CN104557634B - Method for producing dimethyl sulfone - Google Patents
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Abstract
The invention provides a method for producing dimethyl sulfone. The method comprises the following steps: carrying out reaction on slurry containing dimethyl sulfide, a titanium silicalite molecular sieve and peroxide under the condition of oxidizing reaction; carrying out solid-liquid separation on the obtained reaction mixture in a separator, wherein the separator is provided with a first channel and a second channel, the first and second channels are connected through a member with a through hole, the reaction mixture is fed into the first channel, a liquid phase containing dimethyl sulfone is obtained from the second channel, and residues containing the titanium silicalite molecular sieve are obtained at the outlet end of the first channel. The method provided by the invention can be used for effectively improving the effective utilization ratio of an oxidizing agent, the selectivity of dimethyl sulfone and the conversion ratio of dimethyl sulfide and meanwhile can be used for effectively separating the liquid phase containing dimethyl sulfone from a solid-liquid mixture obtained by reaction. In addition, the method provided by the invention still can be used for obtaining the high dimethyl sulfide conversion ratio, the effective utilization ratio of the oxidizing agent and the selectivity of dimethyl sulfone even in long-term operation.
Description
Technical field
The present invention relates to a kind of method producing dimethyl sulfone.
Background technology
Dimethyl sulfone is white crystalline powder, soluble in water, ethanol, benzene, methanol and acetone, is slightly soluble in ether.Under room temperature not
Potassium permanganate variable color can be made, dimethyl sulfone can be oxidized to methanesulfonic acid by strong oxidizer.Dimethyl sulfone aqueous solution is in neutrality.At 25 DEG C
Microsublimation, accelerates to 60 DEG C of rate of sublimation, thus dimethyl sulfone product drying is preferably carried out under cryogenic vacuum.
Dimethyl sulfone is used as organic synthesiss high-temperature solvent and raw material, GC stationary liquid, analytical reagent, food in the industry
Product additive and medicine.Dimethyl sulfone, as a kind of organic sulfur compound, has and strengthens the ability that human body produces insulin, simultaneously
Metabolism to saccharide also has facilitation, is the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound to heal
Close, also the vitamin b needed for metabolism and neurological health, vitamin c, the synthesis of biotin and activation can be worked, quilt
Referred to as " naturally beautify carbonizable substance ".All dimethyl sulfone is contained in the skin of human body, hair, fingernail, skeleton, muscle and each organ,
Dimethyl sulfone is primarily present in Yu Haiyang and soil in nature, is absorbed as nutrient substance, the mankind in plant growing
Can absorb from the foods such as veterinary antibiotics, fish, meat, egg, milk, once lacking health disorders will be caused or disease occurs, be
Human body maintains the main matter of biological element sulphur balance, has therapeutic value and health care to human body diseases, is human survival
Indispensable medicine with health care.Abroad dimethyl sulfone is widely applied as the nutriment of equal importance with vitamin, China
The applied research of dimethyl sulfone is not yet carried out very well, current product is mainly used in exporting.Therefore, dimethyl sulfone is not only one kind
New high-tech product, is also a kind of fine chemical product of high added value.Product is new, market potential is big, and benefit projects, and can go out again
Mouth is earned foreign exchange, and has wide production and application and development prospect.
At present, the product that dimethyl sulfone aoxidizes further as dimethyl sulfoxide, is the main pair that dimethyl sulfoxide produces
Product.In addition, dimethyl sulfone can also directly be obtained through nitric acid oxidation by dimethyl sulfoxide.Specifically, can be sub- by dimethyl
Sulfone with nitric acid oxidation, reacts and is cooled to after terminating at 140-145 DEG C, filters, obtains the crude product of white, needle-shaped crystals.Again through decompression
Distillation, collects 138-145 DEG C of (98.42kpa) fraction and is finished product.
Content of the invention
The present inventor finds in research process, is being aoxidized dimethyl sulfide using peroxide as oxidant
When directly preparing dimethyl sulfone, if being used HTS can effectively improve the effectively utilizes of oxidant as catalyst
Rate and the selectivity of dimethyl sulfone, can also obtain high dimethyl sulfide conversion ratio simultaneously.
, as oxidant, dimethyl sulfide oxidation is directly made using peroxide as catalyst using HTS
During standby dimethyl sulfone, the liquid mixture containing dimethyl sulfide and peroxide can be made to divide by being filled with the titanium silicon of molding
The bed of son sieve is it is also possible to directly by HTS and dimethyl sulfide and peroxide hybrid reaction.Directly titanium silicon is divided
Son sieve and dimethyl sulfide and peroxide hybrid reaction, on the one hand without using the HTS of molding, on the other hand easily
In controlling reaction temperature.
But, obtain after directly needing to react by HTS and dimethyl sulfide and peroxide hybrid reaction
Mixture carries out separating, and could separate HTS with the liquid phase containing dimethyl sulfone.Therefore, liquid-solid separation efficiency is shadow
Ring one of key factor of dimethyl sulfone production efficiency.
It is an object of the invention to provide a kind of with the slurry containing HTS and peroxide and dimethyl sulfide
Method to produce dimethyl sulfone, the method one side can effectively improve the conversion ratio of dimethyl sulfide, the having of oxidant
Effect utilization rate and the selectivity of dimethyl sulfone, on the other hand can efficiently isolate containing two from the mixture that reaction obtains
The liquid phase of methyl sulfone.
The invention provides a kind of method producing dimethyl sulfone, the method includes: will divide containing dimethyl sulfide, titanium silicon
The slurry of son sieve and at least one peroxide is reacted under oxidation reaction condition, and the reactant mixture obtaining is carried out
Solid-liquid separation, obtains the liquid phase containing dimethyl sulfone and the residue containing HTS, described peroxide and described two
The mol ratio of Dimethyl sulfide is more than 2:1；
Described solid-liquid separation is carried out in a kind of separator, and described separator has first passage and second channel, described
First passage has arrival end and the port of export, and described first passage and second channel are adjoined by the component with through hole, described
The average pore size of through hole is less than the mean diameter of described HTS, and described reactant mixture is sent into institute by described arrival end
State in first passage, at least part of liquid phase in described reactant mixture is passed through described through hole and entered in described second channel, from
The described liquid phase containing dimethyl sulfone discharged by described second channel, contains titanium silicon described in the port of export of described first passage obtains
The residue of molecular sieve.
