CN106083666B - A kind of production technology of dimethyl sulfone - Google Patents
A kind of production technology of dimethyl sulfone Download PDFInfo
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- CN106083666B CN106083666B CN201610415003.0A CN201610415003A CN106083666B CN 106083666 B CN106083666 B CN 106083666B CN 201610415003 A CN201610415003 A CN 201610415003A CN 106083666 B CN106083666 B CN 106083666B
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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, a kind of production technology of dimethyl sulfone is specifically disclosed, comprises the following steps (1) oxidation reaction：Dimethyl sulfoxide (DMSO) and hydrogen peroxide are mixed to form mixed liquor in proportion, the catalyst filling in fixed bed reactors, mixed liquor is continuously squeezed into the entrance of fixed bed, mixed liquor is reacted along catalyst bed laminar flow and in the presence of catalyst, mixed liquor, along catalyst bed laminar flow, reaction solution is flowed continually out in fixed bed exit in fixed bed；The catalyst is 2,6 naphthalenedicarboxylic acids；(2) crystallize；(3) separation of solid and liquid.(4) dry.The present invention, as catalyst, greatly accelerates the reaction speed of the oxidation reaction by using 2,6 naphthalenedicarboxylic acids.The present invention may be such that the energy consumption of dimethyl sulfone is reduced using new catalyst, and the production cycle shortens, and production efficiency is improved, economic benefit increase.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of production technology of dimethyl sulfone.
Background technology
Dimethyl sulfone is as a kind of organic sulfur compound, and the ability with generation insulin in enhancing human body is simultaneously to carbohydrate
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 new old
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 industrial production of country's dimethyl sulfone is mainly obtained by dimethyl sulfoxide (DMSO) through nitric acid oxidation at present, and this method is present
Reaction temperature height, high energy consumption, technological process length, the problems such as accessory substance is more, while environmental pollution is more serious.In the prior art,
Patent CN 1150164C disclose the preparation method of dimethyl sulfone, and this method includes oxidation reaction, and cooling is separated out, and is filtered, and is taken off
Water, the step such as drying, wherein, oxidation reaction is dimethyl sulfoxide (DMSO) and hydrogen peroxide reaction generation dimethyl sulfone, dimethyl sulfoxide (DMSO) with
The effective ingredient weight ratio of hydrogen peroxide is 1:0.44~0.65, reaction temperature is 80~150 DEG C, 4~40 hours reaction time.Should
Oxidation reaction does not use catalyst in method, although decreased compared to nitrate method reaction temperature, but temperature is still higher,
Reaction time is long.Patent public affairs CN 103288692 B have opened a kind of method that dimethyl sulfone is prepared by dimethyl sulfoxide (DMSO), the party
It is oxidant that method, which is dimethyl sulfoxide (DMSO) in ozone, and 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 reaction time is 0.1-10 hours.Its reaction temperature and reaction time model
Enclose value larger, from its specification, its preferred reaction temperature is still higher, and the reaction time is preferably 1~5 hour, still
It is partially long.
In summary, need a kind of new process of exploitation badly or improve existing process progress and prepare dimethyl sulfone so that
Preparation method is simple, accelerates reaction speed, while reducing reaction temperature to a certain extent, reduces energy consumption, shortens the production cycle, carry
High efficiency, increases economic benefit.
The content of the invention
The purpose of the present invention is a kind of dimethyl sulfone production technology that reaction speed is fast, reaction temperature is relatively low of exploitation.
