CN108658824A - A method of preparing the mixture containing tert-butyl hydroperoxide using recycling t-butanol solution - Google Patents
A method of preparing the mixture containing tert-butyl hydroperoxide using recycling t-butanol solution Download PDFInfo
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- CN108658824A CN108658824A CN201810811960.4A CN201810811960A CN108658824A CN 108658824 A CN108658824 A CN 108658824A CN 201810811960 A CN201810811960 A CN 201810811960A CN 108658824 A CN108658824 A CN 108658824A
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- butanol solution
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- butanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Abstract
The present invention provides a kind of methods preparing the mixture containing tert-butyl hydroperoxide using recycling t-butanol solution, recycling t-butanol solution and anhydrous tertiary butanol are wherein mixed to get t-butanol solution, t-butanol solution and sulfuric acid are mixed again and carry out esterification, then esterification reaction solution is mixed with the mixed liquor of hydrogen peroxide and sulfuric acid and carries out oxidation reaction, the mixture containing tert-butyl hydroperoxide is obtained, which is the mixture of tert-butyl hydroperoxide and di-t-butyl peroxide.The present invention is mixed using anhydrous tertiary butanol and recycling t-butanol solution, obtain the t-butanol solution suitable for subsequent step, further by reducing the influence of impurity in recycling t-butanol solution to the control of preparation process and preparation condition, the yield of the mixture containing tert-butyl hydroperoxide is improved.
Description
Technical field
It is the present invention relates to the technical field of organic peroxide, more particularly to a kind of to be contained using recycling t-butanol solution preparation
The method of the mixture of tert-butyl hydroperoxide.
Background technology
Tert-butyl hydroperoxide (TBHP) is a kind of alkane hydrogen organic peroxide, is mainly used as polymerisation (polypropylene
After acids emulsion polymerization monomer eliminate etc.) initiator, be also widely used as synthesizing the raw material of other organic peroxides.
Currently, the domestic main method of synthesizing tertiary butyl hydrogen peroxide is tert-butyl alcohol peroxide passivation, and using acid as catalyst, mistake
The oxidant of hydrogen oxide, catalytic oxidation of tert-butanol prepare TBHP.In modern industrial process, peroxidized t-butyl perbenzoate is most
Common process route is using acid as catalyst, and using hydrogen peroxide as oxidant, the catalysis oxidation oxidation tert-butyl alcohol prepares tertiary butyl mistake
Hydrogen oxide, then carry out reacting conjunction with hydroxide (the common sodium hydroxide or potassium hydroxide) aqueous solution and chlorobenzoyl chloride of alkali metal
At peroxidized t-butyl perbenzoate.Compare the synthetic route of TBHP and peroxidized t-butyl perbenzoate, it can be seen that synthesis peroxidating
During t-butyl perbenzoate, first synthesizing tertiary butyl hydrogen peroxide is needed.
Contain more unreacted tert-butyl hydroperoxide in peroxidized t-butyl perbenzoate crude product, generally uses weak base
Property salting liquid washs peroxidized t-butyl perbenzoate crude product, and in washing process, tert-butyl hydroperoxide is reduced to
The tert-butyl alcohol is dissolved in weakly alkaline solution, then is steamed the tert-butyl alcohol by evaporating, and is recycled t-butanol solution.
It is relatively low to recycle t butanol content in t-butanol solution, chromatographic purity is 98% or so, at present still not no good method
Recycling t-butanol solution is further utilized.
Invention content
In view of this, containing tert-butyl hydroperoxide present invention aims at a kind of prepared using recycling t-butanol solution is provided
Mixture method.The present invention is that raw material prepares tert-butyl hydroperoxide using recycling t-butanol solution, realizes recycling uncle
Butanol solution recycles, and the high income of tert-butyl hydroperoxide.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme：
A method of preparing the mixture containing tert-butyl hydroperoxide, including following step using recycling t-butanol solution
Suddenly：
(1) t-butanol solution will be recycled and anhydrous tertiary butanol mixes, and obtain reaction t-butanol solution；The tertiary fourth of recycling
Content >=20wt% of the middle tert-butyl alcohol of alcoholic solution；
The recycling t-butanol solution, is obtained by following steps：
Using base brine solution wash peroxidized t-butyl perbenzoate crude product, will washing feed liquid layering, lower layer be containing
The waste water of the tert-butyl alcohol；
The waste water containing the tert-butyl alcohol is evaporated, it is to recycle t-butanol solution that gained, which evaporates liquid,；
(2) reaction is mixed with t-butanol solution with sulfuric acid and carries out esterification, obtain the esterification of the hydrogen sulfate tert-butyl ester
Liquid；
(3) hydrogen peroxide and sulfuric acid are mixed, obtains acidic oxidation liquid；
(4) the hydrogen sulfate tert-butyl ester esterifying liquid and the acidic oxidation liquid are mixed, makes the hydrogen sulfate tert-butyl ester that oxygen occur
Change reaction, obtains the mixture containing tert-butyl hydroperoxide.
Preferably, the t butanol content in the recycling t-butanol solution is 20~80wt%.
Preferably, the mass ratio of the recycling t-butanol solution and anhydrous tertiary butanol is 1:0.25~4.33；
The content of the tert-butyl alcohol is 84.0~86.0wt% in the reaction t-butanol solution.