The method according to the invention can effectively improve the effective rate of utilization of oxidant and the selectivity of dimethyl sulfone, with
When can also obtain higher dimethyl sulfide conversion ratio.And, the method according to the invention can efficiently obtain from reaction
Liquid-solid mixture in isolate the liquid phase containing dimethyl sulfone.In addition, the method according to the invention good stability, even if when long
Between run, remain able to obtain high dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.
Brief description
Fig. 1 shows a kind of structural representation of separator used in the method according to the invention.
Fig. 2 shows a kind of embodiment of separator used in the method according to the invention.
Fig. 3 shows one kind of the method according to the invention preferred embodiment.
Specific embodiment
The invention provides a kind of method producing dimethyl sulfone, the method includes: will divide containing dimethyl sulfide, titanium silicon
The slurry of son sieve and at least one peroxide is reacted under oxidation reaction condition, and the reactant mixture obtaining is carried out
Solid-liquid separation, obtains the liquid phase containing dimethyl sulfone and the residue containing HTS.
Described peroxide refers to contain the compound of-o-o- key in molecular structure, can be selected from hydrogen peroxide, hydrogen peroxide
Compound and peracid.Obtained from described hydroperoxides refer to that one of hydrogen peroxide molecule hydrogen atom is replaced by organic group
Material.Described peracid refers to contain the organic oxacid of-o-o- key in molecular structure.The instantiation of described peroxide is permissible
Including but not limited to: hydrogen peroxide, tert-butyl hydroperoxide, dicumyl peroxide, cyclohexyl hydroperoxide, peracetic acid and mistake
Oxygen propanoic acid.Preferably, described oxidant is hydrogen peroxide, so can reduce separation costs further.Described hydrogen peroxide can
Think the commonly used in the art hydrogen peroxide existing in a variety of manners.
From the angle of the safety improving the method according to the invention further, the method according to the invention preferably makes
With the hydrogen peroxide existing as an aqueous solution.The method according to the invention, provides as an aqueous solution in described hydrogen peroxide
When, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, for example: 20-80 weight %.On concentration meets
The aqueous solution stating the hydrogen peroxide of requirement can be prepared it is also possible to be commercially available using conventional method, for example: can be being capable of business
The hydrogen peroxide of the hydrogen peroxide of 30 weight %, the hydrogen peroxide of 50 weight % or 70 weight % buied.
The method according to the invention, described oxidant is more than 2:1 with the mol ratio of described dimethyl sulfide, preferably
2.5:1 more than.Described oxidant can be below 20:1 with the mol ratio of described dimethyl sulfide, such as below 10:1, preferably
Below 5:1.Preferably, described oxidant and the mol ratio of dimethyl sulfide are 2.5-10:1.It is highly preferred that described oxidant with
The mol ratio of dimethyl sulfide is 2.5-5:1.
Described HTS is the general name that titanium atom replaces a class zeolite of a part of silicon atom in lattice framework, permissible
Use chemical formula xtio2·sio2Represent.The present invention is not particularly limited for the content of titanium atom in HTS, Ke Yiwei
The conventional selection of this area.Specifically, x can be 0.0001-0.04, preferably 0.01-0.03, more preferably 0.015-
0.025.
Described HTS can be the common HTS with various topological structure, for example: described titanium silicon
Molecular sieve can be selected from the HTS (as ts-1) of mfi structure, the HTS (as ts-2) of mel structure, bea structure
HTS (as ti-beta), the HTS (as ti-mcm-22) of mww structure, the HTS of hexagonal structure
The HTS (as ti-mor) of (as ti-mcm-41, ti-sba-15), mor structure, tun structure HTS (such as
Ti-tun) and other structures HTS (as ti-zsm-48).
Preferably, described HTS is selected from HTS, the HTS of mel structure and the bea of mfi structure
The HTS of structure.It is highly preferred that described HTS is the HTS of mfi structure.
From the selectivity improving the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and dimethyl sulfone further
Angle set out, described HTS be mfi structure HTS, and the crystal grain of this HTS be hollow knot
Structure, the radical length of the chamber portion of this hollow-core construction is 5-300 nanometer, and described HTS is in 25 DEG C, p/p0=
0.10th, adsorption time be the benzene adsorbance recording under conditions of 1 hour be at least 70 milligrams per gram, the low temperature of this HTS
There is hysteresis loop between the adsorption isotherm of N2 adsorption and desorption isotherm.Herein, the HTS with this structure claims
For hollow HTS.Described hollow HTS is commercially available (for example builds Anhydrite commercially available from Sinopec Hunan
The trade mark changing limited company is the molecular sieve of hts) it is also possible to the method according to disclosed in cn1132699c prepares.
Described HTS can be the HTS of the former powder of HTS or molding.
Using HTS as in the various commercial plants of catalyst, such as Ammoximation reaction, hydroxylating and
In epoxidation reaction device, generally after plant running is for a period of time, the catalysis activity of catalyst declines, and needs to carry out in device
Or ex-situ regeneration, even if when carry out regenerating also be difficult to obtain satisfied active when, need to draw off (i.e., catalyst from device
More catalyst changeout), and the current processing method of the catalyst (that is, drawing off agent or dead catalyst) that draws off typically piles up burial,
On the one hand land resource and the inventory space of preciousness are occupied, another aspect HTS production cost is higher, directly discards
Greatly waste without also result in.The present inventor finds in research process, if these are drawn off agent (that is, unloaded
The HTS going out) regenerated after contact under oxidation reaction condition with dimethyl sulfide and oxidant, remain able to obtain
Obtain higher dimethyl sulfide conversion ratio and dimethyl sulfone selectivity, and be obtained in that higher oxidant effective rate of utilization,
In tandem reaction sequence, dimethyl sulfide conversion ratio and dimethyl sulfone selectivity are more stable.Therefore, the method according to the invention,
At least partly described HTS is preferably and draws off agent through regeneration using HTS as the reaction unit of catalyst.
Described draw off agent can be from various be used HTS as the reaction unit of catalyst draw off draw off agent, for example may be used
Think that draw off from oxidation reaction apparatus draws off agent.Specifically, described draw off agent be Ammoximation reaction device draw off agent, hydroxyl
Glycosylation reaction device draw off agent and epoxidation reaction device draw off one or more of agent.More specifically, described draw off
Agent can be cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draw off agent and epoxidation of propylene is anti-
That answers device draws off one or more of agent.
It is not particularly limited drawing off the condition that agent regenerated, suitable choosing can be carried out according to the source drawing off agent
Select, for example: high-temperature roasting and/or solvent washing.
