CN109721515A - A kind of preparation method of sulfone - Google Patents
A kind of preparation method of sulfone Download PDFInfo
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- CN109721515A CN109721515A CN201711048461.6A CN201711048461A CN109721515A CN 109721515 A CN109721515 A CN 109721515A CN 201711048461 A CN201711048461 A CN 201711048461A CN 109721515 A CN109721515 A CN 109721515A
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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, catalyst and acid-exchange resin containing molecular sieve are 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
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 and at least one acid-exchange resin,
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 and at least one are loaded in the catalyst bed
Kind acid-exchange resin.
The acid-exchange resin can be strong-acid ion exchange resin, or weak acid ion exchange tree
Rouge can also be the mixture of strong-acid ion exchange resin and weak-acid ion exchange resin.The acid ion exchange tree
The specific example of the ion-exchange group of rouge can include but is not limited to one or both of sulfonic group, carboxyl and phosphate
Above combination.The full exchange capacity of the acid-exchange resin can be 0.1-15 mols/kg, and preferably 1-12 rubs
You/kilogram.The full exchange capacity refers to the molal quantity of the ion-exchange group contained by the ion exchange resin of Unit Weight,
The measurement of the method according to specified in GB/T8144-2008, can also be from the product information for the ion exchange resin being commercially available
It obtains.In the embodiment of the present invention, the full exchange capacity of acid-exchange resin is from the ion exchange resin being commercially available
It is obtained in product information.
According to the method for the present invention, acid-exchange resin is introduced in catalyst bed, can effectively improve thioether
Conversion ratio and sulfone selectivity.The weight ratio of the acid-exchange resin and the catalyst containing molecular sieve can be 0.01-
0.4:1, preferably 0.02-0.25:1, more preferably 0.05-0.1:1.
The acid-exchange resin can form mixture with the catalyst containing molecular sieve and be seated in catalyst bed
In, acid-exchange resin sublayer and the catalysis jizi for making dumplings containing molecular sieve can also be respectively formed in same catalyst bed
Layer, acid-exchange resin sublayer and the catalyst sublayer containing molecular sieve are preferably by being seated in catalyst bed.
According to the method for the present invention, the catalyst bed is except filling acid-exchange resin and the catalysis containing molecular sieve
Except agent, inert filler can also be loaded, thus to acid-exchange resin in catalyst bed and containing the catalysis of molecular sieve
The content of agent is adjusted.The inert filler can be common various fillers, for example, can selected from Raschig ring, Pall ring,
Cascade ring, arc saddle, square saddle and metal ring intalox.The specific example of the filler can be θ ring and/or β ring.The inert filler
Loadings can be made appropriate choice according to the treating capacity of expected reaction speed and reaction zone, it is specific can satisfy
Subject to 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 X1-1.8/X0.4-0.9=C, 0.05 < C < 0.5, X0.4-0.9For in molecular sieve 0.4-0.9nm range it is micro-
The ratio of the total micropore size abundance of hole aperture Zhan, X1-1.8It 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 Tw/Tk=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 TwFor the micropore of molecular sieve
Pore volume, TkFor 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, during long-time continuous operation, show preferably
Activity stability.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), duration of the contact can be 0.5-36 hours, preferably 1-24 hours, more preferably
1-18 hours, further preferably 2-12 hours.
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,
The isolated solid phase of step (1) 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 ttWith the initial value Δ P of overall presure drop0Ratio be Δ
Pt/ΔP0, 1.1≤Δ Pt/ΔP0≤5;Preferably, 1.2≤Δ Pt/ΔP0≤3;It is highly preferred that 1.2≤Δ Pt/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 %.In the present invention, reaction feed includes whole objects into catalyst bed
Stream.
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 ttIt is initial with overall presure drop
It is worth Δ P0Ratio be Δ Pt/ΔP0, 1.1≤Δ Pt/ΔP0≤5;Preferably, 1.2≤Δ Pt/ΔP0≤3;It is highly preferred that 1.2
≤ΔPt/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
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=X1-1.8/X0.4-0.9, X0.4-0.9For the total micropore size of micropore size Zhan point of 0.4-0.9nm range in molecular sieve
The ratio of cloth amount, X1-1.8For molecular sieve the total micropore size abundance of micropore size Zhan of 1-1.8nm range ratio.
D=Tw/Tk, TwFor the micropore pore volume of molecular sieve, TkFor the total pore volume of molecular sieve.
Embodiment 1-15 is used to illustrate the preparation method of sulfone of the invention.
Embodiment 1
As catalyst, the acid ion of use exchanges the Titanium Sieve Molecular Sieve that the present embodiment is prepared using preparation embodiment 1
Resin is that strongly acidic styrene type cation exchange resin (is purchased from Chemical Plant of Nankai Univ., the trade mark is 001 × 1, full exchange capacity
For 4.5mol/kg).
