CN109232348A - A kind of recoverying and utilizing method of 1,1-bis(t-butylperoxy)cyclohexane soda-wash water - Google Patents
A kind of recoverying and utilizing method of 1,1-bis(t-butylperoxy)cyclohexane soda-wash water Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
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- C07C409/00—Peroxy compounds
- C07C409/16—Peroxy compounds the —O—O— group being bound between two carbon atoms not further substituted by oxygen atoms, i.e. peroxides
- C07C409/18—Peroxy compounds the —O—O— group being bound between two carbon atoms not further substituted by oxygen atoms, i.e. peroxides at least one of the carbon atoms belonging to a ring other than a six-membered aromatic ring
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- C07C2601/14—The ring being saturated
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Abstract
The present invention provides one kind 1, the recoverying and utilizing method of 1- bis(t-butylperoxy) cyclohexane soda-wash water, the present invention uses sulfuric acid solution and described 1, the mixing of 1- bis(t-butylperoxy) cyclohexane soda-wash water, to described 1, the pH value of 1- bis(t-butylperoxy) cyclohexane soda-wash water is adjusted, it is ensured that reduces bringing into for other anion, facilitates subsequent processing；The sodium salt of tert-butyl hydroperoxide can be neutralized in this course simultaneously as tert-butyl hydroperoxide, guarantee that the cyclohexanone and tert-butyl hydroperoxide in soda-wash water become fraction by subsequent vacuum distillation, and carry out raw material reuse.The experimental results showed that recoverying and utilizing method provided by the invention is simple and can be realized the abundant recycling of the sodium salt and cyclohexanone of tert-butyl hydroperoxide in soda-wash water.
Description
Technical field
The present invention relates to organic matter utilization technology fields, more particularly to one kind 1,1- bis(t-butylperoxy) hexamethylene
The recoverying and utilizing method of alkane soda-wash water.
Background technique
1,1- bis(t-butylperoxy) cyclohexane is a kind of yellowish transparency liquid of low volatility, and it is organic to belong to ketal class
Peroxide is mainly used as the initiators for polymerization of styrene and its comonomer etc., polyvinyl chloride, polyethylene, polyphenyl second
Alkene and unsaturated polyester cross-linking agent and silicon rubber vulcanization agent.Currently, in industrial production the most common method be with sulfuric acid or its
His acid is catalyst, prepares 1,1- bis(t-butylperoxy) ring by oxidizer catalytic peroxyester of tert-butyl hydroperoxide
Hexane, in existing synthetic system, tert-butyl hydroperoxide is excessive, and part tert-butyl hydroperoxide after reaction is caused to remain in conjunction
At crude product in, need to be added alkali and washed to remove tert-butyl hydroperoxide therein.In alkaline cleaning procedure, tert-butyl mistake
Hydrogen oxide reacts the sodium salt to form tert-butyl hydroperoxide with sodium salt, and the sodium salt dissolves in soda-wash water.Meanwhile in soda-wash water
There is also the impurity such as the tert-butyl alcohol, cyclohexanone, COD higher, if these water arbitrarily discharge, can cause great burden to waste water.
Currently, application No. is the patents of 201810403151.X to disclose one kind 1,1- bis(t-butylperoxy) cyclohexane
The recoverying and utilizing method of soda-wash water is directly to be evaporated under reduced pressure 1,1- bis(t-butylperoxy) cyclohexane soda-wash water,
Obtaining fraction is the aqueous solution containing cyclohexanone, and bottom liquid is the solution of the sodium salt containing tert-butyl hydroperoxide；And cyclohexanone will be contained
Aqueous solution be used for 1,1-bis(t-butylperoxy)cyclohexane synthesis.But for the sodium salt containing tert-butyl hydroperoxide
Bottom liquid how to handle that there is no open, that is to say, that in the prior art to 1,1- bis(t-butylperoxy) cyclohexane alkali cleaning
The recoverying and utilizing method of water adequately can not be recycled and be utilized to the substance in soda-wash water.