The activity of agent of drawing off through regeneration is originated according to it and different.Usually, the activity drawing off agent through regeneration
Can be the 5-95% of its activity (that is, the activity of fresh HTS) when fresh.Preferably, draw off agent through regenerate
Activity can be its activity when fresh 10-90%, be more preferably the 10-55%(of its activity when fresh such as
30-55%).In the 10-55% that the activity drawing off agent through regeneration is its activity when fresh, can not only obtain and make us full
The dimethyl sulfide conversion ratio of meaning and dimethyl sulfone selectivity, and it is obtained in that the oxidant effectively utilizes improving further
Rate.The activity of described fresh HTS generally more than 90%, usually more than 95%.
Described activity measures by the following method: will draw off agent and fresh HTS as hexamethylene through regenerate respectively
The catalyst of ketone oxamidinating reaction, the condition of this Ammoximation reaction is: HTS, the ammonia of 36 weight % are (with nh3Meter),
The hydrogen peroxide of 30 weight % is (with h2o2Meter), the tert-butyl alcohol and Ketohexamethylene 1:7.5:10:7.5:10 in mass ratio, at atmosheric pressure in
80 DEG C of reaction 2h.Calculate respectively and draw off agent and fresh HTS for the conversion of Ketohexamethylene during catalyst with described through regenerate
Rate, using described conversion ratio as the described activity drawing off agent and fresh HTS through regeneration, wherein, Ketohexamethylene
Conversion ratio=[mole of the Ketohexamethylene of (mole of the mole of the Ketohexamethylene of addition-unreacted Ketohexamethylene)/addition]
×100%.
At least part of HTS be through regeneration reaction unit draw off agent when, with the total amount of described HTS
On the basis of, the content that the reaction unit through regeneration draws off agent is preferably more than 5 weight %, so can not only obtain and preferably carry
The effect of hyperoxia agent effective rate of utilization, and course of reaction is more steadily easy to control, also can obtain higher dimethyl simultaneously
Thioether rate and dimethyl sulfone selectivity.The method according to the invention, even if whole HTS is the reaction through regeneration
When device draws off agent (that is, the content that the reaction unit through regeneration draws off agent is 100 weight %), remain able to obtain satisfactory
Dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.
The present invention one kind preferred embodiment in, at least part of HTS in described slurry live through with
Lower process: contact with least one acid.So can improve further dimethyl sulfone selective simultaneously additionally it is possible to enter one
Step extends the service life of HTS, reduces the operating cost of the inventive method further.For purposes of clarity, hereafter
In, the HTS contacting with acid is referred to as modified HTS.
The content of described modified HTS can be selected according to specific use occasion.Described titanium silicon molecule
Sieve can be with all modified HTSs it is also possible to part be for modified HTS.Usually, divided with described titanium silicon
On the basis of the total amount of son sieve, the content of described modified HTS can be more than 10 weight % (as 10-100 weight %),
It is preferably more than 50 weight %, be specifically as follows 50-90 weight %.
Described acid is general acid, can be one or more of mineral acid, organic acid and ackd salt.Described organic acid can
Think carboxylic acid and/or sulfonic acid, such as c1-c6Aliphatic carboxylic acid, c6-c12Aromatic carboxylic acid, c1-c6Aliphatic sulfonic and c6-
c12Aromatic sulphonic acid.Preferably, described acid is mineral acid, example hydrochloric acid, sulphuric acid, phosphoric acid, nitric acid, perchloric acid and hydrobromic acid etc..
Described acid preferably provides in form of an aqueous solutions, and in aqueous acid, the concentration of acid can be selected according to sour species, does not have
It is particularly limited to, usually, in aqueous acid, the concentration of acid can be 0.01-50 weight %, preferably 20-40 weight %.
Compared with the HTS before acid treatment, condition HTS being processed with acid is so that contact
In ultraviolet-visible (uv-vis) spectrum of HTS afterwards, the peak height of the absworption peak between 240-300nm reduce 2% with
Upper (generally 2-20%, such as 3-8%), reduces by more than 1% (generally 1-10%, such as 1.5- with the pore volume of static determination of nitrogen adsorption
3%).
Usually, in terms of silicon dioxide, described HTS can be 1 with the mol ratio of described acid to HTS:
0.01-10, preferably 1:0.05-8, more preferably 1:0.1-5.Described contact can 0-200 DEG C, preferred 20-180 DEG C, more
Carry out at a temperature of preferably 50-100 DEG C.The time of described contact can be selected according to the species of the temperature of contact and acid
Select.General, the time of described contact can be 0.1-72 hour, preferably 0.5-24 hour (as 5-24 hour).
The method according to the invention, as the catalyst aoxidizing dimethyl sulfide, its consumption can for described HTS
Think the catalytic amount being capable of catalysiss.Specifically, dimethyl sulfide is permissible with the mass ratio of described HTS
For 0.1-50:1.
The method according to the invention, from improve further the mixability between each reactant reaction system, strengthening expand
The angle dissipating and more easily the severe degree of reaction being adjusted is set out, and described slurry can also contain at least one molten
Agent.The species of described solvent is not particularly limited.Usually, described solvent can be selected from water, c1-c6Alcohol, c3-c8Ketone and
c2-c6Nitrile.The instantiation of described solvent can include but is not limited to: water, methanol, ethanol, normal propyl alcohol, isopropanol, tertiary fourth
Alcohol, isobutanol, acetone, butanone and acetonitrile.Preferably, described solvent is selected from water and c1-c6Alcohol.It is highly preferred that described solvent is
Methanol and/or water.
The consumption of described solvent is not particularly limited, and can select for conventional.Usually, the matter of solvent and dimethyl sulfide
Amount ratio can be 1-100:1.Furthermore it is also possible to according to the shape being contacted dimethyl sulfide with oxidant with HTS
The difference of formula, carries out suitable adjustment to the consumption of solvent.
Can be obtained containing dimethyl sulfide, HTS, at least one using various methods commonly used in the art
Peroxide and the slurry of optionally at least one solvent.Specifically, the method obtaining described slurry can be included diformazan
Base thioether, peroxide and optional solvent are mixed with HTS.Angle from the uniformity coefficient improving mixing further
Degree sets out, and preferably first peroxide is mixed homogeneously with HTS, then the mixture obtaining is mixed with dimethyl sulfide.
When described slurry also contains solvent, preferably described solvent and peroxide are configured to solution, then mix with HTS
Close.