Above-mentioned purpose is to be achieved through the following technical solutions：A kind of production technology of dimethyl sulfone, comprises the following steps：
(1) oxidation reaction：Dimethyl sulfoxide (DMSO) and hydrogen peroxide are mixed to form mixed liquor in proportion, catalysis is filled in fixed bed reactors
Agent, mixed liquor is continuously squeezed into the entrance of fixed bed, and mixed liquor is carried out along catalyst bed laminar flow and in the presence of catalyst
Reaction, mixed liquor, along catalyst bed laminar flow, reaction solution is flowed continually out in fixed bed exit in fixed bed；The catalyst
For 2,6- naphthalenedicarboxylic acids；(2) crystallize：Fixed bed exit outflow reaction solution in step (1) is pumped in crystallizer and carried out
Crystallization treatment, generates dimethyl sulfone crystal；(3) separation of solid and liquid：By the liquid and dimethyl in the solidliquid mixture in step (2)
Sulfone crystal is separated, and obtains dimethyl sulfone crystal and Liquid Residue.(4) dry：Enter through the dimethyl sulfone crystal in step (3)
Row drying process, obtains pure product dimethyl sulfone.The present invention is used as dimethyl sulfoxide (DMSO) oxygen by using 2,6- naphthalenedicarboxylic acids
Metaplasia greatly accelerates the reaction speed of the oxidation reaction into the catalyst of dimethyl sulfone, in relatively lower temp (40~60
DEG C) under, the high conversion rate for only needing the short period (20~30min) that dimethyl sulfoxide (DMSO) can be made is reacted up to 95% or so, therefore thick production
The purity of product dimethyl sulfone is of a relatively high, in last handling process only need separate solid catalyst, into dimethyl sulfone crystallization and point
From it is more than 99% high purity dimethyl sulfone product that processing, which is then dried, and can reach purity.The present invention uses new
Catalyst may be such that dimethyl sulfone energy consumption reduction, the production cycle shorten, production efficiency improve, economic benefit increase.
Characterized through research, it is oxidation generation two that NDA is applied to dimethyl sulfoxide (DMSO) in the present invention as catalyst
During methyl sulfone, catalytic reaction is carried out on the sour positions of B of NDA, i.e., NDA is in theory
It is used as a kind of solid acid catalyst, its sour position of i.e. B of avtive spot for playing catalytic action.Experimental study shows, solid acid catalyst
Acid amount on surface has obvious relation with its catalytic activity and selectivity, and the acid of NDA catalyst of the present invention is strong
Degree is more suitable, shows higher catalytic activity for it and provides possibility.In addition, solid NDA itself is porous
Structure, even aperture distribution, specific surface area is larger, is a kind of preferable carrier, can as the avtive spot of its own carrier.
Therefore the making of this catalyst is simple, without preparing synthesis in addition.
Fixed bed reactors have lot of advantages, when completing same production task, and required catalyst amount is minimum；Bed
Residence time of material can strictly be controlled in layer, and Temperature Distribution can be adjusted suitably, be conducive to improving the conversion ratio that chemically reacts and
Selectivity, and catalyst is not easy to wear in fixed bed, is conducive to extending the service life of catalyst.Due to present invention uses 2,
6- naphthalenedicarboxylic acid catalyst so that reaction and residence time that mixed liquor is in fixed bed greatly shorten, to realize continuity
Production is provided may.
Preferably, further technical scheme is：Reaction temperature in step (1) is maintained at 40~60 DEG C, during stop
Between be 20~30min.The above-mentioned reaction temperature of selection and reaction time, are on the one hand due to have used NDA conduct
Catalyst so that only need above-mentioned reaction temperature and reaction time just to reach the conversion ratio of preferable dimethyl sulfoxide (DMSO), can
Reduce energy consumption and production costs, on the other hand at 40~60 DEG C, NDA has preferable catalytic activity.Herein
Reaction time and reaction temperature are the preferably result obtained after test of many times, are not represented in other reaction time
Or the present invention can not be realized in range of reaction temperature or is reached using the technique effect reached after the present invention.
Further technical scheme is：The concentration of the hydrogen peroxide is 5%~15%.Hydrogen peroxide is right as oxidant
There is higher selectivity in the oxidation of dimethyl sulfone, and decomposing hydrogen dioxide solution is oxygen and water, will not produce accessory substance and harmful
Material, product odorless can further reduce separation costs, and its operating condition is gentle, and equipment will not be produced seriously
Corrosion.Therefore, it is environment-friendly according to the inventive method.In addition, the concentration of hydrogen peroxide is unsuitable excessive, it is to avoid oxidation reaction is excessively acute
It is strong to cause local temperature too high, and then cause the generation of accessory substance, or even the activity and service life of catalyst are influenceed, study table
Bright, the present invention uses fixed-bed process, is strict temperature control, and 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 all of a relatively high.