Preferably, in the step (2), the mass fraction of sulfuric acid is 50~98%；
The amount ratio of the substance of the tert-butyl alcohol is 0.249~0.457 in the sulfuric acid and reaction t-butanol solution:1.
Preferably, the temperature of the esterification is 0~30 DEG C.
Preferably, the mass fraction of hydrogen peroxide is 27.5~70% in step (3) hydrogen peroxide；The hydrogen peroxide and
The mass ratio of sulfuric acid is 1:1.15~7.32；
Preferably, uncle in the hydrogen peroxide in step (3) hydrogen peroxide and the step (2) reaction t-butanol solution
The amount ratio of the substance of butanol is 0.975~1.151:1.
Preferably, the temperature of oxidation reaction is 0~40 DEG C in the step (4).
Preferably, after the oxidation reaction further include product separation；The product separation includes the following steps：
Reaction solution obtained by oxidation reaction is subjected to liquid separation, obtains mixture containing tert-butyl hydroperoxide and the lower layer on upper layer
Reuse mother liquor；
The reuse mother liquor is the mixture of sulfuric acid and hydrogen peroxide.
Preferably, it is mixed with hydrogen peroxide instead of sulfuric acid in the reuse mother liquor return to step (3)；
The mass fraction of sulfuric acid is 22.6~35.5% in the reuse mother liquor, the mass fraction of hydrogen peroxide is 4.8~
8.8%；
The mass ratio of the reuse mother liquor and hydrogen peroxide is 1.534~7.714:1.
The present invention provides a kind of methods preparing tert-butyl hydroperoxide using recycling t-butanol solution, wherein will recycling
T-butanol solution and anhydrous tertiary butanol are mixed to get t-butanol solution, then t-butanol solution and sulfuric acid are mixed and be esterified instead
It answers, esterification reaction solution is mixed with the mixture of hydrogen peroxide and sulfuric acid then and carries out oxidation reaction, obtain containing tert-butyl hydroperoxide
The mixture of hydrogen.The present invention is mixed using anhydrous tertiary butanol and recycling t-butanol solution, obtains the tertiary fourth suitable for subsequent step
Alcoholic solution, further by reducing the influence of impurity in recycling t-butanol solution to the control of preparation process and preparation condition,
Improve the yield of the mixture containing tert-butyl hydroperoxide.Embodiment the result shows that, the tertiary fourth of preparation method provided by the invention
Tert-butyl hydroperoxide content can reach 72.69wt% in base hydrogen peroxide mixture, and the content of di-t-butyl peroxide is reachable
To 17.74wt%, yield can reach 94.3%.
Specific implementation mode
The present invention provides a kind of utilizations to recycle the method that t-butanol solution prepares the mixture containing tert-butyl hydroperoxide,
Include the following steps：
(1) t-butanol solution will be recycled and anhydrous tertiary butanol mixes, and obtain reaction t-butanol solution；The tertiary fourth of recycling
Content >=20wt% of the middle tert-butyl alcohol of alcoholic solution；
The recycling t-butanol solution, is obtained by following steps：
Peroxidized t-butyl perbenzoate crude product is washed using base brine solution, by washing feed liquid layering, obtains lower layer
The waste water containing the tert-butyl alcohol；
The waste water containing the tert-butyl alcohol is evaporated, it is to recycle t-butanol solution that gained, which evaporates liquid,；
(2) t-butanol solution is mixed with sulfuric acid and carries out esterification, obtain hydrogen sulfate tert-butyl ester esterifying liquid；
(3) hydrogen peroxide and sulfuric acid are mixed, obtains acidic oxidation liquid；
(4) the hydrogen sulfate tert-butyl ester esterifying liquid and the acidic oxidation liquid are mixed, makes the hydrogen sulfate tert-butyl ester that oxygen occur
Change reaction, obtains the mixture containing tert-butyl hydroperoxide.
The present invention will recycle t-butanol solution and anhydrous tertiary butanol mixing, obtain reaction t-butanol solution.In the present invention
In, it is described recycling t-butanol solution the middle tert-butyl alcohol content >=20wt%, preferably 20~80wt%, more preferably 30~
80wt%；The mass ratio of the recycling t-butanol solution and anhydrous tertiary butanol is preferably 1:0.25~4.33, more preferably 1:0.5
~4, most preferably 1:1~3；The content of the tert-butyl alcohol is preferably 84.0~86.0wt% in the t-butanol solution, more preferably
85wt%.The present invention does not have particular/special requirement to the source of the anhydrous tertiary butanol, uses source known to those skilled in the art
Anhydrous tertiary butanol, such as commercially available anhydrous tertiary butanol.The present invention mixes the recycling t-butanol solution and anhydrous tertiary butanol
Conjunction method does not have particular/special requirement, using mixed method well known to those skilled in the art, can be uniformly mixed the two.
In the present invention, the recycling t-butanol solution is returning in peroxidized t-butyl perbenzoate crude product washing process
Liquid is received, is obtained by following steps：
Peroxidized t-butyl perbenzoate crude product is washed using base brine solution, by washing feed liquid layering, obtains lower layer
The waste water containing the tert-butyl alcohol；
The waste water containing the tert-butyl alcohol is evaporated, it is to recycle t-butanol solution that gained, which evaporates liquid,.
