CN109721514A - A kind of preparation method of sulfone - Google Patents

Abstract

The invention discloses a kind of preparation methods of sulfone, comprising: provides the reaction feed containing at least one thioether, at least one oxidant and optional at least one solvent；So that reaction feed is entered the 1st catalyst bed and flows through the 1st catalyst bed to the n-th catalyst bed, the catalyst containing molecular sieve is loaded in the catalyst bed, when the overall presure drop of catalyst bed is higher than initial overall presure drop, the charging of 1st catalyst bed is divided into the 1st logistics to f logistics, 1st logistics enters the 1st catalyst bed, and the residue stream in addition to the 1st logistics enters the catalyst bed positioned at the 1st catalyst bed downstream.Sulfide oxidation is prepared by sulfone using method of the invention, the raised trend of catalyst bed pressure drop in long-time tandem reaction sequence can be effectively inhibited, system energy consumption is reduced, extends the parallel-adder settle-out time of device.

Description

A kind of preparation method of sulfone

Technical field

The present invention relates to a kind of preparation methods of sulfone.

Background technique

As the Typical Representative of sulfone substance, dimethyl sulfone is white crystalline powder, soluble easily in water, ethyl alcohol, benzene, methanol and Acetone is slightly soluble in ether.Potassium permanganate cannot be made to change colour under room temperature, dimethyl sulfone can be oxidized to methanesulfonic acid by strong oxidizer.Diformazan Base sulfone be used as in the industry organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, food additives and Drug.Dimethyl sulfone is as a kind of organic sulfur compound, the ability that there is enhancing human body to generate insulin, while the metabolism to carbohydrate Also there is facilitation, be the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound healing, also can be to new old Vitamin B, vitamin C, the synthesis of biotin and activation needed for metabolism and neurological health are worked, and referred to as " are beautified naturally Carbonizable substance ".All contain dimethyl sulfone in the skin of human body, hair, nail, bone, muscle and each organ, dimethyl sulfone is in nature It is primarily present in Yu Haiyang and soil in boundary, is absorbed in plant growth as nutriment, the mankind can be from vegetables, water It is absorbed in the foods such as fruit, fish, meat, egg, milk, is that human body maintains biology once health disorders will be caused or disease occurs by lacking The main matter of element sulphur balance has therapeutic value and healthcare function to human body diseases, is human survival and health care Indispensable drug.

Summary of the invention

CN105523974A is disclosed connects dimethyl sulfide and oxidant in fixed bed reactors with Titanium Sieve Molecular Sieve Touching, obtains dimethyl sulfone.But the present inventor has found in the actual operation process, by dimethyl sulfide and oxidant It when haptoreaction, is increased with the extension catalyst bed pressure drop in reaction time, one in fixed bed reactors with Titanium Sieve Molecular Sieve Aspect causes system energy consumption to increase, and on the other hand reduces operation stability and the safety of reactor.

It is an object of the invention to overcome to use fixed bed reactors by thioether and oxidant and molecular sieve haptoreaction system When standby sulfone, extend with the reaction time, catalyst bed pressure drop increases, and causes system energy consumption to increase and the operation for influencing reactor is steady The technical issues of qualitative and safety, a kind of preparation method of sulfone is provided, this method can effectively inhibit continuous for a long time anti- The raised trend of catalyst bed pressure drop during answering extends device parallel-adder settle-out time, improves the safety of device operation.

The present invention provides a kind of preparation methods of sulfone, this method comprises:

Reaction feed containing at least one thioether, at least one oxidant and optional at least one solvent, institute are provided The molar ratio for stating oxidant and the thioether is greater than 2；

Make reaction feed enter the 1st catalyst bed and flow through the 1st catalyst bed under oxidation reaction condition to urge to n-th Agent bed, obtains the product stream containing sulfone, the integer that n is 2 or more, in the catalyst bed filling it is at least one containing point The catalyst of son sieve,

When the overall presure drop of catalyst bed is higher than initial overall presure drop, triage operator is carried out, the triage operator includes will The charging of 1st catalyst bed is divided into the 1st logistics to f logistics, and the integer that f is 2 or more, the 1st logistics enters the 1st catalysis Agent bed, and the 1st catalyst bed and the catalyst bed positioned at the 1st catalyst bed downstream are flowed successively through, remove the 1st logistics Outer residue stream enter positioned at the 1st catalyst bed downstream catalyst bed, and flow successively through the catalyst bed and Catalyst bed positioned at the catalyst bed downstream.

Sulfide oxidation is prepared by sulfone using method of the invention, can effectively inhibit and be catalyzed in long-time tandem reaction sequence The raised trend of agent bed pressure drop reduces system energy consumption, extends the parallel-adder settle-out time of device.

Specific embodiment

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

In the present invention, term "at least one" indicates one or more kinds of.

The present invention provides a kind of preparation method of sulfone, this method includes providing containing at least one thioether, at least one The reaction feed of oxidant and optional at least one solvent.

The thioether refers to the compound for containing-S- key in molecular structure, it is preferable that the thioether is selected from carbon atom number The thioether of 2-18, more preferably dimethyl sulfide and/or thioanisole.

The oxidant can be the various substances for being enough to generate sulfide oxidation into sulfone.Method of the invention is particularly suitable for Carry out the occasion that oxidizing sulfur ether prepares sulfone using peroxide as oxidant.The peroxide, which refers to, contains-O- in molecular structure The compound of O- key can be selected from hydrogen peroxide, organic peroxide and peracid.The organic peroxide refers to hydrogen peroxide Substance obtained from a hydrogen atom or two hydrogen atoms in molecule are replaced by organic group.The peracid refers to molecule knot Contain the organic oxacid of-O-O- key in structure.The specific example of the peroxide can include but is not limited to: hydrogen peroxide, One or both of tert-butyl hydroperoxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid with On.Preferably, the oxidant is hydrogen peroxide.The hydrogen peroxide can be commonly used in the art existing in a variety of manners Hydrogen peroxide, the hydrogen peroxide provided such as in the form of hydrogen peroxide.

According to the method for the present invention, the molar ratio of the oxidant and the thioether is the preferably 2.1-5:1 greater than 2, more Preferably 2.2-3:1.

The reaction feed can contain solvent, can also not contain solvent.It is each anti-in reaction system from further increasing The mixability between object, enhanced dispersion and the angle that more easily severe degree of reaction is adjusted is answered to set out, institute It states reaction feed and preferably comprises at least one solvent.The type of the solvent is not particularly limited.Generally, the solvent can be with Selected from water, C₁-C₆Alcohol, C₃-C₈Ketone and C₂-C₆Nitrile.The specific example of the solvent can include but is not limited to: water, first Alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.

The dosage of the solvent is not particularly limited, and can be conventional selection.Generally, the mass ratio of solvent and thioether can Think 1-200:1, preferably 5-100:1, more preferably 8-60:1, further preferably 10-30:1.

According to the method for the present invention, the reaction feed is made to enter the 1st catalyst bed and flow down in oxidation reaction condition The 1st catalyst bed to the n-th catalyst bed is crossed, the product stream containing sulfone is obtained.In the present invention, the integer that n is 2 or more, n Can be the integer between 2 to 50, preferably 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20, more preferably 2,3,4,5,6,7,8,9 or 10, further preferably 2,3,4 or 5, for example, 2.

According to the method for the present invention, at least one catalyst containing molecular sieve is loaded in the catalyst bed.

According to the method for the present invention, the catalyst bed can also load in addition to loading the catalyst containing molecular sieve Inert filler, so that the content of the catalyst in catalyst bed containing molecular sieve be adjusted.The inert filler can be Common various fillers, such as Raschig ring, Pall ring, cascade ring, arc saddle, square saddle and metal ring intalox can be selected from.It is described to fill out The specific example of material can be θ ring and/or β ring.The loadings of the inert filler can according to expected reaction speed and The treating capacity of reaction zone makes appropriate choice, and is subject to and can satisfy specifically used requirement.

The catalyst containing molecular sieve can be with catalytic activity to sulfide oxidation reaction using molecular sieve as work The catalyst of property ingredient, can be preformed catalyst, or molecular screen primary powder.

The preformed catalyst contains the molecular sieve as active constituent and the carrier as binder, wherein molecular sieve Content can be conventional selection.Generally, on the basis of the total amount of the preformed catalyst, the content of molecular sieve can be 5- 95 weight %, preferably 10-95 weight %, more preferably 70-90 weight %；The content of the carrier can be 5-95 weight Measure %, preferably 5-90 weight %, more preferably 10-30 weight %.The carrier of the preformed catalyst can be conventional selection, Such as aluminium oxide and/or silica.The method for preparing the preformed catalyst is it is known in the art, being no longer described in detail herein.Institute The granular size for stating preformed catalyst is also not particularly limited, and can be made appropriate choice according to concrete shape.Generally, institute The average grain diameter for stating preformed catalyst can be 4-5000 microns, preferably 5-2000 microns, such as 40-1000 microns.It is described flat Equal partial size is volume average particle size, can be measured using laser particle analyzer.

The specific example of molecular sieve in the catalyst containing molecular sieve can include but is not limited to: Titanium Sieve Molecular Sieve, One or more of V-Si molecular sieve and vanadium Titanium Sieve Molecular Sieve.

In the present invention, Titanium Sieve Molecular Sieve is the total of a kind of zeolite of a part of silicon atom in titanium atom substitution lattice framework Claim.The content of titanium atom in Titanium Sieve Molecular Sieve is not particularly limited in the present invention, can be the conventional selection of this field.

In the present invention, Titanium Sieve Molecular Sieve can be the common Titanium Sieve Molecular Sieve with various topological structures, such as: it is described Titanium Sieve Molecular Sieve can be Titanium Sieve Molecular Sieve (such as TS-1), the Titanium Sieve Molecular Sieve (such as TS-2) of MEL structure, the BEA knot of MFI structure The Titanium Sieve Molecular Sieve (such as Ti-Beta) of structure, the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, hexagonal structure titanium silicon molecule Sieve (such as Ti-MCM-41, Ti-SBA-15), the Titanium Sieve Molecular Sieve (such as Ti-MOR) of MOR structure, the Titanium Sieve Molecular Sieve of TUN structure One or more of Titanium Sieve Molecular Sieve (such as Ti-ZSM-48) of (such as Ti-TUN) and other structures.Preferably, the titanium Si molecular sieves are the Titanium Sieve Molecular Sieve of MFI structure, such as titanium-silicon molecular sieve TS-1.

