CN106631929B - A method of producing dimethyl sulfone - Google Patents
A method of producing dimethyl sulfone Download PDFInfo
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- CN106631929B CN106631929B CN201510725257.8A CN201510725257A CN106631929B CN 106631929 B CN106631929 B CN 106631929B CN 201510725257 A CN201510725257 A CN 201510725257A CN 106631929 B CN106631929 B CN 106631929B
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Abstract
The present invention provides a kind of methods for producing dimethyl sulfone, including the slurry containing dimethyl sulfoxide, Titanium Sieve Molecular Sieve and peroxide is reacted under oxidation reaction condition, obtained reaction mixture is sent into separator and is separated by solid-liquid separation, the separator has first passage and second channel, first passage and second channel are adjacent by the component with through-hole, reaction mixture is sent into first passage, the liquid phase containing dimethyl sulfone is obtained from second channel, the residue containing Titanium Sieve Molecular Sieve is obtained by the outlet end of first passage.Method of the invention can effectively improve the conversion ratio of the effective rate of utilization of oxidant, the selectivity of dimethyl sulfone and dimethyl sulfoxide, while efficiently can isolate the liquid phase containing dimethyl sulfone from the liquid-solid mixture that reaction obtains.In addition, even if method long-play of the invention, still is able to obtain higher dimethyl sulfoxide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity.
Description
Technical field
The present invention relates to a kind of methods for producing dimethyl sulfone, and in particular, to prepared by a kind of aoxidize dimethyl sulfoxide
The method of dimethyl sulfone.
Background technique
Dimethyl sulfone is white crystalline powder, and soluble easily in water, ethyl alcohol, benzene, methanol and acetone are slightly soluble in ether.Under room temperature not
Potassium permanganate can be made to change colour, dimethyl sulfone can be oxidized to methanesulfonic acid by strong oxidizer.Dimethyl sulfone aqueous solution is in neutrality.At 25 DEG C
Microsublimation is accelerated to 60 DEG C of rate of sublimation, thus dimethyl sulfone product drying preferably carries out under cryogenic vacuum.
Dimethyl sulfone is used as organic synthesis high-temperature solvent and raw material, GC stationary liquid, analytical reagent, food in the industry
Product additive and drug.Dimethyl sulfone is as a kind of organic sulfur compound, the ability that there is enhancing human body to generate insulin, simultaneously
Also there is facilitation to the metabolism of carbohydrate, be the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound to be cured
It closes, can also work to vitamin B, vitamin C, the synthesis of biotin and activation needed for metabolism and neurological health, quilt
Referred to as " beautify carbonizable substance naturally ".All contain dimethyl sulfone in the skin of human body, hair, nail, bone, muscle and each organ,
Dimethyl sulfone is primarily present in Yu Haiyang and soil in nature, is absorbed in plant growth as nutriment, the mankind
It can be absorbed from the foods such as veterinary antibiotics, fish, meat, egg, milk, once health disorders will be caused or disease occurs by lacking, be
Human body maintains the main matter of biological element sulphur balance, has therapeutic value and healthcare function to human body diseases, is human survival
With the indispensable drug of health care.Foreign countries widely apply using dimethyl sulfone as with vitamin nutriment of equal importance, China
The application study of dimethyl sulfone is not yet carried out very well.Therefore, dimethyl sulfone is not only a kind of new high-tech product, and a kind of
The fine chemical product of high added value.Product is new, great market potential, and benefit is prominent, before having wide production and application and development
Scape.
Currently, the product that dimethyl sulfone is further aoxidized as dimethyl sulfoxide, for the main pair of dimethyl sulfoxide production
Product.In addition, dimethyl sulfone can also be obtained directly by dimethyl sulfoxide through nitric acid oxidation.It specifically, can be by dimethyl Asia
Sulfone with nitric acid oxidation, is cooled to after reaction at 140-145 DEG C, is filtered, is obtained the crude product of white, needle-shaped crystals.Again through depressurizing
Distillation, collecting 138-145 DEG C of (98.42kPa) fraction is finished product.But the dimethyl sulfone yield of this method need into
One step improves.
Summary of the invention
The present inventor has found in the course of the research, using dimethyl sulfoxide as raw material, passes through peroxide oxidation method
When preparing dimethyl sulfone, dimethyl sulfoxide conversion ratio can be significantly improved as catalyst using Titanium Sieve Molecular Sieve, oxidant has
Imitate utilization rate and dimethyl sulfone selectivity.Titanium Sieve Molecular Sieve is being used as catalyst, by peroxide oxidation method by two
When methyl sulfoxide prepares dimethyl sulfone, the liquid mixture containing dimethyl sulfoxide and peroxide can be made by being filled with into
The bed of the Titanium Sieve Molecular Sieve of type, can also be directly by Titanium Sieve Molecular Sieve and dimethyl sulfoxide and peroxide hybrid reaction.Directly
It connects Titanium Sieve Molecular Sieve and dimethyl sulfoxide and peroxide hybrid reaction, on the one hand without using molding Titanium Sieve Molecular Sieve,
On the other hand easily controllable reaction temperature.
But directly Titanium Sieve Molecular Sieve and dimethyl sulfoxide and peroxide hybrid reaction are needed to obtaining after reacting
Mixture is separated, and could separate Titanium Sieve Molecular Sieve and the liquid phase containing dimethyl sulfone.Therefore, liquid-solid separation efficiency is shadow
One of an important factor for ringing dimethyl sulfone production efficiency.
The purpose of the present invention is to provide a kind of with the slurry containing Titanium Sieve Molecular Sieve Yu peroxide and dimethyl sulfoxide
Method to produce dimethyl sulfone, on the one hand this method can effectively improve dimethyl sulfoxide conversion ratio, oxidant effectively sharp
With rate and dimethyl sulfone selectivity, on the other hand can efficiently isolate from the mixture that reaction obtains containing dimethyl sulfone
Liquid phase.
The present invention provides a kind of methods for producing dimethyl sulfone, this method comprises: will contain dimethyl sulfoxide, titanium silicon point
Son sieve, at least one peroxide and at least one solvent slurry reacted under oxidation reaction condition, and will obtain
Reaction mixture is separated by solid-liquid separation, and the liquid phase containing dimethyl sulfone and the residue containing Titanium Sieve Molecular Sieve are obtained；
The separation of solid and liquid carries out in a kind of separator, and the separator has first passage and second channel, described
First passage has arrival end and outlet end, and the first passage and second channel are adjacent by the component with through-hole, described
The average pore size of through-hole is less than the average grain diameter of the Titanium Sieve Molecular Sieve, and the reaction mixture is sent into institute by the arrival end
It states in first passage, at least partly liquid phase in the reaction mixture is entered in the second channel by the through-hole, from
The liquid phase containing dimethyl sulfone is discharged in the second channel, is obtained described containing titanium silicon by the outlet end of the first passage
The residue of molecular sieve.
Method of the invention can effectively improve oxidant effective rate of utilization and dimethyl sulfone selectivity, while can also obtain
Obtain higher dimethyl sulfoxide conversion ratio.Also, it can efficiently be mixed admittedly from the liquid that reaction obtains according to the method for the present invention
The liquid phase containing dimethyl sulfone is isolated in object.In addition, stability is good according to the method for the present invention, even if long-play, still
Higher dimethyl sulfoxide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity can so be obtained.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 show according to the method for the present invention used in separator a kind of structural schematic diagram.
Fig. 2 shows a kind of embodiments of separator used according to the method for the present invention.
Fig. 3 shows a kind of preferred embodiment according to the method for the present invention.
Specific embodiment
The present invention provides a kind of methods for producing dimethyl sulfone, this method comprises: will contain dimethyl sulfoxide, titanium silicon point
The slurry of son sieve and at least one peroxide is reacted under oxidation reaction condition, and obtained reaction mixture is carried out
It is separated by solid-liquid separation, obtains the liquid phase containing dimethyl sulfone and the residue containing Titanium Sieve Molecular Sieve.