When described peroxide is hydrogen peroxide and/or hydroperoxides, the ph value of the liquid phase in described slurry is general
Between 6-7.With the method for the invention it is preferred to add at least one acid in described slurry, the addition of described acid makes
The ph value of the liquid phase in this slurry is for 0.5-5.5 it is preferable that the ph value of liquid phase in this slurry is 1-5.To in described slurry
Add at least one acid so that the ph value of liquid phase in this slurry is preferably 1-5 for 0.5-5.5() can significantly improve for two
The selectivity of methyl sulfone, can also obtain high dimethyl sulfide conversion ratio and oxidant effective rate of utilization simultaneously.And, with do not add
Acid adding is compared, and in the case of remaining condition identical, adds at least one acid so that liquid phase in this slurry in described slurry
Ph value be preferably 1-5 for 0.5-5.5(), even if haptoreaction at lower temperatures, also can obtain essentially identical diformazan
Base thioether rate, higher oxidant effective rate of utilization and dimethyl sulfone selectivity.Although described peroxide is peracid,
The ph value of the liquid phase in described slurry is generally between 3.5-4, but if adds acid in described slurry, by this slurry
The ph value of liquid phase is adjusted to less than 3.5 to being not less than 1, remains able to obtain the effect above.Described ph value refers at 25 DEG C and 1 mark
Under quasi- atmospheric pressure, the ph value of mensure.
The species of described acid can select for conventional, if this acid under oxidation reaction condition will not with reaction system in
There is chemical interaction in each component (including reactant, optional solvent and reaction product).Usually, described acid
Can be mineral acid and/or organic acid, one or more of example hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid, formic acid and acetic acid, preferably
Hydrochloric acid and/or sulphuric acid.Pure acid can be used, it is possible to use aqueous acid.Acid and dimethyl sulfide and oxidant and liquid
In body mixture, the mixing of other components (as solvent) can be carried out it is also possible to carry out outside reactor in reactor.
The consumption of described acid meets previously described requirement by the ph value enabling to the liquid phase in described slurry and is defined.
The method according to the invention, described oxidation reaction condition is not particularly limited, and can be the conventional selection of this area.
Usually, described oxidation reaction condition includes: temperature can be 0-200 DEG C, preferably 20-180 DEG C；In terms of gauge pressure, pressure can
Think 0-3mpa, preferably 0.1-1.5mpa.
The method according to the invention, the slurry containing dimethyl sulfide, peroxide and HTS can be conventional
Various reaction units in reacted, for example: stirred-tank reactor or tubular reactor.
Method according to the invention it is possible to control the temperature in reactor using conventional various methods.For example: permissible
In the periphery setting cooling water jecket of reactor, and the temperature being detected according to the temperature sensor being arranged in reactor is adjusted
The amount of section cooling water, thus by the temperature control of reactor within the scope of suitable.
The method according to the invention, the reactant mixture obtaining is carried out solid-liquid separation, thus obtaining containing dimethyl sulfone
Liquid phase and the residue containing HTS.
Described solid-liquid separation is carried out in a kind of separator, and this separator is capable of efficiently by containing dimethyl sulfone
Liquid phase is separated with HTS.As shown in figure 1, described separator has first passage 1 and second channel 2, described first leads to
Road 1 and second channel 2 are adjoined by the component 3 with through hole, and the average pore size of described through hole is less than described HTS
Mean diameter.Described reactant mixture is sent in described first passage 1 by the arrival end of described first passage 1, logical first
At least part of liquid in the presence of pressure differential between road 1 and second channel 2, in the reactant mixture in first passage 1
Mutually pass through the through hole on component 3 to enter in second channel 2 and discharged by second channel 2.Average hole due to the through hole on component 3
Footpath is less than the mean diameter of HTS, and therefore HTS will not or will not enter in second channel 2 substantially, but protects
Stay in first passage 1 and discharged by the port of export of first passage 1.The method according to the invention, the entrance of described first passage
End is two different ports with the port of export.The method according to the invention, the position relationship between first passage and second channel
It is not limited to shown in Fig. 1, as long as the set-up mode of first passage and second channel is capable of above-mentioned functions.
The described component with through hole can for common various have liquid can be made to enter second from first passage lead to
The component of the through hole in road.Preferably, described component has the pipeline of described through hole for tube wall.
When described component is described pipeline, as shown in Fig. 2 described pipeline 4 can be used cooperatively with a housing 5, institute
State the space that the inwall of pipeline 4 formed as first passage, the sky that the inwall of the outer wall of described pipeline 4 and described housing 5 is formed
Between as second channel；Or, the space of the inwall formation of described pipeline 4 is as second channel, the outer wall of described pipeline 4 and institute
The space of inwall formation stating housing 5 is as first passage.The quantity of the passage that the inwall of described pipeline 4 is formed can be one
Bar or more than two.When the passage that the inwall of described pipeline is formed is one it is preferable that the inwall of described pipeline 4
As first passage, the outer wall of described pipeline 4 is logical as second with the space of the inwall formation of described housing 5 in the space being formed
Road.The quantity of the pipeline in described housing can carry out suitable selection according to treating capacity, can be one or more than two.?
When the quantity of described pipeline is more than one, preferred Existential Space between the adjacent outer wall of pipeline.The internal diameter of described housing can
Suitable selection is carried out with the quantity according to pipeline and external diameter and treating capacity.
Described pipeline is commercially available, it would however also be possible to employ conventional method prepares.Specifically, described pipeline is permissible
For ceramic film filtering element.
Method according to the invention it is possible to by adjust have the size of through hole on the component of through hole, first passage and
The time of staying in first passage for the mixture that pressure differential between second channel and oxidation reaction obtain divides to solid-liquid
From degree regulated and controled.Usually, the pressure differential between first passage and second channel can be 0.01-3mpa, preferably
0.05-2.5mpa, more preferably 0.1-2mpa.
The method according to the invention, the residue containing HTS being obtained by the port of export of described first passage can
Carry out in follow-up equipment for separating liquid from solid further separating Posterior circle use it is also possible to send into for preparing described slurry to circulate
In the described slurry of preparation.The separator that the method according to the invention adopts can be efficiently from the mixture that oxidation reaction obtains
Isolate the liquid phase containing dimethyl sulfone, in the residue containing HTS obtaining, the amount of liquid is few, therefore basis
Residue containing HTS preferably is directly recycled for preparing described slurry by the method for the present invention.
The method according to the invention can also include according to certain time interval, send into rinse in described first passage
Liquid, is rinsed to the component with through hole in separator, and the titanium silicon on the component that will may adhere to have through hole divides
Son sieve flushing is got off.