In the Titanium Sieve Molecular Sieve, based on the element, element silicon: the molar ratio of titanium elements can be 100:0.5-10, preferably For 100:1-8, more preferably 100:1.2-6, further preferably 100:2-4.

In the present invention, V-Si molecular sieve refer to vanadium atom replace lattice framework in a part of silicon atom a kind of zeolite it is total Claim.The V-Si molecular sieve can be the common V-Si molecular sieve with various topological structures, such as: the V-Si molecular sieve It can divide for the vanadium silicon of the V-Si molecular sieve (such as VS-1) of MFI structure, the V-Si molecular sieve (such as VS-2) of MEL structure, BEA structure Son sieve (such as V- β), the V-Si molecular sieve (such as V-MCM-22) of MWW structure, hexagonal structure V-Si molecular sieve (such as V-MCM-41, ) and one or more of the V-Si molecular sieve of MOR structure (such as V-MOR) V-SBA-15.Preferably, the vanadium silicon molecule Sieve is the V-Si molecular sieve of MFI structure.

In the V-Si molecular sieve, based on the element, element silicon: the molar ratio of vanadium can be 100:0.01-5, preferably For 100:0.2-2.5, more preferably 100:0.5-2, further preferably 100:0.6-1.

In the present invention, vanadium Titanium Sieve Molecular Sieve contains vanadium, titanium elements, element silicon, and vanadium and titanium elements replace crystalline substance Part element silicon in framework.The vanadium Titanium Sieve Molecular Sieve can be the common vanadium titanium silicon molecule with various topological structures Sieve, such as: the vanadium Titanium Sieve Molecular Sieve can be vanadium Titanium Sieve Molecular Sieve, the vanadium Titanium Sieve Molecular Sieve of MEL structure, BEA of MFI structure The vanadium titanium of the vanadium Titanium Sieve Molecular Sieve of structure, the vanadium Titanium Sieve Molecular Sieve of MWW structure, the vanadium Titanium Sieve Molecular Sieve of hexagonal structure, MOR structure One or more of si molecular sieves, the vanadium Titanium Sieve Molecular Sieve of TUN structure and vanadium Titanium Sieve Molecular Sieve of other structures.It is preferred that Ground, the vanadium Titanium Sieve Molecular Sieve are the vanadium Titanium Sieve Molecular Sieve of MFI structure.

In the vanadium Titanium Sieve Molecular Sieve, based on the element, element silicon: titanium elements: the molar ratio of vanadium can be 100: 0.5-10:0.01-5, preferably 100:1-8:0.2-2.5, more preferably 100:1.2-6:0.5-2.

According to the method for the present invention, from the angle for the selectivity for further increasing sulfone, the molecular sieve is vanadium silicon point Son sieve and/or vanadium Titanium Sieve Molecular Sieve.

According to the method for the present invention, in a preferred embodiment, the molecular sieve is vanadium Titanium Sieve Molecular Sieve, and institute It states vanadium Titanium Sieve Molecular Sieve and meets X_1-1.8/X_0.4-0.9=C, 0.05 < C < 0.5, X_0.4-0.9For in molecular sieve 0.4-0.9nm range it is micro- The ratio of the total micropore size abundance of hole aperture Zhan, X_1-1.8It is molecular sieve in the total micropore hole micropore size Zhan of 1-1.8nm range The ratio of diameter abundance.Preferably, 0.1≤C≤0.48.

According to the vanadium Titanium Sieve Molecular Sieve of the preferred embodiment, the vanadium Titanium Sieve Molecular Sieve meets T_w/T_k=D, 0.3 < D < 0.7, it is further preferred that 0.4≤D≤0.6, it is further preferred that 0.5≤D≤0.6, wherein T_wFor the micropore of molecular sieve Pore volume, T_kFor the total pore volume of molecular sieve.

In the present invention, micropore size and micropore pore volume use N₂Static adsorptive method measurement.According to the preferred embodiment party Formula, if within the scope of 1-1.8nm micropore size distribution the total micropore size abundance of Zhan ratio < 1% when, this partial pore Pore size distribution is ignored, that is, thinks to be distributed within the scope of 1-1.8nm without micropore.The micropore point of conventional direct hydrothermal synthesis preparation Son sieve, ratio < 1% of the micropore size distribution total micropore size abundance of Zhan, changes through common processing within the scope of 1-1.8nm Property method handle modified micro porous molecular sieve, micropore size is distributed the total micropore size abundance of Zhan within the scope of 1-1.8nm Ratio it is relatively low, generally < 1%.

It can be made using method comprising the following steps according to the vanadium Titanium Sieve Molecular Sieve of the preferred embodiment:

(1) by Titanium Sieve Molecular Sieve and acid solution 40-200 DEG C, preferably 50-180 DEG C, it is 60-180 DEG C more preferable, further excellent It is contacted at a temperature of selecting 80-100 DEG C, isolates solid phase from the mixture that contact obtains；

(2) it is carried out at hydro-thermal after mixing the isolated solid phase of step (1) with silicon source, titanium source, vanadium source, alkali source and water Reason.

In step (1), the Titanium Sieve Molecular Sieve can be fresh titanium si molecular sieves and/or non-fresh Titanium Sieve Molecular Sieve.Institute Fresh Titanium Sieve Molecular Sieve is stated to refer to not yet for being catalyzed the Titanium Sieve Molecular Sieve of reaction；The non-fresh Titanium Sieve Molecular Sieve refers to experience Cross the Titanium Sieve Molecular Sieve of catalysis reaction.The specific example of the non-fresh Titanium Sieve Molecular Sieve can include but is not limited to: be catalyzed Temporary inactivation occurs in reaction process, after regeneration the Titanium Sieve Molecular Sieve (hereinafter referred to as regenerative agent) of activation recovering；It is being catalyzed Permanent inactivation occurs in reaction process, its active Titanium Sieve Molecular Sieve can not be restored being regenerated and (hereinafter referred to as unloaded Agent out)；And regenerative agent and draw off the combination of agent.Preferably, the Titanium Sieve Molecular Sieve is non-fresh Titanium Sieve Molecular Sieve.

The Titanium Sieve Molecular Sieve permanently inactivated drawn off from using Titanium Sieve Molecular Sieve as the device of catalyst, which is referred to as, unloads Agent out draws off agent as discarded molecular sieve, and common method of disposal is accumulation landfill.The present inventor is in the course of the research It was found that it is described draw off agent can be used as production vanadium Titanium Sieve Molecular Sieve raw material, and prepare vanadium Titanium Sieve Molecular Sieve as sulphur The catalyst of ether oxidation reaction is in use, can further delay the trend of catalyst bed pressure drop rise.Therefore, in step (1), The Titanium Sieve Molecular Sieve more preferably draws off agent.It is described draw off agent can be to use Titanium Sieve Molecular Sieve as catalyst from various What is drawn off in reaction unit draws off agent, such as can draw off agent for what is drawn off from oxidation reaction apparatus.Specifically, described to draw off Agent can for Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off agent One or more of.It draws off agent more specifically, described and can draw off agent, phenol for cyclohexanone oxamidinating reaction unit Hydroxylating device draw off agent and propylene ring oxidation reaction device draw off one or more of agent.

It is described from the angle for the catalytic performance for further increasing the vanadium Titanium Sieve Molecular Sieve finally prepared, step (1) Titanium Sieve Molecular Sieve is more preferably the reaction unit using Titanium Sieve Molecular Sieve as catalyst reacted under alkaline environment Draw off agent.It is particularly preferred that described, to draw off agent be that Ammoximation reaction device draws off agent, such as cyclohexanone oxamidinating reaction unit Draw off agent.

It is described to draw off agent for before being contacted with acid solution, preferably progress high-temperature roasting and/or solvent washing to be to remove Attachment removal is drawing off the residuals in agent surface and/or duct.In an example, described to draw off agent and connect with acid solution Before touching, roasted, the roasting can 300-800 DEG C at a temperature of carry out, preferably 350-700 DEG C at a temperature of into Row, more preferably 450-650 DEG C at a temperature of carry out.The duration of the roasting can be 1-12 hours, preferably 1.5-6 Hour.The roasting can carry out in air atmosphere, can also carry out in inert atmosphere.The inert atmosphere can be with For the atmosphere formed by nitrogen and/or group 0 element gas, the group 0 element gas such as argon gas.

The activity for drawing off agent is different according to its source.Generally, the activity for drawing off agent can be the titanium The 5-95% of activity (that is, activity of fresh Titanium Sieve Molecular Sieve) of si molecular sieves when fresh, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94% or 95%.Preferably, through regenerating The activity for drawing off agent can be active 10-90% of Titanium Sieve Molecular Sieve when fresh.It is further preferred that through regenerated The activity for drawing off agent can be active 60% or less of Titanium Sieve Molecular Sieve when fresh.It is further preferred that through regenerating The activity for drawing off agent can be active 30-55% of Titanium Sieve Molecular Sieve when fresh.Through the regenerated work for drawing off agent Property for active 30-55% of Titanium Sieve Molecular Sieve when fresh when, can obtain and better delay catalyst bed pressure drop rise Effect.It is particularly preferred that being active 35- of Titanium Sieve Molecular Sieve when fresh through the regenerated activity for drawing off agent 50%.The activity of the fresh Titanium Sieve Molecular Sieve is generally 90% or more, and usually 95% or more.

The activity measures by the following method: respectively will be through regenerated agent and the fresh Titanium Sieve Molecular Sieve of drawing off as hexamethylene Ketone oxamidinating reaction catalyst, the condition of the Ammoximation reaction are as follows: Titanium Sieve Molecular Sieve, 36 weight % ammonium hydroxide (with NH₃Meter), The hydrogen peroxide of 30 weight % is (with H₂O₂Meter), the tert-butyl alcohol and cyclohexanone 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure In 80 DEG C of reaction 2h.Calculate separately using through it is regenerated draw off agent and fresh Titanium Sieve Molecular Sieve as catalyst when cyclohexanone conversion Rate, and using it as through the regenerated activity for drawing off agent and fresh Titanium Sieve Molecular Sieve, wherein the conversion ratio of cyclohexanone= [mole of the cyclohexanone of (mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/addition] × 100%.

In step (1), the Titanium Sieve Molecular Sieve is preferably to have the Titanium Sieve Molecular Sieve of MFI structure, more preferably TS-1.It adopts TS-1 handle, particularly handle the agent that draws off of TS-1 with this method, can further extend the one way of molecular sieve Service life extends catalyst regeneration cycle.

