CN104557634A - 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 of producing dimethyl sulfone.
Background technology
Dimethyl sulfone is white crystalline powder, and soluble in water, ethanol, benzene, methyl alcohol and acetone, be slightly soluble in ether.Can not make potassium permanganate variable color under normal temperature, dimethyl sulfone can be oxidized to methylsulfonic acid by strong oxidizer.The dimethyl sulfone aqueous solution is in neutral.25 DEG C of microsublimations, accelerate to 60 DEG C of rate of sublimation, thus dimethyl sulfone product drying should carry out under cryogenic vacuum.
Dimethyl sulfone is used as organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, foodstuff additive and medicine in the industry.Dimethyl sulfone, as a kind of organic sulfide, has and strengthens the ability that human body produces Regular Insulin, also have promoter action simultaneously to the metabolism of carbohydrate, is the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound healing, also can work to the synthesis of the vitamins B needed for metabolism and neurological health, vitamins C, vitamin H and activation, be called as " naturally beautifying carbon species ".All dimethyl sulfone is contained in the skin of human body, hair, nail, bone, muscle and each organ, dimethyl sulfone is mainly present in ocean and soil at occurring in nature, absorbed as nutritive substance in plant-growth, the mankind can absorb from the foods such as veterinary antibiotics, fish, meat, egg, milk, health disorders will be caused once lack or disease occurs, it is the essential substance that human body maintains biological element sulphur balance, having therapeutic value and nourishing function to human body diseases, is the indispensable medicine of human survival and health care.Abroad dimethyl sulfone widely applied as the nutritious prod of equal importance with VITAMIN, the applied research of China to dimethyl sulfone is carried out not yet very well, and current product is mainly used in outlet.Therefore, dimethyl sulfone is not only a kind of new high-tech product, is also a kind of fine chemical product of high added value.Product is new, market potential is large, and benefit is given prominence to, and can export goods and earn foreign currency again, have wide production and application and development prospect.
At present, the product that dimethyl sulfone is oxidized further as dimethyl sulfoxide (DMSO) is the principal by product that dimethyl sulfoxide (DMSO) is produced.In addition, dimethyl sulfone can also directly be obtained through nitric acid oxidation by dimethyl sulfoxide (DMSO).Concrete, can by dimethyl sulfoxide (DMSO) at 140-145 DEG C with nitric acid oxidation, cool after reaction terminates, filtration, obtains the crude product of white, needle-shaped crystals.Again through underpressure distillation, collect 138-145 DEG C of (98.42kPa) cut and be finished product.
Summary of the invention
The present inventor finds in research process, when dimethyl sulfone directly being prepared in dimethyl thioether oxidation using superoxide as oxygenant, if use HTS effectively can improve the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfone as catalyzer, high dimethyl thioether transformation efficiency can also be obtained simultaneously.
In employing HTS as catalyzer, when dimethyl sulfone is directly prepared in dimethyl thioether oxidation using superoxide as oxygenant, liquid mixture containing dimethyl thioether and superoxide can be made by being filled with the bed of shaping HTS, also can directly by HTS and dimethyl thioether and superoxide hybrid reaction.Directly by HTS and dimethyl thioether and superoxide hybrid reaction, on the one hand without the need to using shaping HTS, be easy to control temperature of reaction on the other hand.
But, directly HTS and dimethyl thioether and superoxide hybrid reaction are needed the mixture obtained after reacting to be separated, HTS and the liquid phase containing dimethyl sulfone could be separated.Therefore, liquid-solid separation efficiency is one of important factor affecting dimethyl sulfone production efficiency.
Slurry that a kind of use contains HTS and superoxide and dimethyl thioether is the object of the present invention is to provide to carry out the method for production dimethyl sulfone, the method can improve the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone on the one hand effectively, can isolate the liquid phase containing dimethyl sulfone on the other hand efficiently from the mixture be obtained by reacting.
The invention provides a kind of method of producing dimethyl sulfone, the method comprises: reacted under oxidation reaction condition by the slurry containing dimethyl thioether, HTS and at least one superoxide, and the reaction mixture obtained is carried out solid-liquid separation, obtain the liquid phase containing dimethyl sulfone and the residue containing HTS, the mol ratio of described superoxide and described dimethyl thioether is for being greater than 2:1;
Described solid-liquid separation is carried out in a kind of separator, described separator has first channel and second passage, described first channel has inlet end and exit end, described first channel and second passage are adjoined by the component with through hole, the mean pore size of described through hole is less than the median size of described HTS, described reaction mixture is sent in described first channel by described inlet end, at least part of liquid phase in described reaction mixture enters in described second passage by described through hole, the described liquid phase containing dimethyl sulfone is discharged from described second passage, the described residue containing HTS is obtained by the exit end of described first channel.
Effectively can improve the effective rate of utilization of oxygenant and the selectivity of dimethyl sulfone according to method of the present invention, higher dimethyl thioether transformation efficiency can also be obtained simultaneously.Further, the liquid phase containing dimethyl sulfone can be isolated efficiently according to method of the present invention from the liquid-solid mixture be obtained by reacting.In addition, according to method good stability of the present invention, even if long-play, high dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity still can be obtained.
Accompanying drawing explanation
Fig. 1 shows a kind of structural representation according to the separator used in method of the present invention.
Fig. 2 shows a kind of embodiment according to the separator used in method of the present invention.
Fig. 3 shows according to the one of method of the present invention preferred embodiment.
Embodiment
The invention provides a kind of method of producing dimethyl sulfone, the method comprises: reacted under oxidation reaction condition by the slurry containing dimethyl thioether, HTS and at least one superoxide, and the reaction mixture obtained is carried out solid-liquid separation, obtain the liquid phase containing dimethyl sulfone and the residue containing HTS.