Described flushing liquor can be the various liquid substances being capable of above-mentioned functions.First passage and use in separator
In the reactor that described slurry is reacted reaction zone connect when, described flushing be preferably backwash (that is, by flushing liquor by
The port of export of first passage is sent in first passage, and discharges from the arrival end of first passage), thus will be attached to through hole
Component on HTS rinse, and send back in reactor.From guaranteeing dimethyl sulfide and peroxide reaction system
The ratio changing hydrogen will occur the angle of big change to set out due to the entrance of flushing liquor, and preferably described flushing liquor contains diformazan
Base thioether and peroxide and optional solvent, between the dimethyl sulfide in more preferably described flushing liquor and peroxide
Ratio in ratio and previously described slurry is identical.
The time interval of described flushing can carry out suitable selection according to the treating capacity of separator, to guarantee separator energy
Enough from reactant mixture, efficiently isolate the liquid phase containing dimethyl sulfone to be defined.Usually, the time interval of described flushing
It can be 0.5-24 hour.The persistent period rinsed every time is can will be attached to the HTS on the component have through hole
Whole or substantially all flushing is defined.Usually, the persistent period of described flushing can be the 1-30 second.
The method according to the invention can using conventional various methods by described separator be used for carrying out oxidation reaction
Reactor connection, thus the reactant mixture that oxidation reaction is obtained is sent in separator carries out solid-liquid separation.For example, it is possible to
With pipeline, the arrival end of separator is connected with the port of export of reactor.
The mixture containing dimethyl sulfone that the method according to the invention can also include obtaining contact carries out separating, with
Isolate dimethyl sulfone therein.The present invention does not have spy for the method for the dimethyl sulfone isolated in the mixture that contact obtains
Do not limit, can be the conventional selection of this area.For example vacuum fractionation can be carried out by the mixture obtaining contact, thus
Obtain dimethyl sulfone.
The method according to the invention carries out the taking-up of reaction heat before and after being additionally may included in above-mentioned separation of solid and liquid process, such as can
Using the passage after titanium-silicon molecular sieve catalyst is retained in as solid phase in first passage and is discharged by the port of export of first passage
On be connected with heat collector, to take heat produced by reaction away.
Fig. 3 shows one kind of the method according to the invention preferred embodiment.This preferred embodiment in, will
Dimethyl sulfide, the slurry of HTS, at least one peroxide and optional solvent are aoxidized in reactor 6
Reaction；The reactant mixture that oxidation reaction is obtained is sent in the first passage of separator 7, in the presence of pressure differential, reaction
Obtain containing dimethyl sulfone in the second channel (shadow region of in figure) of at least part of liquid phase entrance separator 7 in mixture
Liquid phase a, residue b containing HTS in first passage is sent in heat collector 8, is changed with heat transferring medium
Heat, obtains the residue of temperature reduction, and the residue that this temperature is reduced circulates and is used for preparing slurry.
The invention will be further described with reference to embodiments, but and is not so limited present disclosure.
In following examples and comparative example, if not otherwise specified, used reagent is commercially available reagent.
In following examples and comparative example, pressure is all in terms of gauge pressure.
In following examples and comparative example, hollow HTS used is according to public in Chinese patent cn1132699c
The method preparation opened, its titanium oxide content is 2.5 weight %.
HTS ts-1 used in following examples and comparative example is by journal of natural gas
Chemistry, method preparation described by 9-24 row for page 296, its titanium oxide content in 2001,10 (4): 295-307
For 2.5 weight %.
In following examples and comparative example, it is respectively adopted static nitrogen adsorption method and solid ultraviolet-visible diffuses spectrometry
The pore volume and ultraviolet absorption peak of the HTS after before modified is characterized.Wherein, solid ultraviolet-visible diffusing reflection spectrum
(uv-vis) record on shimadzu uv-3100 type ultraviolet-visible spectrometer；Pore volume is in micromeritics company
Measure on asap2405 type static state n2 absorption apparatus.
The content of each composition in the reactant liquor obtaining in following examples and comparative example, is analyzed using gas chromatography,
It is respectively adopted below equation on this basis to calculate the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and diformazan
The selectivity of base sulfone:
Dimethyl sulfide conversion ratio (%)=[(mole of the dimethyl sulfide of addition-unreacted dimethyl sulfide
Mole)/add dimethyl sulfide mole] × 100%；
Oxidant effective rate of utilization (%)=[mole of the dimethyl sulfone that 2 × reaction generates/(the rubbing of the oxidant of addition
The mole of your amount-unreacted oxidant)] × 100%；
Dimethyl sulfone selectivity (%)=[mole of the dimethyl sulfone that reaction generates/(the rubbing of the dimethyl sulfide of addition
The mole of your amount-unreacted dimethyl sulfide)] × 100%.
Embodiment 1-12 is used for the method for the present invention is described.
Embodiment 1-12 is carried out using the method shown in Fig. 3, uses water as heat transferring medium in heat collector.
Embodiment 1
Hollow for 50g HTS is placed in the methanol solution containing hydrogen peroxide, and (wherein, the content of hydrogen peroxide is 20
Weight %) in, stirring is in paste-like, then by the catalyst charging hole injection response system of reactor.Open liquid phase feed to enter
Material valve, when back pressure to pressure is for 2.0mpa, opens dimethyl sulfide inlet valve, dimethyl sulfide is sent in this response system,
It is carried out continuously reaction.Wherein, in course of reaction, on the basis of the total amount of material in reactor, the content of catalyst is 15 weights
Amount %；In liquid phase feed in reactor, methanol is 2:1 with the mol ratio of hydrogen peroxide, and dimethyl sulfide is rubbed with hydrogen peroxide
Your ratio is 2:5, and the feed rate of dimethyl sulfide is 20ml/min, and the temperature in response system is 45 DEG C, is carried out continuously 100 little
When reaction.
The reactant mixture of output from reactor is sent in separator and carries out solid-liquid separation, obtain containing dimethyl sulfone
Liquid phase and the residue containing HTS (solids content be 83 weight %), the residue containing HTS is followed
Ring is used for preparing liquid phase feed.
Wherein, described separator is formed by ceramic film filtering element and a housing, ceramic membrane filter unit in each separator
(commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm to part, and the internal diameter of membrane tube is
8mm, the external diameter of membrane tube is 12mm) quantity be 2, the internal diameter of housing is 40mm.The quantity of separator is 60, by separator
It is divided into 6 groups, every group is made up of 10 separators, wherein, is in parallel between the separator in same group, be series connection between every group,
During flushing, every time the ceramic film filtering element in 5 separators in every group is rinsed.Reactant mixture is sent into pottery
In the passage of film filtering element, obtain containing two in the passage that formed of inwall of the outer wall by ceramic film filtering element and housing
The liquid phase of methyl sulfone.Pressure in membrane tube is 2.0mpa, and the pressure in space between housing and the outer wall of membrane tube is 1.0mpa.