The peroxide refers to the compound for containing-O-O- key in molecular structure, can be selected from hydrogen peroxide, hydrogen peroxide
Compound and peracid.Obtained from the hydroperoxides refer to that a hydrogen atom in hydrogen peroxide molecule is replaced by organic group
Substance.The peracid refers to the organic oxacid for containing-O-O- key in molecular structure.The specific example of the peroxide can be with
Including but not limited to: hydrogen peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide, cumyl hydroperoxide, cyclohexyl peroxidating
Hydrogen, Peracetic acid and Perpropionic Acid.
Preferably, the oxidant is hydrogen peroxide.The hydrogen peroxide can for it is commonly used in the art in a variety of manners
Existing hydrogen peroxide.From the angle for further increasing safety according to the method for the present invention, side according to the present invention
It is preferable to use existing hydrogen peroxide as an aqueous solution for method.According to the method for the present invention, in the hydrogen peroxide with aqueous solution
When form provides, the concentration of the aqueous hydrogen peroxide solution can be the normal concentration of this field, such as: 20-80 weight %.It is dense
The aqueous solution that degree meets the hydrogen peroxide of above-mentioned requirements can be prepared using conventional method, be also commercially available, such as: it can be with
For the hydrogen peroxide of the hydrogen peroxide for the 30 weight % that can be commercially available, the hydrogen peroxide of 50 weight % or 70 weight %.
For the peroxide as oxidant, dosage, which is subject to, to be oxidized into dimethyl sulfone for dimethyl sulfide.
The molar ratio of the peroxide and the dimethyl sulfoxide can be 0.1-10:1.Higher dimethyl sulfone selection can obtained
Under conditions of property, from the angle for taking into account operating cost, the molar ratio of the peroxide and the dimethyl sulfoxide is preferred
It is still more preferably 1-1.5:1 for 0.2-5:1, further preferably 0.5-2:1.
The Titanium Sieve Molecular Sieve can be the common Titanium Sieve Molecular Sieve with various topological structures, such as: the titanium silicon
Molecular sieve can be selected from Titanium Sieve Molecular Sieve (such as TS-1), Titanium Sieve Molecular Sieve (such as TS-2), the BEA structure of MEL structure of MFI structure
Titanium Sieve Molecular Sieve (such as Ti-Beta), the Titanium Sieve Molecular Sieve (such as Ti-MCM-22) of MWW structure, the Titanium Sieve Molecular Sieve of hexagonal structure
The Titanium Sieve Molecular Sieve (such as Ti-MOR) of (such as Ti-MCM-41, Ti-SBA-15), MOR structure, the Titanium Sieve Molecular Sieve of TUN structure are (such as
) and the Titanium Sieve Molecular Sieve of other structures (such as Ti-ZSM-48) Ti-TUN.
Preferably, the Titanium Sieve Molecular Sieve is selected from Titanium Sieve Molecular Sieve, the Titanium Sieve Molecular Sieve and BEA of MEL structure of MFI structure
The Titanium Sieve Molecular Sieve of structure.It is highly preferred that the Titanium Sieve Molecular Sieve is the Titanium Sieve Molecular Sieve of MFI structure, such as Titanium Sieve Molecular Sieve TS-
1 and/or hollow Titanium Sieve Molecular Sieve.The hollow Titanium Sieve Molecular Sieve is the Titanium Sieve Molecular Sieve of MFI structure, the crystalline substance of the Titanium Sieve Molecular Sieve
Grain is hollow structure, and the radical length of the chamber portion of the hollow structure is 5-300 nanometers, and the Titanium Sieve Molecular Sieve 25 DEG C,
P/P0=0.10, the benzene adsorbance that adsorption time measures under conditions of being 1 hour is at least 70 milligrams per grams, the Titanium Sieve Molecular Sieve
Nitrogen absorption under low temperature adsorption isotherm and desorption isotherm between there are hysteresis loops.The hollow Titanium Sieve Molecular Sieve can be commercially available
(such as being commercially available from the trade mark of Hunan Jianchang Petrochemical Co., Ltd is the molecular sieve of HTS) is obtained, it can also basis
Method disclosed in CN1132699C is prepared.
According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the Titanium Sieve Molecular Sieve TS-
1 urface silicon titanium is not less than body phase silicon titanium ratio, can be further improved oxidant effective rate of utilization in this way, and can further prolong
The single trip use service life of long Titanium Sieve Molecular Sieve.Preferably, the ratio of the urface silicon titanium and the body phase silicon titanium ratio be 1.2 with
On.It is highly preferred that the ratio of the urface silicon titanium and the body phase silicon titanium ratio is 1.2-5.It is further preferred that the surface
Silicon titanium is than being 1.5-4.5 (such as 2.5-4.5) with the ratio of the body phase silicon titanium ratio.It is further preferred that the surface silicon titanium
Than being 2-3 with the ratio of the body phase silicon titanium ratio.Molar ratio of the silicon titanium than referring to silica and titanium oxide, the surface silicon
Titanium ratio is measured using X-ray photoelectron spectroscopy, and the body phase silicon titanium ratio uses x-ray fluorescence spectrometry.
According to the method for the present invention, at least partly Titanium Sieve Molecular Sieve is titanium-silicon molecular sieve TS-1, the Titanium Sieve Molecular Sieve TS-
1 is prepared using method comprising the following steps:
(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and optionally supplements water, obtained
Dispersion liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:(0.5-8): (5-30): (100-
2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N meter is (in the alkali
When source template contains nitrogen, in terms of N；In the alkali source template not Nitrogen element, with OH-Meter)；
(II) optionally, by the dispersion liquid 15-60 DEG C standing 6-24 hours；
(III) by the dispersion liquid that step (I) obtains or the dispersion liquid that step (II) obtains in sealing reaction kettle sequence
Experience stage (1), stage (2) and stage (3) carry out crystallization, the stage (1) 80-150 DEG C crystallization 6-72 hour, the stage (2) drops
For temperature to not higher than 70 DEG C and after at least 0.5 hour residence time, the stage (3) is warming up to 120-200 DEG C crystallization 6-96 hours again.
The alkali source template can be usually used various templates during synthesis of titanium silicon molecular sieve, such as:
The alkali source template can be one or more of quaternary ammonium base, aliphatic amine and aliphatic hydramine.The quaternary ammonium base
It can be various organic level Four ammonium alkali, the aliphatic amine can be various NH3In at least one hydrogen by aliphatic alkyl (such as
Alkyl) replace after the compound that is formed, the aliphatic hydramine can be various NH3In at least one hydrogen by the rouge of hydroxyl
The compound that fat race group (such as alkyl) is formed after replacing.
Specifically, the alkali source template can be the aliphatic amine and formula of the quaternary ammonium base, Formula II expression that indicate selected from Formulas I
One or more of the aliphatic hydramine that III is indicated.
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, R1、R2、R3And R4Specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding
Base, isobutyl group or tert-butyl.
R5(NH2)n(Formula II)
In Formula II, n is an integer of 1 or 2.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, specific example can include but is not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different
Butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For C1-C6Alkylidene, including
C1-C6Straight-chain alkyl-sub and C3-C6Branched alkylidene, specific example can include but is not limited to methylene, ethylidene,
Sub- n-propyl, sub- normal-butyl, sub- n-pentyl or sub- n-hexyl.
(HOR6)mNH(3-m)(formula III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-
C4Branched alkylidene, specific example can include but is not limited to methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is
1,2 or 3.
The specific example of the alkali source template can include but is not limited to: tetramethylammonium hydroxide, tetraethyl hydroxide
Ammonium, tetrapropylammonium hydroxide (the various isomers including tetrapropylammonium hydroxide, such as four n-propyl ammonium hydroxide and tetra isopropyl
Ammonium hydroxide), tetrabutylammonium hydroxide (the various isomers including tetrabutylammonium hydroxide, such as 4-n-butyl ammonium hydroxide and
Four isobutyl group ammonium hydroxide), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, monoethanolamine, diethanol amine
One or more of with triethanolamine.Preferably, the alkali source template is tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen
Change one or more of ammonium and tetrabutylammonium hydroxide.It is highly preferred that the alkali source template is tetrapropyl hydroxide
Ammonium.