It is preferred that, the pH value of mixed liquor is controlled 3~6, and research shows, under the conditions of this, hence it is evident that improved for dimethyl sulfone
Selectivity, while higher dimethyl sulfoxide (DMSO) conversion ratio and oxidant effective rate of utilization can also be obtained.On the one hand, in acid bar
Under part, hydrogen peroxide is relatively stablized, on the other hand, under the conditions of this pH, good acid environment is provided for NDA, is conducive to
Improve its catalytic activity.
Further technical scheme is：Enter dimethyl sulfoxide (DMSO) and hydrogen peroxide in the mixed liquor of fixed bed in step (1)
Effective 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 the 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：Fixed bed reactors are divided at least two reaction zones in step (1), each reaction
Separated between area with porous plate and be provided with gap.Because bed pressure drop is directly proportional to bed height, bed increases, and flow resistance is just
Increase.It is so designed that the problem of can preventing reaction solution concentration and non-uniform temperature in bed effectively reduces bed pressure drop, resistance
It is small；Surface Renewal between liquid-liquid interface between liquid-solid interface is fast, improves the conversion ratio and selectivity of reaction.In order to drop
Low bed layer pressure drop, can control the voidage of beds, the voidage of preferred catalyst bed is 0.3~0.4.
Further technical scheme is：The temperature for the reaction zone that mixed liquor is first flowed through is flowed through after being higher than in step (1)
The temperature of reaction zone.Because this oxidation reaction is exothermic reaction, with the flowing of mixed liquor beds, temperature gradually body
Height, to ensure that catalyst has preferable catalytic efficiency, mixed liquor is after the latter reaction zone of inflow of a reaction zone, to latter
The catalyst of reaction zone is preheated so that reaction temperature is stable in preferably condition, it is to avoid in fixed bed outlet section reaction solution
Temperature is too high and influences catalytic efficiency, or even temperature runaway phenomenon occurs.
Further technical scheme is：The temperature for the reaction zone that mixed liquor is first flowed through is than the reaction zone that is flowed through after mixed liquor
Temperature it is high 3~8 DEG C.Reaction zone is settable 2~4, experiment proves that, catalytic efficiency of catalyst is higher under the conditions of this, oxygen
Change reaction relatively stable, gentle.
Further technical scheme is：Filler is filled with the reaction zone.It is so designed that, is on the one hand conducive to drop
Low bed layer pressure drop, another aspect dilute catalyst, it is to avoid temperature runaway.
Further technical scheme is：The filler and the catalyst in being loaded in the form of the mixture of the two
In the reaction zone.
Further technical scheme is：The beds formed by catalyst and the packing layer interval formed by filler
Filling is in the reaction region.
Further technical scheme is：Liquid Residue in step (2) is flow in fixed bed by blowback.In this way, can carry
The utilization rate of high reactant, improves conversion ratio, while reducing the discharge of waste liquid.The relatively low work of the reaction-ure conversion-age that is particularly suitable for use in
Used under the conditions of skill.
Further technical scheme is：Crystallization operation in step (2) is evaporative crystallization, crystallisation by cooling and vacuum distillation
It is a kind of in crystallization.
In the prior art, because the conversion ratio and selectivity of dimethyl sulfoxide (DMSO) are relatively low, after general preliminary dimethyl sulfone crystallization
It need to dissolve again, the agitation and filtration removal of impurity, recrystallization obtains pure dimethyl sulfone product, or even in order to meet wanting for purity
Ask, repetitious to dimethyl sulfone need to wash, dissolve, crystallize, so, not only complex process, production cycle are long, and product is received
Rate is relatively low.It is of the invention then only need primary crystallization processing can meet the requirement of product purity.
Further technical scheme is：Step (3) can carry out separation of solid and liquid using the technique of centrifugation or filtering.
