CN106083666A - A kind of production technology of dimethyl sulfone - Google Patents
A kind of production technology of dimethyl sulfone Download PDFInfo
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- CN106083666A CN106083666A CN201610415003.0A CN201610415003A CN106083666A CN 106083666 A CN106083666 A CN 106083666A CN 201610415003 A CN201610415003 A CN 201610415003A CN 106083666 A CN106083666 A CN 106083666A
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- dimethyl sulfone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/06—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention belongs to chemical technology field, specifically disclose the production technology of a kind of dimethyl sulfone, comprise the steps (1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, catalyst filling in fixed bed reactors, entrance in fixed bed squeezes into mixed liquor continuously, mixed liquor reacts along catalyst bed laminar flow and under the effect of catalyst, and mixed liquor along catalyst bed laminar flow, flows continually out reactant liquor in fixed bed exit in fixed bed；Described catalyst is 2,6 naphthalenedicarboxylic acids；(2) crystallization；(3) solid-liquid separation.(4) it is dried.The present invention, by using 2,6 naphthalenedicarboxylic acids as catalyst, is greatly accelerated the response speed of this oxidation reaction.The present invention uses novel catalyst that the energy consumption of dimethyl sulfone can be made to reduce, and the production cycle shortens, and production efficiency improves, and economic benefit increases.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to the production technology of a kind of dimethyl sulfone.
Background technology
Dimethyl sulfone, as a kind of organic sulfur compound, has in strengthening human body and produces the ability of insulin simultaneously to saccharide
Metabolism plays a driving role, and is the necessary material of human collagen albumen synthesis.Dimethyl sulfone can promote wound healing, also can be to the oldest
Vitamin B, vitamin C, the synthesis of biotin and activation needed for metabolism and neurological health are worked, and are referred to as " naturally beautifying
Carbonizable substance ".
The commercial production of current domestic dimethyl sulfone is mainly obtained through nitric acid oxidation by dimethyl sulfoxide, and the method exists
The problem such as reaction temperature height, energy consumption height, technological process length, by-product are many, environmental pollution is the most serious simultaneously.In prior art,
Patent CN 1150164C discloses the preparation method of dimethyl sulfone, and the method includes that oxidation reaction, cooling separate out, and filters, de-
Water, the step such as drying, wherein, oxidation reaction is dimethyl sulfoxide and hydrogen peroxide reacts generation dimethyl sulfone, dimethyl sulfoxide with
The active ingredient weight ratio of hydrogen peroxide is 1:0.44～0.65, and reaction temperature is 80～150 DEG C, response time 4～40 hours.Should
In method, oxidation reaction does not use catalyst, although compares nitrate method reaction temperature and decreases, but temperature is the highest,
Response time is long.Patent public affairs CN 103288692 B has opened a kind of method being prepared dimethyl sulfone by dimethyl sulfoxide, the party
Method be dimethyl sulfoxide be oxidant at ozone, HTS is to be oxidized to product dimethyl sulfone under conditions of catalyst, its
Reaction temperature is 40-100 DEG C, and pressure is 0.1-3MPa, and the response time is 0.1-10 hour.Its reaction temperature and response time model
Enclosing value relatively big, from its description, its preferred reaction temperature is the most higher, and the response time is preferably 1～5 hour, still
The longest.
In sum, need a kind of new process of exploitation badly or improve existing technique and be prepared dimethyl sulfone so that
Preparation method is simple, accelerates response speed, reduces reaction temperature to a certain extent simultaneously, reduces energy consumption, shortens the production cycle, carries
High efficiency, increases economic benefit.
Summary of the invention
It is an object of the invention to develop the dimethyl sulfone production technology that a kind of response speed is fast, reaction temperature is relatively low.