Summary of the invention
The purpose of the present invention is to provide a kind of recycling sides of 1,1-bis(t-butylperoxy)cyclohexane soda-wash water
Method, the method adequately can be recycled and be utilized to the substance in soda-wash water.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides the recoverying and utilizing methods of one kind 1,1- bis(t-butylperoxy) cyclohexane soda-wash water, including with
Lower step:
(1) 1,1- bis(t-butylperoxy) cyclohexane soda-wash water is mixed with sulfuric acid solution, obtains mixed liquor；
(2) mixed liquor that the step (1) obtains is evaporated under reduced pressure, obtains fraction and bottom liquid；Contain in the fraction
There are cyclohexanone and tert-butyl hydroperoxide；The bottom liquid is aqueous sodium persulfate solution；
(3) water phase is removed after mixing fraction obtained in the step (2) with tert-butyl hydroperoxide and cyclohexanone, is obtained
To the mixed liquor of tert-butyl hydroperoxide and cyclohexanone；
(4) mixed liquor of the tert-butyl hydroperoxide and cyclohexanone obtained using the step (3) is bis- as raw material preparation 1,1-
(t-butylperoxy) hexamethylene.
Preferably, the pH value of mixed liquor is 5~6 in the step (1).
Preferably, the mass concentration of sulfuric acid solution is 50wt%~98wt% in the step (1).
Preferably, the temperature being evaporated under reduced pressure in the step (2) is 50~80 DEG C, the vacuum degree of the vacuum distillation is-
0.08~-0.1MPa, time of the vacuum distillation is 1~for 24 hours.
Preferably, the temperature mixed in the step (3) is 5~30 DEG C.
Preferably, in the step (4) preparation of 1,1- bis(t-butylperoxy) cyclohexane the following steps are included: by uncle
Butylhydroperoxide is mixed with the mixed liquor of cyclohexanone with sulfuric acid solution, is carried out condensation reaction, is obtained the bis- (t-butyl peroxies of 1,1-
Base) hexamethylene.
Preferably, the temperature of the condensation reaction is 5~30 DEG C, and the time of the condensation reaction is 2.5~5h.
Preferably, after the completion of the condensation reaction, further includes:
The product of the condensation reaction is separated, 1,1- bis(t-butylperoxy) cyclohexane crude product and water phase are obtained
Mother liquor；Contain sulfuric acid in the water phase mother liquor；
By 1, the 1- bis(t-butylperoxy) cyclohexane crude product successively through alkali cleaning, washing, drying and filtering, 1 is obtained,
1- bis(t-butylperoxy) cyclohexane；The water phase mother liquor is used as sulfuric acid solution reuse after mixing with sulfuric acid.
Preferably, tert-butyl hydroperoxide and cyclohexanone rub in the mixed liquor of the tert-butyl hydroperoxide and cyclohexanone
You are than being (2.05~3): 1.
Preferably, cyclohexanone in the mixed liquor of the sulfuric acid in the sulfuric acid solution and tert-butyl hydroperoxide and cyclohexanone
Molar ratio is (1.011~1.733): 1.