Described superoxide refers to the compound containing-O-O-key in molecular structure, can be selected from hydrogen peroxide, hydroperoxide and peracid.Described hydroperoxide refer to that a hydrogen atom in hydrogen peroxide molecule is replaced by organic group and the material obtained.Described peracid refers to the organic oxacid containing-O-O-key in molecular structure.The specific examples of described superoxide can include but not limited to: hydrogen peroxide, tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid.Preferably, described oxygenant is hydrogen peroxide, can reduce separation costs further like this.The hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.
From the angle improved further according to the security of method of the present invention, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.According to method of the present invention, when described hydrogen peroxide provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
According to method of the present invention, the mol ratio of described oxygenant and described dimethyl thioether, for being greater than 2:1, is preferably more than 2.5:1.The mol ratio of described oxygenant and described dimethyl thioether can be below 20:1, as below 10:1, is preferably below 5:1.Preferably, the mol ratio of described oxygenant and dimethyl thioether is 2.5-10:1.More preferably, the mol ratio of described oxygenant and dimethyl thioether is 2.5-5:1.
Described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, can use chemical formula xTiO
2siO
2represent.The present invention is not particularly limited for the content of titanium atom in HTS, can be that the routine of this area is selected.Particularly, x can be 0.0001-0.04, is preferably 0.01-0.03, is more preferably 0.015-0.025.
Described HTS can for the common HTS with various topological framework, such as: described HTS can be selected from the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
Preferably, described HTS is selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure.More preferably, described HTS is the HTS of MFI structure.
From the optionally angle improving the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone further, described HTS is the HTS of MFI structure, and the crystal grain of this HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Herein, the HTS with this structure is called hollow HTS.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Sinopec Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
Described HTS can be the former powder of HTS, also can be shaping HTS.
In employing HTS as in the various full scale plants of catalyzer, as Ammoximation reaction, in hydroxylating and epoxidation reaction device, usually after plant running for some time, the catalytic activity of catalyzer declines, need to carry out in device or ex-situ regeneration, even if when carry out regenerating also be difficult to obtain satisfied active time, catalyzer is needed to draw off (namely from device, more catalyst changeout), and the catalyzer drawn off (namely, drawing off agent or spent catalyst) current treatment process normally piles up and buries, occupy valuable land resources and inventory space on the one hand, HTS production cost is higher on the other hand, directly pass into disuse and also result in great waste.The present inventor finds in research process, if these are drawn off agent (namely, the HTS drawn off) carry out contacting under oxidation reaction condition with oxygenant with dimethyl thioether after regeneration, still higher dimethyl thioether transformation efficiency and dimethyl sulfone selectivity can be obtained, and higher oxygenant effective rate of utilization can be obtained, in tandem reaction sequence dimethyl thioether transformation efficiency and dimethyl sulfone selectivity more stable.Therefore, according to method of the present invention, at least part of described HTS be preferably through regeneration the reaction unit using HTS as catalyzer draw off agent.Described draw off agent can for from various use HTS as the agent that draws off drawn off the reaction unit of catalyzer, such as can for draw off from oxidation reaction apparatus draw off agent.Particularly, draw off described in agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more.More specifically, draw off described in agent can for cyclohexanone oxamidinating reaction unit draw off agent, phenol hydroxylation reaction unit draw off agent and propylene ring oxidation reaction device draw off in agent one or more.
Being not particularly limited drawing off the condition that agent carries out regenerating, appropriate selection can being carried out according to the source drawing off agent, such as: high-temperature roasting and/or solvent wash.
The activity drawing off agent through regeneration is different according to its source.Usually, the activity drawing off agent through regeneration can be the 5-95% of its activity (that is, the activity of fresh titanium si molecular sieves) when fresh.Preferably, the activity drawing off agent through regeneration can be the 10-90% of its activity when fresh, and more preferably the 10-55%(of its activity when fresh is as 30-55%).When the activity drawing off agent through regeneration is the 10-55% of its activity when fresh, gratifying dimethyl thioether transformation efficiency and dimethyl sulfone selectivity can not only be obtained, and the oxygenant effective rate of utilization improved further can be obtained.The activity of described fresh titanium si molecular sieves is generally more than 90%, is generally more than 95%.
Described activity measures by the following method: will draw off through regeneration the catalyzer that agent and fresh titanium si molecular sieves are used as cyclohexanone oxamidinating reaction respectively, the condition of this Ammoximation reaction is: HTS, 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone 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 through regeneration the transformation efficiency that agent and fresh titanium si molecular sieves are pimelinketone during catalyzer with described, using described transformation efficiency as the described activity drawing off agent and fresh titanium si molecular sieves through regeneration, wherein, transformation efficiency=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100% of pimelinketone.
At least part of HTS be through regeneration reaction unit draw off agent time, with the total amount of described HTS for benchmark, the content that reaction unit through regeneration draws off agent is preferably more than 5 % by weight, the effect better improving oxygenant effective rate of utilization can not only be obtained like this, and reaction process is more steadily easy to control, also can obtain higher dimethyl thioether transformation efficiency and dimethyl sulfone selectivity simultaneously.According to method of the present invention, even if whole HTS is the reaction unit through regenerating draw off agent (namely, the content that reaction unit through regeneration draws off agent is 100 % by weight) time, still can obtain gratifying dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity.
One of the present invention preferred embodiment in, at least part of HTS in described slurry lives through following process: with at least one acid contact.Like this can improve further dimethyl sulfone optionally simultaneously, the work-ing life of HTS can also be extended further, reduce the running cost of the inventive method further.For clearly object, hereinafter, the HTS contacted with acid is called the HTS of modification.
The content of the HTS of described modification can be selected according to concrete use occasion.Described HTS can be all the HTS of modification, can be also partly the HTS of modification.Usually, with the total amount of described HTS for benchmark, the content of the HTS of described modification can be more than 10 % by weight (as 10-100 % by weight), is preferably more than 50 % by weight, is specifically as follows 50-90 % by weight.