Further technical scheme is：Drying temperature in step (4) is controlled at 35~85 DEG C.Dimethyl sulfone is at 25 DEG C
Microsublimation, accelerates to 60 DEG C of rate of sublimation, thus the progress easily under cryogenic vacuum of dimethyl sulfone product drying.Therefore drying temperature
It is unsuitable too high, it is to avoid dimethyl sulfone distillation causes product yield to reduce.
Further technical scheme is：Drying temperature in step (4) is controlled at 45~60 DEG C.Drying temperature is preferably not
It is now quickening rate of drying, it is contemplated that vacuum drying more than 60 DEG C.
Further technical scheme is：The dimethyl sulfone crystal of separation, the washing after washing in cold water washing step (3)
Liquid is conveyed into the crystallizer into step (2).In this way, can further improve the product purity of dimethyl sulfone.
Further technical scheme is：Step (3) also includes the step concentrated to the filtrate in step (2) before carrying out
Suddenly.Concentration process can be that evaporation and concentration or membrane filtration are handled, dense by improving dimethyl sulfone after concentration operation
Degree, it is easy to carry out the crystallization operation of dimethyl sulfone.
In summary, NDA catalyst aoxidizes the reaction for generating dimethyl sulfone to dimethyl sulfoxide (DMSO) in the present invention
Higher selectivity is shown, compared with prior art, on the premise of reaction temperature is reduced, the reaction time still can larger journey
The shortening of degree, energy consumption reduction, the production cycle shortens, and production efficiency is improved；Secondly, reacted crude 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
It is longer.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, to help more fully understanding the present invention, but this hair
Bright protection domain is not limited in these embodiments.
Embodiment 1
The production technology for producing dimethyl sulfone by dimethyl sulfoxide (DMSO) is comprised the following steps that：
(1) oxidation reaction:Dimethyl sulfoxide (DMSO) and hydrogen peroxide are mixed to form mixed liquor in proportion, in fixed bed reactors
NDA catalyst is filled, mixed liquor continuously squeezed into by measuring pump in the entrance of fixed bed, mixed liquor is along catalyst
Bed flow is simultaneously reacted in the presence of catalyst, and reaction temperature is maintained at 50 DEG C, and mixed liquor is in fixed bed along catalysis
Agent bed flow, the residence time is 30min, and reaction solution is flowed continually out in fixed bed exit；Wherein, dimethyl sulfoxide (DMSO) and dioxygen
The effective ingredient weight ratio of water is 1:0.55, the concentration of hydrogen peroxide is 10%, and control mixed liquor enters before 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 is first flowed through is than the reaction zone that is flowed through after mixed liquor
Temperature is high about 5 DEG C, and filler, the beds formed by catalyst and the filler interlayer formed by filler are filled with reaction zone
Every filling in the reaction region.
(2) crystallize：The reaction solution of collection in step (1) is conveyed into crystallizing evaporator and carries out crystallization treatment, is generated
Dimethyl sulfone crystal；
(3) separation of solid and liquid：Liquid in solidliquid mixture in step (2) and dimethyl sulfone crystal are subjected to centrifugation point
From obtaining dimethyl sulfone crystal；
(4) dry：Through the dimethyl sulfone crystal in step (3), 45 DEG C of drying process in vacuum desiccator, obtain pure
Product dimethyl sulfone.
Final to can obtain the dimethyl sulfone product that purity is 99.85%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 98.6%,
Dimethyl sulfone is selectively 99.1%.
Embodiment 2
The production technology for producing dimethyl sulfone by dimethyl sulfoxide (DMSO) is comprised the following steps that：
(1) oxidation reaction:Dimethyl sulfoxide (DMSO) is mixed to form mixed liquor in proportion with hydrogen peroxide, is filled out in fixed bed reactors
NDA catalyst is filled, mixed liquor continuously squeezed into by measuring pump in the entrance of fixed bed, mixed liquor is along catalyst bed
Laminar flow is simultaneously reacted in the presence of catalyst, and reaction temperature is maintained at 40 DEG C, and mixed liquor is in fixed bed along catalyst
Bed flow, the residence time is 20min, and reaction solution is flowed continually out in fixed bed exit；；Wherein, dimethyl sulfoxide (DMSO) and dioxygen
The effective ingredient weight ratio of water is 1:0.7, the concentration of hydrogen peroxide is 5%, the pH that control mixed liquor enters before fixed bed reactors
It is worth for 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.It is fixed
Bed reactor is divided into 3 reaction zones, and the temperature for the reaction zone that mixed liquor is first flowed through is than the temperature of the reaction zone flowed through after mixed liquor