The titanium source can be inorganic titanium salt and/or organic titanate, preferably organic titanate.The inorganic titanium salt can
Think TiCl4、Ti(SO4)2And TiOCl2One or more of；The organic titanate can be selected from general formula R7 4TiO4
The compound of expression, wherein R7For the alkyl with 1-6 carbon atom, it is however preferred to have the alkyl of 2-4 carbon atom.
The inorganic silicon source can be silica gel and/or silica solution, preferably silica gel.SiO in the silica solution2Quality hundred
Dividing content can be 10% or more, preferably 15% or more, more preferably 20% or more.In preparation according to the preferred embodiment
Titanium Sieve Molecular Sieve when, do not use organic silicon source, such as organosilan and organosiloxane.
In the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is preferably 100:(1-6): (8-25):
(200-1500), more preferably 100:(2-5): (10-20): (400-1000).
The dispersion liquid that step (I) obtains, which can be sent directly into step (III), carries out crystallization.Preferably, step (I) is obtained
The dispersion liquid that arrives be sent into step (II) 15-60 DEG C at a temperature of stand 6-24 hours.Step (I) and step (III) it
Between carry out step (II) urface silicon titanium of the titanium-silicon molecular sieve TS-1 finally prepared can be significantly improved so that the titanium finally prepared
The urface silicon titanium of si molecular sieves is not less than body phase silicon titanium ratio, can significantly improve the catalysis of the Titanium Sieve Molecular Sieve finally prepared in this way
Performance extends its single trip use service life, and improves oxidant effective rate of utilization.Generally, by step (I) and step
(III) ratio of setting steps (II) between, the urface silicon titanium of the Titanium Sieve Molecular Sieve finally prepared and body phase silicon titanium ratio can be with
In the range of 1.2-5, preferably in the range of 1.5-4.5 (such as in the range of 2.5-4.5), more preferably in the range of 2-3
It is interior.It is described standing more preferably 20-50 DEG C at a temperature of carry out, as carried out at a temperature of 25-45 DEG C.
In step (II), when being stood, dispersion liquid can be placed in sealing container, open container can also be placed in
In stood.Preferably, step (II) carries out in a sealed container, in this way can to avoid during standing into dispersion liquid
It is introduced into foreign matter or moieties volatilization in dispersion liquid is caused to be lost.
After the completion of step (II) described standing, directly the dispersion liquid through standing can be sent into reaction kettle and carry out crystallization,
It is sent into reaction kettle after dispersion liquid through standing can also being carried out redisperse and carries out crystallization, be preferably sent into after progress redisperse anti-
It answers in kettle, can be further improved the dispersing uniformity for carrying out the dispersion liquid of crystallization in this way.The method of the redisperse can be normal
The combination of one or more of rule method, such as stirring, ultrasonic treatment and oscillation.The duration of the redisperse with
The dispersion liquid through standing can be made to be formed subject to uniform dispersion liquid, generally can be 0.1-12 hours, such as 0.5-2 hours.It is described
Redisperse can carry out at ambient temperature, as carried out at a temperature of 15-40 DEG C.
In step (III), temperature is adjusted can be according to specifically adopting to the heating rate of each phase temperature and rate of temperature fall
The type of crystallization device is selected, and is not particularly limited.In general, raising the temperature to stage (1) crystallization temperature
The heating rate of degree can be 0.1-20 DEG C/min, preferably 0.1-10 DEG C/min, more preferably 1-5 DEG C/min.By the stage
(1) rate of temperature fall of temperature to stage (2) temperature can be 1-50 DEG C/min, preferably 2-20 DEG C/min, more preferably 5-
10 DEG C/min.By stage (2) temperature to stage (3) temperature heating rate can be 1-50 DEG C/min, preferably 2-40 DEG C/
Minute, more preferably 5-20 DEG C/min.
In step (III), the crystallization temperature in stage (1) is preferably 110-140 DEG C, and more preferably 120-140 DEG C, further
Preferably 130-140 DEG C.The crystallization time in stage (1) is preferably 6-24 hours, more preferably 6-8 hours.The temperature in stage (2)
Preferably not higher than 50 DEG C.The residence time in stage (2) is preferably at least 1 hour, more preferably 1-5 hours.The crystalline substance in stage (3)
Changing temperature is preferably 140-180 DEG C, and more preferably 160-170 DEG C.The crystallization time in stage (3) is preferably 12-20 hours.
In step (III), in a preferred embodiment, the crystallization temperature in stage (1) is lower than the crystallization of stage (3)
Temperature can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve of preparation in this way.Preferably, the crystallization temperature in stage (1) compares rank
The crystallization temperature of section (3) is 10-50 DEG C low.It is highly preferred that the crystallization temperature in stage (1) is 20-40 lower than the crystallization temperature in stage (3)
℃.In step (III), in another preferred embodiment, when the crystallization time in stage (1) is less than the crystallization of stage (3)
Between, it can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.Preferably, the crystallization time ratio in stage (1)
The crystallization time in stage (3) is 5-24 hours short.It is highly preferred that the crystallization time in stage (1) is 6- shorter than the crystallization time in stage (3)
It is 12 hours, such as 6-8 hours short.In step (III), both preferred embodiments be can be used alone, and can also combine makes
With being preferably applied in combination, i.e., the crystallization temperature and crystallization time in stage (1) and stage (3) meet both preferred implementations simultaneously
The requirement of mode.
In step (III), in another preferred embodiment, the temperature in stage (2) is and to stop not higher than 50 DEG C
Time is at least 0.5 hour, such as 0.5-6 hours, can be further improved the catalytic performance of the Titanium Sieve Molecular Sieve finally prepared in this way.
Preferably, the residence time in stage (2) is at least 1 hour, such as 1-5 hours.The preferred embodiment can be with aforementioned two kinds
Preferred embodiment is used separately, and can also be applied in combination, is preferably applied in combination, i.e. the crystallization temperature in stage (1) and stage (3)
Degree and crystallization time and the temperature in stage (2) and residence time meet the requirement of above-mentioned three kinds of preferred embodiments simultaneously.
Titanium Sieve Molecular Sieve can be recycled from the mixture that step (III) crystallization obtains using conventional method.Specifically, may be used
After being optionally filtered and washed with the mixture for obtaining step (III) crystallization, solid matter is dried and is roasted,
To obtain Titanium Sieve Molecular Sieve.The drying and the roasting can carry out under normal conditions.Generally, the drying can be with
Environment temperature (such as 15 DEG C) to 200 DEG C at a temperature of carry out.The drying can be in environmental pressure (generally 1 normal atmosphere
Pressure) under carry out, can also carry out at reduced pressure.The duration of the drying can be according to dry temperature and pressure
And dry mode is selected, and is not particularly limited.For example, temperature is preferred when the drying carries out under ambient pressure
It is 80-150 DEG C, more preferably 100-120 DEG C, the dry duration is preferably 0.5-5 hours, more preferably 1-3 hours.Institute
State roasting can 300-800 DEG C at a temperature of carry out, preferably carry out at a temperature of 500-700 DEG C, more preferably in 550-650
Carried out at a temperature of DEG C, further preferably 550-600 DEG C at a temperature of carry out.The duration of the roasting can according into
The temperature selection of row roasting generally can be 2-12 hours, preferably 2-5 hours.It is described roasting preferably in air atmosphere into
Row.
According to the method for the present invention, the catalyst that the Titanium Sieve Molecular Sieve is aoxidized as dimethyl sulfoxide, dosage can be with
For the catalytic amount that can be realized catalysis.Specifically, dimethyl sulfoxide and the mass ratio of the Titanium Sieve Molecular Sieve can be
0.1-50:1, preferably 5-30:1.
According to the method for the present invention, the Titanium Sieve Molecular Sieve can be Titanium Sieve Molecular Sieve original powder, or molding titanium
Si molecular sieves, preferably Titanium Sieve Molecular Sieve original powder.