Described acid is general acid, can be one or more in mineral acid, organic acid and acid-salt.Described organic acid can be carboxylic acid and/or sulfonic acid, as C
1-C
6aliphatic carboxylic acid, C
6-C
12aromatic carboxylic acid, C
1-C
6aliphatic sulfonic and C
6-C
12aromatic sulphonic acid.Preferably, described acid is mineral acid, example hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and Hydrogen bromide etc.Described acid preferably provides in form of an aqueous solutions, and in aqueous acid, the concentration of acid can be selected according to the kind of acid, is not particularly limited, and usually, in aqueous acid, the concentration of acid can be 0.01-50 % by weight, is preferably 20-40 % by weight.
With compared with the HTS before acid treatment, the condition processed HTS with acid is to make in ultraviolet-visible (UV-Vis) spectrum of the HTS after contacting, the peak height of the absorption peak between 240-300nm reduces more than 2% and (is generally 2-20%, as 3-8%), reduce by more than 1% (being generally 1-10%, as 1.5-3%) with the pore volume of static determination of nitrogen adsorption.
Usually, HTS is in silicon-dioxide, and the mol ratio of described HTS and described acid can be 1:0.01-10, is preferably 1:0.05-8, is more preferably 1:0.1-5.Described contact can be carried out at the temperature of 0-200 DEG C, preferably 20-180 DEG C, more preferably 50-100 DEG C.The time of described contact can be selected according to the kind of the temperature of contact and acid.General, the time of described contact can be 0.1-72 hour, is preferably 0.5-24 hour (as 5-24 hour).
According to method of the present invention, described HTS is as the catalyzer be oxidized by dimethyl thioether, and its consumption can for realizing the catalytic amount of catalysis.Particularly, the mass ratio of dimethyl thioether and described HTS can be 0.1-50:1.
According to method of the present invention, from the degree of mixing improved further in reaction system between each reactant, enhanced dispersion and more easily to the angle that the severe degree of reaction regulates, described slurry can also contain at least one solvent.The kind of described solvent is not particularly limited.Usually, described solvent can be selected from water, C
1-C
6alcohol, C
3-C
8ketone and C
2-C
6nitrile.The specific examples of described solvent can include but not limited to: water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol, acetone, butanone and acetonitrile.Preferably, described solvent is selected from water and C
1-C
6alcohol.More preferably, described solvent is methyl alcohol and/or water.
The consumption of described solvent is not particularly limited, and can be conventional selection.Usually, the mass ratio of solvent and dimethyl thioether can be 1-100:1.In addition, the form that contact different can also be carried out with oxygenant with HTS according to by dimethyl thioether, suitable adjustment is carried out to the consumption of solvent.
The various methods that this area can be adopted to commonly use obtain the slurry containing dimethyl thioether, HTS, at least one superoxide and optional at least one solvent.Particularly, the method obtaining described slurry can comprise and dimethyl thioether, superoxide and optional solvent being mixed with HTS.From the angle improving the degree of uniformity mixed further, preferably first superoxide is mixed with HTS, then the mixture obtained is mixed with dimethyl thioether.When described slurry is also containing solvent, preferably described solvent and superoxide is mixed with solution, then mixes with HTS.
Described superoxide be hydrogen peroxide and/or hydroperoxide time, the pH value of the liquid phase in described slurry is generally between 6-7.According to method of the present invention, preferably in described slurry, add at least one acid, the addition of described acid makes the pH value of the liquid phase in this slurry be 0.5-5.5, preferably makes the pH value of the liquid phase in this slurry be 1-5.In described slurry, add at least one acid, make the pH value of the liquid phase in this slurry be that 0.5-5.5(is preferably 1-5) selectivity for dimethyl sulfone can be significantly improved, high dimethyl thioether transformation efficiency and oxygenant effective rate of utilization can also be obtained simultaneously.And, with do not add compared with acid, when all the other conditions are identical, at least one acid is added in described slurry, the pH value of the liquid phase in this slurry is made to be that 0.5-5.5(is preferably 1-5), even if contact reacts at lower temperatures, also can obtain substantially identical dimethyl thioether transformation efficiency, higher oxygenant effective rate of utilization and dimethyl sulfone selectivity.Although when described superoxide is peracid, the pH value of the liquid phase in described slurry is generally between 3.5-4, if add acid in described slurry, the pH value of the liquid phase in this slurry being adjusted to lower than 3.5 to being not less than 1, still can obtaining above-mentioned effect.Described pH value refers at 25 DEG C and 1 standard atmosphere pressure, the pH value of mensuration.
The kind of described acid can be conventional selection, as long as this acid chemical interaction can not occur with each component in reaction system (comprising reactant, optional solvent and resultant of reaction) under oxidation reaction condition.Usually, described acid can be mineral acid and/or organic acid, one or more in example hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid and acetic acid, is preferably hydrochloric acid and/or sulfuric acid.Pure acid can be used, also can use aqueous acid.Acid can be carried out with mixing of other component (as solvent) in dimethyl thioether and oxygenant and liquid mixture in reactor, also can carry out outside reactor.
The consumption of described acid is as the criterion so that the pH value of the liquid phase in described slurry can be made to meet previously described requirement.
According to method of the present invention, described oxidation reaction condition is not particularly limited, and can be that the routine of this area is selected.Usually, described oxidation reaction condition comprises: temperature can be 0-200 DEG C, is preferably 20-180 DEG C; In gauge pressure, pressure can be 0-3MPa, is preferably 0.1-1.5MPa.
According to method of the present invention, the slurry containing dimethyl thioether, superoxide and HTS can react in conventional various reaction units, such as: stirred-tank reactor or tubular reactor.
According to method of the present invention, conventional various methods can be adopted to control the temperature in reactor.Such as: cooling water jecket can be set in the periphery of reactor, and regulate the amount of water coolant according to the temperature that the temperature sensor be arranged in reactor detects, thus the temperature of reactor is controlled within suitable scope.