Every 2 hours with flushing liquor (for the mixed solution of dimethyl sulfide and hydrogen peroxide and methanol, between three
Ratio in ratio and liquid phase material is identical) passage on ceramic film filtering element is carried out with the flushing of 5 seconds, and will obtain after rinsing
To mixed liquor send into reactor in.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 1.
Embodiment 2
Dimethyl sulfone is prepared using method same as Example 1, except for the difference that, with the HTS ts-1 generation of equivalent
For hollow HTS.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 1.
Embodiment 3
Dimethyl sulfone is prepared using method same as Example 1, except for the difference that, by auxiliary agent charging aperture in reactor
Send into hydrochloric acid (for the aqueous solution of 25 weight %), the addition of hydrochloric acid makes the ph value of the liquid phase material in reactor for 5.5(not
When adding hydrochloric acid, the ph value of liquid phase material is 6.8).
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 1.
Embodiment 4
Dimethyl sulfone is prepared using method same as Example 1, except for the difference that, by auxiliary agent charging aperture in reactor
Send into hydrochloric acid (for the aqueous solution of 25 weight %), it is 4.5 that the addition of hydrochloric acid makes the ph value of the liquid phase material in reactor.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 1.
Embodiment 5
Dimethyl sulfone is prepared using method same as Example 2, except for the difference that, HTS ts-1 before use,
First processed with acid.Concrete operations are: HTS ts-1 is mixed with hydrochloric acid (mass concentration is the aqueous solution of 36 weight %)
Close, by the mixture obtaining in 90 DEG C of stirring reactions 5 hours, the temperature of the reactant mixture obtaining was carried out after being down to room temperature
Filter, by the solid matter obtaining in 120 DEG C of dryings to constant weight, obtains the HTS of modification.Wherein, HTS ts-1
With sio2Meter, HTS is 1:0.2 with the mol ratio of hcl.Through characterizing, compared with raw material HTS, obtain changes
Property the uv-vis spectrum of HTS in the peak height of absworption peak between 240-300nm reduce 3.1%, inhaled by static nitrogen
The pore volume that attached method measures reduces 1.6%.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 1.
Comparative example 1
Dimethyl sulfone is produced using method same as Example 1, except for the difference that, does not use HTS, but directly
Connect to send in reactor hydrogen peroxide, methanol and dimethyl sulfide according to the ratio of embodiment 1 and reacted, reaction obtains
Mixture carries out separating without separator.Calculate conversion ratio, the effective rate of utilization of oxidant and the dimethyl sulfone of dimethyl sulfide
Selectivity, react the result that proceeds to when 2 hours and 100 and list in Table 1.
Table 1
Embodiment 1 and comparative example 1 are compared as can be seen that to produce dimethyl sulfone, energy using the method for the present invention
Enough significantly improve the selectivity of the conversion ratio of dimethyl sulfide, the effective rate of utilization of oxidant and dimethyl sulfone.
Embodiment 1 and embodiment 2 are compared as can be seen that can be obtained as catalyst using hollow HTS
Obtain more preferable catalytic effect.
Embodiment 1 and embodiment 3 and 4 are compared as can be seen that with acid by the ph value of the liquid phase in reaction paste being
Less than 5.5, it is obtained in that higher dimethyl sulfone selectivity.
Embodiment 4 and embodiment 5 are compared as can be seen that being modified to HTS with sour, and by modification
HTS afterwards can improve the selectivity of dimethyl sulfone and the service life of catalyst as catalyst.
Embodiment 6-12 adopts following methods to measure the activity of HTS.
By HTS, 36 weight % ammonia (with nh3Meter), the hydrogen peroxide of 30 weight % is (with h2o2Meter), the tert-butyl alcohol and
Ketohexamethylene in mass ratio=1:7.5:10:7.5:10 mixing after at atmosheric pressure after 80 DEG C of stirring reactions 2h, by reactant mistake
Filter, with gas chromatography, the composition of liquid phase is analyzed, using below equation calculate Ketohexamethylene conversion ratio and as
The activity of HTS,
The conversion ratio of Ketohexamethylene=[(mole of the mole of the Ketohexamethylene of addition-unreacted Ketohexamethylene)/add
Ketohexamethylene mole] × 100%.
Embodiment 6
(1) prepare modified HTS
It is to carry out the HTS ts-1 drawing off from cyclohexanone oxamidinating course of reaction that the raw molecule using sieves again
Obtained from life, its activity is 50%, and activity when fresh is 95%, and regeneration condition is: roasts in air atmosphere at 550 DEG C
Burn 4h.
Raw molecule sieve is mixed with hydrochloric acid (mass concentration is the aqueous solution of 12 weight %), by the mixture obtaining 80
DEG C stirring reaction 6 hours, the temperature of the reactant mixture obtaining is filtered after being down to room temperature, and the solid matter obtaining is existed
120 DEG C of dryings, to constant weight, obtain the HTS of modification.Wherein, HTS ts-1 is with sio2Meter, HTS with
The mol ratio of hcl is 1:1.Through characterizing, compared with raw material HTS, the uv-vis spectrum of the HTS of the modification obtaining
In absworption peak peak height between 240-300nm reduce 4.8%, reduce 2.1% by the pore volume of static determination of nitrogen adsorption.
(2) prepare dimethyl sulfone
Hollow for 50g HTS is placed in the methanol solution containing hydrogen peroxide, and (wherein, the content of hydrogen peroxide is 30
Weight %) in, stir in paste-like, then by the catalyst charging hole injection response system of reactor.Open liquid phase feed
Inlet valve, when back pressure to pressure is for 2.0mpa, opens dimethyl sulfide inlet valve, dimethyl sulfide is sent into this response system
In, open auxiliary agent inlet valve simultaneously, send into sulphuric acid (for the aqueous solution of 25 weight %) in response system and be carried out continuously reaction.Its
In, in course of reaction, on the basis of the total amount of material in reactor, the content of catalyst is 5 weight %；Liquid phase in reactor
In raw material, methanol is 1:1 with the mol ratio of hydrogen peroxide, and dimethyl sulfide is 1:5 with the mol ratio of hydrogen peroxide, the use of sulphuric acid
It is 3.5 that amount makes the ph value of the liquid phase material in response system, and the feed rate of dimethyl sulfide is 50ml/min, response system
Interior temperature is 55 DEG C, is carried out continuously the reaction of 100 hours.
