent It is contacted at a temperature of being selected in 20-300 DEG C.It is highly preferred that it is described contact 50-250 DEG C at a temperature of carry out.It is further excellent Selection of land, it is described contact 60-200 DEG C at a temperature of carry out.It is further preferred that it is described contact 70-170 DEG C at a temperature of It carries out.The time of the contact can be 0.5-10 hours, preferably 1-8 hours, more preferably 2-5 hours.In the modification It, can be according to contact temperature by the pressure in the container contacted as the Titanium Sieve Molecular Sieve of raw material with the modification liquid in processing Degree is selected, and can be environmental pressure, or pressurization.Generally, will change as the Titanium Sieve Molecular Sieve of raw material with described Property the container that is contacted of liquid in pressure can be 0-5MPa, the pressure is gauge pressure.Preferably, under pressure will Titanium Sieve Molecular Sieve as raw material is contacted with the modification liquid.It is highly preferred that by conduct under self-generated pressure in closed container The Titanium Sieve Molecular Sieve of raw material is contacted with the modification liquid.
In the modification, as the Titanium Sieve Molecular Sieve of raw material and the exposure level of the modification liquid preferably so that, Using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible spectrum, modified Titanium Sieve Molecular Sieve 230-310nm it Between the peak area of absorption peak reduce by 2% or more, the hole of modified Titanium Sieve Molecular Sieve, which holds, reduces 1% or more.Modified titanium silicon point The peak area of absorption peak of the son sieve between 230-310nm preferably reduces 2-30%, more preferably reduction 2.5-15%, further excellent Choosing reduces 3-10%, still more preferably reduction 3-8%, such as reduces 3-6%.The hole of modified Titanium Sieve Molecular Sieve, which holds, preferably to be subtracted Few 1-20%, more preferably reduction 1.5-10%, further preferably reduction 2-6%, such as reduce 2-5%.The Kong Rong is using quiet State determination of nitrogen adsorption.
According to the method for the present invention, it is contacted with thioether and oxidant and carries out oxidation reaction to obtain the mixture containing sulfone Titanium Sieve Molecular Sieve can be the modification Titanium Sieve Molecular Sieve, or the Titanium Sieve Molecular Sieve of the modification and unmodified Titanium Sieve Molecular Sieve.
In one embodiment of the invention, from operation terseness angle, contacted with thioether and oxidant into Row oxidation reaction is to the Titanium Sieve Molecular Sieve that the Titanium Sieve Molecular Sieve for obtaining the mixture containing sulfone is the modification.
In another embodiment of the invention, is contacted with thioether and oxidant and carry out oxidation reaction to be contained The Titanium Sieve Molecular Sieve of the mixture of sulfone is the Titanium Sieve Molecular Sieve and unmodified Titanium Sieve Molecular Sieve of the modification.According to the embodiment party Modified Titanium Sieve Molecular Sieve is applied in combination and can be regulated and controled to catalytic performance with unmodified Titanium Sieve Molecular Sieve, simultaneously by formula The operating cost that processing is modified to Titanium Sieve Molecular Sieve and is generated can also be reduced.In this embodiment, with the titanium silicon point On the basis of the total amount of son sieve, the content of the Titanium Sieve Molecular Sieve of the modification can be 5-95 weight %, the unmodified titanium silicon The content of molecular sieve can be 5-95 weight %.Under the premise of taking into account the operating cost of modification, urged from further increasing The angle for changing performance is set out, and on the basis of the total amount of the Titanium Sieve Molecular Sieve, the content of the Titanium Sieve Molecular Sieve of the modification is preferred For 20-90 weight %, the content of the unmodified Titanium Sieve Molecular Sieve is preferably 10-80 weight %.It is highly preferred that with the titanium On the basis of the total amount of si molecular sieves, the content of the Titanium Sieve Molecular Sieve of the modification is 40-80 weight %, the unmodified titanium silicon The content of molecular sieve is 20-60 weight %.
In using various commercial plants of the Titanium Sieve Molecular Sieve as 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 ex-situ regeneration is needed catalyst from device when being difficult to obtain satisfied activity being regenerated 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 usually 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.By these draw off after agent (that is, the Titanium Sieve Molecular Sieve drawn off) is regenerated with sulphur Ether and oxidant contact under oxidation reaction condition, still are able to obtain preferable catalytic performance, can especially obtain higher Oxidant effective rate of utilization.Therefore, according to the method for the present invention, at least partly described Titanium Sieve Molecular Sieve preferably through it is regenerated with Titanium Sieve Molecular Sieve draws off agent as the reaction unit (in addition to sulfide oxidation reaction unit) of catalyst.It is described to draw off agent and be Use Titanium Sieve Molecular Sieve as the agent that draws off drawn off in the reaction unit of catalyst from various, such as can be to fill from oxidation reaction What is drawn off in setting draws off agent.Specifically, it is described draw off agent be Ammoximation reaction device draw off agent, hydroxylating device unloads Agent and epoxidation reaction device draw off one or more of agent out.More specifically, described, to draw off agent can be hexamethylene Ketone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draws off drawing off for agent and propylene ring oxidation reaction device 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.
It is different according to its source through the regenerated activity for drawing off agent.Generally, through the regenerated activity for drawing off agent It can be the 5-95% of activity (that is, activity of fresh Titanium Sieve Molecular Sieve) of Titanium Sieve Molecular Sieve when fresh.Preferably, through again The raw activity for drawing off agent can be active 10-90% of Titanium Sieve Molecular Sieve when fresh, further preferably fresh When active 30-50%, be still more preferably active 35-45% when fresh.The fresh Titanium Sieve Molecular Sieve Activity generally 90% or more, usually 95% or more.
The activity measures by the following method: respectively will be through regenerated agent and the fresh Titanium Sieve Molecular Sieve of drawing off as hexamethylene Ketone oxamidinating reaction catalyst, the condition of the Ammoximation reaction are as follows: Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH3Meter), The hydrogen peroxide of 30 weight % is (with H2O2Meter), the tert-butyl alcohol and cyclohexanone by weight 1:7.5:10:7.5:10, at atmosheric pressure In 80 DEG C of reaction 2h.Calculate separately using through it is regenerated draw off agent and fresh Titanium Sieve Molecular Sieve as catalyst when cyclohexanone conversion Rate, and using it as through the regenerated activity for drawing off agent and fresh Titanium Sieve Molecular Sieve, wherein the conversion ratio of cyclohexanone= [mole of the cyclohexanone of (mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/addition] × 100%.
According to the method for the present invention, described to draw off the raw material that agent be modified Titanium Sieve Molecular Sieve, it can also be used as not Modified Titanium Sieve Molecular Sieve uses.Preferably, in the modification, the Titanium Sieve Molecular Sieve at least partly as raw material is described Draw off agent, can further extend the single trip use service life in this way, and with it is non-modified draw off agent compared with, sulfone can be significantly improved Selectivity and thioether rate.
According to the method for the present invention, the Titanium Sieve Molecular Sieve is that titanium atom replaces one of a part of silicon atom in lattice framework The general name of class zeolite can use chemical formula xTiO2·SiO2It indicates.The present invention does not have the content of titanium atom in Titanium Sieve Molecular Sieve It is particularly limited to, can be the conventional selection of this field.Specifically, x can be 0.0001-0.05, preferably 0.01-0.03, More preferably 0.015-0.025.
The preparation method of sulfone according to the present invention, the Titanium Sieve Molecular Sieve can be common with various topological structures Titanium Sieve Molecular Sieve, such as: the Titanium Sieve Molecular Sieve can for selected from MFI structure Titanium Sieve Molecular Sieve (such as TS-1), MEL structure Titanium Sieve Molecular Sieve (such as Ti- of Titanium Sieve Molecular Sieve (such as TS-2), the Titanium Sieve Molecular Sieve (such as Ti-Beta) of BEA structure, MWW structure MCM-22), Titanium Sieve Molecular Sieve (such as Ti- of the Titanium Sieve Molecular Sieve (such as Ti-MCM-41, Ti-SBA-15), MOR structure of hexagonal structure MOR), one of the Titanium Sieve Molecular Sieve (such as Ti-TUN) of TUN structure and the Titanium Sieve Molecular Sieve (such as Ti-ZSM-48) of other structures Or it is two or more.