The present invention provides the recoverying and utilizing methods of one kind 1,1- bis(t-butylperoxy) cyclohexane soda-wash water, including with
Lower step: (1) 1,1- bis(t-butylperoxy) cyclohexane soda-wash water with sulfuric acid solution is mixed, obtains mixed liquor；(2) by institute
It states mixed liquor to be evaporated under reduced pressure, obtains fraction and bottom liquid；Contain cyclohexanone and tert-butyl hydroperoxide in the fraction；It is described
Bottom liquid is aqueous sodium persulfate solution；(3) it will obtain going after fraction is mixed with tert-butyl hydroperoxide and cyclohexanone in the step (2)
Except water phase, the mixed liquor of tert-butyl hydroperoxide and cyclohexanone is obtained；(4) tert-butyl hydroperoxide obtained with the step (3)
The mixed liquor of hydrogen and cyclohexanone is that raw material prepares 1,1-bis(t-butylperoxy)cyclohexane.The present invention uses sulfuric acid solution and institute
The mixing of 1,1- bis(t-butylperoxy) cyclohexane soda-wash water is stated, to 1, the 1- bis(t-butylperoxy) cyclohexane soda-wash water
PH value be adjusted, it is ensured that reduce bringing into for other anion, facilitate subsequent processing；In this course may be used simultaneously
The sodium salt of tert-butyl hydroperoxide is neutralized the cyclohexanone and t-butyl peroxy that guarantee in soda-wash water for tert-butyl hydroperoxide
Changing hydrogen becomes fraction by subsequent vacuum distillation, and carries out raw material reuse.The experimental results showed that recycling provided by the invention
Method is simple and can be realized the abundant recycling of the sodium salt and cyclohexanone of tert-butyl hydroperoxide in soda-wash water.
Specific embodiment
The present invention provides the recoverying and utilizing methods of one kind 1,1- bis(t-butylperoxy) cyclohexane soda-wash water, including with
Lower step:
(1) 1,1- bis(t-butylperoxy) cyclohexane soda-wash water is mixed with sulfuric acid solution, obtains mixed liquor；
(2) mixed liquor is evaporated under reduced pressure, obtains fraction and bottom liquid；Contain cyclohexanone and tertiary fourth in the fraction
Base hydrogen peroxide；The bottom liquid is aqueous sodium persulfate solution；
(3) it will obtain removing water phase after fraction is mixed with tert-butyl hydroperoxide and cyclohexanone in the step (2), obtain
The mixed liquor of tert-butyl hydroperoxide and cyclohexanone；
(4) mixed liquor of the tert-butyl hydroperoxide and cyclohexanone obtained using the step (3) is bis- as raw material preparation 1,1-
(t-butylperoxy) hexamethylene.
The present invention mixes 1,1- bis(t-butylperoxy) cyclohexane soda-wash water with sulfuric acid solution, obtains mixed liquor.
The present invention does not have any special restriction to the source of 1, the 1- bis(t-butylperoxy) cyclohexane soda-wash water,
Using the soda-wash water generated in 1,1-bis(t-butylperoxy)cyclohexane production process well known to those skilled in the art.
In the present invention, the quality of the sodium salt of tert-butyl hydroperoxide is dense in 1, the 1- bis(t-butylperoxy) cyclohexane soda-wash water
Degree preferably 2%~7%, the mass concentration of cyclohexanone is preferably 0.01%~3%, and the mass concentration of the tert-butyl alcohol is preferably
0.01%~0.3%, COD content are preferably 10000~70000mg/L.
In the present invention, the mass concentration of the sulfuric acid solution is preferably 50wt%~98wt%, more preferably 60wt%
~90wt%, most preferably 70wt%~80wt%.
The present invention to the no any special restriction of the mixing, using mixed process well known to those skilled in the art into
Row.
In the present invention, the pH value of the mixed liquor is preferably 5~6, more preferably 5.2~5.8, most preferably 5.4~
5.6。
After obtaining mixed liquor, the mixed liquor is evaporated under reduced pressure by the present invention, obtains fraction and bottom liquid；In the fraction
Contain cyclohexanone and tert-butyl hydroperoxide；The bottom liquid is aqueous sodium persulfate solution.
In the present invention, the temperature of the vacuum distillation is preferably 50~80 DEG C, and more preferably 55~75 DEG C, most preferably
60~70 DEG C；The vacuum degree of the vacuum distillation is preferably -0.08~-0.1MPa, more preferably -0.085~-0.095MPa；
The time of the vacuum distillation is preferably 1~for 24 hours, more preferably 5~20h, most preferably 10~15h.In the present invention, described
Vacuum distillation can be using tert-butyl hydroperoxide and cyclohexanone as fraction, and aqueous sodium persulfate solution is separated as bottom liquid, just
In the recycling of subsequent tert-butyl hydroperoxide and cyclohexanone.