In step (1), the acid solution refers to the aqueous solution containing acid.The acid is general acid, for inorganic acid and can be had One or more of machine acid.The organic acid can be one or more of for carboxylic acid, sulfonic acid and peracid, such as C₁-C₆Aliphatic carboxylic acid, C₆-C₁₂Aromatic carboxylic acid, C₁-C₆Aliphatic sulfonic, C₆-C₁₂Aromatic sulphonic acid, peroxide second Acid and Perpropionic Acid.Preferably, the acid is HCl, H₂SO₄、HNO₃、CH₃COOH、HClO₄、H₃PO₄, Peracetic acid and peroxide third One or more of acid.It is highly preferred that the acid is HCl, HNO₃And H₃PO₄One or more of.The acid It is preferred that providing in form of an aqueous solutions, the concentration of sour aqueous acid medium can be selected according to the type of acid, without special It limits, generally, the concentration of sour aqueous acid medium can be 0.5-20mol/L, preferably 1-15mol/L.

In step (1), Titanium Sieve Molecular Sieve: sour molar ratio can be 100:0.005-50, preferably 100:0.1-30, more Preferably 100:2-15, further preferably 100:6-12.The Titanium Sieve Molecular Sieve is with SiO₂Meter, the acid is with H⁺Meter.

In step (1), the duration of the contact can be selected according to the temperature of contact.Generally, described to connect The duration of touching can be 0.5-36 hours, preferably 1-24 hours, more preferably 1-18 hours, further preferably 2-12 Hour.

In step (1), the contact can carry out in air atmosphere, can also carry out in inert atmosphere, preferably It is carried out in air atmosphere.

In step (1), solid phase can be isolated from the mixture that contact obtains using conventional method.For example, can incite somebody to action It contacts obtained mixture to be filtered and/or be centrifuged, to isolate solid phase therein.

In step (2), the silicon source is organic silicon source.The organic silicon source can be various energy under the conditions of hydrolytic condensation The substance of silica is enough formed, such as can be silicon-containing compound shown in Formulas I,

In Formulas I, R₁、R₂、R₃And R₄Respectively C₁-C₄Alkyl.The C₁-C₄Alkyl include C₁-C₄Straight chained alkyl and C₃-C₄Branched alkyl, specific example can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding Base, isobutyl group and tert-butyl.

Preferably, the silicon source be selected from methyl orthosilicate, ethyl orthosilicate, positive n-propyl silicate, positive isopropyl silicate and Positive silicic acid N-butyl.

The isolated solid phase of step (1): the molar ratio of silicon source can be 100:3-40, preferably 100:5-30, step (1) isolated solid phase and the silicon source are with SiO₂Meter.

In step (2), titanium source can be the usually used titanium source of technical field of molecular sieve preparation.Specifically, the titanium source It can be organic titanium source (such as organic titanate) and/or inorganic ti sources (such as inorganic titanium salt).The inorganic ti sources can be TiCl₄、Ti(SO₄)₂、TiOCl₂, titanium hydroxide, titanium oxide, one or more of nitric acid titanium salt and phosphoric acid titanium salt.Institute Stating organic titanium source can be one or more of fatty alcohol titanium and organic titanate.The titanium source is preferably organic titanium Source, more preferably organic titanate, further preferably formula M₄TiO₄Shown in organic titanate, wherein 4 M can phase Together, it can also be different, respectively preferably C₁-C₄Alkyl.The titanium source is still more preferably titanium sulfate, titanium tetrachloride, metatitanic acid One or more of tetra-isopropyl, four n-propyl of metatitanic acid, butyl titanate and tetraethyl titanate.

The isolated solid phase of step (1): the molar ratio of titanium source can be 100:0.1-8, preferably 100:0.2-5.Institute Titanium source is stated with TiO₂Meter, the isolated solid phase of step (1) is with SiO₂Meter.

In step (2), vanadium source is the oxide of vanadium, the halide of vanadium, vanadic acid (metavanadic acid, HVO₃), positive vanadic acid (H₃VO₄)、 Pyrovanadic acid (H₄V₂O₇、H₃V₃O₉), vanadate (aforementioned vanadic acid corresponding salt), the carbonate of vanadium, the nitrate of vanadium, vanadium sulfuric acid One or more of salt, the phosphate of vanadium and hydroxide of vanadium.The specific example in the vanadium source may include but not It is limited to sodium vanadate, ammonium metavanadate, vanadic anhydride, vanadium oxytrichloride, potassium metavanadate, vanadic sulfate, acetyl acetone vanadium and tetrachloro Change one or more of vanadium.Preferably, the vanadium source is one of ammonium metavanadate, sodium vanadate and potassium metavanadate or two Kind or more.

The isolated solid phase of step (1): the molar ratio in vanadium source can be 100:0.1-10, preferably 100:0.3-5, more Preferably 100:0.5-2.The vanadium source is with V₂O₅Meter, the isolated solid phase of step (1) is with SiO₂Meter.

In step (2), the alkali source can be the usually used alkali source of technical field of molecular sieve preparation.Specifically, described Alkali source can be organic base source and/or inorganic alkali source, wherein inorganic alkali source can be ammonia, alkali and sun that cation is alkali metal Ion is one or more of the alkali of alkaline-earth metal.The specific example of the inorganic alkali source can include but is not limited to One or more of ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and barium hydroxide.It is described Organic alkali source can be one or more of urea, amine, hydramine and quaternary ammonium base.

The quaternary ammonium base can be various organic level Four ammonium alkali, and the amine can be in molecular structure containing an amino Compound, the hydramine can be the compound containing at least one amino He at least one hydroxyl in molecular structure.

Specifically, the quaternary ammonium base can be quaternary ammonium base shown in Formula II,

In Formula II, R₅、R₆、R₇And R₈It is identical or different, respectively C₁-C₄Alkyl, including C₁-C₄Straight chained alkyl and C₃- C₄Branched alkyl, such as: R₅、R₆、R₇And R₈Respectively can for methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, Isobutyl group or tert-butyl.

The aliphatic amine that the amine can indicate for formula III,

R⁹(NH₂)_n(formula III)

In formula III, n is an integer of 1 or 2.When n is 1, R⁹For C₁-C₆Alkyl, including C₁-C₆Straight chained alkyl and C₃-C₆ Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, new penta Base, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R⁹For C₁-C₆Alkylidene, including C₁-C₆Straight-chain alkyl-sub and C₃-C₆ Branched alkylidene, such as methylene, ethylidene, sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.

The aliphatic hydramine that the hydramine can indicate for formula IV,

(HOR¹⁰)_mNH_(3-m)(formula IV)

In formula IV, m R¹⁰It is identical or different, respectively C₁-C₄Alkylidene, including C₁-C₄Straight-chain alkyl-sub and C₃-C₄ Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.It is highly preferred that the aliphatic Alcohol amine compound is one or more of monoethanolamine, diethanol amine and triethanolamine.

The specific example of the alkali source can include but is not limited to ammonia, sodium hydroxide, potassium hydroxide, calcium hydroxide, carbonic acid Sodium, potassium carbonate, barium hydroxide, urea, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydrogen In amine-oxides, four pentyl ammonium hydroxide, ethamine, n-butylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine and triethanolamine One or more.

In a preferred embodiment, from the catalytic activity for further increasing the vanadium Titanium Sieve Molecular Sieve finally prepared Angle is set out, and the alkali source is preferably sodium hydroxide, ammonium hydroxide, ethylenediamine, n-butylamine, butanediamine, hexamethylene diamine, monoethanolamine, two One or more of ethanol amine, triethanolamine, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide.

The isolated solid phase of step (1): the molar ratio of alkali source can be 100:0.5-50, preferably 100:1-40, more Preferably 100:5-30.The alkali source is with N or OH^-Meter, wherein when the alkali source contains nitrogen, the alkali source is in terms of N, institute State alkali source not Nitrogen element when, the alkali source is with OH^-Meter, the isolated solid phase of step (1) is with SiO₂Meter.

In step (2), the sequence that the isolated solid phase of step (1), titanium source, vanadium source, alkali source and water mix is not had It is particularly limited to.From the angle for the catalytic activity for further increasing the vanadium Titanium Sieve Molecular Sieve finally prepared, preferably first by silicon source, Titanium source and the mixing of vanadium source, obtained mixture are mixed with alkali source and water, then after the solid phase mixing isolated with step (1) Carry out hydro-thermal process.

In step (2), Titanium Sieve Molecular Sieve and silicon source, titanium source, vanadium source and alkali source are subjected to hydro-thermal process.The dosage of water can be with For conventional selection.Generally, the isolated solid phase of step (1): the molar ratio of water can be 100:20-1000, preferably 100:50-950, more preferably 100:100-900, further preferably 100:200-800, the isolated solid phase of step (1) With SiO₂Meter.

In step (2), the hydro-thermal process can 100-200 DEG C at a temperature of carry out, preferably in 120-180 DEG C of temperature Degree is lower to carry out, more preferably 130-170 DEG C at a temperature of carry out.The duration of the hydro-thermal process can be according to hydro-thermal process Temperature selected.Generally, the duration of the hydro-thermal process can be 0.5-96 hours, preferably 6-72 hours, More preferably 8-56 hours, further preferably 12-24 hours.

In step (2), hydro-thermal process carries out in confined conditions.The hydro-thermal process can carry out at autogenous pressures, It can also carry out under conditions of additionally increasing pressure, preferably carry out at autogenous pressures.In the actual operation process, Ke Yi The hydro-thermal process is carried out in autoclave.

The mixture that step (2) hydro-thermal process obtains can be handled using conventional method, to obtain vanadium titanium silicon point Son sieve.Specifically, the mixture that hydro-thermal process can be obtained is separated by solid-liquid separation, and will be done after the washing of obtained solid phase Dry and optional roasting, to obtain the vanadium Titanium Sieve Molecular Sieve.The drying can carry out under normal conditions, generally Ground, the drying can 50-200 DEG C at a temperature of carry out, preferably 80-180 DEG C at a temperature of carry out, more preferably in 100- It is carried out at a temperature of 160 DEG C.The duration of the drying can be 0.5-6 hours, preferably 1-3 hours.The roasting can With 300-800 DEG C at a temperature of carry out, preferably 400-600 DEG C at a temperature of carry out.The duration of the roasting can be with It is 2-12 hours, preferably 3-6 hours.The roasting can carry out in air atmosphere, can also in inert atmosphere into Row.