In the present invention, the base brine solution is preferably sodium bicarbonate solution；The quality of the sodium bicarbonate solution
Concentration is preferably 1~20wt%, more preferably 5~15wt%；Present invention preferably uses layering slots to be layered, and the present invention is to institute
The concrete type for stating layering slot does not have particular/special requirement, uses layering slot well known to those skilled in the art；The present invention is preferred
Carrying out the evaporation of the waste water containing the tert-butyl alcohol using vaporising device, the temperature of the evaporation is preferably 65~100 DEG C, more preferably 80~
90℃；The time of the evaporation is preferably 1.5~4.5h, more preferably 2~4h；In the present invention, evaporation obtained by the evaporation
Liquid is to recycle t-butanol solution；Evaporation raffinate is circularly used for the washing of peroxidized t-butyl perbenzoate.
The present invention does not have particular/special requirement to other related actual conditions of recycling t-butanol solution, in the specific reality of the present invention
It applies in example, is preferably recycled t-butanol solution according to method disclosed in patent CN102603020A.
After obtaining t-butanol solution, the present invention, which mixes the t-butanol solution with sulfuric acid, carries out esterification, obtains sulphur
Sour hydrogen tert-butyl ester esterifying liquid.In the present invention, the mass fraction of the sulfuric acid is preferably 50~98%, more preferably 60~
90%；The amount ratio of the substance of the tert-butyl alcohol is preferably 0.249~0.457 in the sulfuric acid and t-butanol solution:1, more preferably 0.3
~0.4:1.
In the present invention, the temperature of the esterification is preferably 0~30 DEG C, more preferably 5~25 DEG C.
Present invention preferably uses reaction kettle of the esterification to carry out esterification, concrete type of the present invention to the reaction kettle of the esterification
There is no particular/special requirement, uses reaction kettle of the esterification well known to those skilled in the art；The present invention is preferably by way of dropwise addition
T-butanol solution and sulfuric acid are mixed, in a specific embodiment of the present invention, preferably sulfuric acid is added in reaction kettle of the esterification, then will
T-butanol solution is added drop-wise in sulfuric acid；Or, first t-butanol solution is added in reaction kettle of the esterification, then sulfuric acid is added drop-wise to the tert-butyl alcohol
In solution；Or, t-butanol solution and sulfuric acid are added drop-wise in reaction kettle of the esterification simultaneously.In the present invention, the time of the dropwise addition
Independently >=30min, more preferably 40~50min；The present invention preferably carries out t-butanol solution and sulfuric acid under agitation
Mixing is added dropwise；The present invention does not have particular/special requirement to the rate of the stirring, can stir evenly t-butanol solution and sulfuric acid i.e.
It can；The present invention continues to stir after being preferably added dropwise, it is described continue stirring time preferably >=30min, more preferably 40~
60min；Esterification occurs after the tert-butyl alcohol and sulfuric acid contact, the present invention is stirred by continuing, and makes the tert-butyl alcohol and sulfuric acid reaction
Completely.
The present invention mixes hydrogen peroxide and sulfuric acid, obtains acidic oxidation liquid.In the present invention, peroxidating in the hydrogen peroxide
The mass fraction of hydrogen is preferably 27.5~70%, more preferably 30~60%, most preferably 40~50%；The quality of the sulfuric acid
Score is preferably 50~98%, and more preferably 60~90%；The mass ratio of the hydrogen peroxide and sulfuric acid is preferably 1:1.15~
7.32, more preferably 1:1.30~7.15；Hydrogen peroxide and the step (2) tert-butyl alcohol in step (3) hydrogen peroxide is molten
The amount of the substance of the tert-butyl alcohol is than preferably 0.975~1.151 in liquid:1, more preferably 1~1.1:1.In the present invention, described mixed
The temperature of conjunction is preferably 0~40 DEG C, more preferably 10~30 DEG C.
Present invention preferably uses the mixing that mixing kettle carries out hydrogen peroxide and sulfuric acid；The present invention will preferably by way of dropwise addition
The hydrogen peroxide and sulfuric acid mixing；In a specific embodiment of the present invention, preferably first hydrogen peroxide is added in mixing tank, then by institute
Sulfuric acid is stated to be added drop-wise in hydrogen peroxide；Or, first the sulfuric acid is added in mixing kettle, then the hydrogen peroxide is added drop-wise in sulfuric acid；
Or, the sulfuric acid and hydrogen peroxide are added drop-wise in mixing kettle simultaneously.In the present invention, time of the dropwise addition is preferably independently
>=20min, more preferably 30~40min；The present invention preferably carries out oxidation reaction under agitation；The present invention is to the stirring
Rate there is no particular/special requirement, t-butanol solution and sulfuric acid can be stirred evenly；The present invention is preferably added dropwise subsequent
Continuous stirring, the time for continuing stirring preferably >=10min, more preferably 20~30min；The present invention is stirred by continuing, and is made
Sulfuric acid and hydrogen peroxide are uniformly mixed.
After obtaining hydrogen sulfate tert-butyl ester esterifying liquid and acidic oxidation liquid, the present invention by the hydrogen sulfate tert-butyl ester esterifying liquid and
Acidic oxidation liquid mixes, and makes the hydrogen sulfate tert-butyl ester that oxidation reaction occur, obtains the mixture containing tert-butyl hydroperoxide.The present invention
Directly acidic oxidation liquid obtained by hydrogen sulfate tert-butyl ester esterifying liquid obtained by step (2) and step (3) is mixed, without being appointed
What he is handled.