According to method of the present invention, the reaction mixture obtained is carried out solid-liquid separation, thus the liquid phase obtained containing dimethyl sulfone and the residue containing HTS.
Described solid-liquid separation is carried out in a kind of separator, and this separator can realize the liquid phase containing dimethyl sulfone being separated with HTS efficiently.As shown in Figure 1, described separator has first channel 1 and second passage 2, and described first channel 1 and second passage 2 are adjoined by the component 3 with through hole, and the mean pore size of described through hole is less than the median size of described HTS.Described reaction mixture is sent in described first channel 1 by the inlet end of described first channel 1, under the effect of the pressure difference between first channel 1 and second passage 2, at least part of liquid phase being arranged in the reaction mixture of first channel 1 enters second passage 2 by the through hole on component 3 and is discharged by second passage 2.Mean pore size due to the through hole on component 3 is less than the median size of HTS, and therefore HTS can not or can not enter in second passage 2 substantially, but is retained in first channel 1 and by the exit end of first channel 1 and discharges.According to method of the present invention, the inlet end of described first channel and exit end are two different ports.According to method of the present invention, the position relationship between first channel and second passage is not limited to shown in Fig. 1, as long as the set-up mode of first channel and second passage can realize above-mentioned functions.
The described component with through hole variously can have the component that liquid can be made from first channel to enter the through hole of second passage for common.Preferably, described component is the pipeline that tube wall has described through hole.
When described component is described pipeline, as shown in Figure 2, the space that described pipeline 4 and a housing 5 can be formed with the use of the inwall of, described pipeline 4 is as first channel, and the space that the outer wall of described pipeline 4 and the inwall of described housing 5 are formed is as second passage; Or the space of the inwall formation of described pipeline 4 is as second passage, and the space that the outer wall of described pipeline 4 and the inwall of described housing 5 are formed is as first channel.The quantity of the passage of the inwall formation of described pipeline 4 can be one, also can be more than two.When the passage that the inwall of described pipeline is formed is one, preferably, the space of the inwall formation of described pipeline 4 is as first channel, and the space that the outer wall of described pipeline 4 and the inwall of described housing 5 are formed is as second passage.The quantity of the pipeline in described housing can carry out appropriate selection according to treatment capacity, can be more than one or two.When the quantity of described pipeline is more than one, preferred Existential Space between the outer wall of adjacent pipeline.The internal diameter of described housing can carry out appropriate selection according to the quantity of pipeline and external diameter and treatment capacity.
Described pipeline can be commercially available, and conventional method also can be adopted to prepare.Particularly, described pipeline can be ceramic film filtering element.
According to method of the present invention, the residence time degree to solid-liquid separation of mixture in first channel that the size of through hole, the pressure difference between first channel and second passage and oxidizing reaction on the component of through hole obtain can be had regulate and control by regulating.Usually, the pressure difference between first channel and second passage can be 0.01-3MPa, is preferably 0.05-2.5MPa, is more preferably 0.1-2MPa.
According to method of the present invention, the residue containing HTS obtained by the exit end of described first channel can be cycled to used in the described slurry of preparation, also can send in follow-up equipment for separating liquid from solid and further be separated Posterior circle for preparing described slurry.The separator that method according to the present invention adopts can isolate the liquid phase containing dimethyl sulfone efficiently from the mixture that oxidizing reaction obtains, what obtain is few containing the amount of liquid in the residue of HTS, therefore is preferably used for preparing described slurry by the residue direct circulation containing HTS according to method of the present invention.
Can also comprise according to certain time interval according to method of the present invention, in described first channel, send into washing fluid, the component with through hole in separator is rinsed, rinse so that the HTS had on the component of through hole may be attached to.
Described washing fluid can be the various liquid substance that can realize above-mentioned functions.When the first channel of separator is communicated with the reaction zone of the reactor for being carried out reacting by described slurry, (namely described flushing is preferably back flushing, washing fluid is sent in first channel by the exit end of first channel, and discharge from the inlet end of first channel), thus rinse being attached to the HTS had on the component of through hole, and send back in reactor.From guaranteeing that the angle of large change can not occur due to entering of washing fluid the ratio of dimethyl thioether and hydrogen peroxide in reaction system, preferred described washing fluid contains dimethyl thioether and superoxide and optional solvent, and the dimethyl thioether more preferably in described washing fluid is identical with the ratio in the ratio between superoxide and previously described slurry.
The timed interval of described flushing can carry out appropriate selection according to the treatment capacity of separator, to guarantee that separator can the liquid phase isolated from reaction mixture containing dimethyl sulfone be as the criterion efficiently.Usually, the timed interval of described flushing can be 0.5-24 hour.Time length of each flushing with can by be attached to have HTS on the component of through hole all or basic all flushing be as the criterion.Usually, the time length of described flushing can be 1-30 second.
Conventional various methods can be adopted to be communicated with the reactor being used for carrying out oxidizing reaction by described separator according to method of the present invention, thus carry out solid-liquid separation in reaction mixture oxidizing reaction obtained feeding separator.Such as, with pipeline, the inlet end of separator can be communicated with the exit end of reactor.
Can also comprise according to method of the present invention the mixture containing dimethyl sulfone contact obtained to be separated, to isolate dimethyl sulfone wherein.The present invention is not particularly limited for the method isolating the dimethyl sulfone contacted in the mixture that obtains, can be the routine selection of this area.Such as by carrying out vacuum fractionation by contacting the mixture obtained, thus dimethyl sulfone can be obtained.
The taking-up carrying out reaction heat before and after above-mentioned solid-liquid separation process can also be included according to method of the present invention, be connected with heat collector as being retained in as solid phase on the passage after discharging in first channel and by the exit end of first channel at titanium-silicon molecular sieve catalyst, take the heat that reaction produces away.