The reactant mixture of output from reactor is sent in separator and carries out solid-liquid separation, obtain containing dimethyl sulfone
Liquid phase and the residue containing HTS (solids content be 85 weight %), the residue containing HTS is followed
Ring is used for preparing liquid phase feed.
Wherein, described separator is formed by ceramic film filtering element and a housing, ceramic membrane filter unit in each separator
(commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm to part, and the internal diameter of membrane tube is
8mm, the external diameter of membrane tube is 12mm) quantity be 5, the internal diameter of housing is 100mm.The quantity of separator is 12, will separate
Device is divided into 2 groups, and every group is made up of 6 separators, wherein, is in parallel between the separator in same group, is series connection between every group,
During flushing, every time the ceramic film filtering element in 3 separators in every group is rinsed.Reactant mixture is sent into pottery
In passage on film filtering element, contained in the passage that formed of inwall of the outer wall by ceramic film filtering element and housing
The liquid phase of dimethyl sulfone.Pressure in membrane tube is 0.3mpa, it is normal pressure (that is, 1 mark in the space between housing and the outer wall of membrane tube
Quasi- atmospheric pressure).
Every 1 hour with flushing liquor (for the mixed solution of dimethyl sulfide and hydrogen peroxide and methanol, between three
Ratio in ratio and liquid phase material is identical) passage on ceramic film filtering element is carried out with the flushing of 2 seconds, and will obtain after rinsing
To mixed liquor send into reactor in.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 2.
Embodiment 7
Dimethyl sulfone is prepared using method same as Example 6, except for the difference that, in step (2), the consumption of sulphuric acid makes
The ph value of the liquid phase mixture being formed by dimethyl sulfide, oxidant and solvent is 1.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 2.
Embodiment 8
Dimethyl sulfone is prepared using method same as Example 6, except for the difference that, step does not use sulphuric acid, liquid phase in (2)
The ph value of material is 6.7.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 2.
Embodiment 9
Dimethyl sulfone is prepared using method same as Example 6, except for the difference that, does not carry out step (1), but directly will
Raw molecule in embodiment 6 step (1) sieves as the catalyst to preparing dimethyl sulfone.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 2.
Embodiment 10
(1) prepare modified HTS
It is to carry out the hollow HTS drawing off from phenol hydroxylation reaction unit that the raw molecule using sieves again
Obtained from life, its activity is 30%, and activity when fresh is 96%, and regeneration condition is: roasts in air atmosphere at 570 DEG C
Burn 4h.
Raw molecule sieve is mixed with acetic acid (mass concentration is the aqueous solution of 32 weight %), by the mixture obtaining 60
DEG C stirring reaction 24 hours, the temperature of the reactant mixture obtaining is filtered after being down to room temperature, and the solid matter obtaining is existed
120 DEG C of dryings, to constant weight, obtain the HTS of modification.Wherein, HTS is with sio2Meter, HTS with
ch3The mol ratio of cooh is 1:5.Through characterizing, compared with raw molecule sieve, the uv-vis light of the HTS of the modification obtaining
In spectrum, the absworption peak peak height between 240-300nm reduces 5.5%, reduces 2.2% by the pore volume of static determination of nitrogen adsorption.
(2) prepare dimethyl sulfone
Hollow for 50g HTS is placed in the methanol solution containing hydrogen peroxide, and (wherein, the content of hydrogen peroxide is 50
Weight %) in, stirring is in paste-like, then by the catalyst charging hole injection response system of reactor.Open liquid phase feed to enter
Material valve, when back pressure to pressure is for 2.0mpa, opens dimethyl sulfide inlet valve, dimethyl sulfide is sent in this response system,
Open auxiliary agent inlet valve simultaneously, send into hydrochloric acid (for the aqueous solution of 25 weight %) in response system and be carried out continuously reaction.Wherein,
In course of reaction, on the basis of the total amount of material in reactor, the content of catalyst is 10 weight %；Liquid phase in reactor is former
In material, methanol is 5:1 with the mol ratio of hydrogen peroxide, and dimethyl sulfide is 1:4 with the mol ratio of hydrogen peroxide, the consumption of sulphuric acid
The ph value making the liquid phase material in response system is 3.5, and the feed rate of dimethyl sulfide is 30ml/min, in response system
Temperature be 80 DEG C, be carried out continuously the reaction of 100 hours.
The reactant mixture of output from reactor is sent in separator and carries out solid-liquid separation, obtain containing dimethyl sulfone
Liquid phase and the residue containing HTS (solids content be 88 weight %), the residue containing HTS is followed
Ring is used for preparing liquid phase feed.
Wherein, described separator is formed by ceramic film filtering element and a housing, ceramic membrane filter unit in each separator
(commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm to part, and the internal diameter of membrane tube is
8mm, the external diameter of membrane tube is 12mm) quantity be 5, the internal diameter of housing is 100mm.The quantity of separator is 12, will separate
Device is divided into 2 groups, and every group is made up of 6 separators, wherein, is in parallel between the separator in same group, is series connection between every group,
During flushing, every time the ceramic film filtering element in 3 separators in every group is rinsed.Reactant mixture is sent into pottery
In passage on film filtering element, contained in the passage that formed of inwall of the outer wall by ceramic film filtering element and housing
The liquid phase of dimethyl sulfone.Pressure in membrane tube is 0.3mpa, is normal pressure (that is, 1 mark in the space between housing and the outer wall of membrane tube
Quasi- atmospheric pressure).
Every 1 hour with flushing liquor (for the mixed solution of dimethyl sulfide and hydrogen peroxide and methanol, between three
Ratio in ratio and liquid phase material is identical) passage on ceramic film filtering element is carried out with the flushing of 2 seconds, and will obtain after rinsing
To mixed liquor send into reactor in.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 2.
Embodiment 11
Used in the present embodiment, HTS is by the HTS ts-1 drawing off from propylene oxidation reaction process
Obtained from being regenerated, its activity is 50%, and activity when fresh is 95%, and mean diameter is 0.6 μm, and regeneration condition is:
At 550 DEG C in air atmosphere roasting 4h.