According to the method for the present invention, the slurry also contains at least one solvent, reaction speed to be adjusted, simultaneously
Improve the uniformity of reaction mixture.The type of the solvent is not particularly limited.Generally, the solvent can selected from water,
C1-C6Alcohol, C3-C8Ketone and C2-C6Nitrile.The specific example of the solvent can include but is not limited to: water, methanol, ethyl alcohol,
Normal propyl alcohol, isopropanol, the tert-butyl alcohol, isobutanol, acetone, butanone and acetonitrile.Preferably, the solvent is selected from water and C1-C6Alcohol.
It is highly preferred that the solvent is methanol and/or water.Water as solvent can be the water in various sources, such as: the water of addition；
Oxidant be in the form of hydrogen peroxide existing for hydrogen peroxide when, the water that is present in hydrogen peroxide.
The dosage of the solvent is not particularly limited, and can be conventional selection.Generally, the matter of solvent and dimethyl sulfoxide
Amount is than that can be 1-500:1, preferably 2-400:1, more preferably 3-100:1, such as 5-50:1.
The slurry can be obtained using various methods commonly used in the art.Specifically, the method for the slurry is obtained
It may include mixing dimethyl sulfoxide, peroxide and optional solvent with Titanium Sieve Molecular Sieve.It is mixed from further increasing
The angle of uniformity coefficient set out, preferably first peroxide is uniformly mixed with Titanium Sieve Molecular Sieve, then by obtained mixture with
Dimethyl sulfoxide mixing.When the slurry also contains solvent, the solvent and peroxide are preferably configured to solution, then
It is mixed with Titanium Sieve Molecular Sieve.
The oxidation reaction condition is not particularly limited, and can be the conventional selection of this field.Generally, the oxidation is anti-
Answering condition includes: that temperature can be for 0-200 DEG C, preferably 20-180 DEG C, more preferably 30-120 DEG C, further preferably 40-
90℃；In terms of gauge pressure, pressure can be 0-5MPa, preferably 0.1-3MPa, such as 1-2MPa.
Method according to the invention it is possible to control the temperature in reactor using common various methods.Such as: it can be with
In the periphery setting cooling water jecket of reactor, and adjusted according to the temperature that the temperature sensor being arranged in reactor detects
The amount of cooling water is saved, to controlling the temperature of reactor within the scope of suitable.
According to the method for the present invention, obtained reaction mixture is separated by solid-liquid separation, to obtain containing dimethyl sulfone
Liquid phase and residue containing Titanium Sieve Molecular Sieve.
The separation of solid and liquid carries out in a kind of separator, which can be realized efficiently will be containing dimethyl sulfone
Liquid phase is separated with Titanium Sieve Molecular Sieve.As shown in Figure 1, the separator has first passage 1 and second channel 2, described first is logical
Road 1 and second channel 2 are adjacent by the component 3 with through-hole, and the average pore size of the through-hole is less than the Titanium Sieve Molecular Sieve
Average grain diameter.The reaction mixture is sent into the first passage 1 by the arrival end of the first passage 1, it is logical first
At least partly liquid under the action of pressure difference between road 1 and second channel 2, in the reaction mixture in first passage 1
Mutually is entered in second channel 2 by the through-hole on component 3 and be discharged by second channel 2.Due to the average hole of the through-hole on component 3
Diameter is less than the average grain diameter of Titanium Sieve Molecular Sieve, therefore Titanium Sieve Molecular Sieve will not or will not enter in second channel 2 substantially, but protects
It stays in first passage 1 and is discharged by the outlet end of first passage 1.According to the method for the present invention, the entrance of the first passage
End is two different ports with outlet end.According to the method for the present invention, the positional 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 can be realized above-mentioned function.
The component with through-hole various can have that liquid can be made from first passage to enter second is logical to be common
The component of the through-hole in road.Preferably, the component is the pipeline that tube wall has the through-hole.
When the component is the pipeline, as shown in Fig. 2, pipeline 4 and a shell 5 can be used cooperatively, pipeline 4
The space that inner wall is formed is as first passage, and the space of the inner wall formation of the outer wall and shell 5 of pipeline 4 is as second channel；Or
Person, the space that the inner wall of pipeline 4 is formed are used as second channel, and the space of the inner wall formation of the outer wall and shell 5 of pipeline 4 is as the
One channel.The quantity in the channel that the inner wall of pipeline 4 is formed can be one, or two or more.When the inner wall shape of pipeline 4
At channel be one when, it is preferable that the space that the inner wall of pipeline 4 is formed is used as first passage, the outer wall and shell 5 of pipeline 4
Inner wall formed space as second channel.The quantity of pipeline in the shell can carry out choosing appropriate according to treating capacity
It selects, can be one or two or more.When the quantity of the pipeline is one or more, between the outer wall of adjacent pipeline preferably
There are spaces.The internal diameter of the shell can make appropriate choice according to the quantity and outer diameter and treating capacity of pipeline.It is described
Pipeline is commercially available, and can also be prepared using common method.Specifically, the pipeline can be ceramic membrane filter
Element.
Method according to the invention it is possible to by adjust the size of through-hole on the component with through-hole, first passage and
Residence time of the mixture that pressure difference and oxidation reaction between second channel obtain in first passage comes to solid-liquid point
From degree regulated and controled.Generally, the pressure difference between first passage and second channel can be 0.01-3MPa, preferably
0.05-2.5MPa, more preferably 0.1-2MPa, such as 0.2-1MPa.
It according to the method for the present invention, can by the residue containing Titanium Sieve Molecular Sieve that the outlet end of the first passage obtains
To recycle for preparing slurry, it can also be sent into subsequent equipment for separating liquid from solid after further being separated, will isolate
Titanium Sieve Molecular Sieve recycle for preparing slurry.Used separator can be efficiently anti-from oxidation according to the method for the present invention
The liquid phase containing dimethyl sulfone is isolated in the mixture that should be obtained, liquid in the obtained residue containing Titanium Sieve Molecular Sieve
Amount is few, therefore the residue containing Titanium Sieve Molecular Sieve preferably is directly recycled for preparing and aoxidize instead by method of the invention
The slurry answered.
It according to the method for the present invention can also include being sent into and rinsing in Xiang Suoshu first passage according to certain time interval
Liquid is rinsed the component with through-hole in separator, with the titanium silicon point that will likely be attached on the component with through-hole
Son sieve rinses.
The flushing liquor can be the various liquid substances that can be realized above-mentioned function.In the first passage and use of separator
In the reactor for reacting the slurry reaction zone connection when, it is described flushing preferably backwash (that is, by flushing liquor by
The outlet end of first passage is sent into first passage, and is discharged from the arrival end of first passage), to will be attached to through-hole
Component on Titanium Sieve Molecular Sieve rinse, and send back in reactor.From ensuring dimethyl sulfoxide and peroxide in reaction system
The ratio of compound will not due to flushing liquor entrance and angle that big variation occurs is set out, the preferably described flushing liquor contains diformazan
Base sulfoxide and peroxide and optional solvent, more preferably between the dimethyl sulfoxide and peroxide in the flushing liquor
Ratio in ratio and previously described slurry is identical.
The time interval of the flushing can make appropriate choice according to the treating capacity of separator, to ensure separator energy
It is enough efficiently to be isolated subject to the liquid phase containing dimethyl sulfone from reaction mixture.Generally, the time interval of the flushing
Can be 0.5-24 hour, preferably 0.5-12 hours, more preferably 1-6 hours, such as can be 1-2 hours.It rinses every time
Duration with can the Titanium Sieve Molecular Sieve that be attached on the component with through-hole is whole or it is substantially all rinse for
It is quasi-.Generally, the duration of the flushing can be 1-30 seconds.
It by the separator and can be used to carry out oxidation reaction using common various methods according to the method for the present invention
Reactor connection, be separated by solid-liquid separation so that reaction mixture that oxidation reaction obtains is sent into separator.For example, can be with
The arrival end of separator is connected to the outlet end of reactor with pipeline.
It according to the method for the present invention can also include separating the mixture containing dimethyl sulfone that contact obtains, with
Isolate dimethyl sulfone therein.The present invention is for isolating the method for the dimethyl sulfone in the mixture that contact obtains without spy
It does not limit, can be the conventional selection of this field.Such as can be fractionated by the mixture for obtaining contact, to obtain
Dimethyl sulfone.