Above-mentioned purpose is to be achieved through the following technical solutions: the production technology of a kind of dimethyl sulfone, comprises the steps:
(1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, fills catalysis in fixed bed reactors
Agent, the entrance in fixed bed squeezes into mixed liquor continuously, and mixed liquor is carried out along catalyst bed laminar flow and under the effect of catalyst
Reaction, mixed liquor along catalyst bed laminar flow, flows continually out reactant liquor in fixed bed exit in fixed bed；Described catalyst
For 2,6-naphthalenedicarboxylic acid；(2) crystallization: reactant liquor is flowed out in the fixed bed exit in step (1) and is pumped in crystallizer carry out
Crystallization treatment, generates dimethyl sulfone crystal；(3) solid-liquid separation: by the liquid in the solidliquid mixture in step (2) and dimethyl
Sulfone crystal separates, and obtains dimethyl sulfone crystal and debris.(4) it is dried: the dimethyl sulfone crystal in step (3) enters
Row dried, obtains pure product dimethyl sulfone.The present invention is by using 2,6-naphthalenedicarboxylic acid as dimethyl sulfoxide oxygen
Metaplasia becomes the catalyst of dimethyl sulfone, is greatly accelerated the response speed of this oxidation reaction, at relatively lower temp (40～60
DEG C) under, reaction only needs the short period (20～30min) that the conversion ratio of dimethyl sulfoxide can be made to be up to about 95%, therefore slightly produces
The purity of product dimethyl sulfone is of a relatively high, only needs to separate solid catalyst, become the crystallization of dimethyl sulfone and divide in last handling process
From, then it is dried process and i.e. can reach the high purity dimethyl sulfone product that purity is more than 99%.The present invention uses novel
Catalyst the energy consumption of dimethyl sulfone can be made to reduce, the production cycle shorten, production efficiency improve, economic benefit increase.
Characterizing after deliberation, it is oxidation generation two that NDA is applied to dimethyl sulfoxide in the present invention as catalyst
During methyl sulfone, catalytic reaction is to carry out on the B-acid position of NDA, and i.e. NDA is in theory
As a kind of solid acid catalyst, it plays the avtive spot i.e. B-acid position of catalytic action.Experimentation shows, solid acid catalyst
Acid amount on surface is catalyzed activity with it and selectivity has obvious relation, and the acid of NDA catalyst of the present invention is strong
Degree is more suitable, shows higher catalysis activity for it and provides possibility.It addition, solid NDA self is porous
Structure, even aperture distribution, specific surface area is relatively big, is a kind of preferably carrier, can be as the carrier of the avtive spot of himself.
Therefore the making of this catalyst is simple, it is not necessary to additionally prepare synthesis.
Fixed bed reactors have lot of advantages, and when completing same production task, required catalyst amount is minimum；Bed
In layer, time of staying of material can strictly control, and Temperature Distribution can suitably regulate, be conducive to improving the conversion ratio of chemical reaction and
Selectivity, and fixed bed inner catalyst is the most easy to wear, is conducive to extending the service life of catalyst.Owing to present invention uses 2,
6-naphthalenedicarboxylic acid catalyst so that reaction and time of staying that mixed liquor is in fixed bed be greatly shortened, for realizing seriality
Produce and provide possible.
As preferably, further technical scheme is: the reaction temperature in step (1) is maintained at 40～60 DEG C, during stop
Between be 20～30min.Select above-mentioned reaction temperature and response time, be on the one hand owing to employing NDA conduct
Catalyst so that only need above-mentioned reaction temperature and response time just can reach the conversion ratio of preferable dimethyl sulfoxide, can
On the other hand reducing energy consumption and production costs, at 40～60 DEG C, NDA has and is preferably catalyzed activity.Herein
Response time and reaction temperature are the preferably result obtained after test of many times, do not represent the response time at other
Or the technique effect reached after the present invention can not being realized in range of reaction temperature or reaching to use the present invention.
Further technical scheme is: the concentration of described hydrogen peroxide is 5%～15%.Hydrogen peroxide is as oxidant, right
Oxidation in dimethyl sulfone has higher selectivity, and decomposing hydrogen dioxide solution is oxygen and water, will not produce by-product and be harmful to
Material, product odorless, it is possible to reduce separation costs further, and its operating condition is gentle, will not equipment be produced serious
Corrosion.Therefore, according to the inventive method environmental friendliness.It addition, the concentration of hydrogen peroxide is unsuitable excessive, it is to avoid oxidation reaction is the most acute
The strong generation causing local temperature too high, and then causing by-product, even affects activity and the service life of catalyst, studies table
Bright, the present invention uses fixed-bed process, and for strict temperature control, the concentration of hydrogen peroxide is more suitable 5%～15%, now,
Reaction is more gentle, and the conversion ratio of raw material, the effective rate of utilization of hydrogen peroxide, product yield are the most of a relatively high.