Hollow for 50g HTS is placed in the methanol solution containing hydrogen peroxide, and (wherein, the content of hydrogen peroxide is 50
Weight %) in, stir in paste-like, then by the catalyst charging hole injection response system of reactor.Open liquid phase feed
Inlet valve, when back pressure to pressure is for 2.0mpa, opens dimethyl sulfide inlet valve, dimethyl sulfide is sent into this response system
In, open auxiliary agent inlet valve simultaneously, send into sulphuric acid (for the aqueous solution of 25 weight %) in response system and be carried out continuously reaction.Its
In, in course of reaction, on the basis of the total amount of material in reactor, the content of catalyst is 2 weight %；Liquid phase in reactor
In raw material, methanol is 10:1 with the mol ratio of hydrogen peroxide, and dimethyl sulfide is 1:10 with the mol ratio of hydrogen peroxide, sulphuric acid
It is 3.5 that consumption makes the ph value of the liquid phase material in response system, and the feed rate of dimethyl sulfide is 20ml/min, reaction system
Temperature in system is 100 DEG C, is carried out continuously the reaction of 100 hours.
The reactant mixture of output from reactor is sent in separator and carries out solid-liquid separation, obtain containing dimethyl sulfone
Liquid phase and the residue containing HTS (solids content be 65 weight %), the residue containing HTS is followed
Ring is used for preparing liquid phase feed.
Wherein, described separator is formed by ceramic film filtering element and a housing, ceramic membrane filter unit in each separator
(commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm to part, and the internal diameter of membrane tube is
8mm, the external diameter of membrane tube is 12mm) quantity be 5, the internal diameter of housing is 100mm.The quantity of separator is 12, will separate
Device is divided into 2 groups, and every group is made up of 6 separators, wherein, is in parallel between the separator in same group, is series connection between every group,
During flushing, every time the ceramic film filtering element in 3 separators in every group is rinsed.Reactant mixture is sent into pottery
In passage on film filtering element, contained in the passage that formed of inwall of the outer wall by ceramic film filtering element and housing
The liquid phase of dimethyl sulfone.Pressure in membrane tube is 0.3mpa, is normal pressure (that is, 1 mark in the space between housing and the outer wall of membrane tube
Quasi- atmospheric pressure).
Every 1 hour with flushing liquor (for the mixed solution of dimethyl sulfide and hydrogen peroxide and methanol, between three
Ratio in ratio and liquid phase material is identical) passage on ceramic film filtering element is carried out with the flushing of 2 seconds, and will obtain after rinsing
To mixed liquor send into reactor in.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 2.
Embodiment 12
Prepare dimethyl sulfone using with embodiment 11 identical method, except for the difference that, catalyst will be aoxidized from propylene by (1)
The HTS ts-1 that course of reaction draws off regenerated obtained from regenerative agent；And (2) fresh HTS ts-1
Composition, wherein, regenerative agent is 2:1 with the mass ratio of fresh HTS ts-1.
It is analyzed every 2 hours liquid phases containing dimethyl sulfone to output from separator, calculate dimethyl sulfide
Conversion ratio, the effective rate of utilization of oxidant and dimethyl sulfone selectivity, react the result that proceeds to when 2 hours and 100 and exist
List in table 2.
Table 2
Embodiment 6-12 as a result, it was confirmed that even if at least part of catalyst comes from and draws off agent it is also possible to obtain through regeneration
Obtain high dimethyl sulfide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.
Claims (14)
1. a kind of method producing dimethyl sulfone, the method includes: will be containing dimethyl sulfide, HTS and at least one
The slurry of peroxide is reacted under oxidation reaction condition, and the reactant mixture obtaining is carried out solid-liquid separation, obtains
Liquid phase containing dimethyl sulfone and the residue containing HTS, described peroxide and described dimethyl sulfide mole
Than for more than 2:1；
Described solid-liquid separation is carried out in a kind of separator, and described separator has first passage and a second channel, and described first
Passage has arrival end and the port of export, and described first passage and second channel are adjoined by the component with through hole, described through hole
Average pore size be less than the mean diameter of described HTS, described reactant mixture is sent into described the by described arrival end
In one passage, at least part of liquid phase in described reactant mixture is passed through described through hole and is entered in described second channel, from described
The described liquid phase containing dimethyl sulfone discharged by second channel, contains titanium silicon molecule described in the port of export of described first passage obtains
The residue of sieve,
Wherein, at least partly described HTS is the unloading using HTS as the reaction unit of catalyst through regeneration
Go out agent, described draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction dress
That puts draws off one or more of agent, and the activity drawing off agent through regeneration is the 10-55% of its activity when fresh；
Described oxidation reaction condition includes: temperature is 0-200 DEG C, and in terms of gauge pressure, pressure is 0-3mpa.
2. method according to claim 1, described component has the pipeline of described through hole for tube wall.
3. method according to claim 2, wherein, the space that the inwall of described pipeline is formed as described first passage,
The space of the outer wall of described pipeline and housing composition is as second channel.
4. method according to claim 1, wherein, described draw off agent be cyclohexanone oxamidinating reaction unit draw off agent,
Phenol hydroxylation reaction unit draw off agent and propylene ring oxidation reaction device draw off one or more of agent.
5. method according to claim 4, wherein, the activity drawing off agent through regeneration is its activity when fresh
30-55%.
6. method according to claim 1, wherein, described slurry also contains at least one solvent, described solvent and titanium silicon
The mass ratio of molecular sieve is 1-100:1.
7. method according to claim 1, wherein, the method also includes following the described residue containing HTS
Ring is used for preparing described slurry.
8. method according to claim 1, wherein, described peroxide is 2.5- with the mol ratio of described dimethyl sulfide
10:1, dimethyl sulfide is 0.1-50:1 with the mass ratio of HTS, and described oxidation reaction condition includes: temperature is 20-
180 DEG C, in terms of gauge pressure, pressure is 0.1-1.5mpa.
9. the method according to any one in claim 1 and 4-8, wherein, at least part of titanium silicon in described slurry divides
Son sieve lives through procedure below: contacts 0.1-72 hour at a temperature of 0-200 DEG C with least one acid.
10. method according to claim 9, wherein, described acid is selected from hydrochloric acid, sulphuric acid, phosphoric acid, nitric acid, perchloric acid and hydrogen
Bromic acid.
11. methods according to claim 9, wherein, HTS in terms of silicon dioxide, described HTS and institute
The mol ratio stating acid is 1:0.01-10.
12. methods according to any one in claim 1 and 4-8, wherein, described HTS is to have mfi knot
The HTS of structure.
13. methods according to any one in claim 1 and 6-8, wherein, the method also includes adding in described slurry
Plus at least one sour, it is 0.5-5.5 that the addition of described acid makes the ph value of the liquid phase in this slurry.
14. methods according to claim 1 or 8, wherein, described peroxide be selected from hydrogen peroxide, hydroperoxides and
Peracid.
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