Acid-exchange resin and catalyst are mixed according to weight ratio 0.05:1, obtained mixture is seated in solid
Fixed bed reactor forms catalyst bed, wherein the quantity of catalyst bed is 2, to feed the stream in catalyst bed
On the basis of, the catalyst bed for being located at upstream is expressed as the 1st catalyst bed, the catalyst bed for being located at downstream is indicated
For the 2nd catalyst bed, the 1st catalyst bed and the 2nd catalyst bed are isometrical, and ratio of height to diameter is 5, spatially, the 1st catalysis
Agent bed and the 2nd catalyst bed are adjacent, and in the inlet of the 1st catalyst bed and the 2nd catalyst bed setting liquid point
Cloth device.
The reaction feed that the present embodiment uses contain dimethyl sulfide, as oxidant hydrogen peroxide (hydrogen peroxide with
The forms of 30 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 5:1.
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 and acid-exchange resin haptoreaction being seated in catalyst bed.Its
In, controlling the temperature in the 1st catalyst bed and the 2nd catalyst bed is 30 DEG C, with the 1st catalyst bed and the second catalyst
The total amount meter of the catalyst loaded in bed, the weight (hourly) space velocity (WHSV) of dimethyl sulfide are 120h-1, the inlet pressure of reactor is
0.5MPa, the initial value Δ P of the overall presure drop of catalyst bed0For 11kPa.
During the reaction, the overall presure drop for monitoring catalyst bed, when the overall presure drop of catalyst bed reaches 22kPa, 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 25 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 1080 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 37kPa.It was reacting
Cheng Zhong, continuously monitors the composition of the reaction product stream exported from fixed bed reactors, and calculates dimethyl sulfide conversion ratio
With dimethyl sulfone selectivity, as a result listed in table 2.
Comparative example 1
Dimethyl sulfone is prepared using method same as Example 1, unlike, what is loaded in catalyst bed is to urge
Agent does not include acid-exchange resin.
It is carried out continuously reaction in 890 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.
Comparative example 2
Dimethyl sulfone is prepared using method same as Example 1, unlike, it is grasped in reaction process without fractionation
Make.
It is carried out continuously reaction in 450 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 2
Dimethyl sulfone is prepared using method same as Example 1, unlike, catalyst is prepared by preparation embodiment 2
Vanadium Titanium Sieve Molecular Sieve.
It is carried out continuously reaction in 740 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.
Embodiment 3
Dimethyl sulfone is prepared using method same as Example 1, unlike, catalyst is prepared by preparation embodiment 3
V-Si molecular sieve.
It is carried out continuously reaction in 680 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, catalyst is prepared by preparation embodiment 4
Vanadium 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 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, catalyst is prepared by preparation embodiment 5
Vanadium Titanium Sieve Molecular Sieve.
It is carried out continuously reaction in 940 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 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 550 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 reactiontWith overall presure drop
Initial value Δ P0Ratios delta Pt/ΔP0For 1.2≤Δ Pt/ΔP0When≤1.8, 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 1200 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 19kPa.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 46 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 as catalyst, hand over by the acid ion of use
Changing resin is acidulous acrylic acid's cation exchanger resin (purchased from Chemical Plant of Nankai Univ., the trade mark 110, full exchange capacity
For 12mol/kg).
Acid-exchange resin and catalyst are mixed according to weight ratio 0.1:1, obtained mixture is seated in solid
Fixed bed reactor forms catalyst bed, wherein the quantity of catalyst bed is 2, is flowed in catalyst bed with charging
On the basis of, 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
2nd catalyst bed, the 1st catalyst bed and the 2nd catalyst bed are isometrical, and ratio of height to diameter is 8, spatially, the 1st catalyst
Bed and the 2nd catalyst bed are adjacent, and liquid distribution is arranged in the inlet of the 1st catalyst bed and the 2nd catalyst bed
Device.
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 25 weight % acetone solns) and as solvent acetone, wherein tert-butyl hydroperoxide with
The molar ratio of dimethyl sulfide is 2.1:1, and the mass ratio of acetone and dimethyl sulfide is 9:1.
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 and acid-exchange resin haptoreaction being seated in catalyst bed.Its
In, controlling the temperature in the 1st catalyst bed and the 2nd catalyst bed is 37 DEG C, with the 1st catalyst bed and the second catalyst
The total amount meter of the catalyst loaded in bed, the weight (hourly) space velocity (WHSV) of dimethyl sulfide are 30h-1, the inlet pressure of reactor is
0.4MPa, the initial value Δ P of the overall presure drop of catalyst bed0For 15kPa.
The overall presure drop of catalyst bed, the overall presure drop Δ P at sometime t are monitored during the reactiontWith overall presure drop
Initial value Δ P0Ratios delta Pt/ΔP0For 1.2≤Δ Pt/ΔP0When≤2, triage operator is carried out: by the 1st catalyst bed
Charging is divided into the 1st logistics and the 2nd logistics, and the 1st logistics enters the 1st catalyst bed by the bottom of fixed bed reactors, and successively
The 1st catalyst bed and the 2nd catalyst bed are flowed through, 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 5-20 weight % for the 1st logistics that a preceding triage operator adjacent with the triage operator obtains.
It is carried out continuously reaction in 1300 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 23kPa.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 50 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 3
Dimethyl sulfone is prepared using method same as Example 8, unlike, without triage operator.