3 DEG C of Du Gaoyue, filler and the catalyst in the form of the mixture of the two in loading in the reaction zone.
(2) crystallize：The reaction solution of collection in step (1) is conveyed into crystallizing evaporator and carries out crystallization treatment, is generated
Dimethyl sulfone crystal；
(3) separation of solid and liquid：Liquid in solidliquid mixture in step (2) and dimethyl sulfone crystal are subjected to centrifugation point
From obtaining dimethyl sulfone crystal；
(4) dry：Through the dimethyl sulfone crystal in step (3), 60 DEG C of drying process in vacuum desiccator, obtain pure
Product dimethyl sulfone.
Final to can obtain the dimethyl sulfone product that purity is 99.51%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 97.1%,
Dimethyl sulfone is selectively 97.6%.
Embodiment 3
The production technology for producing dimethyl sulfone by dimethyl sulfoxide (DMSO) is comprised the following steps that：
(1) oxidation reaction:Dimethyl sulfoxide (DMSO) is mixed to form mixed liquor in proportion with hydrogen peroxide, is filled out in fixed bed reactors
NDA catalyst is filled, mixed liquor continuously squeezed into by measuring pump in the entrance of fixed bed, mixed liquor is along catalyst bed
Laminar flow is simultaneously reacted in the presence of catalyst, and reaction temperature is maintained at 60 DEG C, and mixed liquor is in fixed bed along catalyst
Bed flow, the residence time is 25min, and reaction solution is flowed continually out in fixed bed exit；Wherein, dimethyl sulfoxide (DMSO) and hydrogen peroxide
Effective ingredient weight ratio be 1:0.4, the concentration of hydrogen peroxide is 15%, the pH value that control mixed liquor enters before fixed bed reactors
For 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 for the reaction zone that mixed liquor is first flowed through is than the temperature of the reaction zone flowed through after mixed liquor
It is high about 8 DEG C, filler, the beds formed by catalyst and the packing layer interval dress formed by filler are filled with reaction zone
Fill out in the reaction region.
(2) crystallize：The reaction solution of collection in step (1) is conveyed into crystallizing evaporator and carries out crystallization treatment, is generated
Dimethyl sulfone crystal；
(3) separation of solid and liquid：Liquid in solidliquid mixture in step (2) and dimethyl sulfone crystal are subjected to centrifugation point
From obtaining dimethyl sulfone crystal；
(4) dry：Through the dimethyl sulfone crystal in step (3), 35 DEG C of drying process in vacuum desiccator, obtain pure
Product dimethyl sulfone.
Final to can obtain the dimethyl sulfone product that purity is 99.58%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 98.8%,
Dimethyl sulfone is selectively 98.1%.
Embodiment 4
On the basis of embodiment 3, the dimethyl sulfone crystal of separation, the cleaning solution after washing in cold water washing step (4)
It is conveyed into the crystallizer into step (3) crystallization treatment and is dried.
Final to can obtain the dimethyl sulfone product that purity is 99.82%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 91.5%,
Dimethyl sulfone is selectively 96.1%.
Embodiment 5
The production technology for producing dimethyl sulfone by dimethyl sulfoxide (DMSO) is comprised the following steps that：
(1) oxidation reaction:Dimethyl sulfoxide (DMSO) is mixed to form mixed liquor in proportion with hydrogen peroxide, is filled out in fixed bed reactors
NDA catalyst is filled, mixed liquor continuously squeezed into by measuring pump in the entrance of fixed bed, mixed liquor is along catalyst bed
Laminar flow is simultaneously reacted in the presence of catalyst, and reaction temperature is maintained at 50 DEG C, and mixed liquor is in fixed bed along catalyst
Bed flow, the residence time is 30min, and reaction solution is flowed continually out in fixed bed exit；Wherein, dimethyl sulfoxide (DMSO) and hydrogen peroxide
Effective ingredient weight ratio be 1:0.55, the concentration of hydrogen peroxide is 12%, the pH that control mixed liquor enters before fixed bed reactors
It is worth for 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.It is fixed
Bed reactor is divided into 3 reaction zones, and the temperature for the reaction zone that mixed liquor is first flowed through is than the temperature of the reaction zone flowed through after mixed liquor
5 DEG C of Du Gaoyue, is filled with filler, the beds formed by catalyst and the packing layer interval formed by filler in reaction zone
Filling is in the reaction region.