After obtaining fraction and bottom liquid, the present invention goes to remove water after mixing the fraction with tert-butyl hydroperoxide and cyclohexanone
Phase obtains the mixed liquor of tert-butyl hydroperoxide and cyclohexanone.
In the present invention, the tert-butyl hydroperoxide is preferably tert-butyl hydroperoxide solution；In the present invention, described
The mass concentration of tert-butyl hydroperoxide solution is preferably 68%~85%, and more preferably 75%~80%；The present invention is to described
The purity of cyclohexanone does not have any special restriction, using commercial product well known to those skilled in the art.
In the present invention, tert-butyl hydroperoxide and cyclohexanone in the mixed liquor of the tert-butyl hydroperoxide and cyclohexanone
Molar ratio be preferably (2.05~3): 1, more preferably (2.2~2.6): 1, most preferably (2.4~2.5): 1.
In the present invention, the temperature that the fraction is mixed with tert-butyl hydroperoxide and cyclohexanone is preferably 5~30 DEG C, more
Preferably 10~20 DEG C, most preferably 14~16 DEG C.In the present invention, the fraction and tert-butyl hydroperoxide and cyclohexanone are mixed
Conjunction preferably carries out under stirring conditions, and the rate of the stirring is preferably 15~150r/min, more preferably 50~150r/
Min, most preferably 100~150r/min；In the present invention, the time of the stirring is preferably 10min or more, and more preferably 15
~30min, most preferably 20~25min.In the present invention, the stirring can promote cyclohexanone and tert-butyl mistake in fraction
The mixing of hydrogen oxide and promote separating for cyclohexanone and tert-butyl hydroperoxide and water phase.
After the completion of mixing, the present invention preferably stands the mixed product, obtains upper organic phase and lower layer's water phase, and
The water phase is removed, the mixed liquor of tert-butyl hydroperoxide and cyclohexanone is obtained.In the present invention, the time of the standing is excellent
It is selected as 15min or more, more preferably 20~30min.
In the present invention, it is also preferable to include the tert-butyl alcohols in the mixed liquor of the tert-butyl hydroperoxide and cyclohexanone.At this
In invention, the presence of the tert-butyl alcohol reacts no influence, tert-butyl hydroperoxide for tert-butyl hydroperoxide and cyclohexanone
Mixed liquor with cyclohexanone can be directly as raw material reuse.
After obtaining the mixed liquor of tert-butyl hydroperoxide and cyclohexanone, the present invention is by the tert-butyl hydroperoxide and hexamethylene
The mixed liquor of ketone is that raw material prepares 1,1-bis(t-butylperoxy)cyclohexane.
In the present invention, the preparation of 1, the 1- bis(t-butylperoxy) cyclohexane preferably includes following steps: by uncle
Butylhydroperoxide is mixed with the mixed liquor of cyclohexanone with sulfuric acid solution, is carried out condensation reaction, is obtained the bis- (t-butyl peroxies of 1,1-
Base) hexamethylene.
Tert-butyl hydroperoxide is preferably mixed with the mixed liquor of cyclohexanone with sulfuric acid solution and carries out condensation reaction by the present invention.
In the present invention, hexamethylene in the mixed liquor of the sulfuric acid in the sulfuric acid solution and tert-butyl hydroperoxide and cyclohexanone
The molar ratio of ketone is preferably (1.011~1.733): 1, more preferably (1.2~1.5): 1.
In the present invention, the mass concentration of the sulfuric acid solution is preferably 60~70%, and more preferably 65%.In the present invention
In, the sulfuric acid solution is preferably obtained after diluting by the concentrated sulfuric acid；The dilution is preferably water and/or 1,1- bis- with diluent
The water phase mother liquor generated in (t-butylperoxy) hexamethylene production process.