Activity using the vanadium Titanium Sieve Molecular Sieve according to the preferred embodiment as the catalyst containing molecular sieve Component can obtain the sulfone selectivity further increased, especially reaction is (such as compared with low reaction temperatures compared with Titanium Sieve Molecular Sieve Not higher than 60 DEG C, preferably no greater than 55 DEG C) under, using the vanadium Titanium Sieve Molecular Sieve according to the preferred embodiment as catalyst Higher sulfone selectivity can be obtained, while the effect for preferably inhibiting catalyst bed pressure drop rise can also be obtained.With vanadium silicon point Son sieve is compared with conventional vanadium Titanium Sieve Molecular Sieve, can obtain preferably catalysis effect according to the vanadium Titanium Sieve Molecular Sieve of the preferred embodiment Fruit, and can further delay the ascendant trend of the overall presure drop of catalyst bed.

According to the method for the present invention, the dosage of the catalyst containing molecular sieve, which is subject to, can be realized catalysis.One As, the weight (hourly) space velocity (WHSV) of thioether can be 0.1-300h^-1, preferably 1-150h^-1, more preferably 5-100h^-1, further preferably For 10-80h^-1, the weight (hourly) space velocity (WHSV) is in terms of the total amount of the catalyst containing molecular sieve loaded in whole catalyst beds.

According to the method for the present invention, when the overall presure drop of catalyst bed is higher than initial overall presure drop, triage operator, institute are carried out Stating triage operator includes that the charging of the 1st catalyst bed is divided into the 1st logistics to f logistics, and the 1st logistics enters the 1st and urges Agent bed, and the 1st catalyst bed and the catalyst bed positioned at the 1st catalyst bed downstream are flowed successively through, remove the 1st object Residue stream outside stream enters the catalyst bed positioned at the 1st catalyst bed downstream, and flow successively through the catalyst bed with And the catalyst bed positioned at the catalyst bed downstream.When the overall presure drop of catalyst bed increases, carrying out triage operator can To effectively inhibit the trend of catalyst bed overall presure drop rising, so that the overall presure drop that ascendant trend is presented originally is fallen after rise, thus Extend the parallel-adder settle-out time of device.In the present invention, the overall presure drop of catalyst bed refers to the 1st catalyst bed to the n-th catalysis The pressure drop of agent bed.

According to the method for the present invention, in a preferred embodiment, in the stagnation pressure that can effectively inhibit catalyst bed Under the premise of falling-rising is high, from the angle for reducing triage operator frequency, preferably meet in the overall presure drop of catalyst bed following The triage operator is carried out when condition: the sometime overall presure drop Δ P under t_tWith the initial value Δ P of overall presure drop₀Ratio be Δ P_t/ΔP₀, 1.1≤Δ P_t/ΔP₀≤5；Preferably, 1.2≤Δ P_t/ΔP₀≤3；It is highly preferred that 1.2≤Δ P_t/ΔP₀≤2.5。 The initial value of overall presure drop is depending on the concrete condition of reaction unit, generally, Δ P₀For not higher than 100kPa, more preferably not Higher than 80kPa, it is further preferably not higher than 60kPa.Generally, Δ P₀For 5-50kPa, preferably 8-30kPa, more preferably 10-25kPa。

According to the method for the present invention, f indicates the logistics in addition to the 1st logistics separated from the charging of the 1st catalyst bed Highest number, such as: when f is 3, indicate the charging of the 1st catalyst bed being divided into the 1st logistics, the 2nd logistics and the 3rd logistics, 1st logistics enters the 1st catalyst bed, and the 2nd logistics and the 3rd logistics enter the catalyst bed positioned at the 1st catalyst bed downstream Layer.F can be 2 or more integer, the preferably integer of 2-10, such as 2,3,4,5,6,7,8,9 or 10.It is highly preferred that f is 2-6 Integer, for example, 2.In each triage operator the value of f can according to the amount of remaining logistics, the quantity of catalyst bed and The feeding position (that is, catalyst bed that remaining logistics flows into) of remaining logistics is selected.In the amount and catalysis of remaining logistics When the inflow position of the negligible amounts of agent bed and/or remaining logistics is single, the value of f can be smaller, such as can be 2-5, Preferably 2-3, more preferably 2 (that is, the charging of the 1st catalyst bed is divided into the 1st logistics and the 2nd logistics)；In remaining logistics Amount and when quantity is more and/or the in-position of remaining logistics is more of catalyst bed, the value of f can be larger, such as It can be 6-10.

According to the method for the present invention, the 1st logistics that triage operator obtains enters the 1st catalyst bed, and residue stream enters Catalyst bed positioned at the 1st catalyst bed downstream.1st logistics and the relative scale of remaining logistics are can inhibit catalyst bed Subject to the overall presure drop of layer increases.According to the method for the present invention, on the basis of the charging of the 1st catalyst bed, the residue logistics Content is 5-50 weight %, can more effectively inhibit the overall presure drop of catalyst bed to increase in this way.Generally, with reaction feed Total amount on the basis of, the total amount of the remaining logistics obtained from first time triage operator to last time triage operator can be reaction The at most 50 weight % of charging, such as 5-50 weight %, preferably 10-48 weight %.In the present invention, reaction feed includes entering to urge Whole logistics of agent bed.

According to the method for the present invention, the residue stream that triage operator obtains enters appointing positioned at the 1st catalyst bed downstream Meaning catalyst bed.

In one embodiment, the remaining logistics that a triage operator obtains is sent into and is located at the 1st catalyst bed The same catalyst bed in downstream, the value of f is preferably 2 at this time, that is, by the charging of the 1st catalyst bed be divided into the 1st logistics and 2nd logistics, the 1st logistics enter the 1st catalyst bed, and the 2nd logistics enters the same catalyst positioned at the 1st catalyst bed downstream Bed.The embodiment particularly suitable for remaining logistics capacity less, catalyst bed negligible amounts or the amount of remaining logistics compared with Few occasion.

In another embodiment, the residue that a triage operator obtains is streamed into positioned at the 1st catalyst bed The different catalysts bed in downstream, the value of f is preferably greater than 2 at this time.For example, can be by the charging of the 1st catalyst bed point For the 1st logistics, the 2nd logistics and the 3rd logistics, the 1st logistics enters the 1st catalyst bed, and the 2nd logistics enters the 2nd catalyst bed, 3rd logistics enters the 3rd catalyst bed.The embodiment particularly suitable for the quantity of catalyst bed more and remaining logistics capacity compared with Big occasion.

According to the method for the present invention, triage operator can carry out once, can also carry out repeatedly, such as carry out m times, m 2 Above integer, specific value can be selected according to the overall presure drop setting value of reactor, with can be by catalyst bed Subject to overall presure drop control within a predetermined range, meet the following conditions: the sometime overall presure drop Δ P under t_tIt is initial with overall presure drop It is worth Δ P₀Ratio be Δ P_t/ΔP₀, 1.1≤Δ P_t/ΔP₀≤5；Preferably, 1.2≤Δ P_t/ΔP₀≤3；It is highly preferred that 1.2 ≤ΔP_t/ΔP₀≤2.5。

Multiple triage operator is being carried out, such as when m triage operator of progress, the residue that the m-1 times triage operator obtains The remaining logistics that stream and the m times triage operator obtain can be sent into identical catalyst bed, can also be by the m times triage operator Obtained at least partly residue streams the catalyst bed entered into the residue stream obtained positioned at the m-1 times triage operator The catalyst bed in downstream.

It streams as the residue for obtaining the m-1 times triage operator and the m times triage operator into identical catalyst bed A kind of embodiment of layer, is 2 (that is, n is 2) with the quantity of catalyst bed, and the charging of the 1st catalyst bed is split into the For 1 logistics and the 2nd logistics (that is, f is 2), the triage operator can operate in the following way: initial reaction stage, react into Material enters the 1st catalyst bed and flows successively through the 1st catalyst bed and the 2nd catalyst bed, in the total of catalyst bed When pressure drop rise, the charging (that is, reaction feed) of the 1st catalyst is divided into the 1st logistics and the 2nd logistics, the 1st logistics enters the 1st Catalyst bed, the 2nd logistics enter the 2nd catalyst bed, keep the 1st logistics and the 2nd logistics and its feeding manner, until catalysis When the overall presure drop of agent bed rises again, the charging of the 1st catalyst bed is again split into the 1st logistics and the 2nd logistics, is divided again The 1st logistics that stream obtains enters the 1st catalyst bed, the 2nd object that the 2nd logistics shunted again and preceding primary shunting obtain Stream enters the 2nd catalyst bed together, and so on, until stopping charging.

The residue obtained as the remaining logistics and the m times triage operator that obtain the m-1 times triage operator stream into A kind of embodiment of different catalyst beds, at least partly residue that the m times triage operator can be obtained stream into The catalyst bed in the catalyst bed downstream that the remaining logistics obtained positioned at the m-1 times triage operator is entered.Such as: the The residue stream that m-1 triage operator obtains respectively enters the 2nd catalyst bed and the 3rd catalyst bed, the m times shunting behaviour Making obtained remaining logistics can be into the catalyst bed positioned at the 3rd catalyst bed downstream be fully entered, can also be by m The 2nd catalyst bed and/or the 3rd catalyst bed, remainder are sent into part in the remaining logistics that secondary triage operator obtains It is sent into the catalyst bed for being located at the 3rd catalyst downstream.

When carrying out a triage operator, the feeding manner that triage operator obtains continues to that the overall presure drop of catalyst bed reaches To the setting value of reaction unit.When carrying out multiple triage operator, the reaction feed mode that the m-1 times triage operator obtains is held Continue the m times triage operator.

According to the method for the present invention, the 1st catalyst bed to the n-th catalyst bed can be set in same reactor In, it also can be set in different reactors, partial catalyst bed can also be arranged in same reactor, remainder Divided catalyst bed is arranged in different reactors.That is, the 1st catalyst bed to the n-th catalyst bed can be set one It in a reactor, also can be set in y reactor, y is the integer positioned at section [2, n].For being arranged in same reaction Catalyst bed in device, from the angle convenient for operating and reducing energy consumption, preferably by the catalyst bed in same reactor Layer is arranged to spatially as adjoining.Liquid distribution trough can be set between adjacent catalyst bed, so that entering catalysis The charging of agent bed more uniformly spreading in catalyst bed.