(2) crystallize：The reaction solution of collection in step (1) is conveyed into crystallizing evaporator and carries out crystallization treatment, is generated
Dimethyl sulfone crystal；
(3) separation of solid and liquid：Liquid in solidliquid mixture in step (2) and dimethyl sulfone crystal are subjected to centrifugation point
From obtaining dimethyl sulfone crystal and raffinate, raffinate be delivered into fixed bed reactors entrance by pump；
(4) dry：Through the dimethyl sulfone crystal in step (3), 45 DEG C of drying process in vacuum desiccator, obtain pure
Product dimethyl sulfone.
Final to can obtain the dimethyl sulfone product that purity is 99.58%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 99.3%,
Dimethyl sulfone is selectively 99.1%.
Embodiment 6
The production technology for producing dimethyl sulfone by dimethyl sulfoxide (DMSO) is comprised the following steps that：
(1) oxidation reaction:Dimethyl sulfoxide (DMSO) is mixed to form mixed liquor in proportion with hydrogen peroxide, is filled out in fixed bed reactors
NDA catalyst is filled, mixed liquor continuously squeezed into by measuring pump in the entrance of fixed bed, mixed liquor is along catalyst bed
Laminar flow is simultaneously reacted in the presence of catalyst, and reaction temperature is maintained at 45 DEG C, and mixed liquor is in fixed bed along catalyst
Bed flow, the residence time is 20min, and reaction solution is flowed continually out in fixed bed exit；Wherein, dimethyl sulfoxide (DMSO) and hydrogen peroxide
Effective ingredient weight ratio be 1:0.55, the concentration of hydrogen peroxide is 10%, the pH that control mixed liquor enters before fixed bed reactors
It is worth for 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.It is fixed
Bed reactor is divided into 3 reaction zones, and the temperature for the reaction zone that mixed liquor is first flowed through is than the temperature of the reaction zone flowed through after mixed liquor
5 DEG C of Du Gaoyue, is filled with filler, the beds formed by catalyst and the packing layer interval formed by filler in reaction zone
Filling is in the reaction region.
(2) crystallize：The reaction solution of collection in step (1) is conveyed into crystallizing evaporator and carries out crystallization treatment, is generated
Dimethyl sulfone crystal；
(3) separation of solid and liquid：Liquid in solidliquid mixture in step (2) and dimethyl sulfone crystal are subjected to centrifugation point
From obtaining dimethyl sulfone crystal；
(4) dry：Through the dimethyl sulfone crystal in step (3), 35 DEG C of drying process in vacuum desiccator, obtain pure
Product dimethyl sulfone.
Final to can obtain the dimethyl sulfone product that purity is 99.56%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 97.2%,
Dimethyl sulfone is selectively 99.1%.
Embodiment 7
The production technology for producing dimethyl sulfone by dimethyl sulfoxide (DMSO) is comprised the following steps that：
(1) oxidation reaction:Dimethyl sulfoxide (DMSO) is mixed to form mixed liquor in proportion with hydrogen peroxide, is filled out in fixed bed reactors
NDA catalyst is filled, mixed liquor continuously squeezed into by measuring pump in the entrance of fixed bed, mixed liquor is along catalyst bed
Laminar flow is simultaneously reacted in the presence of catalyst, and reaction temperature is maintained at 50 DEG C, and mixed liquor is in fixed bed along catalyst
Bed flow, the residence time is 30min, and reaction solution is flowed continually out in fixed bed exit；Wherein, dimethyl sulfoxide (DMSO) and hydrogen peroxide
Effective ingredient weight ratio be 1:0.55, the concentration of hydrogen peroxide is 10%, the pH that control mixed liquor enters before fixed bed reactors
It is worth for 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.It is fixed
Bed reactor is divided into 3 reaction zones, and the temperature for the reaction zone that mixed liquor is first flowed through is than the temperature of the reaction zone flowed through after mixed liquor
5 DEG C of Du Gaoyue, is filled with filler, the beds formed by catalyst and the packing layer interval formed by filler in reaction zone
Filling is in the reaction region.