Present invention preferably uses synthesis reactors to carry out oxidation reaction, and the present invention is not special to the concrete type of the synthesis reactor
It is required that using synthesis reactor well known to those skilled in the art.The present invention is preferably by way of dropwise addition by the hydrogen sulfate
Tert-butyl ester esterifying liquid and the mixing of acidic oxidation liquid；In a specific embodiment of the present invention, preferably first acidic oxidation liquid is added and is closed
It is added drop-wise in acidic oxidation liquid in kettle, then by the hydrogen sulfate tert-butyl ester esterifying liquid；Or, first by the hydrogen sulfate tert-butyl ester ester
Change liquid to be added in synthesis reactor, then the acidic oxidation drop is added in hydrogen sulfate tert-butyl ester esterifying liquid；Or, by the hydrogen sulfate
Tert-butyl ester esterifying liquid and acidic oxidation liquid are added drop-wise in synthesis reactor simultaneously.In the present invention, the time of the dropwise addition is preferably independent
Ground >=30min, more preferably 40~50min；The present invention preferably carries out oxidation reaction under agitation；The present invention is to described
The rate of stirring does not have particular/special requirement, can stir evenly t-butanol solution and sulfuric acid；The present invention is preferably added dropwise
After continue to stir, it is described continue stirring time preferably >=3h, more preferably 4~5h；The hydrogen sulfate tert-butyl ester is in sulfuric acid and peroxide
Oxidation reaction occurs under the conditions of changing existing for hydrogen, the present invention is stirred by continuing, and making the hydrogen sulfate tert-butyl ester, the reaction was complete.
In the present invention, after the oxidation reaction preferably further include product separation；The product separation preferably includes following
Step：
Reaction solution obtained by the oxidation reaction is subjected to liquid separation, obtain upper layer mixture containing tert-butyl hydroperoxide and
The reuse mother liquor of lower layer；
The reuse mother liquor is the mixture of sulfuric acid and hydrogen peroxide.
Present invention preferably uses liquid separation slots to carry out liquid separation；The present invention does not have the liquid separation slot and specific liquid separation condition
Particular/special requirement can be by oxidation liquid liquid separation using method well known to those skilled in the art.In the present invention, divide
Upper layer obtained by liquid is the mixture containing tert-butyl hydroperoxide, including tert-butyl hydroperoxide and di-t-butyl peroxide；
The mixture can be sold directly as product, can also be detached tert-butyl hydroperoxide and di-t-butyl peroxide；The present invention couple
The separation method of the tert-butyl hydroperoxide and di-t-butyl peroxide does not have particular/special requirement, ripe using those skilled in the art
The separation method known.
In the present invention, lower layer obtained by the liquid separation is reuse mother liquor；The reuse mother liquor is the mixed of sulfuric acid and hydrogen peroxide
Close object.The mass fraction of sulfuric acid is preferably 22.6~35.5% in the reuse mother liquor, and more preferably 25~35%, most preferably
30%；The mass fraction of hydrogen peroxide is preferably 4.8~8.8% in the reuse mother liquor, and more preferably 5~8%, most preferably
6~7%.
In the present invention, the reuse mother liquor, which is preferably returned in step (3), replaces sulfuric acid and hydrogen peroxide to mix, and obtains acidity
Oxidation solution；When the reuse mother liquor is mixed with hydrogen peroxide, the mass ratio of the reuse mother liquor and hydrogen peroxide is preferably 1.534~
7.714:1, more preferably 2~7:1, most preferably 3~6:1.The present invention by the mixture of sulfuric acid obtained by liquid separation and hydrogen peroxide into
Row reuse both avoids industrial wastewater discharge, and is conducive to environmental protection, and saves energy raw material, helps to reduce manufacturing cost.
It is prepared containing tert-butyl hydroperoxide using recycling t-butanol solution to provided by the invention with reference to embodiment
The method of mixture is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) 164kg20.84wt% recycling t-butanol solutions are put into 706kg anhydrous tertiary butanols with agitating device
Reaction vessel in, open agitating device stirring, until anhydrous tertiary butanol is completely dissolved, stirring terminates, and obtains 870kg mass
Score is 85% t-butanol solution；
The recycling t-butanol solution is obtained by following steps：By peroxidized t-butyl perbenzoate and alkalescent saline solution
Mixture imported into layering slot and be layered, upper layer is peroxidized t-butyl perbenzoate, and lower layer is the waste water containing the tert-butyl alcohol, contains uncle
The waste water of butanol enters vaporising device；Make the waste water containing the tert-butyl alcohol in vaporising device, be evaporated at 75 DEG C of temperature, is evaporated
4h obtains evaporation liquid and steams raffinate, and the washing steamed raffinate and be further recycling in peroxidized t-butyl perbenzoate is described
Evaporate the aqueous solution that liquid is the tert-butyl alcohol containing 20.84wt%.Wherein, the alkalescent brine is that the sodium bicarbonate of 3.0wt% is molten
Liquid.