According to the method for the present invention, the temperature in catalyst bed can be 20-200 DEG C, preferably 25-180 DEG C, more excellent It is selected as 30-120 DEG C.In terms of gauge pressure, the inlet pressure in the reactor with catalyst bed can be 0-3MPa, preferably 0.1-2.5MPa, more preferably 0.2-1MPa.According to the method for the present invention, contain preferred embodiment described previously in catalyst Vanadium Titanium Sieve Molecular Sieve when, even if the temperature of catalyst bed is lower, such as not higher than 60 DEG C (30-60 DEG C), be preferably no greater than 50 DEG C (such as 35-50 DEG C), it can also effectively improve the selectivity for sulfone.

According to the method for the present invention, the effluent of the n-th catalyst bed contains the sulfone as reaction product, can be using normal The effluent of n-th catalyst bed is separated (such as distillation) by rule method, thus obtain sulfone, optional solvent and Unreacted thioether that may be present.Sulfone as product can export, or be sent into further progress in other refined units Purifying.The solvent and unreacted thioether isolated 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, pressure is gauge pressure.

In following embodiment and comparative example, Kong Rong and pore-size distribution are in Micromeritics company ASAP2405 static nitrogen It is measured on adsorption instrument；A mole composition for molecular sieve is surveyed on Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer It is fixed；X-ray diffraction analysis (XRD) carries out on Siemens D5005 type X-ray diffractometer.

In following embodiment and comparative example, the content of each ingredient in the reaction solution that is obtained using gas chromatography analysis, Following formula is respectively adopted on the basis of this to calculate thioether rate 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%；

Sulfone selectivity (%)=[mole/(the unreacted thioether of the mole-of the thioether of addition for the sulfone that reaction generates Mole)] × 100%.

In following embodiment and comparative example, using the activity of following methods measurement Titanium Sieve Molecular Sieve.

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 in mass ratio=1:7.5:10:7.5:10 mixing after at atmosheric pressure after 80 DEG C are stirred to react 2h, will react Object filtering, analyzed with composition of the gas chromatography to liquid phase, be calculated using the following equation the conversion ratio of cyclohexanone and by its As the activity of Titanium Sieve Molecular Sieve,

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

Preparation embodiment 1-12 is used to prepare molecular sieve.

Prepare embodiment 1

This preparation embodiment does not contain the Titanium Sieve Molecular Sieve of vanadium using hydrothermal crystallization method preparation.

Ethyl orthosilicate, isopropyl titanate are mixed with tetrapropylammonium hydroxide, and appropriate distilled water is added and is stirred, just Silester: isopropyl titanate: tetrapropylammonium hydroxide: the molar ratio of water be 100:3:20:2000, wherein ethyl orthosilicate with SiO₂Meter, isopropyl titanate is with TiO₂Meter；It hydrolyzes 1 hour, then is stirred at 75 DEG C 3 hours at normal pressure and 60 DEG C, it then will mixing Liquid is put into stainless steel sealing reaction kettle, places 72 hours in 170 DEG C of constant temperature, obtains the mixture of crystallization product；By the mixture Filtering is collected solid matter and is washed with water, and 60 minutes dry in 110 DEG C, obtains molecular screen primary powder.Molecular screen primary powder is existed It is roasted 3 hours in 550 DEG C of air atmospheres, obtains Titanium Sieve Molecular Sieve, XRD analysis confirms that the Titanium Sieve Molecular Sieve is MFI structure, is Titanium-silicon molecular sieve TS-1, nature parameters are listed in table 1.

Prepare embodiment 2

This preparation embodiment prepares vanadium Titanium Sieve Molecular Sieve using hydrothermal crystallization method.

Ethyl orthosilicate, ammonium metavanadate, isopropyl titanate are mixed with tetrapropylammonium hydroxide, and appropriate distilled water is added and stirs Mix mixing, ethyl orthosilicate: isopropyl titanate: ammonium metavanadate: tetrapropylammonium hydroxide: the molar ratio of water is 100:3:1:20: 2000, wherein ethyl orthosilicate is with SiO₂Meter, isopropyl titanate is with TiO₂Meter, ammonium metavanadate is with V₂O₅Meter；In normal pressure and 60 DEG C of water Solution 1 hour, then stirred at 75 DEG C 3 hours, mixed liquor is then put into stainless steel sealing reaction kettle, places 72 in 170 DEG C of constant temperature Hour, obtain the mixture of crystallization product；The mixture is filtered, solid matter is collected and is washed with water, and in 110 DEG C dry 60 Minute, obtain molecular screen primary powder.Molecular screen primary powder is roasted 3 hours in 550 DEG C of air atmospheres, obtains vanadium Titanium Sieve Molecular Sieve, Its XRD crystalline phase figure and preparation embodiment 1 are consistent, and what is illustrated is the molecular sieve with MFI structure, and nature parameters are in table 1 In list.

Prepare embodiment 3

This preparation embodiment prepares V-Si molecular sieve using hydrothermal crystallization method.

Ethyl orthosilicate, ammonium metavanadate are mixed with tetrapropylammonium hydroxide, and appropriate distilled water is added and is stirred, just Silester: ammonium metavanadate: tetrapropylammonium hydroxide: the molar ratio of water be 100:1:20:2000, wherein ethyl orthosilicate with SiO₂Meter, ammonium metavanadate is with V₂O₅Meter；It hydrolyzes 1 hour in normal pressure and 60 DEG C, then is stirred 3 hours at 75 DEG C, then put mixed liquor Enter stainless steel sealing reaction kettle, is placed 72 hours in 170 DEG C of constant temperature, obtain the mixture of crystallization product；The mixture is filtered, It collects solid matter to be washed with water, and 60 minutes dry in 110 DEG C, obtains molecular screen primary powder.By molecular screen primary powder in 550 DEG C of skies It is roasted 3 hours in gas atmosphere, obtains V-Si molecular sieve, XRD crystalline phase figure and preparation embodiment 1 are consistent, and what is illustrated is tool There is the molecular sieve of MFI structure, nature parameters are listed in table 1.

Prepare embodiment 4

This preparation embodiment prepares vanadium Titanium Sieve Molecular Sieve.

(1) under room temperature (20 DEG C) and normal pressure (1 standard atmospheric pressure), Titanium Sieve Molecular Sieve (is used and preparation 1 phase of embodiment With method preparation) be beaten with the combined of 1mol/L, mixed serum is then handled 12 in 80 DEG C of mixing It after hour, is separated by solid-liquid separation, collects solid matter.Wherein, Titanium Sieve Molecular Sieve is (with SiO₂Meter) with HCl (with H⁺Meter) mole Than for 100:8.

(2) ethyl orthosilicate as silicon source, the titanium sulfate as titanium source and the ammonium metavanadate as vanadium source are mixed, is connect Obtained mixture is mixed with sodium hydrate aqueous solution after, step (1) obtained solid matter is added and is uniformly mixed, will mix It closes object to be placed in autoclave, be handled 12 hours at 170 DEG C, wherein Titanium Sieve Molecular Sieve: silicon source: titanium source: vanadium source: alkali source: water Molar ratio be 100:10:2:1:15:250, Titanium Sieve Molecular Sieve is with SiO₂Meter, alkali is with OH^-Meter, silicon source SiO₂Meter, titanium source is with TiO₂ Meter, vanadium source is with V₂O₅Meter.

After the completion of processing, obtained reaction mixture is filtered, collects solid phase and after being washed with water, by solid phase in 110 DEG C drying 120 minutes, then roasted 3 hours in 550 DEG C of air atmospheres, obtain vanadium Titanium Sieve Molecular Sieve, XRD crystalline phase figure Consistent with preparation embodiment 1, what is illustrated is the molecular sieve with MFI structure, and nature parameters are listed in table 1.

Prepare embodiment 5

This preparation embodiment prepares vanadium Titanium Sieve Molecular Sieve.

This preparation embodiment uses method identical with preparation embodiment 4 to prepare vanadium Titanium Sieve Molecular Sieve, unlike, it uses Titanium Sieve Molecular Sieve be by cyclohexanone oxamidinating reaction unit draw off agent (fresh dose using with the identical side of preparation embodiment 1 Method preparation) obtained from 500 DEG C roast 4 hours in air atmosphere, which is 45%, when fresh Activity is 96%.

Vanadium Titanium Sieve Molecular Sieve is obtained, XRD crystalline phase figure and preparation embodiment 1 are consistent, and what is illustrated is with MFI structure Molecular sieve, nature parameters list in table 1.

Prepare embodiment 6

This preparation embodiment uses Titanium Sieve Molecular Sieve identical with preparation embodiment 5.

(1) solid matter is prepared using method identical with preparation 5 step of embodiment (1).

(2) solid matter that step (1) obtains is mixed with ammonium metavanadate aqueous solution, wherein Titanium Sieve Molecular Sieve and inclined vanadium The molar ratio of sour ammonium and water is 10:2:20, and Titanium Sieve Molecular Sieve is with SiO₂Meter, ammonium metavanadate is with V₂O₅Meter, is stirred in normal pressure and 50 DEG C It mixes 3 hours, then filters mixture, collect solid matter, be washed with water, solid matter is 60 minutes dry at 110 DEG C, it connects Roasted 3 hours in 550 DEG C of air atmospheres, obtain load vanadium Titanium Sieve Molecular Sieve.

Prepare embodiment 7

This preparation embodiment prepares vanadium Titanium Sieve Molecular Sieve.

The Titanium Sieve Molecular Sieve that this preparation embodiment uses is (fresh dose is adopted by the agent that draws off of cyclohexanone oxamidinating reaction unit Prepared with the identical method of preparation embodiment 1, wherein the content of titanium oxide is 1.5mol%) at 550 DEG C in air atmosphere Obtained from roasting 2 hours, which is 32%, and activity when fresh is 95%.

(1) under room temperature (20 DEG C) and normal pressure (1 standard atmospheric pressure), by the aqueous solution of nitric acid of Titanium Sieve Molecular Sieve and 8mol/L It is mixed with beating, after mixed serum to be then mixed to processing 2h at 95 DEG C, is separated by solid-liquid separation, collects solid matter.Its In, Titanium Sieve Molecular Sieve is (with SiO₂Meter) and HNO₃(with H⁺Meter) molar ratio be 100:12.

(2) ethyl orthosilicate as silicon source, the titanium tetrachloride as titanium source and the sodium vanadate as vanadium source are mixed, is connect Obtained mixture is mixed with sodium hydrate aqueous solution after, step (1) obtained solid matter is added and is uniformly mixed, will mix It closes object to be placed in autoclave, be handled 18 hours at 140 DEG C, wherein Titanium Sieve Molecular Sieve: silicon source: titanium source: vanadium source: alkali source: water Molar ratio be 100:5:1:0.5:7.5:600, Titanium Sieve Molecular Sieve is with SiO₂Meter, alkali is with OH^-Meter, silicon source SiO₂Meter, titanium source with TiO₂Meter, vanadium source is with V₂O₅Meter.