It according to the method for the present invention can also include the taking-up for carrying out reaction heat before and after above-mentioned separation of solid and liquid process, such as may be used
To be retained in as solid phase in first passage and by the channel after the discharge of the outlet end of first passage in titanium-silicon molecular sieve catalyst
Upper connection heat collector reacts generated heat to take away.
Fig. 3 shows a kind of preferred embodiment according to the method for the present invention.It, will in the preferred embodiment
Dimethyl sulfoxide, Titanium Sieve Molecular Sieve, at least one peroxide and optional solvent slurry aoxidized in reactor 6
Reaction；The reaction mixture that oxidation reaction is obtained is sent into the first passage of separator 7, under the action of pressure difference, reaction
At least partly liquid phase in mixture, which enters in the second channel (shadow region in figure) of separator 7, to be obtained containing dimethyl sulfone
Liquid phase A, the residue B in first passage containing Titanium Sieve Molecular Sieve is sent into heat collector 8, is changed with heat transferring medium
Heat obtains the residue of temperature reduction, and is used for the residue circulation that the temperature reduces to prepare slurry.
The invention will be further described with reference to embodiments, but is not so limited the scope of the present invention.
In following embodiment and comparative example, if not otherwise specified, used reagent is commercially available analytical reagents, pressure
Power is in terms of gauge pressure.
In following embodiment and comparative example, the content of each ingredient in the reaction solution analyzed using gas chromatography,
Following formula is respectively adopted on this basis to calculate dimethyl sulfoxide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone
Selectivity:
Dimethyl sulfoxide conversion ratio (%)=[(the unreacted dimethyl sulfoxide of the mole-of the dimethyl sulfoxide of addition
Mole)/be added dimethyl sulfoxide mole] × 100%；
Oxidant effective rate of utilization (%)=[mole/(mole of the oxidant of addition for the dimethyl sulfone that reaction generates
Amount-unreacted oxidant mole)] × 100%；
Dimethyl sulfone selectivity (%)=[mole for the dimethyl sulfone that reaction generates/(dimethyl sulfoxide of addition rubs
That amount-unreacted dimethyl sulfoxide mole)] × 100%.
In the embodiment and comparative example of the step of preparation Titanium Sieve Molecular Sieve included below, X-ray diffraction analysis exists
It is carried out on Siemens D5005 type X-ray diffractometer, with sample and authentic specimen, the five fingers spread out between 2 θ is 22.5 ° -25.0 °
The crystallinity for penetrating the ratio of the sum of diffracted intensity (peak height) of characteristic peak to indicate sample relative to authentic specimen；Fourier transform
Infrared spectrum analysis carries out on 8210 type Fourier infrared spectrograph of Nicolet；Silicon titanium is than referring to silica and titanium oxide
Molar ratio, urface silicon titanium are surveyed using the ESCALab250 type x-ray photoelectron spectroscopy of Thermo Scientific company
Fixed, body phase silicon titanium ratio is measured using Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer.
Embodiment 1-13 is for illustrating method of the invention.
Embodiment 1
Titanium Sieve Molecular Sieve used in the present embodiment is titanium-silicon molecular sieve TS-1, referring to Zeolites, 1992, Vol.12 the
The preparation of method described in 943-950 pages, the specific method is as follows.
(20 DEG C) at room temperature, by 22.5 grams of tetraethyl orthosilicates and 7.0 grams of tetrapropylammonium hydroxide as template
Mixing, and 59.8 grams of distilled water are added, it is hydrolyzed 1.0 hours after being stirred in normal pressure and 60 DEG C, obtains tetraethyl orthosilicate
Hydrating solution.With vigorous stirring, it is slowly added into Xiang Suoshu hydrating solution anhydrous by 1.1 grams of butyl titanates and 5.0 grams
Gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid by solution composed by isopropanol.This colloid is placed in
Stainless steel seals in reaction kettle, places 36 hours in 170 DEG C of at a temperature of constant temperature, obtains the mixture of crystallization product.It will obtain
Mixture filtering, it is 60 minutes dry in 110 DEG C after the solid matter water used wash collected, then roast 6 at 500 DEG C
Hour, to obtain titanium-silicon molecular sieve TS-1, titanium oxide content is 2.8 weight %.
Titanium-silicon molecular sieve TS-1 is placed in the methanol solution containing hydrogen peroxide, stirring is in paste-like, then by reacting
In the catalyst charging hole injection reaction system of kettle.Liquid phase feed inlet valve is opened, when back pressure to pressure is 2.0MPa, opens two
Dimethyl sulfoxide is sent into the reaction system by methyl sulfoxide inlet valve, is carried out continuously reaction.Wherein, in reaction process, reaction
In device charging, the mass ratio of methanol and dimethyl sulfoxide is 5:1, and the molar ratio of dimethyl sulfoxide and hydrogen peroxide is 1:1.5, two
The mass ratio of methyl sulfoxide and titanium-silicon molecular sieve TS-1 is 5:1, and the feed rate of dimethyl sulfoxide is 80mL/ minutes, reaction system
Temperature in system is 45 DEG C.
It is separated by solid-liquid separation, is obtained containing dimethyl sulfone by being sent into separator from the reaction mixture exported in reactor
Liquid phase and residue (solid content be 83 weight %) containing Titanium Sieve Molecular Sieve, the residue containing Titanium Sieve Molecular Sieve is followed
Ring is for preparing liquid phase feed.Pressure in membrane tube is 2.0MPa, and the pressure in space between shell and the outer wall of membrane tube is
1.0MPa。
Wherein, the separator is formed by ceramic film filtering element and a shell, ceramic membrane filter member in each separator
Part (is commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm, and the internal diameter of membrane tube is
8mm, the outer diameter of membrane tube are 12mm) quantity be 2, the internal diameter of shell is 40mm.The quantity of separator is 60, by separator
It is divided into 6 groups, every group is made of 10 separators, wherein it is in parallel between the separator in same group, is series connection between every group,
When flushing, the ceramic film filtering element in 5 separators in every group is rinsed every time.Reaction mixture is sent into ceramics
In the channel of film filtering element, obtain in the channel formed by the outer wall of ceramic film filtering element and the inner wall of shell containing two
The liquid phase of methyl sulfone.
Every 2 hours with flushing liquor (for dimethyl sulfoxide and hydrogen peroxide and the mixed solution of methanol, between three
Ratio in ratio and liquid phase material is identical) flushing in 5 seconds is carried out to the channel on ceramic film filtering element, and obtained after rinsing
To mixed liquor be sent into reactor in.The liquid phase containing dimethyl sulfone exported from separator is analyzed every 2 hours,
Calculate dimethyl sulfoxide conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, reaction proceeds to 2 hours and 120 small
When result listed in table 1.
Embodiment 2
Dimethyl sulfone is produced using method same as Example 1, unlike, the titanium-silicon molecular sieve TS-1 used uses
Following methods preparation.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from
Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:4:12:
400, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is sealed in beaker using sealed membrane
24 hours are stood room temperature (being 25 DEG C, similarly hereinafter) after mouthful, is stirred 2 hours followed by magnetic agitation at 35 DEG C, weight is allowed to
New dispersion.By again disperse after dispersion liquid be transferred to sealing reaction kettle in, 140 DEG C the experience first stage crystallization 6 hours, connect
Mixture is cooled to after 30 DEG C of experience second stage stop 2 hours, continue in sealing reaction kettle in 170 DEG C at a temperature of
Undergo phase III crystallization 12 hours (be wherein, 2 DEG C/min by the heating rate of room temperature to first stage crystallization temperature,
By first stage crystallization temperature to second stage treatment temperature rate of temperature fall be 5 DEG C/min, by second stage treatment temperature to
The heating rate of phase III crystallization temperature is 10 DEG C/min), without filtering and purge step after gained crystallization product is taken out
Suddenly, it directly dries 2 hours in 110 DEG C, is then roasted 3 hours at 550 DEG C, obtain molecular sieve.The XRD crystalline phase figure of gained sample
Consistent with titanium-silicon molecular sieve TS-1 prepared by embodiment 1, what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fu
In vertical leaf transformation infrared spectrogram, in 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, the titanium silicon molecule
In sieve, titanium oxide content is 3.5 weight %, and urface silicon titanium/body phase silicon titanium ratio is 2.58 (titanium silicon molecules prepared by embodiment 1
In sieve, 1.05) urface silicon titanium/body phase silicon titanium ratio is.The result that reaction proceeds to 2 hours and 250 hours is listed in table 1.