2) first the t-butanol solution that step (1) obtains is added in reaction kettle of the esterification, then under stirring and controlled
Temperature processed is 0~30 DEG C and is added drop-wise to 370Kg sulfuric acid (mass fraction 80%) in the t-butanol solution that time for adding is
45min continues to stir 30min after being added dropwise, obtains hydrogen sulfate tert-butyl ester esterifying liquid；
(3) stirring simultaneously control whipping temp be 0~40 DEG C between under conditions of, by 515Kg hydrogen peroxide (mass fractions
It fills 3080Kg reuses liquid 65%) to be slowly added drop-wise to (mass fraction of sulfur acid is the 34.6%, mass fraction containing hydrogen peroxide
For in mixing kettle 5.4%), time for adding 30min continues to stir 25min after dropwise addition, obtains acidic oxidation liquid；
(4) under conditions of controlling reaction temperature is between 0~40 DEG C simultaneously for stirring, the sulfuric acid that will be obtained by step (2)
Hydrogen tert-butyl ester esterifying liquid is slowly added drop-wise in the synthesis reactor for filling acidic oxidation liquid, and time for adding 45min continues to stir after dropwise addition
3.5h is mixed, reaction product is obtained；
(5) reaction product is introduced into liquid separation slot liquid separation, obtains mother liquor 3935Kg (its of lower layer's water phase sulfur acid and hydrogen peroxide
The mass fraction of middle sulfur acid is 34.6%, the mass fraction containing hydrogen peroxide is 5.4%), and by 3080Kg mother liquors therein
It is directed back to as reuse mother liquor in the mixing kettle of step (3), continues to serve as lower secondary response.The mother liquor reclamation rate of this step is
78.27%, remaining 850Kg mother liquors can be used as acidification liquid of the mixture containing tert-butyl hydroperoxide after alkali cleaning or give over to
The production of other industrial products is used.Mixture 900Kg of the upper oil phase containing tert-butyl hydroperoxide is obtained after liquid separation, is examined through GC
It surveys, the content of tert-butyl hydroperoxide is 75.14%, and the content of di-t-butyl peroxide is 15.49%, yield 94.3%.
Embodiment 2
(1) 165kgkg20.98wt% recycling t-butanol solutions and 705kg anhydrous tertiary butanols are put into stirring dress
In the reaction vessel set, agitating device stirring is opened, until anhydrous tertiary butanol is completely dissolved, stirring terminates, and obtains 870kg matter
Amount score is 85% t-butanol solution；
The recycling t-butanol solution is obtained by following steps：By peroxidized t-butyl perbenzoate and alkalescent saline solution
Mixture imported into layering slot and be layered, upper layer is peroxidized t-butyl perbenzoate, and lower layer is the waste water containing the tert-butyl alcohol, is entered
Vaporising device；Make the waste water containing the tert-butyl alcohol in vaporising device, be evaporated at 75 DEG C of temperature, evaporate 4h, obtain evaporation liquid and
Steam raffinate, the raffinate that steams further is recycling in the washing of peroxidized t-butyl perbenzoate, the evaporation liquid for containing
The aqueous solution of the 20.98wt% tert-butyl alcohols.Wherein, the alkalescent brine is the sodium bicarbonate solution of 3.0wt%.
(2) first 381Kg sulfuric acid (mass fraction 90%) is added in reaction kettle of the esterification, then under stirring and
It is added drop-wise to controlled at 0~30 DEG C of t-butanol solution by 870Kg steps (1) in the sulfuric acid, time for adding is
60min continues to stir 20min after being added dropwise, obtains hydrogen sulfate tert-butyl ester esterifying liquid；
(3) stirring simultaneously control whipping temp be 0~40 DEG C between under conditions of, by 2380Kg reuse liquid (sulfur acids
Mass fraction be 35.3%, the mass fraction containing hydrogen peroxide is 5.2%) to be slowly added drop-wise to fill 650Kg hydrogen peroxide (quality point
Number is in mixing kettle 50%), time for adding 55min continues to stir 10min, obtains acidic oxidation liquid after dropwise addition；
(4) under conditions of controlling reaction temperature is between 0~40 DEG C simultaneously for stirring, the sulfuric acid that will be obtained by step (2)
Hydrogen tert-butyl ester esterifying liquid is slowly added drop-wise in the synthesis reactor for filling acidic oxidation liquid, and time for adding 60min continues to stir after dropwise addition
3h is mixed, reaction product is obtained；
(5) reaction product is introduced into liquid separation slot liquid separation, obtains mother liquor 3350Kg (its of lower layer's water phase sulfur acid and hydrogen peroxide
The mass fraction of middle sulfur acid is 35.3%, the mass fraction containing hydrogen peroxide is 5.2%), and by 2380Kg mother liquors therein
It is directed back to as reuse mother liquor in the mixing kettle of step (3), continues to serve as lower secondary response.The mother liquor reclamation rate of this step is
71.04%, remaining 970Kg mother liquors can be used as acidification liquid of the mixture containing tert-butyl hydroperoxide after alkali cleaning or give over to
The production of other industrial products is used.Mixture 900Kg of the upper oil phase containing tert-butyl hydroperoxide is obtained after liquid separation, is examined through GC
It surveys, the content of tert-butyl hydroperoxide is 66.07%, and the content of di-t-butyl peroxide is 23.51%, yield 95.1%.