After the completion of processing, obtained reaction mixture is filtered, collects solid phase and after being washed with water, by solid phase in 150 DEG C drying 80 minutes, then roast 6h in 480 DEG C of air atmospheres, obtain vanadium Titanium Sieve Molecular Sieve, XRD crystalline phase figure and system Standby embodiment 1 is consistent, and what is illustrated is the molecular sieve with MFI structure, and nature parameters are listed in table 1.

Prepare embodiment 8

Vanadium Titanium Sieve Molecular Sieve is prepared using method identical with preparation embodiment 7, unlike, the Titanium Sieve Molecular Sieve of use The fresh Titanium Sieve Molecular Sieve of agent is drawn off to be formed in preparation embodiment 7, to obtain vanadium Titanium Sieve Molecular Sieve, XRD crystalline phase figure Consistent with preparation embodiment 1, what is illustrated is the molecular sieve with MFI structure, and nature parameters are listed in table 1.

Prepare embodiment 9

This preparation embodiment prepares vanadium Titanium Sieve Molecular Sieve.

The Titanium Sieve Molecular Sieve that this preparation embodiment uses is (fresh dose is adopted by the agent that draws off of cyclohexanone oxamidinating reaction unit Prepared with the identical method of preparation embodiment 1, wherein the content of titanium oxide is 4.6mol%) at 580 DEG C in air atmosphere Obtained from roasting 1.5 hours, which is 48%, and activity when fresh is 96%.

(1) under room temperature (20 DEG C) and normal pressure (1 standard atmospheric pressure), the phosphoric acid of Titanium Sieve Molecular Sieve and 15mol/L is water-soluble Liquid is mixed with beating, and after mixed serum to be then mixed to processing 3h at 90 DEG C, is separated by solid-liquid separation, collects solid matter. Wherein, Titanium Sieve Molecular Sieve is (with SiO₂Meter) and H₃PO₄(with H⁺Meter) molar ratio be 100:6.

(2) by the ethyl orthosilicate as silicon source, four n-propyl of metatitanic acid as titanium source and as the potassium metavanadate in vanadium source After then mixing obtained mixture with sodium hydrate aqueous solution, it is equal that the solid matter mixing that step (1) obtains is added in mixing It is even, mixture is placed in autoclave, is handled 16 hours at 160 DEG C, wherein Titanium Sieve Molecular Sieve: silicon source: titanium source: vanadium source: Alkali source: the molar ratio of water is 100:21:4.1:2:30:800, and Titanium Sieve Molecular Sieve is with SiO₂Meter, alkali is with OH^-Meter, silicon source SiO₂Meter, Titanium source is with TiO₂Meter, vanadium source is with V₂O₅Meter.

After the completion of processing, obtained reaction mixture is filtered, collects solid phase and after being washed with water, by solid phase in 160 DEG C drying 70 minutes, then roast 4h in 520 DEG C of air atmospheres, obtain vanadium Titanium Sieve Molecular Sieve, XRD crystalline phase figure and system Standby embodiment 1 is consistent, and what is illustrated is the molecular sieve with MFI structure, and nature parameters are listed in table 1.

Prepare embodiment 10

Vanadium Titanium Sieve Molecular Sieve is prepared using method identical with preparation embodiment 9, unlike, the Titanium Sieve Molecular Sieve of use The fresh Titanium Sieve Molecular Sieve of agent is drawn off to be formed in preparation embodiment 9, to obtain vanadium Titanium Sieve Molecular Sieve, XRD crystalline phase figure Consistent with preparation embodiment 1, what is illustrated is the molecular sieve with MFI structure, and nature parameters are listed in table 1.

Prepare embodiment 11

Processing is carried out to Titanium Sieve Molecular Sieve using method identical with preparation 9 step of embodiment (1) and prepares vanadium titanium silicon molecule Sieve, unlike, the solid matter that step (1) is isolated is 70 minutes dry in 160 DEG C, then in 520 DEG C of air atmospheres 4h is roasted, obtains vanadium Titanium Sieve Molecular Sieve, XRD crystalline phase figure and preparation embodiment 1 are consistent, and what is illustrated is with MFI structure Molecular sieve, nature parameters list in table 1.

Prepare embodiment 12

Vanadium Titanium Sieve Molecular Sieve is prepared using method identical with preparation embodiment 9, unlike, without step (1), and It is to use in step (1) to replace the solid matter in step (2) as the Titanium Sieve Molecular Sieve of raw material, obtains vanadium Titanium Sieve Molecular Sieve, XRD crystalline phase figure and preparation embodiment 1 are consistent, and what is illustrated is the molecular sieve with MFI structure, and nature parameters are in table 1 It lists.

Table 1

Sample source	Silicon: titanium: vanadium molar ratio *	C	D
				Prepare embodiment 1	100:3.1:0	<0.1	0.91
Prepare embodiment 2	100:2.8:0.9	<0.1	0.89
				Prepare embodiment 3	100:0:0.9	<0.1	0.92
Prepare embodiment 4	100:2.9:0.8	0.22	0.61
				Prepare embodiment 5	100:2.6:0.9	0.37	0.54
Prepare embodiment 6	100:2.6:0.9**	0.09	0.68
				Prepare embodiment 7	100:1.4:1.1	0.18	0.50
Prepare embodiment 8	100:1.6:1.0	0.13	0.64
				Prepare embodiment 9	100:4.3:0.8	0.47	0.56
Prepare embodiment 10	100:4.5:0.7	0.24	0.69
				Prepare embodiment 11	100:4.1:0.7	0.36	0.43
Prepare embodiment 12	100:4.6:0.8	0.12	0.71

*: the molar ratio of silicon, titanium and vanadium in the molecular sieve of preparation, based on the element；When silicon and titanium or vanadium molar ratio are greater than When 1000, titanium or vanadium are in terms of 0.

*: for non-skeleton vanadium.

C=X_1-1.8/X_0.4-0.9, X_0.4-0.9For the total micropore size of micropore size Zhan point of 0.4-0.9nm range in molecular sieve The ratio of cloth amount, X_1-1.8For molecular sieve the total micropore size abundance of micropore size Zhan of 1-1.8nm range ratio.

D=T_w/T_k, T_wFor the micropore pore volume of molecular sieve, T_kFor the total pore volume of molecular sieve.

Embodiment 1-15 is used to illustrate the preparation method of sulfone of the invention.

Embodiment 1

The Titanium Sieve Molecular Sieve that the present embodiment is prepared using preparation embodiment 1 is as catalyst.

Catalyst packing is formed into catalyst bed in fixed bed reactors, wherein the quantity of catalyst bed is 2, On the basis of to feed the flow direction in catalyst bed, the catalyst bed for being located at upstream is expressed as the 1st catalyst bed, it will Catalyst bed positioned at downstream is expressed as the 2nd catalyst bed, and the 1st catalyst bed and the 2nd catalyst bed are isometrical, Gao Jing Than being 5, spatially, the 1st catalyst bed and the 2nd catalyst bed are adjacent, and are catalyzed in the 1st catalyst bed and the 2nd Liquid distribution trough is arranged in the inlet of agent bed.

The reaction feed that the present embodiment uses contain dimethyl sulfide, as oxidant hydrogen peroxide (hydrogen peroxide with The forms of 20 weight % hydrogen peroxide provides) and as solvent methanol, wherein the molar ratio of hydrogen peroxide and dimethyl sulfide is The mass ratio of 2.5:1, methanol and dimethyl sulfide is 10:1.

Reaction feed is entered into the 1st catalyst bed from the bottom of fixed bed reactors and flows successively through the 1st catalyst bed Layer and the 2nd catalyst bed, with the catalyst haptoreaction being seated in catalyst bed.Wherein, the 1st catalyst bed is controlled It is 35 DEG C with the temperature in the 2nd catalyst bed, with the catalyst that is loaded in the 1st catalyst bed and the second catalyst bed Total amount meter, the weight (hourly) space velocity (WHSV) of dimethyl sulfide are 50h^-1, the inlet pressure of reactor is 0.2MPa, the overall presure drop of catalyst bed Initial value Δ P₀For 12kPa.

During the reaction, the overall presure drop for monitoring catalyst bed, when the overall presure drop of catalyst bed reaches 25kPa, into Row triage operator:

The charging of 1st catalyst bed is divided into the 1st logistics and the 2nd logistics, on the basis of the total amount of reaction feed, the 2nd The content of logistics is 20 weight %, and the 1st logistics enters the 1st catalyst bed by the bottom of fixed bed reactors, and flows successively through 1st catalyst bed and the 2nd catalyst bed, the 2nd logistics enter the 2nd catalyst bed.1 triage operator is carried out altogether, and The feeding manner for keeping the triage operator to be formed.

It is carried out continuously reaction in 900 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 36kPa.In reaction process In, continuously monitor the composition of the reaction product stream exported from fixed bed reactors, and calculate dimethyl sulfide conversion ratio and Dimethyl sulfone selectivity, is as a result listed in table 2.

Comparative example 1

Dimethyl sulfone is prepared using method same as Example 1, unlike, it is grasped in reaction process without shunting Make.

It is carried out continuously reaction in 400 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 39kPa.In reaction process In, continuously monitor the composition of the reaction product stream exported from fixed bed reactors, and calculate dimethyl sulfide conversion ratio and Dimethyl sulfone selectivity, is as a result listed in table 2.

Embodiment 2

Dimethyl sulfone is prepared using method same as Example 1, unlike, using the vanadium of the preparation preparation of embodiment 2 Titanium Sieve Molecular Sieve replaces the Titanium Sieve Molecular Sieve in embodiment 1.

It is carried out continuously reaction in 690 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 40kPa.In reaction process In, continuously monitor the composition of the reaction product stream exported from fixed bed reactors, and calculate dimethyl sulfide conversion ratio and Dimethyl sulfone selectivity, is as a result listed in table 2.

Embodiment 3

Dimethyl sulfone is prepared using method same as Example 1, unlike, using the vanadium of the preparation preparation of embodiment 3 Si molecular sieves replace the Titanium Sieve Molecular Sieve in embodiment 1.