Embodiment 3
Dimethyl sulfone is produced using method same as Example 2, unlike, when preparing titanium-silicon molecular sieve TS-1, the
Triphasic crystallization temperature is also 140 DEG C.Titanium-silicon molecular sieve TS-1 one prepared by the XRD crystalline phase figure and embodiment 1 of gained sample
It causes, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby inhale
Peak is received, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 4.21, titanium oxide
Content is 3.1 weight %.The result that reaction proceeds to 2 hours and 170 hours is listed in table 1.
Embodiment 4
Dimethyl sulfone is produced using method same as Example 2, unlike, when preparing titanium-silicon molecular sieve TS-1, the
The crystallization temperature in one stage is 110 DEG C.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by embodiment 1,
What is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby absorb
Peak shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.37, and titanium oxide contains
Amount is 3.2 weight %.The result that reaction proceeds to 2 hours and 170 hours is listed in table 1.
Embodiment 5
Dimethyl sulfone is produced using method same as Example 2, unlike, when preparing titanium-silicon molecular sieve TS-1, the
The crystallization time in one stage is 12 hours.Titanium-silicon molecular sieve TS-1 one prepared by the XRD crystalline phase figure and embodiment 1 of gained sample
It causes, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby inhale
Peak is received, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 3.78, titanium oxide
Content is 3.4 weight %.The result that reaction proceeds to 2 hours and 170 hours is listed in table 1.
Embodiment 6
Dimethyl sulfone is produced using method same as Example 2, unlike, when preparing titanium-silicon molecular sieve TS-1, the
Two-stage is to be cooled to 70 DEG C to stop 2 hours.Titanium-silicon molecular sieve TS-1 prepared by the XRD crystalline phase figure and embodiment 1 of gained sample
Unanimously, what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby occur
Absorption peak shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.75, oxidation
Ti content is 3.1 weight %.The result that reaction proceeds to 2 hours and 190 hours is listed in table 1.
Embodiment 7
Dimethyl sulfone is produced using method same as Example 2, unlike, when preparing titanium-silicon molecular sieve TS-1, the
Two-stage is to be cooled to 30 DEG C to stop 0.2 hour.Titanium Sieve Molecular Sieve TS- prepared by the XRD crystalline phase figure and embodiment 1 of gained sample
1 is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby go out
Existing absorption peak, shows that titanium has entered framework of molecular sieve, and in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.14, oxygen
Change Ti content is 2.4 weight %.The result that reaction proceeds to 2 hours and 100 hours is listed in table 1.
Embodiment 8
Dimethyl sulfone is produced using method same as Example 2, unlike, when preparing titanium-silicon molecular sieve TS-1, no
By second stage.The XRD crystalline phase figure of gained sample is consistent with titanium-silicon molecular sieve TS-1 prepared by embodiment 1, illustrates
It is the TS-1 molecular sieve with MFI structure；In 960cm in fourier-transform infrared spectrogram-1Nearby there is absorption peak, shows titanium
Into framework of molecular sieve, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 1.08, and titanium oxide content is 2.5 weights
Measure %.
The result that reaction proceeds to 2 hours and 100 hours is listed in table 1.
Embodiment 9
Dimethyl sulfone is produced using method same as Example 2, unlike, when preparing titanium-silicon molecular sieve TS-1, water
Dispersion liquid does not stand 12 hours at room temperature, but is sent directly into reaction kettle and carries out crystallization.The XRD crystalline phase figure of gained sample with
The titanium-silicon molecular sieve TS-1 of 1 step of embodiment (1) preparation is consistent, and what is illustrated is the TS-1 molecular sieve with MFI structure；Fu
In 960cm in vertical leaf transformation infrared spectrum-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, the Titanium Sieve Molecular Sieve
In, urface silicon titanium/body phase silicon titanium ratio is 1.18, and titanium oxide content is 3.5 weight %.
The result that reaction proceeds to 2 hours and 160 hours is listed in table 1.
Table 1
Embodiment 10
The titanium-silicon molecular sieve TS-1 that the present embodiment uses is prepared using following methods.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from
Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:2:10:
600, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is close using sealed membrane in beaker
It is honored as a queen and stands 10 hours at 40 DEG C, be stirred 0.5 hour followed by magnetic agitation at 25 DEG C, be allowed to disperse again.It will weigh
Dispersion liquid after new dispersion is transferred in sealing reaction kettle, 130 DEG C the experience first stage crystallization 8 hours, then by mixture
After being cooled to 50 DEG C of experience second stage stops 5 hours, continues the temperature in sealing reaction kettle in 170 DEG C and undergo the phase III
Crystallization 16 hours (are wherein, 1 DEG C/min by the heating rate of room temperature to first stage crystallization temperature, by first stage crystalline substance
The rate of temperature fall for changing temperature to second stage treatment temperature is 10 DEG C/min, by second stage treatment temperature to phase III crystalline substance
The heating rate for changing temperature is 20 DEG C/min), without filtering and washing step after gained crystallization product is taken out, directly in 120
DEG C drying 3 hours, then roast 2 hours at 580 DEG C, acquisition molecular sieve.The XRD crystalline phase figure and embodiment 1 of gained sample are made
Standby titanium-silicon molecular sieve TS-1 is consistent, and what is illustrated is the titanium-silicon molecular sieve TS-1 with MFI structure；Fourier-transform infrared
In spectrogram, in 960cm-1Nearby there is absorption peak, shows that titanium has entered framework of molecular sieve, in the Titanium Sieve Molecular Sieve, surface silicon
Titanium ratio/body phase silicon titanium ratio is 2.25, and titanium oxide content is 2.6 weight %.
Titanium-silicon molecular sieve TS-1 is placed in the methanol solution containing tert-butyl hydroperoxide, stirring is to being in paste-like, so
Afterwards by the catalyst charging hole injection reaction system of reaction kettle.Liquid phase feed inlet valve is opened, back pressure to pressure is 2.0MPa
When, dimethyl sulfoxide inlet valve is opened, dimethyl sulfoxide is sent into the reaction system and is carried out continuously reaction.Wherein, it reacted
Cheng Zhong, in the charging of reactor, the mass ratio of methanol and dimethyl sulfoxide is 20:1, dimethyl sulfoxide and tert-butyl hydroperoxide
Molar ratio be 1:1.2, the mass ratio of dimethyl sulfoxide and titanium-silicon molecular sieve TS-1 is 15:1, the feed rate of dimethyl sulfoxide
It is 50mL/ minutes, the temperature in reaction system is 55 DEG C.
It is separated by solid-liquid separation, is obtained containing dimethyl sulfone by being sent into separator from the reaction mixture exported in reactor
Liquid phase and residue (solid content be 88 weight %) containing Titanium Sieve Molecular Sieve, the residue containing Titanium Sieve Molecular Sieve is followed
Ring is for preparing liquid phase feed.
Wherein, the separator is formed by ceramic film filtering element and a shell, ceramic membrane filter member in each separator
Part (is commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm, and the internal diameter of membrane tube is
8mm, the outer diameter of membrane tube are 12mm) quantity be 5, the internal diameter of shell is 100mm.The quantity of separator is 12, will be separated
Device is divided into 2 groups, and every group is made of 6 separators, wherein and it is in parallel between the separator in same group, is series connection between every group,
When flushing, the ceramic film filtering element in 3 separators in every group is rinsed every time.Reaction mixture is sent into ceramics
In channel on film filtering element, contained in the channel formed by the outer wall of ceramic film filtering element and the inner wall of shell
The liquid phase of dimethyl sulfone.