Embodiment 3
(1) 262kg50.15wt% t-butanol solutions and 606kg anhydrous tertiary butanols are put into the anti-of agitating device
It answers in container, opens agitating device stirring, until anhydrous tertiary butanol is completely dissolved, stirring terminates, and obtains 868kg mass fractions
For 85% t-butanol solution；
The recycling t-butanol solution is obtained by following steps：By peroxidized t-butyl perbenzoate and alkalescent saline solution
Mixture imported into layering slot and be layered, upper layer is peroxidized t-butyl perbenzoate, and lower layer is the waste water containing the tert-butyl alcohol, is entered
Vaporising device；Make the waste water containing the tert-butyl alcohol in vaporising device, be evaporated at 85 DEG C of temperature, evaporate 3.5h, obtains evaporation liquid
With steam raffinate, the raffinate that steams further is recycling in the washing of peroxidized t-butyl perbenzoate, the evaporation liquid for containing
The aqueous solution of the 50.15wt% tert-butyl alcohols.Wherein, the alkalescent brine is the sodium bicarbonate solution of 5.0wt%.
(2) under conditions of controlling reaction temperature is between 0~30 DEG C simultaneously for stirring, by 270Kg sulfuric acid, (mass fraction is
90%) it is slowly added drop-wise in reaction kettle of the esterification simultaneously with the t-butanol solution of step (1), time for adding 30min is added dropwise
After continue stir 50min, obtain hydrogen sulfate tert-butyl ester esterifying liquid；
(3) stirring simultaneously control whipping temp be 0~40 DEG C between under conditions of, by 490Kg hydrogen peroxide (mass fractions
For 70%) with 3780Kg reuses liquid (mass fraction of sulfur acid is 35.5%, the mass fraction containing hydrogen peroxide is 8.8%) simultaneously
It is slowly added drop-wise in mixing kettle, time for adding 40min, continues to stir 30min after dropwise addition, obtain acidic oxidation liquid.
(4) under conditions of controlling reaction temperature is between 0~40 DEG C simultaneously for stirring, the sulfuric acid that will be obtained by step (2)
It acidic oxidation liquid that hydrogen tert-butyl ester esterifying liquid and step (3) obtain while being slowly added drop-wise in synthesis reactor, time for adding is
65min continues to stir 4h after dropwise addition, obtains reaction product；
(5) reaction product is introduced into liquid separation slot liquid separation, obtains mother liquor 4513Kg (its of lower layer's water phase sulfur acid and hydrogen peroxide
The mass fraction of middle sulfur acid is 35.5%, the mass fraction containing hydrogen peroxide is 8.8%), and by 3780Kg mother liquors therein
It is directed back to as reuse mother liquor in the mixing kettle of step (3), continues to serve as lower secondary response.The mother liquor reclamation rate of this step is
83.76%, remaining 733Kg mother liquors can be used as acidification liquid of the mixture containing tert-butyl hydroperoxide after alkali cleaning or give over to
The production of other industrial products is used.Mixture 895Kg of the upper oil phase containing tert-butyl hydroperoxide is obtained after liquid separation, is examined through GC
It surveys, the content of tert-butyl hydroperoxide is 72.69%, and the content of di-t-butyl peroxide is 17.74%, yield 94.3%.
Embodiment 4
(1) 267kg51.03wt% t-butanol solutions and 605kg anhydrous tertiary butanols are put into the anti-of agitating device
It answers in container, opens agitating device stirring, until anhydrous tertiary butanol is completely dissolved, stirring terminates, and obtains 872kg mass fractions
For 85% t-butanol solution；
The recycling t-butanol solution is obtained by following steps：By peroxidized t-butyl perbenzoate and alkalescent saline solution
Mixture imported into layering slot and be layered, upper layer is peroxidized t-butyl perbenzoate, and lower layer is the waste water containing the tert-butyl alcohol, is entered
Vaporising device；(2) make the waste water containing the tert-butyl alcohol in vaporising device, be evaporated at 90 DEG C of temperature, evaporate 3.0h, evaporated
Liquid and steam raffinate, the raffinate that steams further is recycling in the washing of peroxidized t-butyl perbenzoate, the evaporation liquid for containing
The aqueous solution of the 51.03wt% tert-butyl alcohols.Wherein, the alkalescent brine is the sodium bicarbonate solution of 10.0wt%.
(2) t-butanol solution in step (1) is added in reaction kettle of the esterification, then under stirring and controls temperature
815Kg sulfuric acid (mass fraction 60%) is added drop-wise in the tert-butyl alcohol by degree for 0~30 DEG C, time for adding 60min, drop
It adds and continues to stir 60min after finishing, obtain hydrogen sulfate tert-butyl ester esterifying liquid；
(3) stirring simultaneously control whipping temp be 0~40 DEG C between under conditions of, by 1275Kg hydrogen peroxide (quality divide
Number fills 3640Kg reuses liquid (mass fraction of sulfur acid be 24.8%, the quality containing hydrogen peroxide is divided 30%) to be slowly added drop-wise to
Number is in mixing kettle 4.8%), time for adding 35min continues to stir 45min, obtains acidic oxidation liquid after dropwise addition.