Preferably, the pH value of mixed liquor controls 3～6, and research shows, under the conditions of this, hence it is evident that improve for dimethyl sulfone
Selectivity, simultaneously can also obtain higher dimethyl sulfoxide conversion ratio and oxidant effective rate of utilization.On the one hand, at acid bar
Under part, hydrogen peroxide is more stable, on the other hand, under the conditions of this pH, provides good acid environment for NDA, is conducive to
Improve its catalysis activity.
Further technical scheme is: enter dimethyl sulfoxide and hydrogen peroxide in the mixed liquor of fixed bed in step (1)
Active ingredient weight ratio be 1:0.4～0.7.Under the conditions of this, oxidant effective rate of utilization is higher.
Further technical scheme is: the particle diameter of described NDA is 1.2～1.8mm, and porosity is more than
25%, specific surface area is more than 260m2/g.Under the conditions of this, the better catalytic activity of NDA, service life is longer, and
Easily-activated regeneration.
Further technical scheme is: in step (1), fixed bed reactors are divided at least two reaction zone, respectively react
Separate with porous plate between district and be provided with gap.Owing to bed pressure drop is directly proportional to bed height, bed increases, and flow resistance is just
Increase.It is so designed that, reaction solution concentration and the problem of non-uniform temperature in bed can be prevented, effectively reduce bed pressure drop, resistance
Little；Surface Renewal between liquid-liquid interface and between liquid-solid interface is fast, improves conversion ratio and the selectivity of reaction.In order to drop
Low bed layer pressure drop, can control the voidage of beds, and the voidage of preferred catalyst bed is 0.3～0.4.
Further technical scheme is: in step (1), the temperature of the reaction zone that mixed liquor first flows through flows through after being higher than
The temperature of reaction zone.Owing to this oxidation reaction is exothermic reaction, along with the flowing of mixed liquor beds, temperature gradually body
Height, for ensureing that catalyst has preferable catalytic efficiency, mixed liquor is after the inflow of a reaction zone behind a reaction zone, to rear one
The catalyst of reaction zone preheats so that reaction temperature is stable in preferably condition, it is to avoid at fixed bed outlet section reactant liquor
Temperature is too high and affects catalytic efficiency, temperature runaway phenomenon even occurs.
Further technical scheme is: the temperature of the reaction zone that mixed liquor first flows through is than the reaction zone flowed through after mixed liquor
Temperature high 3～8 DEG C.Reaction zone can arrange 2～4, experiment proves that, under the conditions of this, the catalytic efficiency of catalyst is higher, oxygen
Change reaction relatively stable, gentle.
Further technical scheme is: be filled with filler in described reaction zone.It is so designed that, is on the one hand conducive to fall
Low bed layer pressure drop, on the other hand dilute catalyst, it is to avoid temperature runaway.
Further technical scheme is: described filler and described catalyst load with the form of the mixture of the two in
In described reaction zone.
Further technical scheme is: the beds formed by catalyst and the packing layer formed by filler interval
Filling is in the reaction region.
Further technical scheme is: the debris in step (2) is flow in fixed bed by blowback.So, can carry
The utilization rate of high reactant, improves conversion ratio, reduces the discharge of waste liquid simultaneously.It is particularly suited for the work that reaction-ure conversion-age is relatively low
Use under the conditions of skill.
Further technical scheme is: the crystallization operation in step (2) is evaporative crystallization, crystallisation by cooling and decompression distillation
One in crystallization.
In prior art, owing to conversion ratio and the selectivity of dimethyl sulfoxide are relatively low, after the crystallization of general preliminary dimethyl sulfone
Need to again dissolve, the agitation and filtration removal of impurity, recrystallization obtains pure dimethyl sulfone product, even in order to meet wanting of purity
Ask, need to washing repetitious to dimethyl sulfone, dissolve, crystallize, so, not only complex process, production cycle are long, and product is received
Rate is relatively low.The present invention the most only needs primary crystallization to process the requirement that can meet product purity.