In the present invention, the mixing of the mixed liquor and sulfuric acid solution of the tert-butyl hydroperoxide and cyclohexanone is preferably being stirred
It is carried out under the conditions of mixing；The rate of the stirring is preferably 50~150r/min, more preferably 100r/min；The time of the stirring
Preferably 10min or more, more preferably 15~20min.
In the present invention, the temperature of the condensation reaction is preferably 5~30 DEG C, and more preferably 10~25 DEG C, most preferably
15~20 DEG C；The time of the condensation reaction is preferably 2.5~5h, more preferably 3~4h.In the present invention, the condensation is anti-
It should preferably carry out under agitation；The rate of the stirring is preferably 50~150r/min, more preferably 100r/min.
In the present invention, after the condensation reaction it is also preferable to include:
The product of the condensation reaction is separated, 1,1- bis(t-butylperoxy) cyclohexane crude product and water phase are obtained
Mother liquor；Contain sulfuric acid in the water phase mother liquor；
By 1, the 1- bis(t-butylperoxy) cyclohexane crude product successively through alkali cleaning, washing, drying and filtering, 1 is obtained,
1- bis(t-butylperoxy) cyclohexane；The water phase mother liquor is used as sulfuric acid solution reuse after mixing with sulfuric acid.
Product of the present invention preferably by the condensation reaction separates, and obtains 1,1- bis(t-butylperoxy) cyclohexane
Crude product and water phase mother liquor；Contain sulfuric acid in the water phase mother liquor.The product of the condensation reaction is preferably introduced layering by the present invention
Slot is layered, and is obtained upper layer 1,1- bis(t-butylperoxy) cyclohexane crude product and lower layer's water phase mother liquor, is then separated.
After obtaining 1,1- bis(t-butylperoxy) cyclohexane crude product and water phase mother liquor, the present invention is preferably bis- by 1, the 1-
(t-butylperoxy) hexamethylene crude product successively through alkali cleaning, washing, drying and filtering, obtains 1,1- bis(t-butylperoxy) ring
Hexane；The water phase mother liquor is used as sulfuric acid solution reuse after mixing with sulfuric acid.
The not special restriction of operation of the present invention to the alkali cleaning, washing, drying and filtering, using those skilled in the art
The technical solution of the purification of 1,1-bis(t-butylperoxy)cyclohexane crude product known to member.
In order to further illustrate the present invention, below with reference to embodiment to 1,1- bis(t-butylperoxy) provided by the invention
The processing method of hexamethylene soda-wash water is described in detail, but they cannot be interpreted as to the limit to the scope of the present invention
It is fixed.
Embodiment 1
The sulfuric acid solution for being 50% with mass concentration is by 1000kg 1,1-bis(t-butylperoxy)cyclohexane soda-wash water
The pH value of (tert-butyl hydroperoxide: 1.18%, sodium hydroxide: 4.5%, cyclohexanone: 0.081%, COD:32300mg/L) is adjusted to
5.5, vacuum distillation 6h is carried out under conditions of vacuum degree is -0.085MPa, temperature is 60 DEG C, obtains fraction 18kg (tert-butyl
Hydrogen peroxide: 64.12%, cyclohexanone: 4.3%), bottom liquid 1050kg (tert-butyl hydroperoxide: 0.025%, cyclohexanone:
0.003%, COD:1150mg/L).