(4) under conditions of controlling reaction temperature is between 0~40 DEG C simultaneously for stirring, the sulfuric acid that will be obtained by step (2)
Hydrogen tert-butyl ester esterifying liquid is slowly added drop-wise in the synthesis reactor for filling acidic oxidation liquid, and time for adding 30min continues to stir after dropwise addition
6h is mixed, reaction product is obtained；
(5) reaction product is introduced into liquid separation slot liquid separation, obtains mother liquor 5707Kg (its of lower layer's water phase sulfur acid and hydrogen peroxide
The mass fraction of middle sulfur acid is 24.8%, the mass fraction containing hydrogen peroxide is 4.8%), and by 3640Kg mother liquors therein
It is directed back in the mixing kettle described in step (2) as reuse mother liquor, continues to serve as lower secondary response.The mother liquor reclamation rate of this step
Be 63.03%, remaining 2110Kg mother liquors can be used as acidification liquid of the mixture containing tert-butyl hydroperoxide after alkali cleaning or
The production of other industrial products is given over to use.Mixture 895Kg of the upper oil phase containing tert-butyl hydroperoxide is obtained after liquid separation, through GC
The content of detection, tert-butyl hydroperoxide is 76.23%, and the content of di-t-butyl peroxide is 14.81%, and yield is
93.8%.
Embodiment 5
(1) 632kg79.30wt% t-butanol solutions and 240kg anhydrous tertiary butanols are put into the anti-of agitating device
It answers in container, opens agitating device stirring, until anhydrous tertiary butanol is completely dissolved, stirring terminates, and obtains 872kg mass fractions
For 85% t-butanol solution；
The recycling t-butanol solution is obtained by following steps：By peroxidized t-butyl perbenzoate and alkalescent saline solution
Mixture imported into layering slot and be layered, upper layer is peroxidized t-butyl perbenzoate, and lower layer is the waste water containing the tert-butyl alcohol, is entered
Vaporising device；Make the waste water containing the tert-butyl alcohol in vaporising device, be evaporated at 95 DEG C of temperature, evaporate 2.0h, obtains evaporation liquid
With steam raffinate, the raffinate that steams further is recycling in the washing of peroxidized t-butyl perbenzoate, the evaporation liquid for containing
The aqueous solution of the 79.30wt% tert-butyl alcohols.Wherein, the alkalescent brine is the sodium bicarbonate solution of 15.0.0wt%.
(2) first 630Kg sulfuric acid (mass fraction 70%) is added in reaction kettle of the esterification, then under stirring and
Controlled at 0~30 DEG C, the t-butanol solution of step A is added drop-wise in the sulfuric acid, time for adding 50min, is added dropwise
After continue stir 50min, obtain hydrogen sulfate tert-butyl ester esterifying liquid；
(3) stirring simultaneously control whipping temp be 0~40 DEG C between under conditions of, by 4340Kg reuse liquid (sulfur acids
Mass fraction be 22.7%, the mass fraction containing hydrogen peroxide is 6.1%) to be slowly added drop-wise to fill 1450Kg hydrogen peroxide (quality
Score is time for adding 55min in mixing kettle 27.5%), continues to stir 20min after dropwise addition, obtains acidic oxidation liquid.
(4), will be by step B under conditions of controlling reaction temperature is between 0~40 DEG C simultaneously for stirring) obtained hydrogen sulfate
Tert-butyl ester esterifying liquid is slowly added drop-wise in the synthesis reactor for filling acidic oxidation liquid, and time for adding 75min continues to stir after dropwise addition
5.5h obtains reaction product；
(5) reaction product is introduced into liquid separation slot liquid separation, obtains mother liquor 6394Kg (its of lower layer's water phase sulfur acid and hydrogen peroxide
The mass fraction of middle sulfur acid is 22.7%, the mass fraction containing hydrogen peroxide is 6.1%), and by 4340Kg mother liquors therein
It is directed back in the mixing kettle described in step (3) as reuse mother liquor, continues to serve as lower secondary response.The mother liquor reclamation rate of this step
Be 67.88%, remaining 2054Kg mother liquors can be used as acidification liquid of the mixture containing tert-butyl hydroperoxide after alkali cleaning or
The production of other industrial products is given over to use.Mixture 898Kg of the upper oil phase containing tert-butyl hydroperoxide is obtained after liquid separation, through GC
The content of detection, tert-butyl hydroperoxide is 65.89%, and the content of di-t-butyl peroxide is 23.92%, and yield is
95.0%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method preparing the mixture containing tert-butyl hydroperoxide using recycling t-butanol solution, includes the following steps：
(1) t-butanol solution will be recycled and anhydrous tertiary butanol mixes, and obtain reaction t-butanol solution；The recycling tert-butyl alcohol is molten
Content >=20wt% of the middle tert-butyl alcohol of liquid；
The recycling t-butanol solution, is obtained by following steps：
Peroxidized t-butyl perbenzoate crude product is washed using base brine solution, by washing feed liquid layering, lower layer is containing tertiary fourth
The waste water of alcohol；
The waste water containing the tert-butyl alcohol is evaporated, it is to recycle t-butanol solution that gained, which evaporates liquid,；
(2) reaction is mixed with t-butanol solution with sulfuric acid and carries out esterification, obtain hydrogen sulfate tert-butyl ester esterifying liquid；
(3) hydrogen peroxide and sulfuric acid are mixed, obtains acidic oxidation liquid；
(4) the hydrogen sulfate tert-butyl ester esterifying liquid and the acidic oxidation liquid are mixed, makes the hydrogen sulfate tert-butyl ester that oxidation occur anti-
It answers, obtains the mixture containing tert-butyl hydroperoxide.