(2) crystallize：The reaction solution of collection in step (1) is conveyed into crystallizing evaporator and carries out crystallization treatment, is generated
Dimethyl sulfone crystal；
(3) separation of solid and liquid：Liquid in solidliquid mixture in step (2) and dimethyl sulfone crystal are subjected to centrifugation point
From obtaining dimethyl sulfone crystal；
(4) dry：Through the dimethyl sulfone crystal in step (3), 85 DEG C of drying process in vacuum desiccator, obtain pure
Product dimethyl sulfone.
Final to can obtain the dimethyl sulfone product that purity is 99.76%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 94.1%,
Dimethyl sulfone is selectively 95.1%.
Embodiment 8
Except crystallisation by cooling is used in step (3), other be the same as Examples 1 finally can obtain the dimethyl that purity is 99.05%
The conversion ratio of sulfone product, wherein dimethyl sulfoxide (DMSO) is 83.1%, and dimethyl sulfone is selectively 97.6%.
Embodiment 9
Except in step (3) using vacuum distillation crystallization, other be the same as Examples 1, finally can obtain that purity is 99.71% two
The conversion ratio of methyl sulfone product, wherein dimethyl sulfoxide (DMSO) is 98.4%, and dimethyl sulfone is selectively 99.1%.
Embodiment 10
Except the middle isolated dimethyl sulfone crystal by the way of filtering of step (4), other be the same as Examples 1 can finally be obtained
To the dimethyl sulfone product that purity is 99.31%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 96.2%, and dimethyl sulfone is selectively
97.1%.
Comparative example 1
Except being not added with NDA catalyst, other be the same as Examples 1.The purity of dimethyl sulfone product after refined is only
90.01%, the wherein conversion ratio of dimethyl sulfoxide (DMSO) is 23.2%, and dimethyl sulfone is selectively 81.3%.
Comparative example 2
NDA catalyst is replaced with into titanium-silicon molecular sieve catalyst, other be the same as Examples 1.Diformazan after refined
The purity of base sulfone product is only 95.11%, and wherein the conversion ratio of dimethyl sulfoxide (DMSO) is 72.1%, and dimethyl sulfone is selectively
97.1%.
Pass through comparative example 1 and comparative example 1 and comparative example 2, it is known that, the present invention in use NDA as with
The catalyst of dimethyl sulfoxide (DMSO) oxidation generation dimethyl sulfone, under identical stoichiometry and reaction condition, dimethyl is sub-
The conversion ratio of sulfone and the selectivity of dimethyl sulfone are greatly improved, i.e. the purity of crude product dimethyl sulfone can be greatly
Increase, the refined dimethyl sulfone product that purity is more than 99% is can reach by the method for the identical purification condition present invention.Therefore
Compared with the prior art, energy consumption reduction, the production cycle shortens the present invention, and production efficiency is improved, and aftertreatment technology is simple in addition.
Pass through comparing embodiment 3 and embodiment 4, it is known that, in cold water washing step (4) after the dimethyl sulfone crystal of separation.
The product purity of dimethyl sulfone is can further improve, but the conversion ratio of dimethyl sulfoxide (DMSO) and the yield of product can be reduced, it is right
This step of addition is contemplated that when output requires higher product to product purity, the cleaning solution after washing is sent into crystallizer
Crystallization treatment can reduce the loss of product.