By 690kg tert-butyl hydroperoxide (mass fraction 85%) and 315kg cyclohexanone (mass fraction 99%) and
In 5 DEG C, revolving speed to be stirred 10min under the conditions of 120r/min, standing separates lower layer's water phase, obtains tertiary fourth fraction described in 18kg
The mixed liquor 960.16kg of base hydrogen peroxide and cyclohexanone；
By 129.23kg sulfuric acid (mass fraction 98%) and 770.77kg water phase mother liquor, (sulfuric acid mass fraction is
53.6%) the sulfuric acid solution 900kg of catalysis is obtained to be stirred 30min under the conditions of 120r/min in 5 DEG C, revolving speed；
The sulfuric acid of catalysis described in the mixed liquor and 900kg of tert-butyl hydroperoxide described in 960.16kg and cyclohexanone is molten
Liquid mixing obtains reaction product in 5 DEG C, revolving speed to react 5h under the conditions of 120r/min；
The reaction product is stood into 1h layering, obtains upper layer 1,1- bis(t-butylperoxy) cyclohexane crude product and
The mother liquor of 1006.93kg lower layer water phase sulfur acid, and the mother liquor 770.77kg of lower layer's water phase sulfur acid is mixed into system with sulfuric acid
The standby sulfuric acid solution reuse as catalysis, by upper layer 1,1- bis(t-butylperoxy) cyclohexane crude product 850.73kg is successively passed through
After crossing alkali cleaning, washing, drying and filtering, 1,1- bis(t-butylperoxy) cyclohexane finished product 827.64kg is obtained.
Embodiment 2
The sulfuric acid solution for being 50% with mass concentration is by 1000kg 1,1-bis(t-butylperoxy)cyclohexane soda-wash water
The pH value of (tert-butyl hydroperoxide: 2.58%, sodium hydroxide: 3.5%, cyclohexanone: 0.121%, COD:69200mg/L) is adjusted to
5.7, vacuum distillation 12h is carried out under conditions of vacuum degree is -0.095MPa, temperature is 70 DEG C, obtains fraction 39kg (tert-butyl
Hydrogen peroxide: 66.03%, cyclohexanone: 2.9%), bottom liquid 1020kg (tert-butyl hydroperoxide: 0.0047%, cyclohexanone:
0.0077%, COD:730mg/L).
By 786.7kg tert-butyl hydroperoxide (mass fraction 80%) and 315kg cyclohexanone (mass fraction 99%)
With fraction described in 39kg in 10 DEG C, revolving speed to be stirred 30min under the conditions of 130r/min, standing separates lower layer's water phase, obtains
The mixed liquor 1053.78kg of tert-butyl hydroperoxide and cyclohexanone；
By 209.03kg sulfuric acid (mass fraction 98%) and 590.73kg water phase mother liquor, (sulfuric acid mass fraction is
49.3%) the sulfuric acid solution 800kg of catalysis is obtained to be stirred 30min under the conditions of 130r/min in 10 DEG C, revolving speed；
By the sulfuric acid of catalysis described in the mixed liquor and 800kg of tert-butyl hydroperoxide described in 1053.78kg and cyclohexanone
Solution mixing obtains reaction product in 10 DEG C, revolving speed to react 4.5h under the conditions of 130r/min；
The reaction product is stood into 1h layering, obtains upper layer 1,1- bis(t-butylperoxy) cyclohexane crude product and
The mother liquor of 1006.77kg lower layer water phase sulfur acid, and the mother liquor 590.97kg of lower layer's water phase sulfur acid is mixed into system with sulfuric acid
The standby sulfuric acid solution reuse as catalysis, by upper layer 1,1- bis(t-butylperoxy) cyclohexane crude product 844.52kg is successively passed through
After crossing alkali cleaning, washing, drying and filtering, 1,1- bis(t-butylperoxy) cyclohexane finished product 822.49kg is obtained.
Embodiment 3
The sulfuric acid solution for being 98% with mass concentration is by 1000kg 1,1-bis(t-butylperoxy)cyclohexane soda-wash water
The pH value of (tert-butyl hydroperoxide: 4.80%, sodium hydroxide: 3.8%, cyclohexanone: 0.26%, COD:11200mg/L) is adjusted to
5.2, vacuum distillation 18h is carried out under conditions of vacuum degree is -0.082MPa, temperature is 80 DEG C, obtains fraction 72kg (tert-butyl
Hydrogen peroxide: 66.5%, cyclohexanone: 3.55%), bottom liquid 1060kg (tert-butyl hydroperoxide: 0.011%, cyclohexanone:
0.0042%, COD:640mg/L).