2. according to the method described in claim 1, it is characterized in that, the t butanol content in the recycling t-butanol solution is 20
~80wt%.
3. according to the method described in claim 1, it is characterized in that, the quality of the recycling t-butanol solution and anhydrous tertiary butanol
Than being 1:0.25~4.33；
The content of the tert-butyl alcohol is 84.0~86.0wt% in the reaction t-butanol solution.
4. according to the method described in claim 1, it is characterized in that, in the step (2), the mass fraction of sulfuric acid is 50~
98%；
The amount ratio of the substance of the tert-butyl alcohol is 0.249~0.457 in the sulfuric acid and reaction t-butanol solution:1.
5. method according to claim 1 or 4, which is characterized in that the temperature of the esterification is 0~30 DEG C.
6. according to the method described in claim 1, it is characterized in that, the quality of hydrogen peroxide is divided in the step (3) hydrogen peroxide
Number is 27.5~70%；The mass ratio of the hydrogen peroxide and sulfuric acid is 1:1.15~7.32.
7. method according to claim 1 or 6, which is characterized in that the hydrogen peroxide in step (3) hydrogen peroxide and institute
The amount ratio for stating the substance of the tert-butyl alcohol in step (2) reaction t-butanol solution is 0.975~1.151:1.
8. according to the method described in claim 1, it is characterized in that, the temperature of oxidation reaction is 0~40 in the step (4)
℃。
9. according to the method described in claim 1, it is characterized in that, further including product separation after the oxidation reaction；The production
Object separation includes the following steps：
Reaction solution obtained by oxidation reaction is subjected to liquid separation, obtains time of the mixture and lower layer containing tert-butyl hydroperoxide on upper layer
Use mother liquor；
The reuse mother liquor is the mixture of sulfuric acid and hydrogen peroxide.
10. according to the method described in claim 9, it is characterized in that, the reuse mother liquor return to step (3) in replace sulfuric acid with
Hydrogen peroxide mixes；
The mass fraction of sulfuric acid is 22.6~35.5% in the reuse mother liquor, the mass fraction of hydrogen peroxide is 4.8~
8.8%；
The mass ratio of the reuse mother liquor and hydrogen peroxide is 1.534~7.714:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020169322A1 (en) | 2019-02-22 | 2020-08-27 | Nouryon Chemicals International B.V. | Process for producing an organic peroxide |
| CN112574084A (en) * | 2020-12-28 | 2021-03-30 | 山东久日化学科技有限公司 | Waste liquid treatment process and device in TPO production process |
| CN112608210A (en) * | 2020-11-27 | 2021-04-06 | 信汇科技有限公司 | Method for improving selectivity of peroxide prepared by oxidizing alkane |
| CN113454064A (en) * | 2019-02-22 | 2021-09-28 | 诺力昂化学品国际有限公司 | Process for producing organic peroxide |
| CN114621124A (en) * | 2022-04-19 | 2022-06-14 | 湖南东隅石化科技有限公司 | Method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857563A (en) * | 2010-06-13 | 2010-10-13 | 江苏强盛化工有限公司 | Preparation method for mixture containing tert-butyl hydroperoxide |
| CN102603020A (en) * | 2012-03-29 | 2012-07-25 | 江苏强盛功能化学股份有限公司 | Method for treating waste water generated by washing of tert-butyl peroxybenzoate with weakly alkaline saline solution |
-
2018
- 2018-07-23 CN CN201810811960.4A patent/CN108658824A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857563A (en) * | 2010-06-13 | 2010-10-13 | 江苏强盛化工有限公司 | Preparation method for mixture containing tert-butyl hydroperoxide |
| CN102603020A (en) * | 2012-03-29 | 2012-07-25 | 江苏强盛功能化学股份有限公司 | Method for treating waste water generated by washing of tert-butyl peroxybenzoate with weakly alkaline saline solution |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020169322A1 (en) | 2019-02-22 | 2020-08-27 | Nouryon Chemicals International B.V. | Process for producing an organic peroxide |
| CN113454064A (en) * | 2019-02-22 | 2021-09-28 | 诺力昂化学品国际有限公司 | Process for producing organic peroxide |
| US11407714B2 (en) | 2019-02-22 | 2022-08-09 | Nouryon Chemicals International B.V. | Process for producing an organic peroxide |
| CN113454064B (en) * | 2019-02-22 | 2023-10-03 | 诺力昂化学品国际有限公司 | Method for producing organic peroxides |
| CN112608210A (en) * | 2020-11-27 | 2021-04-06 | 信汇科技有限公司 | Method for improving selectivity of peroxide prepared by oxidizing alkane |
| CN112608210B (en) * | 2020-11-27 | 2022-05-10 | 信汇科技有限公司 | Method for improving selectivity of peroxide prepared by oxidizing alkane |
| CN112574084A (en) * | 2020-12-28 | 2021-03-30 | 山东久日化学科技有限公司 | Waste liquid treatment process and device in TPO production process |
| CN114621124A (en) * | 2022-04-19 | 2022-06-14 | 湖南东隅石化科技有限公司 | Method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide |
| CN114621124B (en) * | 2022-04-19 | 2024-02-13 | 湖南东隅石化科技有限公司 | Method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide |
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