Fig. 3 shows according to the one of method of the present invention preferred embodiment.This preferred embodiment in, the slurry of dimethyl thioether, HTS, at least one superoxide and optional solvent is carried out oxidizing reaction in reactor 6; Reaction mixture oxidizing reaction obtained is sent in the first channel of separator 7, under the effect of pressure difference, at least part of liquid phase in reaction mixture enters in the second passage (shadow region in figure) of separator 7 the liquid phase A obtained containing dimethyl sulfone, the residue B containing HTS in first channel is sent in heat collector 8, heat exchange is carried out with heat transferring medium, obtain the residue that temperature reduces, and the residue that this temperature reduces is cycled to used in preparation slurry.
Below in conjunction with embodiment, the invention will be further described, but therefore do not limit content of the present invention.
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 gauge pressure.
In following examples and comparative example, hollow HTS used is prepared according to method disclosed in Chinese patent CN1132699C, and its titanium oxide content is 2.5 % by weight.
In following examples and comparative example, titanium-silicon molecular sieve TS-1 used is by Journal of Natural Gas Chemistry, 2001, in 10 (4): 295-307 the 296th page of 9-24 capable described by method prepare, its titanium oxide content is 2.5 % by weight.
In following examples and comparative example, static nitrogen adsorption method and solid ultraviolet-visible diffuse reflectance spectroscopy is adopted to characterize the pore volume of the HTS after before modified and ultraviolet absorption peak respectively.Wherein, solid UV-Vis diffuse reflection spectroscopy (UV-Vis) records on SHIMADZU UV-3100 type ultraviolet-visible spectrometer; Pore volume measures on the static n2 absorption apparatus of the ASAP2405 type of Micromeritics company.
In following examples and comparative example, adopt vapor-phase chromatography to analyze the content of each composition in the reaction solution obtained, adopt following formula to calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone on this basis respectively:
Dimethyl thioether transformation efficiency (%)=[molar weight of the dimethyl thioether of (molar weight of the molar weight-unreacted dimethyl thioether of the dimethyl thioether added)/add] × 100%;
Oxygenant effective rate of utilization (%)=[molar weight/(molar weight of the molar weight-unreacted oxygenant of the oxygenant added) of the dimethyl sulfone that 2 × reaction generates] × 100%;
Dimethyl sulfone selectivity (%)=[molar weight/(molar weight of the molar weight-unreacted dimethyl thioether of the dimethyl thioether added) of the dimethyl sulfone that reaction generates] × 100%.
Embodiment 1-12 is for illustration of method of the present invention.
Embodiment 1-12 adopts the method shown in Fig. 3 to carry out, and uses water as heat transferring medium in heat collector.
Embodiment 1
Hollow for 50g HTS is placed in the methanol solution (wherein, the content of hydrogen peroxide is 20 % by weight) containing hydrogen peroxide, stirs in paste-like, then inject reactive system by the catalyst charging hole of reactor.Open liquid phase feed feed valve, when back pressure to pressure is 2.0MPa, open dimethyl thioether feed valve, dimethyl thioether is sent in this reactive system, react continuously.Wherein, in reaction process, with the total amount of material in reactor for benchmark, the content of catalyzer is 15 % by weight; In liquid phase feed in reactor, the mol ratio of methyl alcohol and hydrogen peroxide is 2:1, and the mol ratio of dimethyl thioether and hydrogen peroxide is 2:5, and the feeding rate of dimethyl thioether is 20mL/min, temperature in reactive system is 45 DEG C, carries out the reaction of 100 hours continuously.
The reaction mixture exported from reactor is sent in separator and carries out solid-liquid separation, obtain the liquid phase containing dimethyl sulfone and the residue (solids content is 83 % by weight) containing HTS, the residue containing HTS is cycled to used in preparation liquid phase feed.
Wherein, described separator is formed by ceramic film filtering element and a housing, in each separator, ceramic film filtering element (is purchased the ceramic microfiltration membrane pipe from Jiangsu Jiuwu High-Tech Co., Ltd., membrane pore size is 0.2 μm, the internal diameter of film pipe is 8mm, the external diameter of film pipe is 12mm) quantity be 2, the internal diameter of housing is 40mm.The quantity of separator is 60, separator is divided into 6 groups, and often group is made up of 10 separators, wherein, being in parallel between the separator in same group, is often series connection between group, during flushing, the ceramic film filtering element in 5 separators in every group is rinsed at every turn.Reaction mixture is sent in the passage of ceramic film filtering element, in the passage formed by the outer wall of ceramic film filtering element and the inwall of housing, obtain the liquid phase containing dimethyl sulfone.Pressure in film pipe is 2.0MPa, and the pressure in the space between the outer wall of housing and film pipe is 1.0MPa.
(be the mixing solutions of dimethyl thioether and hydrogen peroxide and methyl alcohol every 2 hours with washing fluid, ratio between three is identical with the ratio in liquid phase material) passage on ceramic film filtering element is carried out to the flushing of 5 seconds, and the mixed solution obtained after rinsing is sent in reactor.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in Table 1.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare dimethyl sulfone, unlike, replace hollow HTS with the titanium-silicon molecular sieve TS-1 of equivalent.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in Table 1.
Embodiment 3
The method identical with embodiment 1 is adopted to prepare dimethyl sulfone, unlike, in reactor, hydrochloric acid (being the aqueous solution of 25 % by weight) is sent into by auxiliary agent opening for feed, the addition of hydrochloric acid makes the pH value of the liquid phase material in reactor be 5.5(when not adding hydrochloric acid, and the pH value of liquid phase material is 6.8).
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in Table 1.
Embodiment 4
The method identical with embodiment 1 is adopted to prepare dimethyl sulfone, unlike, in reactor, send into hydrochloric acid (being the aqueous solution of 25 % by weight) by auxiliary agent opening for feed, the addition of hydrochloric acid makes the pH value of the liquid phase material in reactor be 4.5.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in Table 1.