Every 1 hour with flushing liquor (for dimethyl sulfoxide and hydrogen peroxide and the mixed solution of methanol, between three
Ratio in ratio and liquid phase material is identical) flushing in 2 seconds is carried out to the channel on ceramic film filtering element, and obtained after rinsing
To mixed liquor be sent into reactor in.
The liquid phase containing dimethyl sulfone exported from separator is analyzed every 2 hours, calculates dimethyl sulfoxide
Conversion ratio, oxidant effective rate of utilization and dimethyl sulfone selectivity, reaction proceed to 2 hours and 250 hours results in table 2
It lists.
Embodiment 11
Dimethyl sulfone is produced using method same as in Example 10, unlike, use hollow Titanium Sieve Molecular Sieve
(the hollow Titanium Sieve Molecular Sieve for being HTS for the trade mark purchased from Hunan Jianchang Petrochemical Co., Ltd).
The result that reaction proceeds to 2 hours and 150 hours is listed in table 2.
Embodiment 12
The titanium-silicon molecular sieve TS-1 that the present embodiment uses is prepared using following methods.
First butyl titanate is dissolved in alkali source template tetrapropylammonium hydroxide solution, silica gel is then added and (is purchased from
Qingdao silica gel factory), dispersion liquid is obtained, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:5:18:
1000, silicon source is with SiO2Meter, titanium source is with TiO2Meter, alkali source template is in terms of N.Above-mentioned dispersion liquid is utilized into sealed membrane in beaker
8 hours are stood at 45 DEG C after sealing；Dispersion liquid through standing is transferred in sealing reaction kettle, in 140 DEG C of experience first stage
Crystallization 6 hours, then mixture is cooled to after 40 DEG C of experience second stage stop 1 hour, continue in sealing reaction kettle in
Undergo phase III crystallization 12 hours (wherein, by the heating speed of room temperature to first stage crystallization temperature at a temperature of 160 DEG C
Rate is 5 DEG C/min, is 5 DEG C/min by the rate of temperature fall of first stage crystallization temperature to second stage treatment temperature, by second
Phase process temperature to phase III crystallization temperature heating rate be 5 DEG C/min), by gained crystallization product take out after without
Filtering and washing step are directly dried 2 hours in 110 DEG C, are then roasted 3 hours at 550 DEG C, and molecular sieve is obtained.Gained sample
The XRD crystalline phase figure of product is consistent with titanium-silicon molecular sieve TS-1 prepared by embodiment 1, and what is illustrated is the titanium silicon with MFI structure
Molecular sieve TS-1；In Fourier Transform Infrared Spectroscopy figure, in 960cm-1Nearby there is absorption peak, shows that titanium has entered molecule sieve skeleton
Frame, in the Titanium Sieve Molecular Sieve, urface silicon titanium/body phase silicon titanium ratio is 2.71, and titanium oxide content is 4.3 weight %.
Titanium-silicon molecular sieve TS-1 is placed in the acetone soln containing cumyl hydroperoxide, stirring is in paste-like, then
By in the catalyst charging hole injection reaction system of reaction kettle.Liquid phase feed inlet valve is opened, when back pressure to pressure is 1.5MPa,
Dimethyl sulfoxide inlet valve is opened, dimethyl sulfoxide is sent into the reaction system, reaction is carried out continuously.Wherein, reaction process
In, in reactor feed, the mass ratio of acetone and dimethyl sulfoxide is 5:1, and dimethyl sulfoxide and cumyl hydroperoxide rub
You are than being 1:1, and the mass ratio of dimethyl sulfoxide and titanium-silicon molecular sieve TS-1 is 30:1, and the input and output material rate of dimethyl sulfoxide is
30mL/ minutes, the temperature in reaction system was 80 DEG C.
It is separated by solid-liquid separation, is obtained containing dimethyl sulfone by being sent into separator from the reaction mixture exported in reactor
Liquid phase and residue (solid content be 84 weight %) containing Titanium Sieve Molecular Sieve, the residue containing Titanium Sieve Molecular Sieve is followed
Ring is for preparing liquid phase feed.
Wherein, the separator is formed by ceramic film filtering element and a shell, ceramic membrane filter member in each separator
Part (is commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm, and the internal diameter of membrane tube is
8mm, the outer diameter of membrane tube are 12mm) quantity be 5, the internal diameter of shell is 100mm.The quantity of separator is 12, will be separated
Device is divided into 2 groups, and every group is made of 6 separators, wherein and it is in parallel between the separator in same group, is series connection between every group,
When flushing, the ceramic film filtering element in 3 separators in every group is rinsed every time.Reaction mixture is sent into ceramics
In channel on film filtering element, contained in the channel formed by the outer wall of ceramic film filtering element and the inner wall of shell
The liquid phase of dimethyl sulfone.Pressure in membrane tube is 0.3MPa, is normal pressure (that is, 1 mark in the space between shell and the outer wall of membrane tube
Quasi- atmospheric pressure).
Every 1 hour with flushing liquor (for dimethyl sulfoxide and hydrogen peroxide and the mixed solution of methanol, between three
Ratio in ratio and liquid phase material is identical) flushing in 2 seconds is carried out to the channel on ceramic film filtering element, and obtained after rinsing
To mixed liquor be sent into reactor in.
The result that reaction proceeds to 2 hours and 250 hours is listed in table 2.
Embodiment 13
The Titanium Sieve Molecular Sieve that the present embodiment uses is prepared by titanium-silicon molecular sieve TS-1 prepared by embodiment 1 and embodiment 12
The mixture of titanium-silicon molecular sieve TS-1, in the mixture, the content of titanium-silicon molecular sieve TS-1 prepared by embodiment 12 are 60 weights
Measure %.
Titanium Sieve Molecular Sieve is placed in the acetonitrile solution containing hydrogen peroxide, stirring is to being in paste-like, then by reaction kettle
Catalyst charging hole injection reaction system in.Liquid phase feed inlet valve is opened, when back pressure to pressure is 2.0MPa, opens diformazan
Base sulfoxide inlet valve, dimethyl sulfoxide is sent into the reaction system, is carried out continuously reaction.Wherein, in reaction process, reactor
In charging, the mass ratio of acetonitrile and dimethyl sulfoxide is 10:1, and the molar ratio of dimethyl sulfoxide and hydrogen peroxide is 1:1.2, two
Methyl sulfoxide and the mass ratio of Titanium Sieve Molecular Sieve are 10:1, and the input and output material rate of dimethyl sulfoxide is 20mL/ minutes, reaction system
Interior temperature is 90 DEG C.
It is separated by solid-liquid separation, is obtained containing dimethyl sulfone by being sent into separator from the reaction mixture exported in reactor
Liquid phase and residue (solid content be 71 weight %) containing Titanium Sieve Molecular Sieve, the residue containing Titanium Sieve Molecular Sieve is followed
Ring is for preparing liquid phase feed.
Wherein, the separator is formed by ceramic film filtering element and a shell, ceramic membrane filter member in each separator
Part (is commercially available from the ceramic micro filter membrane tube of Jiangsu Jiuwu High-Tech Co., Ltd., membrane aperture is 0.2 μm, and the internal diameter of membrane tube is
8mm, the outer diameter of membrane tube are 12mm) quantity be 5, the internal diameter of shell is 100mm.The quantity of separator is 12, will be separated
Device is divided into 2 groups, and every group is made of 6 separators, wherein and it is in parallel between the separator in same group, is series connection between every group,
When flushing, the ceramic film filtering element in 3 separators in every group is rinsed every time.Reaction mixture is sent into ceramics
In channel on film filtering element, contained in the channel formed by the outer wall of ceramic film filtering element and the inner wall of shell
The liquid phase of dimethyl sulfone.Pressure in membrane tube is 0.3MPa, is normal pressure (that is, 1 mark in the space between shell and the outer wall of membrane tube
Quasi- atmospheric pressure).