Further technical scheme is: step (3) can use technique that is centrifugal or that filter to carry out solid-liquid separation.
Further technical scheme is: the baking temperature in step (4) controls at 35～85 DEG C.Dimethyl sulfone is at 25 DEG C
Microsublimation, accelerates to 60 DEG C of rate of sublimation, thus dimethyl sulfone product drying is easily carried out under cryogenic vacuum.Therefore baking temperature
Unsuitable too high, it is to avoid dimethyl sulfone distillation causes product yield to reduce.
Further technical scheme is: the baking temperature in step (4) controls at 45～60 DEG C.Baking temperature is the most not
More than 60 DEG C, now for accelerating rate of drying, it is contemplated that vacuum drying.
Further technical scheme is: the dimethyl sulfone crystal separated in cold water washing step (3), the washing after washing
Liquid is conveyed in the crystallizer to step (2).So, can further improve the product purity of dimethyl sulfone.
Further technical scheme is: step (3) also includes the step concentrating the filtrate in step (2) before carrying out
Suddenly.Concentration process can be evaporation and concentration, it is also possible to be that membrane filtration processes, dense by improve dimethyl sulfone after concentration operation
Degree, it is easy to carry out the crystallization operation of dimethyl sulfone.
In sum, in the present invention, NDA catalyst generates the reaction of dimethyl sulfone to dimethyl sulfoxide oxidation
Showing higher selectivity, compared to existing technology, on the premise of reducing reaction temperature, the response time still can relatively great Cheng
The shortening of degree, energy consumption reduces, and the production cycle shortens, and production efficiency improves；Secondly, reacted thick product dimethyl sulfone
Purity is of a relatively high, therefore aftertreatment technology is simple.Again, the source of catalyst and preparation are simple, and catalyst service life
Longer.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, to help being more fully understood that the present invention, but this
Bright protection domain is not limited in these embodiments.
Embodiment 1
By specifically comprising the following steps that of the production technology of DMSO production dimethyl sulfone
(1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, in fixed bed reactors
Filling NDA catalyst, the entrance in fixed bed squeezes into mixed liquor continuously by dosing pump, and mixed liquor is along catalyst
Bed flow also reacts under the effect of catalyst, and reaction temperature is maintained at 50 DEG C, and mixed liquor is edge catalysis in fixed bed
Agent bed flow, the time of staying is 30min, flows continually out reactant liquor in fixed bed exit；Wherein, dimethyl sulfoxide and dioxygen
The active ingredient weight ratio of water is 1:0.55, and the concentration of hydrogen peroxide is 10%, before controlling mixed liquor entrance fixed bed reactors
PH value is 4；The particle diameter of NDA is 1.2～1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.Gu
Fixed bed reactor is divided into 3 reaction zones, and the temperature of the reaction zone that mixed liquor first flows through is than the reaction zone flowed through after mixed liquor
Temperature is high about 5 DEG C, is filled with filler in reaction zone, catalyst the beds formed and the filler interlayer formed by filler
Every filling in the reaction region.
(2) crystallization: be conveyed in crystallizing evaporator by the reactant liquor of the collection in step (1) and carry out crystallization treatment, generates
Dimethyl sulfone crystal；
(3) solid-liquid separation: the liquid in the solidliquid mixture in step (2) and dimethyl sulfone crystal are centrifuged point
From, obtain dimethyl sulfone crystal；
(4) it is dried: the 45 DEG C of dried in vacuum desiccator of the dimethyl sulfone crystal in step (3), obtains pure
Product dimethyl sulfone.
Final available purity is the dimethyl sulfone product of 99.85%, and wherein the conversion ratio of dimethyl sulfoxide is 98.6%,
Dimethyl sulfone selectivity is 99.1%.