Embodiment 5
The method identical with embodiment 2 is adopted to prepare dimethyl sulfone, unlike, titanium-silicon molecular sieve TS-1 before use, first processes with acid.Concrete operations are: mixed with hydrochloric acid (mass concentration is the aqueous solution of 36 % by weight) by titanium-silicon molecular sieve TS-1, by the mixture that obtains 90 DEG C of stirring reactions 5 hours, filter after the temperature of the reaction mixture obtained is down to room temperature, the solid matter obtained is dried to constant weight at 120 DEG C, obtains the HTS of modification.Wherein, titanium-silicon molecular sieve TS-1 is with SiO
2meter, the mol ratio of HTS and HCl is 1:0.2.Through characterizing, compared with raw material HTS, the peak height of the absorption peak in the UV-Vis spectrum of the HTS of the modification obtained between 240-300nm reduces 3.1%, reduces 1.6% by the pore volume of static determination of nitrogen adsorption.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in Table 1.
Comparative example 1
Adopt the method production dimethyl sulfone identical with embodiment 1, unlike, do not use HTS, but directly hydrogen peroxide, methyl alcohol and dimethyl thioether are reacted according in the ratio feeding reactor of embodiment 1, the mixture be obtained by reacting is separated without separator.Calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in Table 1.
Table 1
Embodiment 1 and comparative example 1 are compared and can find out, adopts method of the present invention to carry out production dimethyl sulfone, the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone can be significantly improved.
Embodiment 1 and embodiment 2 are compared and can find out, adopts hollow HTS can obtain better catalytic effect as catalyzer.
Embodiment 1 and embodiment 3 and 4 are compared and can find out, is less than 5.5 with acid by the pH value of the liquid phase in reaction paste, higher dimethyl sulfone selectivity can be obtained.
Embodiment 4 and embodiment 5 are compared and can find out, with acid, modification is carried out to HTS, and modified HTS can be improved the selectivity of dimethyl sulfone and the work-ing life of catalyzer as catalyzer.
Embodiment 6-12 adopts following methods to measure the activity of HTS.
By HTS, 36 % by weight ammoniacal liquor (with NH
3meter), the hydrogen peroxide of 30 % by weight is (with H
2o
2meter), the trimethyl carbinol and pimelinketone in mass ratio=1:7.5:10:7.5:10 mixing after at atmosheric pressure after 80 DEG C of stirring reaction 2h, reactant is filtered, analyze with the composition of vapor-phase chromatography to liquid phase, adopt the transformation efficiency of following formulae discovery pimelinketone and it can be used as the activity of HTS
The transformation efficiency of pimelinketone=[molar weight of the pimelinketone of (molar weight of the molar weight-unreacted pimelinketone of the pimelinketone added)/add] × 100%.
Embodiment 6
(1) HTS of modification is prepared
The raw molecule sieve used obtains for being carried out regenerating by the titanium-silicon molecular sieve TS-1 drawn off from cyclohexanone oxamidinating reaction process, and its activity is 50%, and the activity when fresh is 95%, and regeneration condition is: at 550 DEG C in air atmosphere roasting 4h.
Raw molecule sieve is mixed with hydrochloric acid (mass concentration is the aqueous solution of 12 % by weight), by the mixture that obtains 80 DEG C of stirring reactions 6 hours, filter after the temperature of the reaction mixture obtained is down to room temperature, the solid matter obtained is dried to constant weight at 120 DEG C, obtains the HTS of modification.Wherein, titanium-silicon molecular sieve TS-1 is with SiO
2meter, the mol ratio of HTS and HCl is 1:1.Through characterizing, compared with raw material HTS, the absorption peak peak height in the UV-Vis spectrum of the HTS of the modification obtained between 240-300nm reduces 4.8%, reduces 2.1% by the pore volume of static determination of nitrogen adsorption.
(2) dimethyl sulfone is prepared
Hollow for 50g HTS is placed in the methanol solution (wherein, the content of hydrogen peroxide is 30 % by weight) containing hydrogen peroxide, is stirred in paste-like, then inject reactive system by the catalyst charging hole of reactor.Open liquid phase feed feed valve, when back pressure to pressure is 2.0MPa, open dimethyl thioether feed valve, dimethyl thioether is sent in this reactive system, open auxiliary agent feed valve simultaneously, in reactive system, send into sulfuric acid (being the aqueous solution of 25 % by weight) react continuously.Wherein, in reaction process, with the total amount of material in reactor for benchmark, the content of catalyzer is 5 % by weight; In liquid phase feed in reactor, the mol ratio of methyl alcohol and hydrogen peroxide is 1:1, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:5, the consumption of sulfuric acid makes the pH value of the liquid phase material in reactive system be 3.5, the feeding rate of dimethyl thioether is 50mL/min, temperature in reactive system is 55 DEG C, carries out the reaction of 100 hours continuously.
The reaction mixture exported from reactor is sent in separator and carries out solid-liquid separation, obtain the liquid phase containing dimethyl sulfone and the residue (solids content is 85 % by weight) containing HTS, the residue containing HTS is cycled to used in preparation liquid phase feed.
Wherein, described separator is formed by ceramic film filtering element and a housing, in each separator, ceramic film filtering element (is purchased the ceramic microfiltration membrane pipe from Jiangsu Jiuwu High-Tech Co., Ltd., membrane pore size is 0.2 μm, the internal diameter of film pipe is 8mm, the external diameter of film pipe is 12mm) quantity be 5, the internal diameter of housing is 100mm.The quantity of separator is 12, separator is divided into 2 groups, and often group is made up of 6 separators, wherein, being in parallel between the separator in same group, is often series connection between group, during flushing, the ceramic film filtering element in 3 separators in every group is rinsed at every turn.Reaction mixture is sent in the passage on ceramic film filtering element, in the passage formed by the outer wall of ceramic film filtering element and the inwall of housing, obtain the liquid phase containing dimethyl sulfone.Pressure in film pipe is 0.3MP
a, be normal pressure (that is, 1 standard atmospheric pressure) in the space between the outer wall of housing and film pipe.