Every 1 hour with flushing liquor (for dimethyl sulfoxide and hydrogen peroxide and the mixed solution of methanol, between three
Ratio in ratio and liquid phase material is identical) flushing in 2 seconds is carried out to the channel on ceramic film filtering element, and obtained after rinsing
To mixed liquor be sent into reactor in.
The result that reaction proceeds to 2 hours and 220 hours is listed in table 2.
Table 2
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (37)
1. a kind of method for producing dimethyl sulfone, this method comprises: dimethyl sulfoxide, Titanium Sieve Molecular Sieve, at least one will be contained
The slurry of peroxide and at least one solvent is reacted under oxidation reaction condition, and obtained reaction mixture is carried out
It is separated by solid-liquid separation, obtains the liquid phase containing dimethyl sulfone and the residue containing Titanium Sieve Molecular Sieve, at least partly Titanium Sieve Molecular Sieve is
Titanium-silicon molecular sieve TS-1, the urface silicon titanium of the titanium-silicon molecular sieve TS-1 and the ratio of body phase silicon titanium ratio are 1.2-5, the silicon
Molar ratio of the titanium than referring to silica and titanium oxide, the urface silicon titanium are measured using X-ray photoelectron spectroscopy, the body
Phase silicon titanium ratio uses x-ray fluorescence spectrometry；
The titanium-silicon molecular sieve TS-1 is prepared using method comprising the following steps:
(I) inorganic silicon source is dispersed in the aqueous solution containing titanium source and alkali source template, and optionally supplements water, dispersed
Liquid, in the dispersion liquid, silicon source: titanium source: alkali source template: the molar ratio of water is 100:(0.5-8): (5-30): (100-
2000), the inorganic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the alkali source template is with OH-Or N meter；
(II) by the dispersion liquid 15-60 DEG C standing 6-24 hours；
(III) dispersion liquid that step (I) obtains or the dispersion liquid that step (II) obtains sequentially are undergone in sealing reaction kettle
Stage (1), stage (2) and stage (3) to carry out crystallization, the stage (1) 80-150 DEG C crystallization 6-72 hours；Stage (2) cooling
It is extremely not higher than 70 DEG C and the residence time is at least 0.5 hour；Stage (3) is warming up to 120-200 DEG C, then crystallization 6-96 hours；
The separation of solid and liquid carries out in a kind of separator, the separator have first passage and second channel, described first
Channel has arrival end and outlet end, and the first passage and second channel are adjacent by the component with through-hole, the through-hole
Average pore size be less than the average grain diameter of the Titanium Sieve Molecular Sieve, the reaction mixture is sent into described the by the arrival end
In one channel, at least partly liquid phase in the reaction mixture is entered in the second channel by the through-hole, from described
The liquid phase containing dimethyl sulfone is discharged in second channel, is obtained described containing titanium silicon molecule by the outlet end of the first passage
The residue of sieve.
2. according to the method described in claim 1, wherein, the component is the pipeline that tube wall has the through-hole.
3. according to the method described in claim 2, wherein, space that the inner wall of the pipeline is formed as the first passage,
The space that the outer wall of the pipeline and a shell are constituted is as second channel.
4. method described in any one of -3 according to claim 1, wherein the urface silicon titanium and the body phase silicon titanium ratio
Ratio be 1.5-4.5.
5. according to the method described in claim 1, wherein, the stage, (1) was in 110-140 DEG C of crystallization.
6. according to the method described in claim 5, wherein, the stage, (1) was in 120-140 DEG C of crystallization.
7. according to the method described in claim 6, wherein, the stage, (1) was in 130-140 DEG C of crystallization.
8. according to claim 1 with the method described in any one of 5-7, wherein the crystallization time in stage (1) is 6-8 hours.
9. according to the method described in claim 1, wherein, the residence time in stage (2) is 1-5 hours.
10. according to the method described in claim 1, wherein, the stage (3) is warming up to 140-180 DEG C.
11. according to the method described in claim 10, wherein, the stage (3) is warming up to 160-170 DEG C.
12. according to claim 1, method described in any one of 10 and 11, wherein the stage (3) crystallization 12-20 hours again.
13. according to the method described in claim 1, wherein, stage (1) and stage (3) meet one of the following conditions or two
Person:
Condition 1: the crystallization temperature in stage (1) is lower than the crystallization temperature of stage (3)；
Condition 2: the crystallization time in stage (1) is less than the crystallization time of stage (3).
14. according to the method for claim 13, wherein condition 1: crystallization temperature of the crystallization temperature in stage (1) than the stage (3)
Spend low 10-50 DEG C.
15. according to the method for claim 14, wherein condition 1: crystallization temperature of the crystallization temperature in stage (1) than the stage (3)
Spend low 20-40 DEG C.
16. according to the method for claim 13, wherein condition 2: the crystallization time in stage (1) than the stage (3) crystallization when
Between it is 5-24 hours short.
17. according to the method for claim 16, wherein condition 2: the crystallization time in stage (1) than the stage (3) crystallization when
Between it is 6-12 hours short.
18. according to claim 1, method described in any one of 5-7 and 13-17, wherein the stage (2) is cooled to and is not higher than
50 DEG C, and the residence time is at least 1 hour.
19. according to claim 1, method described in any one of 5-7 and 13-17, wherein the titanium source is inorganic titanium salt
And/or organic titanate；The alkali source template be one or both of quaternary ammonium base, aliphatic amine and aliphatic hydramine with
On；The inorganic silicon source is silica gel and/or silica solution.
20. according to the method for claim 19, wherein the alkali source template is quaternary ammonium base.
21. according to the method for claim 20, wherein the alkali source template is tetrapropylammonium hydroxide.
22. according to the method for claim 19, wherein the inorganic titanium salt is TiCl4、Ti(SO4)2And TiOCl2In one
Kind is two or more；The organic titanate is selected from general formula R7 4TiO4The compound of expression, R7Selected from 2-4 carbon atom
Alkyl.
23. according to claim 1-3, method described in any one of 5-7,9-11 and 13-17, wherein the dimethyl is sub-
Sulfone and the mass ratio of the Titanium Sieve Molecular Sieve are 0.1-50:1.
24. according to the method for claim 23, wherein the dimethyl sulfoxide and the mass ratio of the Titanium Sieve Molecular Sieve are
5-30:1.
25. according to claim 1-3, method described in any one of 5-7,9-11 and 13-17, wherein the peroxide
Molar ratio with the dimethyl sulfoxide is 0.1-10:1.
26. according to the method for claim 25, wherein the molar ratio of the peroxide and the dimethyl sulfoxide is
0.2-5:1.
27. according to the method for claim 26, wherein the molar ratio of the peroxide and the dimethyl sulfoxide is
0.5-2:1.
28. according to the method for claim 27, wherein the molar ratio of the peroxide and the dimethyl sulfoxide is 1-
1.5:1.
29. according to claim 1-3, method described in any one of 5-7,9-11 and 13-17, wherein the peroxide
Selected from hydrogen peroxide, organic hydroperoxide and peracid.
30. according to the method for claim 29, wherein the peroxide be selected from hydrogen peroxide, tert-butyl hydroperoxide,
Ethylbenzene hydroperoxide and cumyl hydroperoxide.
31. according to claim 1-3, method described in any one of 5-7,9-11 and 13-17, wherein the solvent is selected from
Water, C1-C10Alcohol, C3-C10Ketone and C2-C10Nitrile.
32. according to claim 1-3, method described in any one of 5-7,9-11 and 13-17, wherein the oxidation reaction
Condition includes: that temperature is 0-200 DEG C；In terms of gauge pressure, pressure 0-5MPa.
33. according to the method for claim 32, wherein temperature is 20-180 DEG C.
34. according to the method for claim 33, wherein temperature is 30-120 DEG C.
35. according to the method for claim 34, wherein temperature is 40-90 DEG C.
36. according to the method for claim 32, wherein in terms of gauge pressure, pressure 0.1-3MPa.
37. according to the method for claim 36, wherein in terms of gauge pressure, pressure 1-2MPa.
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| CN104557634A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing dimethyl sulfone |
| CN104944441A (en) * | 2014-03-31 | 2015-09-30 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon molecular sieve |
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