Preferably, the Titanium Sieve Molecular Sieve is Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve of MEL structure, six selected from MFI structure One or more of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve of BEA structure of square structure.It is highly preferred that the titanium silicon point Son 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 point Son sieve is the Titanium Sieve Molecular Sieve of MFI structure, and the crystal grain of the Titanium Sieve Molecular Sieve is hollow structure, the chamber portion of the hollow structure Radical length is 5-300 nanometers, and the Titanium Sieve Molecular Sieve is in 25 DEG C, P/P0=0.10, adsorption time is to survey under conditions of 1 hour The benzene adsorbance obtained is at least 70 milligrams per grams, the adsorption isotherm and desorption isotherm of the nitrogen absorption under low temperature of the Titanium Sieve Molecular Sieve Between there are hysteresis loops.The hollow Titanium Sieve Molecular Sieve, which is commercially available, (such as to be commercially available from Hunan to build feldspathization share limited The trade mark of company be HTS molecular sieve), can also the method according to disclosed in CN1132699C be prepared.
According to the method for the present invention, when the Titanium Sieve Molecular Sieve uses template during the preparation process, the titanium silicon molecule Sieve can be the Titanium Sieve Molecular Sieve that experienced the process (such as roasting process) for removed template method, or do not undergo and be used for The Titanium Sieve Molecular Sieve of the process (such as roasting process) of removed template method can also be the mixture of the two.
According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the Titanium Sieve Molecular Sieve TS- 1 urface silicon titanium is not less than body phase silicon titanium ratio, can be further improved oxidant effective rate of utilization in this way, and can further prolong The single trip use service life of long Titanium Sieve Molecular Sieve.Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio be 1.2 with On.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 surface Silicon titanium is than being 1.5-4.5 (such as 2.2-4.5) with the ratio of the body phase silicon titanium ratio.It is further preferred that the surface silicon titanium Than being 2-3, such as 2.2-2.8 with the ratio of the body phase silicon titanium ratio.Molar ratio of the silicon titanium than referring to silica and titanium oxide, The urface silicon titanium is measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio is surveyed using x ray fluorescence spectrometry It is fixed.
According to the method for the present invention, from the catalytic performance for further increasing Titanium Sieve Molecular Sieve and further extend titanium silicon molecule The angle in the single trip use service life of sieve is set out, and at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the Titanium Sieve 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, obtained Dispersion liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:(0.5-8): (5-30): (100- 2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N meter is (in the alkali When source template contains nitrogen, in terms of N；In the alkali source template not Nitrogen element, with OH-Meter)；
(B) optionally, by the dispersion liquid in 15-60 DEG C of standing 6-24h；
(C) dispersion liquid that step (A) obtains or the dispersion liquid that step (B) obtains sequentially are undergone in sealing reaction kettle Stage (1), stage (2) and stage (3) carry out crystallization, and the stage (1) is in 80-150 DEG C of crystallization 6-72 hours (h), stage (2) cooling To after not higher than 70 DEG C and residence time at least 0.5h, the stage (3) is warming up to 120-200 DEG C of crystallization 6-96h again.
It is " optional " to indicate inessential, it can be understood as " with or without ", " including or not including " in the present invention.
The alkali source template can be usually used various templates during synthesis of titanium silicon molecular sieve, such as: The alkali source template can be one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine.The quaternary ammonium base It can be various organic level Four ammonium alkali, the aliphatic amine can be various NH3In at least one hydrogen by aliphatic alkyl (such as Alkyl) replace after the compound that is formed, the aliphatic hydramine can be various NH3In at least one hydrogen by the rouge of hydroxyl The compound that fat race group (such as alkyl) is formed after replacing.
Specifically, the alkali source template can be the aliphatic amine and formula of the quaternary ammonium base, Formula II expression that indicate selected from Formulas I One or more of the aliphatic hydramine that III is indicated.
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane Base, R1、R2、R3And R4Specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group or tert-butyl.
R5(NH2)n(Formula II)
In Formula II, n is an integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6 Branched alkyl, specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different Butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including C1-C6Straight-chain alkyl-sub and C3-C6Branched alkylidene, specific example can include but is not limited to methylene, ethylidene, Sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3- C4Branched alkylidene, specific example can include but is not limited to methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.
The specific example of the alkali source template can include but is not limited to: tetramethylammonium hydroxide, tetraethyl hydroxide Ammonium, tetrapropylammonium hydroxide (the various isomers including tetrapropylammonium hydroxide, such as four n-propyl ammonium hydroxide and tetra isopropyl Ammonium hydroxide), tetrabutylammonium hydroxide (the various isomers including tetrabutylammonium hydroxide, such as 4-n-butyl ammonium hydroxide and Four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine One or more of with triethanolamine.Preferably, the alkali source template is tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen Change one or more of ammonium and tetrabutylammonium hydroxide.It is highly preferred that the alkali source template is tetrapropyl hydroxide Ammonium.
The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can Think TiCl4、Ti(SO4)2And TiOCl2One or more of；The organic titanate can be general formula R7 4TiO4Table The compound shown, wherein R7For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom, such as metatitanic acid Four butyl esters.
The inorganic silicon source can be silica gel and/or silica solution, preferably silica gel.SiO in the silica solution2Quality hundred Dividing content can be 10% or more, preferably 15% or more, more preferably 20% or more.In preparation according to the preferred embodiment Titanium Sieve Molecular Sieve when, do not use organic silicon source, such as organosilan and organosiloxane.
In the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is preferably 100:(1-6): (8-25): (200-1500), more preferably 100:(2-5): (10-20): (400-1000).
The dispersion liquid that step (A) obtains, which can be sent directly into step (C), carries out crystallization.Preferably, step (A) is obtained Dispersion liquid be sent into step (B) in 15-60 DEG C at a temperature of stand 6-24h.It is walked between step (A) and step (C) Suddenly (B) can significantly improve the urface silicon titanium of the titanium-silicon molecular sieve TS-1 finally prepared, so that the Titanium Sieve Molecular Sieve finally prepared Urface silicon titanium be not less than body phase silicon titanium ratio, the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared can be significantly improved in this way, prolonged Its long single trip use service life.Generally, pass through setting steps (B), the titanium silicon finally prepared between step (A) and step (C) The urface silicon titanium of molecular sieve and the ratio of body phase silicon titanium ratio can be in the range of 1.2-5, preferably in the range of 1.5-4.5 (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 to stand more preferably 20-50 DEG C at a temperature of carry out, as carried out at a temperature of 25-45 DEG C.
In step (B), when being stood, dispersion liquid can be placed in sealing container, open container can also be placed in In stood.Preferably, step (B) 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 step (B), after the completion of the standing, directly the dispersion liquid through standing can be sent into reaction kettle and carry out crystalline substance Change, be sent into reaction kettle after the dispersion liquid through standing can also being carried out redisperse and carry out crystallization, is preferably sent after progress redisperse Enter in reaction kettle, can be further improved the dispersing uniformity for carrying out the dispersion liquid of crystallization in this way.The method of the redisperse can be with For the combination of one or more of conventional method, such as stirring, ultrasonic treatment and oscillation.The redisperse it is lasting when Between be subject to the dispersion liquid through standing can be made to form uniform dispersion liquid, generally can be 0.1-12h.The redisperse can be It is carried out under environment temperature, as carried out at a temperature of 15-40 DEG C.
In step (C), temperature is adjusted to the heating rate of each phase temperature and rate of temperature fall can use according to specific The type of crystallization device selected, be not particularly limited.In general, raising the temperature to stage (1) crystallization temperature Heating rate 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 The rate of temperature fall spent to stage (2) temperature can be for 1-50 DEG C/min, and 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 (C), the crystallization temperature in stage (1) is preferably 110-140 DEG C, more preferably 120-140 DEG C, further excellent It is selected as 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24h, more preferably 6-8h.The temperature in stage (2) is preferably not Higher than 50 DEG C.The crystallization temperature in stage (3) is preferably 140-180 DEG C, and more preferably 160-170 DEG C.The crystallization time in stage (3) Preferably 12-20h, more preferably 12-16h.