(be the mixing solutions of dimethyl thioether and hydrogen peroxide and methyl alcohol every 1 hour with washing fluid, ratio between three is identical with the ratio in liquid phase material) passage on ceramic film filtering element is carried out to the flushing of 2 seconds, and the mixed solution obtained after rinsing is sent in reactor.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in table 2.
Embodiment 7
The method identical with embodiment 6 is adopted to prepare dimethyl sulfone, unlike, in step (2), the consumption of sulfuric acid makes the pH value of the liquid phase mixture formed by dimethyl thioether, oxygenant and solvent be 1.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in table 2.
Embodiment 8
The method identical with embodiment 6 is adopted to prepare dimethyl sulfone, unlike, step does not use sulfuric acid in (2), and the pH value of liquid phase material is 6.7.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in table 2.
Embodiment 9
The method identical with embodiment 6 is adopted to prepare dimethyl sulfone, unlike, do not carry out step (1), but directly the raw molecule sieve in embodiment 6 step (1) is prepared dimethyl sulfone as catalyzer.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in table 2.
Embodiment 10
(1) HTS of modification is prepared
The raw molecule sieve used obtains for the hollow HTS drawn off from phenol hydroxylation reaction unit being carried out regenerating, and its activity is 30%, and the activity when fresh is 96%, and regeneration condition is: at 570 DEG C in air atmosphere roasting 4h.
Raw molecule sieve is mixed with acetic acid (mass concentration is the aqueous solution of 32 % by weight), by the mixture that obtains 60 DEG C of stirring reactions 24 hours, filter after the temperature of the reaction mixture obtained is down to room temperature, the solid matter obtained is dried to constant weight at 120 DEG C, obtains the HTS of modification.Wherein, HTS is with SiO
2meter, HTS and CH
3the mol ratio of COOH is 1:5.Through characterizing, compared with sieving with raw molecule, the absorption peak peak height in the UV-Vis spectrum of the HTS of the modification obtained between 240-300nm reduces 5.5%, reduces 2.2% by the pore volume of static determination of nitrogen adsorption.
(2) dimethyl sulfone is prepared
Hollow for 50g HTS is placed in the methanol solution (wherein, the content of hydrogen peroxide is 50 % by weight) containing hydrogen peroxide, stirs in paste-like, then inject reactive system by the catalyst charging hole of reactor.Open liquid phase feed feed valve, when back pressure to pressure is 2.0MPa, open dimethyl thioether feed valve, dimethyl thioether is sent in this reactive system, open auxiliary agent feed valve simultaneously, in reactive system, send into hydrochloric acid (being the aqueous solution of 25 % by weight) react continuously.Wherein, in reaction process, with the total amount of material in reactor for benchmark, the content of catalyzer is 10 % by weight; In liquid phase feed in reactor, the mol ratio of methyl alcohol and hydrogen peroxide is 5:1, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:4, the consumption of sulfuric acid makes the pH value of the liquid phase material in reactive system be 3.5, the feeding rate of dimethyl thioether is 30mL/min, temperature in reactive system is 80 DEG C, carries out the reaction of 100 hours continuously.
The reaction mixture exported from reactor is sent in separator and carries out solid-liquid separation, obtain the liquid phase containing dimethyl sulfone and the residue (solids content is 88 % by weight) containing HTS, the residue containing HTS is cycled to used in preparation liquid phase feed.
Wherein, described separator is formed by ceramic film filtering element and a housing, in each separator, ceramic film filtering element (is purchased the ceramic microfiltration membrane pipe from Jiangsu Jiuwu High-Tech Co., Ltd., membrane pore size is 0.2 μm, the internal diameter of film pipe is 8mm, the external diameter of film pipe is 12mm) quantity be 5, the internal diameter of housing is 100mm.The quantity of separator is 12, separator is divided into 2 groups, and often group is made up of 6 separators, wherein, being in parallel between the separator in same group, is often series connection between group, during flushing, the ceramic film filtering element in 3 separators in every group is rinsed at every turn.Reaction mixture is sent in the passage on ceramic film filtering element, in the passage formed by the outer wall of ceramic film filtering element and the inwall of housing, obtain the liquid phase containing dimethyl sulfone.Pressure in film pipe is 0.3MPa, is normal pressure (that is, 1 standard atmospheric pressure) in the space between the outer wall of housing and film pipe.
(be the mixing solutions of dimethyl thioether and hydrogen peroxide and methyl alcohol every 1 hour with washing fluid, ratio between three is identical with the ratio in liquid phase material) passage on ceramic film filtering element is carried out to the flushing of 2 seconds, and the mixed solution obtained after rinsing is sent in reactor.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in table 2.
Embodiment 11
The HTS used in the present embodiment is for being undertaken regenerating by the titanium-silicon molecular sieve TS-1 drawn off from propylene oxidation reaction process and obtaining, its activity is 50%, activity when fresh is 95%, and median size 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 (wherein, the content of hydrogen peroxide is 50 % by weight) containing hydrogen peroxide, is stirred in paste-like, then inject reactive system by the catalyst charging hole of reactor.Open liquid phase feed feed valve, when back pressure to pressure is 2.0MPa, open dimethyl thioether feed valve, dimethyl thioether is sent in this reactive system, open auxiliary agent feed valve simultaneously, in reactive system, send into sulfuric acid (being the aqueous solution of 25 % by weight) react continuously.Wherein, in reaction process, with the total amount of material in reactor for benchmark, the content of catalyzer is 2 % by weight; In liquid phase feed in reactor, the mol ratio of methyl alcohol and hydrogen peroxide is 10:1, the mol ratio of dimethyl thioether and hydrogen peroxide is 1:10, the consumption of sulfuric acid makes the pH value of the liquid phase material in reactive system be 3.5, the feeding rate of dimethyl thioether is 20mL/min, temperature in reactive system is 100 DEG C, carries out the reaction of 100 hours continuously.