Embodiment 2
By specifically comprising the following steps that of the production technology of DMSO production dimethyl sulfone
(1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, fill out in fixed bed reactors
Filling NDA catalyst, the entrance in fixed bed squeezes into mixed liquor continuously by dosing pump, and mixed liquor is along catalyst bed
Laminar flow also reacts under the effect of catalyst, and reaction temperature is maintained at 40 DEG C, mixed liquor in fixed bed along catalyst
Bed flow, the time of staying is 20min, flows continually out reactant liquor in fixed bed exit；；Wherein, dimethyl sulfoxide and dioxygen
The active ingredient weight ratio of water is 1:0.7, and the concentration of hydrogen peroxide is 5%, controls the pH before mixed liquor enters fixed bed reactors
Value is 6；The particle diameter of NDA is 1.2～1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.Fixing
Bed reactor is divided into 3 reaction zones, and the temperature of the reaction zone that mixed liquor first flows through is than the temperature of the reaction zone flowed through after mixed liquor
Du Gaoyue 3 DEG C, filler and described catalyst load with the form of the mixture of the two in described reaction zone.
(2) crystallization: be conveyed in crystallizing evaporator by the reactant liquor of the collection in step (1) and carry out crystallization treatment, generates
Dimethyl sulfone crystal；
(3) solid-liquid separation: the liquid in the solidliquid mixture in step (2) and dimethyl sulfone crystal are centrifuged point
From, obtain dimethyl sulfone crystal；
(4) it is dried: the 60 DEG C of dried in vacuum desiccator of the dimethyl sulfone crystal in step (3), obtains pure
Product dimethyl sulfone.
Final available purity is the dimethyl sulfone product of 99.51%, and wherein the conversion ratio of dimethyl sulfoxide is 97.1%,
Dimethyl sulfone selectivity is 97.6%.
Embodiment 3
By specifically comprising the following steps that of the production technology of DMSO production dimethyl sulfone
(1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, fill out in fixed bed reactors
Filling NDA catalyst, the entrance in fixed bed squeezes into mixed liquor continuously by dosing pump, and mixed liquor is along catalyst bed
Laminar flow also reacts under the effect of catalyst, and reaction temperature is maintained at 60 DEG C, mixed liquor in fixed bed along catalyst
Bed flow, the time of staying is 25min, flows continually out reactant liquor in fixed bed exit；Wherein, dimethyl sulfoxide and hydrogen peroxide
Active ingredient weight ratio be 1:0.4, the concentration of hydrogen peroxide is 15%, controls mixed liquor and enters the pH value before fixed bed reactors
It is 3；The particle diameter of NDA is 1.2～1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.Fixed bed
Reactor is divided into 2 reaction zones, and the temperature of the reaction zone that mixed liquor first flows through is than the temperature of the reaction zone flowed through after mixed liquor
High about 8 DEG C, reaction zone is filled with filler, catalyst the beds formed and the packing layer formed by filler interval dress
Fill out in the reaction region.
(2) crystallization: be conveyed in crystallizing evaporator by the reactant liquor of the collection in step (1) and carry out crystallization treatment, generates
Dimethyl sulfone crystal；
(3) solid-liquid separation: the liquid in the solidliquid mixture in step (2) and dimethyl sulfone crystal are centrifuged point
From, obtain dimethyl sulfone crystal；
(4) it is dried: the 35 DEG C of dried in vacuum desiccator of the dimethyl sulfone crystal in step (3), obtains pure
Product dimethyl sulfone.
Final available purity is the dimethyl sulfone product of 99.58%, and wherein the conversion ratio of dimethyl sulfoxide is 98.8%,
Dimethyl sulfone selectivity is 98.1%.
Embodiment 4
On the basis of embodiment 3, the dimethyl sulfone crystal separated in cold water washing step (4), the cleaning mixture after washing
It is conveyed in the crystallizer to step (3) crystallization treatment and is dried.
Final available purity is the dimethyl sulfone product of 99.82%, and wherein the conversion ratio of dimethyl sulfoxide is 91.5%,
Dimethyl sulfone selectivity is 96.1%.