In step (C), in a preferred embodiment, the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3) Degree, can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve of preparation in this way.Preferably, the temperature of the crystallization in stage (1) compares rank The crystallization temperature of section (3) is 10-50 DEG C low.It is highly preferred that the crystallization temperature in stage (1) is 20-40 lower than the crystallization temperature in stage (3) ℃.In step (C), in another preferred embodiment, the crystallization time in stage (1) is less than the crystallization time of stage (3), It can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.Preferably, the crystallization time in stage (1) compares the stage (3) the short 5-24h of crystallization time.It is highly preferred that the crystallization time in stage (1) is 6-12h shorter than the crystallization time in stage (3), such as Short 6-8h.In step (C), both preferred embodiments be may be used alone, can also be used in combination, and preferably combination makes With that is, the crystallization temperature and crystallization time in stage (1) and stage (3) meet the requirements of both preferred embodiments simultaneously.
In step (C), in another preferred embodiment, the temperature in stage (2) is not higher than 50 DEG C, and when stopping Between be at least 0.5h, such as 0.5-6h, can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.Preferably, The temperature in stage (2) is at least 1h, such as 1-5h.The preferred embodiment can be separated with aforementioned two kinds of preferred embodiments It uses, can also be applied in combination, preferably be applied in combination, is i.e. the crystallization temperature and crystallization time in stage (1) and stage (3) and rank The temperature of section (2) and residence time meet the requirement of above-mentioned three kinds of preferred embodiments simultaneously.
Titanium Sieve Molecular Sieve can be recycled from the mixture that step (C) crystallization obtains using conventional method.It specifically, can be with After the mixture that step (C) crystallization obtains optionally is filtered and washed, solid matter is dried and is roasted, thus Obtain Titanium Sieve Molecular Sieve.The drying and the roasting can carry out under normal conditions.Generally, the drying can be in ring Border temperature (such as 15 DEG C) is to carrying out at a temperature of 200 DEG C.The drying can be under environmental pressure (generally 1 standard atmospheric pressure) It carries out, can also carry out at reduced pressure.The duration of the drying can according to dry temperature and pressure and Dry mode is selected, and is not particularly limited.For example, temperature is preferably 80- when the drying carries out under ambient pressure 150 DEG C, more preferably 100-120 DEG C, dry duration are preferably 0.5-5h, more preferably 1-3h.The roasting can be with 300-800 DEG C at a temperature of carry out, preferably carry out at a temperature of 500-700 DEG C, more preferably 550-650 DEG C at a temperature of It carries out.The duration of the roasting can select according to the temperature roasted, generally can be 2-12h, preferably 2- 5h.The roasting carries out preferably in air atmosphere.
According to the method for the present invention, above two preferred titanium-silicon molecular sieve TS-1 can be used as unmodified titanium silicon molecule Sieve, can also be used as the raw material of modified Titanium Sieve Molecular Sieve, can also both be used as unmodified Titanium Sieve Molecular Sieve, also as modification Titanium Sieve Molecular Sieve raw material.
The topological structure of above-described Titanium Sieve Molecular Sieve is not only suitable for modified Titanium Sieve Molecular Sieve, is also applied for unmodified Titanium Sieve Molecular Sieve.The Titanium Sieve Molecular Sieve of the modification can be using with phase homeomorphism with the unmodified Titanium Sieve Molecular Sieve The Titanium Sieve Molecular Sieve of structure, can also be using the Titanium Sieve Molecular Sieve with different topology structure.
According to the method for the present invention, catalyst of the Titanium Sieve Molecular Sieve as oxidation reaction, dosage is can be realized catalysis It can be catalytic amount subject to function.Furthermore it is also possible to be selected according to the way of contact of thioether and oxidant and Titanium Sieve Molecular Sieve It selects.For example, thioether and oxidant are sent into fixed bed reaction in the bed that Titanium Sieve Molecular Sieve is seated in fixed bed reactors When in device with Titanium Sieve Molecular Sieve haptoreaction, the weight (hourly) space velocity (WHSV) of thioether can be 0.1-500h-1, preferably 5-500h-1, more excellent It is selected as 10-150h-1, such as 40-80h-1.For another example being connect Titanium Sieve Molecular Sieve is mixed to form slurry with thioether and oxidant When touching, the weight ratio of thioether and Titanium Sieve Molecular Sieve can be 0.1-50:1, preferably 2-50:1.
The preparation method of sulfone according to the present invention, the oxidant are selected from peroxide.The specific example of the oxidant It can include but is not limited to: hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, dicumyl peroxide, cyclohexyl peroxide Change hydrogen, Peracetic acid and Perpropionic Acid.Preferably, the oxidant is hydrogen peroxide, can further decrease be separated into this way This.The hydrogen peroxide can be hydrogen peroxide existing in a variety of manners commonly used in the art.
From the angle for further increasing safety according to the method for the present invention, preferably make according to the method for the present invention With existing hydrogen peroxide as an aqueous solution.According to the method for the present invention, it is provided as an aqueous solution in the hydrogen peroxide When, the concentration of the aqueous hydrogen peroxide solution can be the normal concentration of this field, such as: 20-80 weight %.On concentration meets The aqueous solution for stating the hydrogen peroxide of requirement can be prepared using conventional method, be also commercially available, such as: can be being capable of quotient The hydrogen peroxide of the hydrogen peroxide of the 30 weight % bought, the hydrogen peroxide of 50 weight % or 70 weight %.
The dosage of the oxidant can be conventional selection, be not particularly limited.Generally, mole of oxidant and thioether Than that can be 2:1 or more.The molar ratio of oxidant and thioether can be 20:1 hereinafter, as 10:1 hereinafter, preferably 5:1 hereinafter, More preferably 3:1 is hereinafter, further preferably 2.5:1 or less.Preferably, the molar ratio of oxidant and thioether is 2-2.5:1.
According to the method for the present invention, from further increase in reaction system between each reactant mixability, strengthen expand The angle for dissipating and more easily the severe degree of reaction being adjusted is set out, preferably by thioether and oxidant and titanium silicon molecule Sieve is contacted in the presence of at least one solvent.That is, in a solvent by thioether and disperse oxidant, reaction solution is formed, it will The reaction solution is contacted with Titanium Sieve Molecular Sieve.The type of the solvent is not particularly limited.Generally, the solvent can be selected from Water, C1-C6Alcohol, C3-C8Ketone and C2-C6Nitrile.The specific example of the solvent can include but is not limited to: water, methanol, second Alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.Water as solvent can be various sources Water is hydrogen peroxide in the oxidant, and when hydrogen peroxide provides as an aqueous solution, the water in aqueous hydrogen peroxide solution can To be used as solvent.
The dosage of the solvent is not particularly limited, and can be conventional selection.Generally, the weight ratio of solvent and thioether can Think 0.1-1000:1, preferably 0.5-500:1, more preferably 1-200:1, further preferably 2-100:1, such as 2-20:1.
According to the method for the present invention, the oxidation reaction carries out under conditions of being enough becomes sulfone for sulfide oxidation.Generally Ground, temperature can be 0-200 DEG C, preferably 20-180 DEG C, more preferably 40-90 DEG C.In terms of gauge pressure, the pressure of the oxidation reaction Power can be 0-3MPa, preferably 0.1-2.5MPa, such as 0.5-2.5MPa.
According to the method for the present invention, the thioether can be selected according to the type of expected sulfone.For example, in preparation two When methyl sulfone, the thioether can be dimethyl sulfide；When preparing lauseto neu, the thioether can be thioanisole.It is described Thioether may be the mixture of two or more thioethers, can prepare the sulfone of two or more types simultaneously in this way, such as: the thioether It can be dimethyl sulfide and thioanisole, dimethyl sulfone and thioanisole can be prepared simultaneously in this way.