The reaction mixture exported from reactor is sent in separator and carries out solid-liquid separation, obtain the liquid phase containing dimethyl sulfone and the residue (solids content is 65 % by weight) containing HTS, the residue containing HTS is cycled to used in preparation liquid phase feed.
Wherein, described separator is formed by ceramic film filtering element and a housing, in each separator, ceramic film filtering element (is purchased the ceramic microfiltration membrane pipe from Jiangsu Jiuwu High-Tech Co., Ltd., membrane pore size is 0.2 μm, the internal diameter of film pipe is 8mm, the external diameter of film pipe is 12mm) quantity be 5, the internal diameter of housing is 100mm.The quantity of separator is 12, separator is divided into 2 groups, and often group is made up of 6 separators, wherein, being in parallel between the separator in same group, is often series connection between group, during flushing, the ceramic film filtering element in 3 separators in every group is rinsed at every turn.Reaction mixture is sent in the passage on ceramic film filtering element, in the passage formed by the outer wall of ceramic film filtering element and the inwall of housing, obtain the liquid phase containing dimethyl sulfone.Pressure in film pipe is 0.3MPa, is normal pressure (that is, 1 standard atmospheric pressure) in the space between the outer wall of housing and film pipe.
(be the mixing solutions of dimethyl thioether and hydrogen peroxide and methyl alcohol every 1 hour with washing fluid, ratio between three is identical with the ratio in liquid phase material) passage on ceramic film filtering element is carried out to the flushing of 2 seconds, and the mixed solution obtained after rinsing is sent in reactor.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in table 2.
Embodiment 12
The method identical with embodiment 11 is adopted to prepare dimethyl sulfone, unlike, the regenerator that the titanium-silicon molecular sieve TS-1 drawn off from propylene oxidation reaction process is undertaken regenerating by (1) and obtains by catalyzer; And (2) fresh titanium silicalite TS-1 composition, wherein, the mass ratio of regenerator and fresh titanium silicalite TS-1 is 2:1.
Analyzed the liquid phase containing dimethyl sulfone exported from separator every 2 hours, calculate the selectivity of the transformation efficiency of dimethyl thioether, the effective rate of utilization of oxygenant and dimethyl sulfone, the result of reacting when proceeding to 2 hours and 100 is listed in table 2.
Table 2
The result of embodiment 6-12 confirms, even if at least part of catalyzer comes from draw off agent through what regenerate, also can obtain high dimethyl thioether transformation efficiency, oxygenant effective rate of utilization and dimethyl sulfone selectivity.
Claims (14)
1. produce the method for dimethyl sulfone for one kind, the method comprises: reacted under oxidation reaction condition by the slurry containing dimethyl thioether, HTS and at least one superoxide, and the reaction mixture obtained is carried out solid-liquid separation, obtain the liquid phase containing dimethyl sulfone and the residue containing HTS, the mol ratio of described superoxide and described dimethyl thioether is for being greater than 2:1;
Described solid-liquid separation is carried out in a kind of separator, described separator has first channel and second passage, described first channel has inlet end and exit end, described first channel and second passage are adjoined by the component with through hole, the mean pore size of described through hole is less than the median size of described HTS, described reaction mixture is sent in described first channel by described inlet end, at least part of liquid phase in described reaction mixture enters in described second passage by described through hole, the described liquid phase containing dimethyl sulfone is discharged from described second passage, the described residue containing HTS is obtained by the exit end of described first channel.
2. method according to claim 1, described component is the pipeline that tube wall has described through hole.
3. method according to claim 2, wherein, the space of the inwall formation of described pipeline is as described first channel, and the space that the outer wall of described pipeline and a housing are formed is as second passage.
4. method according to claim 1, wherein, at least part of described HTS be through regeneration the reaction unit using HTS as catalyzer draw off agent.
5. method according to claim 4, wherein, described in draw off agent be Ammoximation reaction device draw off agent, hydroxylating device draw off agent and epoxidation reaction device draw off in agent one or more.
6. method according to claim 1, wherein, described slurry is also containing at least one solvent, and the mass ratio of described solvent and HTS is 1-100:1.
7. method according to claim 1, wherein, the method also comprises the described residue containing HTS is cycled to used in the described slurry of preparation.
8. method according to claim 1, wherein, the mol ratio of described superoxide and described dimethyl thioether is 2.5-10:1, the mass ratio of dimethyl thioether and HTS is 0.1-50:1, described oxidation reaction condition comprises: temperature is 0-200 DEG C, in gauge pressure, pressure is 0-3MPa.
9. at least part of HTS according to the method in claim 1 and 4-8 described in any one, wherein, in described slurry lives through following process: at the temperature of 0-200 DEG C, contact 0.1-72 hour with at least one acid.
10. method according to claim 9, wherein, described acid is selected from hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, perchloric acid and Hydrogen bromide.
11. methods according to claim 9, wherein, HTS is in silicon-dioxide, and the mol ratio of described HTS and described acid can be 1:0.01-10.
12. according to the method in claim 1 and 4-8 described in any one, and wherein, described HTS is the HTS with MFI structure.
13. according to the method in claim 1 and 6-8 described in any one, and wherein, the method also comprises adds at least one acid in described slurry, and the addition of described acid makes the pH value of the liquid phase in this slurry be 0.5-5.5.
14. methods according to claim 1 or 8, wherein, described superoxide is selected from hydrogen peroxide, hydroperoxide and peracid.
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