By 915.52kg tert-butyl hydroperoxide (mass fraction 75%) and 315kg cyclohexanone (mass fraction 99%)
With fraction described in 72kg in 10 DEG C, revolving speed to be stirred 30min under the conditions of 100r/min, standing separates lower layer's water phase, obtains
The mixed liquor 1053.78kg of tert-butyl hydroperoxide and cyclohexanone；
By 209.03kg sulfuric acid (mass fraction 98%) and 590.73kg water phase mother liquor, (sulfuric acid mass fraction is
49.3%) the sulfuric acid solution 800kg of catalysis is obtained to be stirred 30min under the conditions of 100r/min in 10 DEG C, revolving speed；
By the sulfuric acid of catalysis described in the mixed liquor and 800kg of tert-butyl hydroperoxide described in 1053.78kg and cyclohexanone
Solution mixing, at 10 DEG C, revolving speed reacts 4.5h under the conditions of being 100r/min, obtains reaction product；
The reaction product is stood into 1h layering, obtains upper layer 1,1- bis(t-butylperoxy) cyclohexane crude product and
The mother liquor of 1006.77kg lower layer water phase sulfur acid, and the mother liquor 590.97kg of lower layer's water phase sulfur acid is mixed into system with sulfuric acid
The standby sulfuric acid solution reuse as catalysis, by upper layer 1,1- bis(t-butylperoxy) cyclohexane crude product 844.52kg is successively passed through
After crossing alkali cleaning, washing, drying and filtering, 1,1- bis(t-butylperoxy) cyclohexane finished product 822.49kg is obtained.
As seen from the above embodiment, method provided by the invention makes 1,1- bis(t-butylperoxy) cyclohexane soda-wash water
Recycle abundant recycling that is simple and can be realized the sodium salt and cyclohexanone of tert-butyl hydroperoxide in soda-wash water.
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. one kind 1, the recoverying and utilizing method of 1- bis(t-butylperoxy) cyclohexane soda-wash water, comprising the following steps:
(1) 1,1- bis(t-butylperoxy) cyclohexane soda-wash water is mixed with sulfuric acid solution, obtains mixed liquor；
(2) mixed liquor obtained in the step (1) is evaporated under reduced pressure, obtains fraction and bottom liquid；Contain in the fraction
Cyclohexanone and tert-butyl hydroperoxide；The bottom liquid is aqueous sodium persulfate solution；
(3) water phase is removed after mixing fraction obtained in the step (2) with tert-butyl hydroperoxide and cyclohexanone, obtains uncle
The mixed liquor of butylhydroperoxide and cyclohexanone；
(4) mixed liquor of the tert-butyl hydroperoxide and cyclohexanone obtained using the step (3) prepares bis- (the tertiary fourths of 1,1- as raw material
Base peroxy) hexamethylene.
2. recoverying and utilizing method as described in claim 1, which is characterized in that in the step (1) pH value of mixed liquor be 5~
6。
3. recoverying and utilizing method as claimed in claim 1 or 2, which is characterized in that the quality of sulfuric acid solution in the step (1)
Concentration is 50wt%~98wt%.
4. recoverying and utilizing method as described in claim 1, which is characterized in that the temperature of vacuum distillation is in the step (2)
50~80 DEG C, the vacuum degree of the vacuum distillation is -0.08~-0.1MPa, the time of the vacuum distillation is 1~for 24 hours.
5. recoverying and utilizing method as described in claim 1, which is characterized in that the temperature mixed in the step (3) is 5~30
℃。
6. recoverying and utilizing method as described in claim 1, which is characterized in that the bis- (t-butyl peroxies of 1,1- in the step (4)
Base) hexamethylene preparation the following steps are included: tert-butyl hydroperoxide is mixed with the mixed liquor of cyclohexanone with sulfuric acid solution, into
Row condensation reaction obtains 1,1- bis(t-butylperoxy) cyclohexane.
7. recoverying and utilizing method as claimed in claim 6, which is characterized in that the temperature of the condensation reaction is 5~30 DEG C, institute
The time for stating condensation reaction is 2.5~5h.