According to the method for the present invention, the mixture containing sulfone that oxidation reaction obtains can be divided using conventional method From, so that target product sulfone is obtained, and such as: the mixture containing sulfone can be distilled, to obtain target product sulfone.It is right In excessive thioether, use can be recycled.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, used reagent is commercially available reagent, and pressure is gauge pressure.
In following embodiment and comparative example, the content of each ingredient in the reaction solution analyzed using gas chromatography, Following formula is respectively adopted on this basis and calculates thioether rate, oxidant effective rate of utilization and sulfone selectivity:
Thioether rate (%)=[(mole of the unreacted thioether of the mole-of the thioether of addition)/sulphur being added The mole of ether] × 100%；
Oxidant effective rate of utilization=[mole for the sulfone that 2 × reaction generates/(mole-of the oxidant of addition is not The mole of the oxidant of reaction)] × 100%；
Sulfone selectivity=[mole/(the unreacted thioether mole of the mole-of the thioether of addition for the sulfone that reaction generates Amount)] × 100%.
In following embodiment and comparative example, static nitrogen adsorption method and solid ultraviolet-visible diffuse reflectance spectrum method is respectively adopted The Kong Rong and ultraviolet absorption peak of Titanium Sieve Molecular Sieve after before modified are characterized.Wherein, solid ultraviolet-visible diffuse reflectance spectrum (UV-Vis) analysis carries out on SHIMADZU UV-3100 type ultraviolet-visible spectrometer；Static nitrogen is adsorbed on It is carried out on the 2405 type static state n2 absorption apparatus of ASAP of Micromeritics company.
It is related to below through determining Titanium Sieve Molecular Sieve using following methods in the regenerated embodiment and comparative example for drawing off agent The activity of (including regenerative agent and fresh dose):
By Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH3Meter), the hydrogen peroxide of 30 weight % is (with H2O2Meter), the tert-butyl alcohol With cyclohexanone by weight after=1:7.5:10:7.5:10 mixing at atmosheric pressure after 80 DEG C are stirred to react 2 hours, will be anti- It answers object to filter, liquid phase is analyzed with gas-chromatography, be calculated using the following equation the conversion ratio of cyclohexanone and as titanium The activity of si molecular sieves,
The conversion ratio of cyclohexanone=[(the unreacted cyclohexanone mole of the mole-of the cyclohexanone of addition)/it is added The mole of cyclohexanone] × 100%.
In the embodiment and comparative example of the step of preparation Titanium Sieve Molecular Sieve included below, X-ray diffraction analysis exists It is carried out on Siemens D5005 type X-ray diffractometer, with sample and authentic specimen, the five fingers spread out between 2 θ is 22.5 ° -25.0 ° The crystallinity for penetrating the ratio of the sum of diffracted intensity (peak height) of characteristic peak to indicate sample relative to authentic specimen；Fourier transform Infrared spectrum analysis carries out on 8210 type Fourier transformation infrared spectrometer 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 spectroscopy of Thermo Scientific company Measurement, body phase silicon titanium ratio are measured using Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer.
Embodiment 1-17 is for illustrating the present invention.
Embodiment 1
(1) Titanium Sieve Molecular Sieve used in the present embodiment is titanium-silicon molecular sieve TS-1, referring to Zeolites, 1992, The preparation of method described in the 943-950 pages of Vol.12, the specific method is as follows.
(20 DEG C) at room temperature mix 22.5g tetraethyl orthosilicate with 7.0g as the tetrapropylammonium hydroxide of template It closes, and 59.8g distilled water is added, it is molten in normal pressure and 60 DEG C of hydrolysis 1.0h, the hydrolysis for obtaining tetraethyl orthosilicate after being stirred Liquid.With vigorous stirring, it is slowly added into Xiang Suoshu hydrating solution by 1.1g butyl titanate and 5.0g anhydrous isopropyl alcohol institute The solution of composition obtains clear colloid by gained mixture in 75 DEG C of stirring 3h.It is anti-that this colloid is placed in stainless steel sealing It answers in kettle, places 36h in 170 DEG C of at a temperature of constant temperature, obtain the mixture of crystallization product.Obtained mixture is filtered, is received After collecting obtained solid matter water used wash, in 110 DEG C of dry 1h, then in 500 DEG C of roasting 6h, to obtain Titanium Sieve Molecular Sieve TS-1, titanium oxide content are 2.8 weight %.
(2) by step (1) preparation titanium-silicon molecular sieve TS-1 and contain HNO3(HNO3Mass concentration 10%) and peroxide be The aqueous solution mixing for changing hydrogen (mass concentration of hydrogen peroxide is 7.5%), by obtained mixture at 70 DEG C in closed container It is stirred to react 5h, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry at 120 DEG C It is dry to constant weight, obtain modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and peroxidating The molar ratio of hydrogen is 1:0.1.Compared with raw material Titanium Sieve Molecular Sieve, in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 230-310nm reduces 3.5%, is held by the hole of static determination of nitrogen adsorption and reduces 2.6%.
(3) Titanium Sieve Molecular Sieve by the modification of step (2) preparation is seated in isometrical fixed bed reactors, forms catalyst Bed, wherein the quantity of catalyst bed is 1 layer.
Dimethyl sulfide, hydrogen peroxide (being provided in the form of the hydrogen peroxide of 30 weight %) and methanol are mixed, liquid is formed Body mixture.Then, the liquid mixture is sent into fixed bed reactors and modified Titanium Sieve Molecular Sieve haptoreaction.Its In, in liquid mixture, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1:2, and the weight ratio of dimethyl sulfide and methanol is 1:1, the weight (hourly) space velocity (WHSV) of liquid mixture are 60h-1.Temperature in catalyst bed is 45 DEG C, the pressure in fixed bed reactors For 0.6MPa.
It is carried out continuously reaction, is mixed during the reaction with the reaction that gas-chromatography monitoring is exported from fixed bed reactors The composition of object, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.It is listed by table 1 The result that the reaction mixture that reactor exports under reaction time determines is listed in table 1.
Embodiment 2
Dimethyl sulfone is prepared using method same as Example 1, unlike, in step (3), filled in catalyst bed What is filled out is the titanium silicon molecule of the modification of titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (1) and 1 step of embodiment (2) preparation The mixture of sieve, on the basis of the total amount of the mixture, the content of modified Titanium Sieve Molecular Sieve is 50 weight %.It is listed by table 1 Reaction time under reactor export reaction mixture determine result listed in table 1.
Embodiment 3
(1) Titanium Sieve Molecular Sieve modified using method preparation identical with 1 step of embodiment (2), unlike, as original The Titanium Sieve Molecular Sieve of material is through regenerated titanium-silicon molecular sieve TS-1 (titanium silicon molecule drawn off from phenol hydroxylation reaction unit Sieve TS-1 and use the identical method preparation with 1 step of embodiment (1), the Titanium Sieve Molecular Sieve drawn off 570 DEG C at a temperature of in sky 5h is roasted in gas atmosphere and is regenerated, and the activity after regeneration is 35%, 96%) activity when fresh is.With raw material Titanium Sieve Molecular Sieve It compares, the peak area of the absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification between 230-310nm is reduced 3.3%, held by the hole of static determination of nitrogen adsorption and reduces 2.8%.
(2) using identical method prepares dimethyl sulfone with 1 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 3 step of embodiment (1) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines is listed in table 1.
Comparative example 1
Dimethyl sulfone is prepared using method same as Example 3, unlike, in step (3), filled in catalyst bed Fill out be using with 3 step of embodiment (1) in as raw material through the regenerated titanium drawn off from phenol hydroxylation reaction unit Silicalite TS-1.The result that the reaction mixture that reactor exports under the reaction time listed by table 1 determines arranges in table 1 Out.
Comparative example 2
Dimethyl sulfone is prepared using method same as Example 3, unlike, processing is modified in step (1) When, nitric acid (that is, aqueous solution is free of hydrogen peroxide) is used only.The reaction that reactor exports under the reaction time listed by table 1 mixes The result that object determines is closed to list in table 1.