Experiment proves that, after NDA catalyst used in the present invention is recycled through 5 times, its catalytic efficiency
Still there are 95~98% used for the first time, through 10 recyclings, its catalytic efficiency still has 90% or so used for the first time.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (17)
1. a kind of production technology of dimethyl sulfone, it is characterised in that comprise the following steps：
(1) oxidation reaction：Dimethyl sulfoxide (DMSO) and hydrogen peroxide are mixed to form mixed liquor in proportion, filled in fixed bed reactors
Catalyst, continuously squeezes into mixed liquor, mixed liquor is along catalyst bed laminar flow and in the presence of catalyst in the entrance of fixed bed
Reacted, mixed liquor, along catalyst bed laminar flow, reaction solution is flowed continually out in fixed bed exit in fixed bed；It is described to urge
Agent is 2,6- naphthalenedicarboxylic acids；
(2) crystallize：Fixed bed exit outflow reaction solution in step (1) is pumped in crystallizer and carries out crystallization treatment, it is raw
Into dimethyl sulfone crystal；
(3) separation of solid and liquid：Liquid in solidliquid mixture in step (2) is separated with dimethyl sulfone crystal, two are obtained
Methyl sulfone crystal and Liquid Residue；
(4) dry：Processing is dried through the dimethyl sulfone crystal in step (3), pure product dimethyl sulfone is obtained.
2. the production technology of dimethyl sulfone according to claim 1, it is characterised in that the reaction temperature in step (1) is protected
Hold at 40~60 DEG C, the residence time is 20~30min.
3. the production technology of dimethyl sulfone according to claim 2, it is characterised in that the concentration of the hydrogen peroxide is 5%
~15%.
4. the production technology of dimethyl sulfone according to claim 3, it is characterised in that enter fixed bed in step (1)
The effective ingredient weight ratio of dimethyl sulfoxide (DMSO) and hydrogen peroxide is 1 in mixed liquor:0.4~0.7.
5. the production technology of dimethyl sulfone according to claim 4, it is characterised in that the particle diameter of the NDA
For 1.2~1.8mm, porosity is more than 25%, and specific surface area is more than 260m2/g。
6. the production technology of the dimethyl sulfone according to Claims 1 to 5 any one, it is characterised in that solid in step (1)
Fixed bed reactor, which is divided into, to be separated with porous plate between at least two reaction zones, each reaction zone and is provided with gap.
7. the production technology of dimethyl sulfone according to claim 6, it is characterised in that mixed liquor is first flowed through in step (1)
Reaction zone temperature be higher than after the temperature of reaction zone that flows through.
8. the production technology of dimethyl sulfone according to claim 7, it is characterised in that the reaction zone that mixed liquor is first flowed through
The temperature of reaction zone of the temperature than being flowed through after mixed liquor is high 3~8 DEG C.
9. the production technology of dimethyl sulfone according to claim 8, it is characterised in that filled out in the reaction zone
Material.
10. the production technology of dimethyl sulfone according to claim 9, it is characterised in that the filler and the catalyst
In being loaded in the form of the mixture of the two in the reaction zone.
11. the production technology of dimethyl sulfone according to claim 9, it is characterised in that the catalyst formed by catalyst
Bed and the packing layer interval filling that is formed by filler are in the reaction region.
12. the production technology of dimethyl sulfone according to claim 1, it is characterised in that the Liquid Residue in step (2) passes through
Blowback is flow in fixed bed.
13. the production technology of dimethyl sulfone according to claim 5, it is characterised in that the crystallization operation in step (2) is
It is a kind of in evaporative crystallization, crystallisation by cooling and vacuum distillation crystallization.
14. the production technology of dimethyl sulfone according to claim 5, it is characterised in that step (3) can be using centrifugation or mistake
The technique of filter carries out separation of solid and liquid.
15. the production technology of dimethyl sulfone according to claim 13, it is characterised in that the drying temperature in step (4)
Control is at 35~85 DEG C.
16. the production technology of dimethyl sulfone according to claim 14, it is characterised in that the drying temperature in step (4)
Control is at 45~60 DEG C.
17. the production technology of the dimethyl sulfone according to claim 12~16 any one, it is characterised in that cold water is washed
The dimethyl sulfone crystal of separation in step (3), the cleaning solution after washing is conveyed into the crystallizer into step (2).
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