8. recoverying and utilizing method as claimed in claim 6, which is characterized in that after the completion of the condensation reaction further include:
The product of the condensation reaction is separated, 1,1- bis(t-butylperoxy) cyclohexane crude product is obtained and water phase is female
Liquid；Contain sulfuric acid in the water phase mother liquor；
By 1, the 1- bis(t-butylperoxy) cyclohexane crude product successively through alkali cleaning, washing, drying and filtering, it is bis- to obtain 1,1-
(t-butylperoxy) hexamethylene；The water phase mother liquor is used as sulfuric acid solution reuse after mixing with sulfuric acid.
9. recoverying and utilizing method as described in claim 1 or 6, which is characterized in that the tert-butyl hydroperoxide and cyclohexanone
Mixed liquor in tert-butyl hydroperoxide and the molar ratio of cyclohexanone be (2.05~3): 1.
10. recoverying and utilizing method as claimed in claim 6, which is characterized in that sulfuric acid and tert-butyl in the sulfuric acid solution
The molar ratio of cyclohexanone is (1.011~1.733) in the mixed liquor of hydrogen peroxide and cyclohexanone: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811267834.3A CN109232348A (en) | 2018-10-29 | 2018-10-29 | A kind of recoverying and utilizing method of 1,1-bis(t-butylperoxy)cyclohexane soda-wash water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811267834.3A CN109232348A (en) | 2018-10-29 | 2018-10-29 | A kind of recoverying and utilizing method of 1,1-bis(t-butylperoxy)cyclohexane soda-wash water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113292472A (en) * | 2021-05-26 | 2021-08-24 | 常熟市滨江化工有限公司 | Recycling treatment method for dialkyl peroxide-white carbon black waste |
| CN113290024A (en) * | 2021-05-26 | 2021-08-24 | 常熟市滨江化工有限公司 | Resource recycling treatment method for organic peroxide-calcium carbonate waste |
| CN114409581A (en) * | 2022-02-10 | 2022-04-29 | 江苏强盛功能化学股份有限公司 | Method for recovering waste oil as byproduct of 2, 5-dimethyl-2, 5-di (hydrogen peroxide) hexane |
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| CN107176721A (en) * | 2017-07-17 | 2017-09-19 | 江苏强盛功能化学股份有限公司 | A kind of method of wastewater treatment containing benzoic acid |
| CN108409624A (en) * | 2018-04-28 | 2018-08-17 | 江苏强盛功能化学股份有限公司 | A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of hexamethylene soda-wash water |
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| CN107176721A (en) * | 2017-07-17 | 2017-09-19 | 江苏强盛功能化学股份有限公司 | A kind of method of wastewater treatment containing benzoic acid |
| CN108409624A (en) * | 2018-04-28 | 2018-08-17 | 江苏强盛功能化学股份有限公司 | A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of hexamethylene soda-wash water |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113292472A (en) * | 2021-05-26 | 2021-08-24 | 常熟市滨江化工有限公司 | Recycling treatment method for dialkyl peroxide-white carbon black waste |
| CN113290024A (en) * | 2021-05-26 | 2021-08-24 | 常熟市滨江化工有限公司 | Resource recycling treatment method for organic peroxide-calcium carbonate waste |
| CN113290024B (en) * | 2021-05-26 | 2022-07-19 | 常熟市滨江化工有限公司 | Resource recycling treatment method for organic peroxide-calcium carbonate waste |
| CN114409581A (en) * | 2022-02-10 | 2022-04-29 | 江苏强盛功能化学股份有限公司 | Method for recovering waste oil as byproduct of 2, 5-dimethyl-2, 5-di (hydrogen peroxide) hexane |
| CN114409581B (en) * | 2022-02-10 | 2023-12-29 | 江苏强盛功能化学股份有限公司 | Recovery method of 2, 5-dimethyl-2, 5-bis (hydrogen peroxide) hexane byproduct waste oil |
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