Comparative example 3
Dimethyl sulfone is prepared using method same as Example 3, unlike, processing is modified in step (1) When, hydrogen peroxide (that is, aqueous solution is free of nitric acid) is used only.The reaction that reactor exports under the reaction time listed by table 1 mixes The result that object determines is closed to list in table 1.
Comparative example 4
Dimethyl sulfone is prepared using method same as Example 3, unlike, processing is modified in step (1) When, nitric acid with etc. the HCl of quality replace (that is, aqueous solution contains hydrogen peroxide and HCl).It is anti-under the reaction time listed by table 1 The result that the reaction mixture for answering device to export determines is listed in table 1.
Table 1
Embodiment 4
(1) sky for being HTS for the trade mark purchased from Hunan Jianchang Petrochemical Co., Ltd as the Titanium Sieve Molecular Sieve of raw material Heart Titanium Sieve Molecular Sieve, titanium oxide content are 2.5 weight %.
By hollow Titanium Sieve Molecular Sieve and contain HNO3(HNO3Mass concentration be 10%) and hydrogen peroxide (hydrogen peroxide Mass concentration is aqueous solution mixing 5%), obtained mixture is stirred under 120 DEG C of pressure itselfs in closed container anti- 4h is answered, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry to perseverance at 120 DEG C Weight, obtains modified Titanium Sieve Molecular Sieve.Wherein, hollow Titanium Sieve Molecular Sieve is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide rub You are than being 1:0.4.Compared with raw material Titanium Sieve Molecular Sieve, in 230- in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak between 310nm reduces 4.6%, is held by the hole of static determination of nitrogen adsorption and reduces 3.8%.
(2) Titanium Sieve Molecular Sieve by the modification of step (1) preparation is seated in isometrical fixed bed reactors, forms catalyst Bed, wherein the quantity of catalyst bed is 1 layer.
Dimethyl sulfide, hydrogen peroxide (being provided in the form of the hydrogen peroxide of 40 weight %) and water are mixed, liquid is formed Mixture.Then, the liquid mixture is sent into fixed bed reactors and is connect with the catalyst bed containing Titanium Sieve Molecular Sieve Touching reaction.Wherein, in liquid mixture, the molar ratio of dimethyl sulfide and hydrogen peroxide is 1:2.2, dimethyl sulfide and water The weight ratio of (not including the water in hydrogen peroxide) is 1:2, and the weight (hourly) space velocity (WHSV) of liquid mixture is 80h-1.Temperature in catalyst bed Degree is 60 DEG C, and the pressure in fixed bed reactors is 1.2MPa.
It is carried out continuously reaction, is mixed during the reaction with the reaction that gas-chromatography monitoring is exported from fixed bed reactors The composition of object, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.It is listed by table 2 The result that the reaction mixture that reactor exports under reaction time determines is listed in table 2.
Embodiment 5
Dimethyl sulfone is prepared using method same as Example 4, unlike, in step (2), filled in catalyst bed What is filled out is the titanium of the modification prepared in 4 step of embodiment (1) as the hollow Titanium Sieve Molecular Sieve and 4 step of embodiment (2) of raw material The mixture of si molecular sieves, wherein on the basis of the total amount of the mixture, the content of modified Titanium Sieve Molecular Sieve is 80 weights Measure %.The result that the reaction mixture that reactor exports under the reaction time listed by table 2 determines is listed in table 2.
Embodiment 6
(1) Titanium Sieve Molecular Sieve modified using method preparation identical with 4 step of embodiment (1), unlike, preparation changes Property Titanium Sieve Molecular Sieve when the raw material that uses be through the regenerated hollow titanium silicon drawn off from cyclohexanone oxamidinating reaction unit point (the hollow Titanium Sieve Molecular Sieve is identical as the source of hollow Titanium Sieve Molecular Sieve of raw material as 4 step of embodiment (1), draws off for son sieve Hollow Titanium Sieve Molecular Sieve 550 DEG C at a temperature of in air atmosphere roast 6h and regenerate, the activity after regeneration be 40%, newly 97%) activity when fresh is.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 4.8%, is held by the hole of static determination of nitrogen adsorption and reduces 3.5%.
(2) using identical method prepares dimethyl sulfone with 4 step of embodiment (2), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 6 step of embodiment (1) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 2 determines is listed in table 2.
Comparative example 5
Dimethyl sulfone is prepared using method same as Example 4, unlike, in step (2), filled in catalyst bed What is filled out is hollow Titanium Sieve Molecular Sieve of 4 step of embodiment (1) as raw material.Reactor exports under the reaction time listed by table 2 Reaction mixture determine result listed in table 2.
Table 2
Embodiment 7
(1) it is prepared as the Titanium Sieve Molecular Sieve of raw material using following methods in the present embodiment.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:4:12: 400, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is sealed in beaker using sealed membrane It is stood for 24 hours after mouthful room temperature (being 25 DEG C, similarly hereinafter), followed by magnetic agitation in 35 DEG C of stirring 2h, is allowed to disperse again.It will weigh Dispersion liquid after new dispersion is transferred in sealing reaction kettle, and in 140 DEG C of experience first stage crystallization 6h, then mixture cools down After stopping 2h to 30 DEG C of experience second stage, continue in sealing reaction kettle in 170 DEG C of at a temperature of experience phase III crystallization 12h (wherein, by the heating rate of room temperature to first stage crystallization temperature be 2 DEG C/min, by first stage crystallization temperature to The rate of temperature fall of second stage treatment temperature is 5 DEG C/min, by second stage treatment temperature to the liter of phase III crystallization temperature Warm rate is 10 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly in 110 DEG C of drying 2h, so Afterwards in 550 DEG C of roasting 3h, molecular sieve is obtained.The titanium silicon molecule of XRD crystalline phase figure and 1 step of embodiment (1) preparation of gained sample Sieve TS-1 is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；In Fourier Transform Infrared Spectroscopy figure, In 960cm-1Nearby there is absorption peak, show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, titanium oxide content is 3.5 weights Measure %, urface silicon titanium/body phase silicon titanium ratio be 2.58 (1 step of embodiment (1) preparation Titanium Sieve Molecular Sieve in, urface silicon titanium/ 1.05) body phase silicon titanium ratio is.
(2) Titanium Sieve Molecular Sieve modified using method preparation identical with 1 step of embodiment (2), unlike, raw material is The titanium-silicon molecular sieve TS-1 of 7 step of embodiment (1) preparation.Compared with raw material Titanium Sieve Molecular Sieve, the titanium silicon molecule of obtained modification The peak area of absorption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.4%, by static determination of nitrogen adsorption Hole, which holds, reduces 2.7%.
(3) using identical method prepares dimethyl sulfone with 1 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 7 step of embodiment (2) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Embodiment 8
(1) using identical method prepares titanium-silicon molecular sieve TS-1 with 7 step of embodiment (1), unlike, the phase III Crystallization temperature be also 140 DEG C.The titanium-silicon molecular sieve TS-1 one of XRD crystalline phase figure and 1 step of embodiment (1) preparation of gained sample It causes, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby inhale Peak is received, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 4.21, titanium oxide Content is 3.1 weight %.
(2) Titanium Sieve Molecular Sieve modified using method preparation identical with 7 step of embodiment (2), unlike, raw material is The titanium-silicon molecular sieve TS-1 of 8 step of embodiment (1) preparation.Compared with raw material Titanium Sieve Molecular Sieve, the titanium silicon molecule of obtained modification The peak area of absorption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.3%, by static determination of nitrogen adsorption Hole, which holds, reduces 2.5%.
(3) using identical method prepares dimethyl sulfone with 7 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 8 step of embodiment (2) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Embodiment 9
(1) using identical method prepares titanium-silicon molecular sieve TS-1 with 7 step of embodiment (1), unlike, the first stage Crystallization temperature be 110 DEG C.The titanium-silicon molecular sieve TS-1 one of XRD crystalline phase figure and 1 step of embodiment (1) preparation of gained sample It causes, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby inhale Peak is received, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.37, titanium oxide Content is 3.2 weight %.