Embodiment 5
By specifically comprising the following steps that of the production technology of DMSO production dimethyl sulfone
(1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, fill out in fixed bed reactors
Filling NDA catalyst, the entrance in fixed bed squeezes into mixed liquor continuously by dosing pump, and mixed liquor is along catalyst bed
Laminar flow also reacts under the effect of catalyst, and reaction temperature is maintained at 50 DEG C, mixed liquor in fixed bed along catalyst
Bed flow, the time of staying is 30min, flows continually out reactant liquor in fixed bed exit；Wherein, dimethyl sulfoxide and hydrogen peroxide
Active ingredient weight ratio be 1:0.55, the concentration of hydrogen peroxide is 12%, controls mixed liquor and enters the pH before fixed bed reactors
Value is 4；The particle diameter of NDA is 1.2～1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.Fixing
Bed reactor is divided into 3 reaction zones, and the temperature of the reaction zone that mixed liquor first flows through is than the temperature of the reaction zone flowed through after mixed liquor
Du Gaoyue 5 DEG C, is filled with filler in reaction zone, catalyst the beds formed and the packing layer formed by filler interval
Filling is in the reaction region.
(2) crystallization: be conveyed in crystallizing evaporator by the reactant liquor of the collection in step (1) and carry out crystallization treatment, generates
Dimethyl sulfone crystal；
(3) solid-liquid separation: the liquid in the solidliquid mixture in step (2) and dimethyl sulfone crystal are centrifuged point
From, obtain dimethyl sulfone crystal and residual liquid, by pump, residual liquid is delivered to fixed bed reactors entrance；
(4) it is dried: the 45 DEG C of dried in vacuum desiccator of the dimethyl sulfone crystal in step (3), obtains pure
Product dimethyl sulfone.
Final available purity is the dimethyl sulfone product of 99.58%, and wherein the conversion ratio of dimethyl sulfoxide is 99.3%,
Dimethyl sulfone selectivity is 99.1%.
Embodiment 6
By specifically comprising the following steps that of the production technology of DMSO production dimethyl sulfone
(1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, fill out in fixed bed reactors
Filling NDA catalyst, the entrance in fixed bed squeezes into mixed liquor continuously by dosing pump, and mixed liquor is along catalyst bed
Laminar flow also reacts under the effect of catalyst, and reaction temperature is maintained at 45 DEG C, mixed liquor in fixed bed along catalyst
Bed flow, the time of staying is 20min, flows continually out reactant liquor in fixed bed exit；Wherein, dimethyl sulfoxide and hydrogen peroxide
Active ingredient weight ratio be 1:0.55, the concentration of hydrogen peroxide is 10%, controls mixed liquor and enters the pH before fixed bed reactors
Value is 4；The particle diameter of NDA is 1.2～1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.Fixing
Bed reactor is divided into 3 reaction zones, and the temperature of the reaction zone that mixed liquor first flows through is than the temperature of the reaction zone flowed through after mixed liquor
Du Gaoyue 5 DEG C, is filled with filler in reaction zone, catalyst the beds formed and the packing layer formed by filler interval
Filling is in the reaction region.
(2) crystallization: be conveyed in crystallizing evaporator by the reactant liquor of the collection in step (1) and carry out crystallization treatment, generates
Dimethyl sulfone crystal；
(3) solid-liquid separation: the liquid in the solidliquid mixture in step (2) and dimethyl sulfone crystal are centrifuged point
From, obtain dimethyl sulfone crystal；
(4) it is dried: the 35 DEG C of dried in vacuum desiccator of the dimethyl sulfone crystal in step (3), obtains pure
Product dimethyl sulfone.
Final available purity is the dimethyl sulfone product of 99.56%, and wherein the conversion ratio of dimethyl sulfoxide is 97.2%,
Dimethyl sulfone selectivity is 99.1%.
Embodiment 7
By specifically comprising the following steps that of the production technology of DMSO production dimethyl sulfone
(1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, fill out in fixed bed reactors
Filling NDA catalyst, the entrance in fixed bed squeezes into mixed liquor continuously by dosing pump, and mixed liquor is along catalyst bed
Laminar flow also reacts under the effect of catalyst, and reaction temperature is maintained at 50 DEG C, mixed liquor in fixed bed along catalyst
Bed flow, the time of staying is 30min, flows continually out reactant liquor in fixed bed exit；Wherein, dimethyl sulfoxide and hydrogen peroxide
Active ingredient weight ratio be 1:0.55, the concentration of hydrogen peroxide is 10%, controls mixed liquor and enters the pH before fixed bed reactors
Value is 4；The particle diameter of NDA is 1.2～1.8mm, and porosity is more than 25%, and specific surface area is more than 260m2/g.Fixing
Bed reactor is divided into 3 reaction zones, and the temperature of the reaction zone that mixed liquor first flows through is than the temperature of the reaction zone flowed through after mixed liquor
Du Gaoyue 5 DEG C, is filled with filler in reaction zone, catalyst the beds formed and the packing layer formed by filler interval
Filling is in the reaction region.