It is carried out continuously reaction in 630 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 38kPa.In reaction process In, continuously monitor the composition of the reaction product stream exported from fixed bed reactors, and calculate dimethyl sulfide conversion ratio and Dimethyl sulfone selectivity, is as a result listed in table 2.

Embodiment 4

Dimethyl sulfone is prepared using method same as Example 1, unlike, using the vanadium of the preparation preparation of embodiment 4 Titanium Sieve Molecular Sieve replaces the Titanium Sieve Molecular Sieve in embodiment 1.

It is carried out continuously reaction in 780 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 37kPa.In reaction process In, continuously monitor the composition of the reaction product stream exported from fixed bed reactors, and calculate dimethyl sulfide conversion ratio and Dimethyl sulfone selectivity, is as a result listed in table 2.

Embodiment 5

Dimethyl sulfone is prepared using method same as Example 1, unlike, using the vanadium of the preparation preparation of embodiment 5 Titanium Sieve Molecular Sieve replaces the Titanium Sieve Molecular Sieve in embodiment 1.

It is carried out continuously reaction in 890 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 35kPa.In reaction process In, continuously monitor the composition of the reaction product stream exported from fixed bed reactors, and calculate dimethyl sulfide conversion ratio and Dimethyl sulfone selectivity, is as a result listed in table 2.

Embodiment 6

Dimethyl sulfone is prepared using method same as Example 1, unlike, catalyst is prepared by preparation embodiment 6 Load vanadium Titanium Sieve Molecular Sieve.

It is carried out continuously reaction in 520 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 41kPa.In reaction process In, continuously monitor the composition of the reaction product stream exported from fixed bed reactors, and calculate dimethyl sulfide conversion ratio and Dimethyl sulfone selectivity, is as a result listed in table 2.

Embodiment 7

Dimethyl sulfone is prepared using method same as Example 1, unlike, multiple triage operator is carried out, it is specific to grasp It is as follows to make mode:

The overall presure drop of catalyst bed, the overall presure drop Δ P at sometime t are monitored during the reaction_tWith overall presure drop Initial value Δ P₀Ratios delta P_t/ΔP₀For 1.2≤Δ P_t/ΔP₀When≤2, triage operator is carried out:

The charging of 1st catalyst bed is divided into the 1st logistics and the 2nd logistics, the 1st logistics by fixed bed reactors bottom Into the 1st catalyst bed, and the 1st catalyst bed and the 2nd catalyst bed are flowed successively through, the 2nd logistics enters the 2nd catalysis Agent bed.

The feeding manner that each triage operator is formed is kept to triage operator next time, and triage operator is to preceding primary next time The charging of the 1st catalyst bed that triage operator is formed is shunted, the charging of the 2nd catalyst bed be this triage operator with And before this triage operator each secondary triage operator obtain all the 2nd logistics.The 2nd logistics that each triage operator is isolated Account for the 5-10 weight % for the 1st logistics that a preceding triage operator adjacent with the triage operator obtains.

It is carried out continuously reaction in 1080 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 17kPa.Pass through shunting Operation, from distributed in reaction feed all the 2nd logistics (that is, after last time triage operator, the 2nd catalyst bed Charging) it accounts for when reaction starts into 42 weight % of the reaction feed of the 1st catalyst bed.

During the reaction, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and is calculated Dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, are as a result listed in table 2.

Table 2

Embodiment 8

The vanadium Titanium Sieve Molecular Sieve that the present embodiment is prepared using preparation embodiment 7 is as catalyst.

Catalyst packing is formed into catalyst bed in fixed bed reactors, wherein the quantity of catalyst bed is 2, On the basis of to feed the flow direction in catalyst bed, the catalyst bed for being located at upstream is expressed as the 1st catalyst bed, it will Catalyst bed positioned at downstream is expressed as the 2nd catalyst bed, and the 1st catalyst bed and the 2nd catalyst bed are isometrical, Gao Jing Than being 8, spatially, the 1st catalyst bed and the 2nd catalyst bed are adjacent, and are catalyzed in the 1st catalyst bed and the 2nd Liquid distribution trough is arranged in the inlet of agent bed.

The reaction feed that the present embodiment uses contains dimethyl sulfide, tert-butyl hydroperoxide (the tertiary fourth as oxidant Base hydrogen peroxide is provided in the form of 23 weight % acetonitrile solutions) and as solvent acetonitrile, wherein tert-butyl hydroperoxide with The molar ratio of dimethyl sulfide is 2.2:1, and the mass ratio of acetonitrile and dimethyl sulfide is 15:1.

Reaction feed is entered into the 1st catalyst bed from the bottom of fixed bed reactors and flows successively through the 1st catalyst bed Layer and the 2nd catalyst bed, with the catalyst haptoreaction being seated in catalyst bed.Wherein, the 1st catalyst bed is controlled It is 45 DEG C with the temperature in the 2nd catalyst bed, with the catalyst that is loaded in the 1st catalyst bed and the second catalyst bed Total amount meter, the weight (hourly) space velocity (WHSV) of dimethyl sulfide are 30h^-1, the inlet pressure of reactor is 0.25MPa, the stagnation pressure of catalyst bed The initial value Δ P of drop₀For 14kPa.

The overall presure drop of catalyst bed, the overall presure drop Δ P at sometime t are monitored during the reaction_tWith overall presure drop Initial value Δ P₀Ratios delta P_t/ΔP₀For 1.2≤Δ P_t/ΔP₀When≤1.8, triage operator is carried out: by the 1st catalyst bed Charging be divided into the 1st logistics and the 2nd logistics, the 1st logistics enters the 1st catalyst bed by the bottom of fixed bed reactors, and according to Secondary to flow through the 1st catalyst bed and the 2nd catalyst bed, the 2nd logistics enters the 2nd catalyst bed.

The feeding manner that each triage operator is formed is kept to triage operator next time, and triage operator is to preceding primary next time The charging of the 1st catalyst bed that triage operator is formed is shunted, the charging of the 2nd catalyst bed be this triage operator with And before this triage operator each secondary triage operator obtain all the 2nd logistics.The 2nd logistics that each triage operator is isolated Account for the 5-15 weight % for the 1st logistics that a preceding triage operator adjacent with the triage operator obtains.

It is carried out continuously reaction in 1150 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 21kPa.Pass through shunting Operation, from distributed in reaction feed all the 2nd logistics (that is, after last time triage operator, the 2nd catalyst bed Charging) it accounts for when reaction starts into 48 weight % of the reaction feed of the 1st catalyst bed.

During the reaction, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and is calculated Dimethyl sulfide conversion ratio and dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, are as a result listed in table 3.

Comparative example 2

Dimethyl sulfone is prepared using method same as Example 8, unlike, without triage operator.

It is carried out continuously reaction in 420 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 41kPa.In reaction process In, continuously monitor the composition of the reaction product stream exported from fixed bed reactors, and calculate dimethyl sulfide conversion ratio and Dimethyl sulfone selectivity, is as a result listed in table 3.

Embodiment 9

Dimethyl sulfone is prepared using method same as Example 8, unlike, catalyst is using preparation embodiment 8 The vanadium Titanium Sieve Molecular Sieve of preparation.

It is carried out continuously reaction in 990 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 23kPa.It is grasped by shunting Make, from distributed in reaction feed all the 2nd logistics (that is, after last time triage operator, the 2nd catalyst bed into Material) it accounts for when reaction starts into 49 weight % of the reaction feed of the 1st catalyst bed.

During the reaction, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and is calculated Dimethyl sulfide conversion ratio and dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, are as a result listed in table 3.

Table 3

Embodiment 10

The vanadium Titanium Sieve Molecular Sieve that the present embodiment is prepared using preparation embodiment 9 is as catalyst.

Catalyst packing is formed into catalyst bed in fixed bed reactors, wherein the quantity of catalyst bed is 2 It is a, on the basis of flow direction in catalyst bed to feed, the catalyst bed for being located at upstream is expressed as the 1st catalyst bed, The catalyst bed for being located at downstream is expressed as the 2nd catalyst bed, the 1st catalyst bed and the 2nd catalyst bed are isometrical, high Diameter ratio is 4, and spatially, the 1st catalyst bed and the 2nd catalyst bed are adjacent, and urge in the 1st catalyst bed and the 2nd Liquid distribution trough is arranged in the inlet of agent bed.

The reaction feed that the present embodiment uses contains that thioanisole, (Perpropionic Acid is with 30 as the Perpropionic Acid of oxidant The form of weight % t-butanol solution provides) and as solvent the tert-butyl alcohol, wherein the molar ratio of Perpropionic Acid and thioanisole For 2.3:1, the mass ratio of the tert-butyl alcohol and thioanisole is 30:1.

Reaction feed is entered into the 1st catalyst bed from the bottom of fixed bed reactors and flows successively through the 1st catalyst bed Layer and the 2nd catalyst bed, with the catalyst haptoreaction being seated in catalyst bed.Wherein, the 1st catalyst bed is controlled It is 50 DEG C with the temperature in the 2nd catalyst bed, with the catalyst that is loaded in the 1st catalyst bed and the second catalyst bed Total amount meter, the weight (hourly) space velocity (WHSV) of thioanisole are 18h^-1, the inlet pressure of reactor is 1MPa, the overall presure drop of catalyst bed just Initial value Δ P₀For 10kPa.

During the reaction, the overall presure drop for monitoring catalyst bed, when the overall presure drop of catalyst bed reaches 20kPa, into Row triage operator: being divided into the 1st logistics and the 2nd logistics for the charging of the 1st catalyst bed, on the basis of the total amount of reaction feed, The content of 2nd logistics is 30 weight %, and the 1st logistics enters the 1st catalyst bed by the bottom of fixed bed reactors, and successively flows The 1st catalyst bed and the 2nd catalyst bed are crossed, the 2nd logistics enters the 2nd catalyst bed.1 triage operator is carried out altogether, And the feeding manner for keeping the triage operator to be formed.

It is carried out continuously reaction in 780 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 28kPa.In reaction process In, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and calculate thioanisole conversion ratio and benzene Methyl sulfone selectivity, is as a result listed in table 4.

Comparative example 3

Dimethyl sulfone is prepared using method same as in Example 10, unlike, without triage operator.

It is carried out continuously reaction in 340 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 29kPa.In reaction process In, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and calculate thioanisole conversion ratio and benzene Methyl sulfone selectivity, is as a result listed in table 4.