(2) Titanium Sieve Molecular Sieve modified using method preparation identical with 7 step of embodiment (2), unlike, raw material is The titanium-silicon molecular sieve TS-1 of 9 step of embodiment (1) preparation.Compared with raw material Titanium Sieve Molecular Sieve, the titanium silicon molecule of obtained modification The peak area of absorption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.4%, by static determination of nitrogen adsorption Hole, which holds, reduces 2.4%.
(3) using identical method prepares dimethyl sulfone with 7 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 9 step of embodiment (2) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Embodiment 10
(1) using identical method prepares titanium-silicon molecular sieve TS-1 with 7 step of embodiment (1), unlike, the first stage Crystallization time be 12h.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (1), What is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby absorb Peak shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 3.78, and titanium oxide contains Amount is 3.4 weight %.
(2) Titanium Sieve Molecular Sieve modified using method preparation identical with 7 step of embodiment (2), unlike, raw material is The titanium-silicon molecular sieve TS-1 of 10 step of embodiment (1) preparation.Compared with raw material Titanium Sieve Molecular Sieve, the titanium silicon molecule of obtained modification The peak area of absorption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.2%, by static determination of nitrogen adsorption Hole, which holds, reduces 2.5%.
(3) using identical method prepares dimethyl sulfone with 7 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 10 step of embodiment (2) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Embodiment 11
(1) using identical method prepares titanium-silicon molecular sieve TS-1 with 7 step of embodiment (1), unlike, second stage It is to be cooled to 70 DEG C of stop 2h.The titanium-silicon molecular sieve TS-1 one of XRD crystalline phase figure and 1 step of embodiment (1) preparation of gained sample It causes, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby inhale Peak is received, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.75, titanium oxide Content is 3.1 weight %.
(2) Titanium Sieve Molecular Sieve modified using method preparation identical with 7 step of embodiment (2), unlike, raw material is The titanium-silicon molecular sieve TS-1 of 11 step of embodiment (1) preparation.Compared with raw material Titanium Sieve Molecular Sieve, the titanium silicon molecule of obtained modification The peak area of absorption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.3%, by static determination of nitrogen adsorption Hole, which holds, reduces 2.4%.
(3) using identical method prepares dimethyl sulfone with 7 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 11 step of embodiment (2) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Embodiment 12
(1) using identical method prepares titanium-silicon molecular sieve TS-1 with 7 step of embodiment (1), unlike, second stage It is to be cooled to 30 DEG C of stop 0.2h.The titanium-silicon molecular sieve TS-1 of XRD crystalline phase figure and 1 step of embodiment (1) preparation of gained sample Unanimously, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby occur Absorption peak shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.14, oxidation Ti content is 3.1 weight %.
(2) Titanium Sieve Molecular Sieve modified using method preparation identical with 7 step of embodiment (2), unlike, raw material is The titanium-silicon molecular sieve TS-1 of 12 step of embodiment (1) preparation.Compared with raw material Titanium Sieve Molecular Sieve, the titanium silicon molecule of obtained modification The peak area of absorption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.5%, by static determination of nitrogen adsorption Hole, which holds, reduces 2.5%.
(3) using identical method prepares dimethyl sulfone with 7 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 12 step of embodiment (2) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Embodiment 13
(1) using identical method prepares titanium-silicon molecular sieve TS-1 with 7 step of embodiment (1), unlike, without the Two-stage.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by 1 step of embodiment (1), illustrates It is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absorption peak, shows titanium Into framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.08, and titanium oxide content is 2.5 weights Measure %.
(2) Titanium Sieve Molecular Sieve modified using method preparation identical with 7 step of embodiment (2), unlike, raw material is The titanium-silicon molecular sieve TS-1 of 13 step of embodiment (1) preparation.Compared with raw material Titanium Sieve Molecular Sieve, the titanium silicon molecule of obtained modification The peak area of absorption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.4%, by static determination of nitrogen adsorption Hole, which holds, reduces 2.6%.
(3) using identical method prepares dimethyl sulfone with 7 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 13 step of embodiment (2) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Embodiment 14
(1) using identical method prepares titanium-silicon molecular sieve TS-1 with 7 step of embodiment (1), unlike, aqueous dispersions It does not stand at room temperature for 24 hours, but is sent directly into reaction kettle and carries out crystallization.The XRD crystalline phase figure and 1 step of embodiment of gained sample Suddenly the titanium-silicon molecular sieve TS-1 of (1) preparation is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier In transform infrared spectroscopy figure, in 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, the Titanium Sieve Molecular Sieve In, titanium oxide content is 3.5 weight %, and urface silicon titanium/body phase silicon titanium ratio is 1.18.
(2) Titanium Sieve Molecular Sieve modified using method preparation identical with 7 step of embodiment (2), unlike, raw material is The titanium-silicon molecular sieve TS-1 of 14 step of embodiment (1) preparation.Compared with raw material Titanium Sieve Molecular Sieve, the titanium silicon molecule of obtained modification The peak area of absorption peak in the UV-Vis spectrum of sieve between 230-310nm reduces 3.5%, by static determination of nitrogen adsorption Hole, which holds, reduces 2.2%.
(3) using identical method prepares dimethyl sulfone with 7 step of embodiment (3), unlike, it is filled in catalyst bed What is filled out is the Titanium Sieve Molecular Sieve of the modification of 14 step of embodiment (2) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Comparative example 6
Dimethyl sulfone is prepared using method identical with 7 step of embodiment (3), unlike, it is loaded in catalyst bed Be titanium-silicon molecular sieve TS-1 using 7 step of embodiment (1) identical method preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 3 determines is listed in table 3.
Table 3
Embodiment 15
(1) it is prepared as the Titanium Sieve Molecular Sieve of raw material using following methods in the present embodiment.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:2:10: 600, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is close using sealed membrane in beaker It is honored as a queen in 40 DEG C of standing 10h, is stirred 0.5h at 25 DEG C followed by magnetic agitation, is allowed to disperse again.It will disperse again Dispersion liquid afterwards is transferred in sealing reaction kettle, and in 130 DEG C of experience first stage crystallization 8h, mixture is then cooled to 50 DEG C After undergoing second stage to stop 5h, continues the temperature in sealing reaction kettle in 170 DEG C and undergo phase III crystallization 16h (wherein, It is 1 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first 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, directly in 120 DEG C of drying 3h, then 580 2h is roasted at DEG C, obtains molecular sieve.The titanium-silicon molecular sieve TS-1 of XRD crystalline phase figure and 1 step of embodiment (1) preparation of gained sample Unanimously, what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；In Fourier Transform Infrared Spectroscopy figure, in 960cm-1 Nearby there is absorption peak, show that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.25, titanium oxide content is 2.6 weight %.
(2) by step (1) preparation titanium-silicon molecular sieve TS-1 and contain HNO3(HNO3Mass concentration 15%) and peroxide be The aqueous solution mixing for changing hydrogen (mass concentration of hydrogen peroxide is 8%), obtained mixture is stirred in closed container at 150 DEG C Reaction 3h is mixed, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, by obtained solid matter in 120 DEG C of dryings To constant weight, modified Titanium Sieve Molecular Sieve is obtained.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and hydrogen peroxide Molar ratio be 1:2.Through characterizing, compared with raw material Titanium Sieve Molecular Sieve, the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification In the peak area of absorption peak between 230-310nm reduce 5.5%, held by the hole of static determination of nitrogen adsorption and reduce 4.3%.
(3) Titanium Sieve Molecular Sieve by the modification of step (2) preparation is seated in fixed bed reactors, forms catalyst bed Layer, wherein the quantity of catalyst bed is 1 layer.