(2) crystallization: be conveyed in crystallizing evaporator by the reactant liquor of the collection in step (1) and carry out crystallization treatment, generates
Dimethyl sulfone crystal；
(3) solid-liquid separation: the liquid in the solidliquid mixture in step (2) and dimethyl sulfone crystal are centrifuged point
From, obtain dimethyl sulfone crystal；
(4) it is dried: the 85 DEG C of dried in vacuum desiccator of the dimethyl sulfone crystal in step (3), obtains pure
Product dimethyl sulfone.
Final available purity is the dimethyl sulfone product of 99.76%, and wherein the conversion ratio of dimethyl sulfoxide is 94.1%,
Dimethyl sulfone selectivity is 95.1%.
Embodiment 8
Except using crystallisation by cooling in step (3), other are with embodiment 1, and final available purity is the dimethyl of 99.05%
Sulfone product, wherein the conversion ratio of dimethyl sulfoxide is 83.1%, and dimethyl sulfone selectivity is 97.6%.
Embodiment 9
Except using decompression distillation crystallization in step (3), other are with embodiment 1, and final available purity is the two of 99.71%
Methyl sulfone product, wherein the conversion ratio of dimethyl sulfoxide is 98.4%, and dimethyl sulfone selectivity is 99.1%.
Embodiment 10
Except using the mode isolated dimethyl sulfone crystal filtered in step (4), other finally can obtain with embodiment 1
To the dimethyl sulfone product that purity is 99.31%, wherein the conversion ratio of dimethyl sulfoxide is 96.2%, and dimethyl sulfone selectivity is
97.1%.
Comparative example 1
Except being not added with NDA catalyst, other are with embodiment 1.The purity of the dimethyl sulfone product after Jing Zhi is only
90.01%, wherein the conversion ratio of dimethyl sulfoxide is 23.2%, and dimethyl sulfone selectivity is 81.3%.
Comparative example 2
NDA catalyst is replaced with titanium-silicon molecular sieve catalyst, and other are with embodiment 1.Diformazan after Jing Zhi
The purity of base sulfone product is only 95.11%, and wherein the conversion ratio of dimethyl sulfoxide is 72.1%, and dimethyl sulfone selectivity is
97.1%.
By comparative example 1 and comparative example 1 and comparative example 2, it is known that, the present invention uses NDA as with
Dimethyl sulfoxide oxidation generates the catalyst of dimethyl sulfone, and under identical stoichiometry and reaction condition, dimethyl is sub-
The conversion ratio of sulfone and the selectivity of dimethyl sulfone are greatly improved, and the purity of i.e. thick product dimethyl sulfone can be greatly
Increase, can reach, by the method for the identical purification condition present invention, the refined dimethyl sulfone product that purity is more than 99%.Therefore
Hinge structure of the present invention, energy consumption reduces, and the production cycle shortens, and production efficiency improves, and additionally aftertreatment technology is simple.
By comparing embodiment 3 and embodiment 4, it is known that, after the dimethyl sulfone crystal separated in cold water washing step (4).
Can further improve the product purity of dimethyl sulfone, but the conversion ratio of DMSO and the yield of product can be reduced, right
It is contemplated that add this step when output requires higher product to product purity, the cleaning mixture after washing is sent in crystallizer
Crystallization treatment can reduce the loss of product.