It is carried out continuously reaction in 460 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 25kPa.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 prepared by preparation embodiment 8
Vanadium Titanium Sieve Molecular Sieve.
It is carried out continuously reaction in 1150 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 24kPa.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 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 as catalyst, hand over by the acid ion of use
Changing resin is large hole strong acid styrene system cation exchange resin (purchased from Chemical Plant of Nankai Univ., trade mark D072, total exchange
Capacity is 4.2mol/kg).
Acid-exchange resin and catalyst are mixed according to weight ratio 0.08:1, obtained mixture is seated in solid
Fixed bed reactor forms catalyst bed, wherein the quantity of catalyst bed is 2, is flowed in catalyst bed with charging
On the basis of, 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
2nd catalyst bed, the 1st catalyst bed and the 2nd catalyst bed are isometrical, and ratio of height to diameter is 5, spatially, the 1st catalyst
Bed and the 2nd catalyst bed are adjacent, and liquid distribution is arranged in the inlet of the 1st catalyst bed and the 2nd catalyst bed
Device.
The reaction feed that the present embodiment uses contains that thioanisole, (Peracetic acid is with 36 as the Peracetic acid of oxidant
The form of weight % t-butanol solution provides) and as solvent the tert-butyl alcohol, wherein the molar ratio of Peracetic acid and thioanisole
For 2.4:1, the mass ratio of the tert-butyl alcohol and thioanisole is 20:1.
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 and acid-exchange resin haptoreaction being seated in catalyst bed.Its
In, controlling the temperature in the 1st catalyst bed and the 2nd catalyst bed is 55 DEG C, with the 1st catalyst bed and the second catalyst
The total amount meter of the catalyst loaded in bed, the weight (hourly) space velocity (WHSV) of thioanisole are 32h-1, the inlet pressure of reactor is 1.5MPa,
The initial value Δ P of the overall presure drop of catalyst bed0For 12kPa.
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 32 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 850 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 25kPa.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 370 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 26kPa.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 780 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 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 800 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 26kPa.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 510 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 25kPa.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 900 hours, at the end of reaction, the stagnation pressure of catalyst bed is reduced to 26kPa.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 760 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 (24)
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 and at least one acid-exchange resin,
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 ttWith the initial value Δ P of overall presure drop0Ratios delta Pt/ΔP0
For 1.1≤Δ Pt/ΔP0≤5;Preferably, 1.2≤Δ Pt/ΔP0≤3;It is highly preferred that 1.2≤Δ Pt/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. according to the method described in claim 1, wherein, the weight of the acid-exchange resin and the catalyst containing molecular sieve
Amount is than being 0.01-0.4:1, preferably 0.02-0.25:1, more preferably 0.05-0.1:1.
9. method described in any one of -8 according to claim 1, 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.
10. according to the method described in claim 9, wherein, the molecular sieve is vanadium Titanium Sieve Molecular Sieve, the vanadium Titanium Sieve Molecular Sieve
Meet X1-1.8/X0.4-0.9=C, 0.05 < C < 0.5, it is preferable that 0.1≤C≤0.48, X0.4-0.9For 0.4-0.9nm model in molecular sieve
The ratio of the total micropore size abundance of the micropore size Zhan enclosed, X1-1.8It is total in the micropore size Zhan of 1-1.8nm range for molecular sieve
The ratio of micropore size abundance.
11. method according to claim 9 or 10, wherein the vanadium Titanium Sieve Molecular Sieve meets Tw/Tk=D, 0.3 < D <
0.7, it is preferable that 0.4≤D≤0.6, it is highly preferred that 0.5≤D≤0.6, wherein TwFor the micropore pore volume of molecular sieve, TkTo divide
The total pore volume of son sieve.
12. method described in 0 or 11 according to claim 1, wherein in the vanadium Titanium Sieve Molecular Sieve, based on the element, element silicon:
Titanium elements: 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.
13. method described in any one of 0-12 according to claim 1, wherein the vanadium Titanium Sieve Molecular Sieve use including with
It is prepared by the method for lower 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.
14. according to the method for claim 13, 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.
15. method described in 3 or 14 according to claim 1, 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.
16. method described in any one of 3-15 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.
17. method described in any one of 3-16 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.
18. method described in any one of 3-17 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.
19. method described in any one of 3-18 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.
20. method described in any one of 3-19 according to claim 1, wherein the Titanium Sieve Molecular Sieve is with MFI structure
Titanium Sieve Molecular Sieve, preferably TS-1.
21. method described in any one of -20 according to claim 1, wherein the molar ratio of the oxidant and the thioether
For 2.1-5:1, preferably 2.2-3:1.
22. method described in any one of -21 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.
23. method described in any one of -22 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 are further preferably not higher than 50 DEG C;With catalyst
The inlet pressure of the reactor of bed is 0-3MPa, and preferably 0.1-2.5MPa, the pressure is gauge pressure.
24. method described in any one of -23 according to claim 1, wherein the thioether is dimethyl sulfide and/or benzene
Methyl sulfide.
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CN201711048461.6A CN109721515B (en) | 2017-10-31 | 2017-10-31 | Preparation method of sulfone |
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