Dimethyl sulfide, tert-butyl hydroperoxide and acetonitrile are mixed, liquid mixture is formed.Then, by the liquid Mixture is sent into fixed bed reactors and the catalyst bed haptoreaction containing Titanium Sieve Molecular Sieve.Wherein, liquid mixture In, the molar ratio of dimethyl sulfide and tert-butyl hydroperoxide is 1:2.5, and the weight ratio of dimethyl sulfide and acetonitrile is 1:5, liquid The weight (hourly) space velocity (WHSV) of body mixture is 80h-1.Temperature in catalyst bed is 80 DEG C, and the pressure in fixed bed reactors is 2.5MPa。
It is carried out continuously reaction, is mixed during the reaction with the reaction that gas-chromatography monitoring is exported from fixed bed reactors The composition of object, and calculate dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.It is listed by table 4 The result that the reaction mixture that reactor exports under reaction time determines is listed in table 4.
Embodiment 16
(1) Titanium Sieve Molecular Sieve modified using method preparation identical with 15 step of embodiment (2), unlike, as The Titanium Sieve Molecular Sieve of raw material is through regenerated titanium-silicon molecular sieve TS-1 (titanium silicon point drawn off from propylene ring oxidation reaction device Son sieve TS-1 uses the identical method preparation with 15 step of embodiment (1), the Titanium Sieve Molecular Sieve drawn off 580 DEG C at a temperature of in 3h is roasted in air atmosphere and is regenerated, and the activity after regeneration is 40%, 95%) activity when fresh is.With raw material titanium silicon molecule Sieve is compared, and the peak area of the absorption peak in the UV-Vis spectrum of the Titanium Sieve Molecular Sieve of obtained modification between 230-310nm subtracts Few 5.3%, held by the hole of static determination of nitrogen adsorption and reduces 4.8%.
(2) using identical method prepares dimethyl sulfone with 15 step of embodiment (3), unlike, in catalyst bed What is loaded is the Titanium Sieve Molecular Sieve of the modification of 16 step of embodiment (1) preparation.
The result that the reaction mixture that reactor exports under the reaction time listed by table 4 determines is listed in table 4.
Embodiment 17
(1) it is prepared as the Titanium Sieve Molecular Sieve of raw material using following methods in the present embodiment.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:5:18: 1000, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is utilized into sealed membrane in beaker In 45 DEG C of standing 8h after sealing；Dispersion liquid through standing is transferred in sealing reaction kettle, in 140 DEG C of experience first stage crystallization 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, obtain molecular sieve.The XRD crystalline phase figure and 1 step of embodiment of gained sample Suddenly the titanium-silicon molecular sieve TS-1 of (1) preparation is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier In transform infrared spectroscopy figure, in 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, the Titanium Sieve Molecular Sieve In, urface silicon titanium/body phase silicon titanium ratio is 2.71, and titanium oxide content is 4.3 weight %.
(2) by step (1) preparation titanium-silicon molecular sieve TS-1 and contain HNO3(HNO3Mass concentration 10%) and peroxide be The aqueous solution mixing for changing hydrogen (mass concentration of hydrogen peroxide is 2%), obtained mixture is stirred in closed container at 170 DEG C Reaction 2.5h is mixed, the temperature of obtained reaction mixture, which is cooled to room temperature, to be filtered, and obtained solid matter is dry at 120 DEG C It is dry to constant weight, obtain modified Titanium Sieve Molecular Sieve.Wherein, titanium-silicon molecular sieve TS-1 is with SiO2Meter, Titanium Sieve Molecular Sieve and peroxidating The molar ratio of hydrogen is 1:1.Through characterizing, compared with raw material Titanium Sieve Molecular Sieve, the UV-Vis light of the Titanium Sieve Molecular Sieve of obtained modification The peak area of absorption peak in spectrum between 230-310nm reduces 5.7%, is held by the hole of static determination of nitrogen adsorption and is reduced 4.1%.
(3) Titanium Sieve Molecular Sieve by the modification of step (2) preparation is seated in fixed bed reactors, forms catalyst bed Layer, wherein the quantity of catalyst bed is 1 layer.
Thioanisole, Perpropionic Acid and acetone are mixed, liquid mixture is formed.Then, the liquid mixture is sent Enter in fixed bed reactors with the catalyst bed haptoreaction containing Titanium Sieve Molecular Sieve.Wherein, in liquid mixture, benzene first sulphur The molar ratio of ether and Perpropionic Acid is 1:2.5, and the weight ratio of thioanisole and acetone is 1:15, the weight (hourly) space velocity (WHSV) of liquid mixture For 40h-1.Temperature in catalyst bed is 90 DEG C, and the pressure in fixed bed reactors is 3MPa.
It is carried out continuously reaction, is mixed during the reaction with the reaction that gas-chromatography monitoring is exported from fixed bed reactors The composition of object, and calculate thioether rate, oxidant effective rate of utilization and lauseto neu selectivity.The reaction time listed by table 4 The result that the reaction mixture of lower reactor output determines is listed in table 4.
Table 4
Embodiment 1-17's as a result, it was confirmed that can effectively promote the titanium silicon molecule as catalyst according to the method for the present invention The catalytic performance of sieve extends the single trip use service life of Titanium Sieve Molecular Sieve, reduces the regeneration frequency of Titanium Sieve Molecular Sieve.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (51)

1. a kind of preparation method of sulfone, this method are included under oxidation reaction condition, by least one thioether and at least one oxygen Agent is contacted with Titanium Sieve Molecular Sieve, obtains the mixture containing sulfone, and the thioether is dimethyl sulfide, and the oxidant was selected from Oxide, the Titanium Sieve Molecular Sieve is modified Titanium Sieve Molecular Sieve or the Titanium Sieve Molecular Sieve is modified Titanium Sieve Molecular Sieve Modification, the unmodified Titanium Sieve Molecular Sieve are undergone with the Titanium Sieve Molecular Sieve of unmodified Titanium Sieve Molecular Sieve, the modification Modification is not undergone, and the modification includes will be as the Titanium Sieve Molecular Sieve of raw material and by nitric acid, hydrogen peroxide and water group At modification liquid contact, in the modification, be as the Titanium Sieve Molecular Sieve of raw material and the molar ratio of the peroxide 1:0.01-5, the molar ratio of the peroxide and the nitric acid are 1:0.01-50, the Titanium Sieve Molecular Sieve of the modification and described Unmodified Titanium Sieve Molecular Sieve is respectively titanium-silicon molecular sieve TS-1 and/or hollow Titanium Sieve Molecular Sieve, and the Titanium Sieve Molecular Sieve is with two Silica meter.
2. according to the method described in claim 1, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The molar ratio of peroxide is stated as 1:0.05-3, the molar ratio of the peroxide and the nitric acid is 1:0.1-20, the titanium Si molecular sieves are in terms of silica.
3. according to the method described in claim 2, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material The molar ratio of peroxide is stated as 1:0.1-2, the molar ratio of the peroxide and the nitric acid is 1:0.2-10, the titanium silicon Molecular sieve is in terms of silica.
4. according to the method described in claim 3, wherein, in the modification, the peroxide and the nitric acid Molar ratio is 1:0.5-5.
5. according to the method described in claim 4, wherein, in the modification, the peroxide and the nitric acid Molar ratio is 1:0.6-3.5.
6. method described in any one of -5 according to claim 1, wherein in the modification liquid, peroxide and nitric acid Concentration is respectively 0.1-50 weight %.
7. according to the method described in claim 6, wherein, in the modification liquid, the concentration of peroxide and nitric acid is respectively 0.5-30 weight %.
8. according to the method described in claim 7, wherein, in the modification liquid, the concentration of peroxide and nitric acid is respectively 1- 25 weight %.
9. method described in any one of -5 according to claim 1, wherein the titanium in the modification, as raw material Si molecular sieves and the modification liquid 10-350 DEG C at a temperature of contacted, the contact is in the container that pressure is 0-5MPa It carries out, the pressure is gauge pressure；The duration of the contact is 0.5-10 hours.
10. according to the method described in claim 9, wherein, Titanium Sieve Molecular Sieve and institute in the modification, as raw material State modification liquid 20-300 DEG C at a temperature of contacted, duration of the contact is 2-5 hours.
11. according to the method described in claim 10, wherein, in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 50-250 DEG C at a temperature of contacted.
12. according to the method for claim 11, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The modification liquid 60-200 DEG C at a temperature of contacted.