Experiment proves that, NDA catalyst used in the present invention through 5 times recycle after, its catalytic efficiency
Still having the 95～98% of first use, recycle through 10 times, its catalytic efficiency still has about the 90% of first use.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. the production technology of a dimethyl sulfone, it is characterised in that comprise the steps:
(1) oxidation reaction: DMSO and hydrogen peroxide are mixed in proportion formation mixed liquor, fills in fixed bed reactors
Catalyst, the entrance in fixed bed squeezes into mixed liquor continuously, and mixed liquor is along catalyst bed laminar flow and under the effect of catalyst
Reacting, mixed liquor along catalyst bed laminar flow, flows continually out reactant liquor in fixed bed exit in fixed bed；Described urge
Agent is 2,6-naphthalenedicarboxylic acid；
(2) crystallization: reactant liquor is flowed out in the fixed bed exit in step (1) and is pumped in crystallizer carry out crystallization treatment, raw
Become dimethyl sulfone crystal；
(3) solid-liquid separation: the liquid in the solidliquid mixture in step (2) is separated with dimethyl sulfone crystal, obtains two
Methyl sulfone crystal and debris；
(4) it is dried: the dimethyl sulfone crystal in step (3) is dried process, obtains pure product dimethyl sulfone.
The production technology of dimethyl sulfone the most according to claim 1, it is characterised in that the reaction temperature in step (1) is protected
Holding at 40～60 DEG C, the time of staying is 20～30min.
The production technology of dimethyl sulfone the most according to claim 2, it is characterised in that the concentration of described hydrogen peroxide is 5%
～15%.
The production technology of dimethyl sulfone the most according to claim 3, it is characterised in that enter fixed bed in step (1)
In mixed liquor, dimethyl sulfoxide is 1:0.4～0.7 with the active ingredient weight ratio of hydrogen peroxide.
The production technology of dimethyl sulfone the most according to claim 4, it is characterised in that the particle diameter of described NDA
Being 1.2～1.8mm, porosity is more than 25%, and specific surface area is more than 260m2/g。
6. according to the production technology of the dimethyl sulfone described in Claims 1 to 5 any one, it is characterised in that solid in step (1)
Fixed bed reactor is divided at least two reaction zone, separates with porous plate and be provided with gap between each reaction zone.
The production technology of dimethyl sulfone the most according to claim 6, it is characterised in that in step (1), mixed liquor first flows through
The temperature of reaction zone be higher than after the temperature of reaction zone that flows through.
The production technology of dimethyl sulfone the most according to claim 7, it is characterised in that the reaction zone that mixed liquor first flows through
Temperature is higher than the temperature of the reaction zone flowed through after mixed liquor 3～8 DEG C.
The production technology of dimethyl sulfone the most according to claim 8, it is characterised in that be filled with in described reaction zone
Material.
The production technology of dimethyl sulfone the most according to claim 9, it is characterised in that described filler and described catalyst
In loading with the form of the mixture of the two in described reaction zone；Or the beds that formed by catalyst and by filler shape
The packing layer interval filling become is in the reaction region；Or the debris in step (2) is flow in fixed bed by blowback；Or step
(2) crystallization operation in is a kind of in evaporative crystallization, crystallisation by cooling and decompression distillation crystallization；Or step (3) can use centrifugal or
The technique filtered carries out solid-liquid separation；Or the baking temperature in step (4) controls at 35～85 DEG C；Or being dried in step (4)
Temperature controls at 45～60 DEG C；Or the dimethyl sulfone crystal separated in cold water washing step (3), the cleaning mixture after washing is conveyed into
In crystallizer to step (2).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100440A (en) * | 1985-04-01 | 1986-07-16 | 华东化工学院 | A kind of method for preparing sulfoxide |
| CN1397548A (en) * | 2001-07-13 | 2003-02-19 | 徐连成 | Process for preparing dimethyl sulfone |
| CN102675767A (en) * | 2011-03-08 | 2012-09-19 | 保龄宝生物股份有限公司 | Novel PVC (polyvinyl chloride) plasticizer |
| CN104557627A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100440A (en) * | 1985-04-01 | 1986-07-16 | 华东化工学院 | A kind of method for preparing sulfoxide |
| CN1397548A (en) * | 2001-07-13 | 2003-02-19 | 徐连成 | Process for preparing dimethyl sulfone |
| CN102675767A (en) * | 2011-03-08 | 2012-09-19 | 保龄宝生物股份有限公司 | Novel PVC (polyvinyl chloride) plasticizer |
| CN104557627A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfone |
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