Embodiment 11

Benzyl sulfone is prepared using method same as in Example 10, unlike, catalyst is that preparation embodiment 10 is made Standby vanadium Titanium Sieve Molecular Sieve.It is carried out continuously reaction in 730 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 29kPa. During the reaction, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and calculates thioanisole Conversion ratio and benzyl sulfone selectivity, are as a result listed in table 4.

Embodiment 12

Benzyl sulfone is prepared using method same as in Example 10, unlike, catalyst is that preparation embodiment 11 is made Standby vanadium Titanium Sieve Molecular Sieve.

It is carried out continuously reaction in 750 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 28kPa.In reaction process In, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and calculate thioanisole conversion ratio and benzene Methyl sulfone selectivity, is as a result listed in table 4.

Embodiment 13

Benzyl sulfone is prepared using method same as in Example 10, unlike, catalyst is that preparation embodiment 12 is made Standby vanadium Titanium Sieve Molecular Sieve.

It is carried out continuously reaction in 490 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 27kPa.In reaction process In, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and calculate thioanisole conversion ratio and benzene Methyl sulfone selectivity, is as a result listed in table 4.

Embodiment 14

Benzyl sulfone is prepared using method same as in Example 10, unlike, catalyst is prepared by preparation embodiment 1 Titanium Sieve Molecular Sieve.

It is carried out continuously reaction in 820 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 27kPa.In reaction process In, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and calculate thioanisole conversion ratio and benzene Methyl sulfone selectivity, is as a result listed in table 4.

Embodiment 15

Benzyl sulfone is prepared using method same as in Example 10, unlike, catalyst is prepared by preparation embodiment 3 V-Si molecular sieve.

It is carried out continuously reaction in 710 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 27kPa.In reaction process In, the composition of the reaction product stream exported from fixed bed reactors is continuously monitored, and calculate thioanisole conversion ratio and benzene Methyl sulfone selectivity, is as a result listed in table 4.

Table 4

Embodiment 1-15's as a result, it was confirmed that when sulfide oxidation being prepared sulfone using method of the invention, can effectively inhibit The trend of catalyst bed pressure drop rise extends the parallel-adder settle-out time of reactor, mentions so as to be effectively reduced operation energy consumption The safety of high device operation.

The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (23)

1. a kind of preparation method of sulfone, this method comprises:

Reaction feed containing at least one thioether, at least one oxidant and optional at least one solvent, the oxygen are provided Agent and the molar ratio of the thioether are greater than 2；

So that reaction feed is entered the 1st catalyst bed and flows through the 1st catalyst bed to the n-th catalyst under oxidation reaction condition Bed, obtains the product stream containing sulfone, the integer that n is 2 or more, and filling is at least one in the catalyst bed contains molecular sieve Catalyst,

When the overall presure drop of catalyst bed is higher than initial overall presure drop, triage operator is carried out, the triage operator includes urging the 1st The charging of agent bed is divided into the 1st logistics to f logistics, and the integer that f is 2 or more, the 1st logistics enters the 1st catalyst bed Layer, and the 1st catalyst bed and the catalyst bed positioned at the 1st catalyst bed downstream are flowed successively through, in addition to the 1st logistics Residue stream enters the catalyst bed positioned at the 1st catalyst bed downstream, and flows successively through the catalyst bed and be located at The catalyst bed in the catalyst bed downstream.

2. m is 2 or more according to the method described in claim 1, wherein, the triage operator is carried out primary or carried out m times Integer.

3. according to the method described in claim 2, wherein, remaining logistics and the m times shunting that the m-1 times triage operator obtains It operates obtained residue to stream into identical catalyst bed, or at least partly residue that the m times triage operator is obtained The catalyst bed for being located at the catalyst bed downstream that the residue stream that the m-1 times triage operator obtains enters is sent into logistics.

4. according to the method in claim 2 or 3, wherein on the basis of the charging of the 1st catalyst bed, the residue The content of stream is 5-50 weight %.

5. method described in any one of -4 according to claim 1, wherein the overall presure drop of catalyst bed meets the following conditions Triage operator described in Shi Jinhang: the sometime overall presure drop Δ P under t_tWith the initial value Δ P of overall presure drop₀Ratios delta P_t/ΔP₀ For 1.1≤Δ P_t/ΔP₀≤5；Preferably, 1.2≤Δ P_t/ΔP₀≤3；It is highly preferred that 1.2≤Δ P_t/ΔP₀≤2.5。

6. according to the method described in claim 5, wherein, Δ P₀For not higher than 100kPa, preferably 5-50kPa, more preferably 8- 30kPa, further preferably 10-25kPa.

7. method described in any one of -6 according to claim 1, wherein the 1st catalyst bed to the n-th catalyst bed is set It sets in a reactor, or is arranged in y reactor, y is the integer positioned at section [2, n]；

The catalyst bed being preferably located in same reactor is spatially adjacent.

8. method according to any one of claims 1-7, wherein the molecular sieve is selected from Titanium Sieve Molecular Sieve, vanadium One or more of si molecular sieves and vanadium Titanium Sieve Molecular Sieve.

9. according to the method described in claim 8, wherein, the molecular sieve is vanadium Titanium Sieve Molecular Sieve, the vanadium Titanium Sieve Molecular Sieve Meet X_1-1.8/X_0.4-0.9=C, 0.05 < C < 0.5, it is preferable that 0.1≤C≤0.48, X_0.4-0.9For 0.4-0.9nm model in molecular sieve The ratio of the total micropore size abundance of the micropore size Zhan enclosed, X_1-1.8It is total in the micropore size Zhan of 1-1.8nm range for molecular sieve The ratio of micropore size abundance.

10. method according to claim 8 or claim 9, wherein the vanadium Titanium Sieve Molecular Sieve meets T_w/T_k=D, 0.3 < D < 0.7, Preferably, 0.4≤D≤0.6, it is highly preferred that 0.5≤D≤0.6, wherein T_wFor the micropore pore volume of molecular sieve, T_kFor molecular sieve Total pore volume.

11. method according to claim 9 or 10, wherein in the vanadium Titanium Sieve Molecular Sieve, based on the element, element silicon: titanium Element: the molar ratio of vanadium is 100:0.5-10:0.01-5, preferably 100:1-8:0.2-2.5, more preferably 100:1.2- 6:0.5-2.

12. the method according to any one of claim 9-11, wherein it includes following that the vanadium Titanium Sieve Molecular Sieve, which uses, It is prepared by the method for step:

(1) by Titanium Sieve Molecular Sieve and acid solution in 40-200 DEG C, preferably 50-180 DEG C, 60-180 DEG C more preferable, further preferred 80- It is contacted at a temperature of 100 DEG C, isolates solid phase from the mixture that contact obtains；

(2) hydro-thermal process is carried out after mixing the isolated solid phase of step (1) with silicon source, titanium source, vanadium source, alkali source and water.

13. according to the method for claim 12, wherein in step (1), Titanium Sieve Molecular Sieve: sour molar ratio is 100: 0.005-50, preferably 100:0.1-30, more preferably 100:2-15, the Titanium Sieve Molecular Sieve is with SiO₂Meter, the acid is with H⁺ Meter；

Preferably, the acid is HCl, H₂SO₄、HNO₃、CH₃COOH、HClO₄、H₃PO₄, one of Peracetic acid and Perpropionic Acid Or it is two or more.

14. method according to claim 12 or 13, wherein in step (1), the duration of the contact is 0.5-36 Hour, preferably 1-24 hours, more preferably 1-18 hours, further preferably 2-12 hours.

15. method described in any one of 2-14 according to claim 1, wherein in step (2), step (1) is isolated Solid phase: silicon source: titanium source: vanadium source: the molar ratio of alkali source is 100:3-40:0.1-8:0.1-10:0.5-50, preferably 100:5- 30:0.2-5:0.3-5:1-40, the isolated solid phase of step (1) and the silicon source are with SiO₂Meter, the titanium source is with TiO₂Meter, The vanadium source is with V₂O₅Meter, the alkali source is with N or OH^-Meter.

16. method described in any one of 2-15 according to claim 1, wherein hydro-thermal process described in step (2) is in 100- 200 DEG C, preferably 120-180 DEG C, it is 130-170 DEG C more preferable at a temperature of carry out；

Preferably, in step (2), duration of the hydro-thermal process is 0.5-96 hours, preferably 6-72 hours, more preferably It is 8-56 hours, further preferably 12-24 hours；

Preferably, in step (2), the isolated solid phase of step (1): the molar ratio of water be 100:20-1000, preferably 100: 50-950, more preferably 100:100-900, further preferably 100:200-800, the isolated solid phase of step (1) with SiO₂Meter.

17. method described in any one of 2-16 according to claim 1, wherein it is alkali that the alkali source, which is selected from ammonia, cation, One or more of the alkali of metal, alkali, urea, amine, hydramine and quaternary ammonium base that cation is alkaline-earth metal；

The silicon source is selected from one or more of organic silicon source；

The titanium source is selected from one or more of inorganic titanium salt and organic titanate；

The vanadium source be one of the oxide of vanadium, the halide of vanadium, vanadic acid, positive vanadic acid, pyrovanadic acid, vanadate, vanadic salts or It is two or more.

18. method described in any one of 2-17 according to claim 1, wherein the Titanium Sieve Molecular Sieve is Ammoximation reaction Device draws off agent, and preferably cyclohexanone oxamidinating reaction unit draws off agent；

Preferably, the activity for drawing off agent is that this draws off active 5-95% of agent when fresh, and preferably it is when fresh Active 10-90%, more preferably its active 60% when fresh hereinafter, further preferably its work when fresh The active 35-50% that the 30-55% of property is still more preferably it when fresh.

19. method described in any one of 2-18 according to claim 1, wherein the Titanium Sieve Molecular Sieve is with MFI structure Titanium Sieve Molecular Sieve, preferably TS-1.

20. method described in any one of -19 according to claim 1, wherein the molar ratio of the oxidant and the thioether For 2.1-5:1, preferably 2.2-3:1.

21. method described in any one of -20 according to claim 1, wherein the oxidant is peroxide, more preferably For hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl hydroperoxide, Peracetic acid One or more of with Perpropionic Acid.

22. method described in any one of -21 according to claim 1, wherein the oxidation reaction condition includes: that temperature is 20-200 DEG C, preferably 30-120 DEG C, more preferably not above 60 DEG C, more preferably not above 50 DEG C；With catalyst bed Reactor inlet pressure be 0-3MPa, preferably 0.1-2.5MPa, the pressure be gauge pressure.

23. method described in any one of -22 according to claim 1, wherein the thioether is dimethyl sulfide and/or benzene Methyl sulfide.