13. method described in any one of -5 according to claim 1, wherein the titanium in the modification, as raw material The exposure level of si molecular sieves and the modification liquid makes, using on the basis of the Titanium Sieve Molecular Sieve as raw material, in ultraviolet-visible light In spectrum, the peak area of absorption peak of the modified Titanium Sieve Molecular Sieve between 230-310nm reduces by 2% or more；Modified titanium silicon point The hole of son sieve, which holds, reduces 1% or more, and the Kong Rong is using static determination of nitrogen adsorption.
14. according to the method for claim 13, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 2-30%；The Kong Rong of modified Titanium Sieve Molecular Sieve 1-20% is reduced, the Kong Rong is using static determination of nitrogen adsorption.
15. according to the method for claim 14, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 2.5-15%；The hole of modified Titanium Sieve Molecular Sieve Hold and reduce 1.5-10%, the Kong Rong is using static determination of nitrogen adsorption.
16. according to the method for claim 15, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 3-10%；The Kong Rong of modified Titanium Sieve Molecular Sieve 2-6% is reduced, the Kong Rong is using static determination of nitrogen adsorption.
17. according to the method for claim 16, wherein in the modification, as raw material Titanium Sieve Molecular Sieve with The exposure level of the modification liquid makes, modified in ultraviolet-visible spectrum using on the basis of the Titanium Sieve Molecular Sieve as raw material The peak area of absorption peak of the Titanium Sieve Molecular Sieve between 230-310nm reduce 3-8%.
18. method described in any one of -5 according to claim 1, wherein the Titanium Sieve Molecular Sieve is unmodified titanium silicon Molecular sieve and modified Titanium Sieve Molecular Sieve, on the basis of the total amount of the Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve of the modification Content is 5-95 weight %, and the content of the unmodified Titanium Sieve Molecular Sieve is 5-95 weight %.
19. according to the method for claim 18, wherein the Titanium Sieve Molecular Sieve is unmodified Titanium Sieve Molecular Sieve and modification Titanium Sieve Molecular Sieve, on the basis of the total amount of the Titanium Sieve Molecular Sieve, the content of the Titanium Sieve Molecular Sieve of the modification is 20-90 weight % is measured, the content of the unmodified Titanium Sieve Molecular Sieve is 10-80 weight %.
20. according to the method for claim 19, wherein the Titanium Sieve Molecular Sieve is unmodified Titanium Sieve Molecular Sieve and modification Titanium Sieve Molecular Sieve, on the basis of the total amount of the Titanium Sieve Molecular Sieve, the content of the Titanium Sieve Molecular Sieve of the modification is 40-80 weight Measure %；The content of the unmodified Titanium Sieve Molecular Sieve is 20-60 weight %.
21. method described in any one of -5 according to claim 1, wherein at least partly Titanium Sieve Molecular Sieve is from least A kind of reaction unit draws off agent, it is described draw off agent be Ammoximation reaction device draw off agent, hydroxylating device is drawn off Agent and epoxidation reaction device draw off agent.
22. according to the method described in claim 1, wherein, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the titanium The urface silicon titanium of silicalite TS-1 is not less than body phase silicon titanium ratio, mole of the silicon titanium than referring to silica and titanium oxide Than the urface silicon titanium is measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses x ray fluorescence spectrometry Measurement.
23. according to the method for claim 22, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is More than 1.2.
24. according to the method for claim 23, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5。
25. according to the method for claim 24, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.5-4.5。
26. according to the method for claim 25, wherein the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 2- 3。
27. according to claim 1 with the method described in any one of 22-26, wherein at least partly Titanium Sieve Molecular Sieve is titanium silicon Molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 are 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, dispersed Liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:(0.5-8): (5-30): (100- 2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N meter；
(B) optionally, by the dispersion liquid in 15-60 DEG C of standing 6-24h；
(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, and the stage (1) is in 80-150 DEG C of crystallization 6-72h；Stage (2) is cooled to not higher than 70 DEG C and residence time at least 0.5h；Stage (3) is warming up to 120-200 DEG C, then crystallization 6-96h.
28. according to the method for claim 27, wherein the stage (1) is in 110-140 DEG C of crystallization 6-8h.
29. according to the method for claim 28, wherein the stage, (1) was in 120-140 DEG C of crystallization.
30. according to the method for claim 29, wherein the stage, (1) was in 130-140 DEG C of crystallization.
31. according to the method for claim 27, wherein the residence time in stage (2) is 1-5 hours.
32. according to the method for claim 27, wherein the stage (3) is warming up to 140-180 DEG C, then crystallization 12-20h.
33. according to the method for claim 32, wherein the stage (3) is warming up to 160-170 DEG C.
34. according to the method for claim 27, wherein stage (1) and stage (3) meet one of the following conditions or The two:
Condition 1: the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3)；
Condition 2: the crystallization time in stage (1) is less than the crystallization time of stage (3).
35. according to the method for claim 34, wherein condition 1: crystallization temperature of the crystallization temperature in stage (1) than the stage (3) Spend low 10-50 DEG C.
36. according to the method for claim 35, wherein condition 1: crystallization temperature of the crystallization temperature in stage (1) than the stage (3) Spend low 20-40 DEG C.
37. according to the method for claim 34, wherein condition 2: the crystallization time in stage (1) than the stage (3) crystallization when Between it is 5-24 hours short.
38. according to the method for claim 37, wherein condition 2: the crystallization time in stage (1) than the stage (3) crystallization when Between it is 6-12 hours short.
39. according to the method for claim 27, wherein the stage (2) is cooled to not higher than 50 DEG C, and the residence time is at least 1 hour.
40. according to the method for claim 27, wherein the titanium source is inorganic titanium salt and/or organic titanate；The alkali Source template is one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine；The inorganic silicon source be silica gel and/ Or silica solution.
41. according to the method for claim 40, wherein the alkali source template is quaternary ammonium base.
42. according to the method for claim 41, wherein the alkali source template is tetrapropylammonium hydroxide.
43. according to the method for claim 40, wherein the inorganic titanium salt is TiCl4、Ti(SO4)2And TiOCl2In one Kind is two or more；The organic titanate is selected from general formula R7 4TiO4The compound of expression, R7Selected from 2-4 carbon atom Alkyl.
44. method described in any one of -5 and 22-26 according to claim 1, wherein the oxidant and the thioether Molar ratio is 2-20:1.
45. according to the method for claim 44, wherein the molar ratio of the oxidant and the thioether is 2-10:1.
46. according to the method for claim 45, wherein the molar ratio of the oxidant and the thioether is 2-5:1.
47. method described in any one of -5 and 22-26 according to claim 1, wherein the peroxide as oxidant selects From hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid And Perpropionic Acid.
48. according to the method for claim 47, wherein the peroxide as oxidant is hydrogen peroxide.
49. method described in any one of -5 and 22-26 according to claim 1, wherein the oxidation reaction is 0- in temperature 200 DEG C and pressure carry out under conditions of being 0-3MP, and the pressure is gauge pressure.
50. according to the method for claim 49, wherein the temperature of the oxidation reaction is 20-180 DEG C.
51. according to the method for claim 50, wherein the temperature of the oxidation reaction is 40-90 DEG C.
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Publication number Priority date Publication date Assignee Title
CN104291352A (en) * 2014-09-30 2015-01-21 浙江大学 Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation
CN104557624A (en) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 Method for preparing dimethyl sulfone
CN104944441A (en) * 2014-03-31 2015-09-30 中国石油化工股份有限公司 Method for synthesizing titanium-silicon molecular sieve

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104557624A (en) * 2013-10-29 2015-04-29 中国石油化工股份有限公司 Method for preparing dimethyl sulfone
CN104944441A (en) * 2014-03-31 2015-09-30 中国石油化工股份有限公司 Method for synthesizing titanium-silicon molecular sieve
CN104291352A (en) * 2014-09-30 2015-01-21 浙江大学 Method for preparing and modifying titanium silicalite molecular sieve catalyst and application of titanium silicalite molecular sieve catalyst in ketone oximation

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