CN108373435A - A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of -3,3,5- trimethyl-cyclohexane soda-wash waters - Google Patents
A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of -3,3,5- trimethyl-cyclohexane soda-wash waters Download PDFInfo
- Publication number
- CN108373435A CN108373435A CN201810403134.6A CN201810403134A CN108373435A CN 108373435 A CN108373435 A CN 108373435A CN 201810403134 A CN201810403134 A CN 201810403134A CN 108373435 A CN108373435 A CN 108373435A
- Authority
- CN
- China
- Prior art keywords
- tert
- trimethylcyclohexanones
- bis
- trimethyl
- butylperoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of 1,1 bis(t-butylperoxy)s 3,3, the recoverying and utilizing method of 5 trimethyl-cyclohexane soda-wash waters, by 1,1 bis(t-butylperoxy) 3,3,5 trimethyl-cyclohexane soda-wash waters are evaporated under reduced pressure, and fraction water and bottom liquid are obtained；Contain 3,3,5 trimethylcyclohexanones in the fraction water；The bottom liquid is the sodium salt of tert-butyl hydroperoxide；Water phase is removed after the fraction water is mixed with tert-butyl hydroperoxide, obtains tert-butyl hydroperoxide and 3, the mixed liquor of 3,5 trimethylcyclohexanones；1,1 bis(t-butylperoxy), 3,3,5 trimethyl-cyclohexane is prepared by raw material of the mixed liquor of the tert-butyl hydroperoxide and 3,3,5 trimethylcyclohexanones.The experimental results showed that recoverying and utilizing method provided by the invention is simple and can realize the sodium salt of tert-butyl hydroperoxide and 3 in soda-wash water, the abundant recycling of 3,5 trimethylcyclohexanones.
Description
Technical field
The present invention relates to organic matter utilization technology field, more particularly to one kind bis(t-butylperoxy) -3 1,1-,
The recoverying and utilizing method of 3,5- trimethyl-cyclohexane soda-wash waters.
Background technology
In current industrial production, 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes be all by 3,3,
5- trimethylcyclohexanones react preparation with tert-butyl hydroperoxide in acid condition.Due to tert-butyl hydroperoxide excess, portion
Branch enters in the crude product that synthesis obtains, and needs to remove by alkali cleaning.Such as the patent of invention of Publication No. CN102850249A
The method that purification is disclosed in " preparation method of 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes " is：Will after
Handle kettle in 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes crude product successively pass through alkali cleaning, washing, drying and
After filtering, 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane finished products are obtained.
Since tert-butyl hydroperoxide just enters the sodium salt of formation tert-butyl hydroperoxide in soda-wash water after alkali cleaning, and
There is also the tert-butyl alcohol, 3, the impurity such as 3,5- trimethylcyclohexanones, COD higher can be to useless if these water arbitrarily discharged
Water process causes great burden, and tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones as important reaction raw materials,
How to separate and recover and is used as problem to be solved.
Invention content
The purpose of the present invention is to provide a kind of 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters
Recoverying and utilizing method.Recoverying and utilizing method provided by the invention is simple, and can realize tert-butyl hydroperoxide and 3,3,5-
The recycling of trimethylcyclohexanone.
The present invention provides a kind of recycling of 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters profits
With method, include the following steps：
(1) by 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters are evaporated under reduced pressure, are evaporated
Fen Shui and bottom liquid；Contain 3,3,5- trimethylcyclohexanones in the fraction water；The bottom liquid is the sodium salt of tert-butyl hydroperoxide；
(2) the fraction water that the step (1) obtains is mixed with tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones
After remove water phase, obtain tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones；
(3) mixed liquor of the tert-butyl hydroperoxide obtained with the step (2) and 3,3,5- trimethylcyclohexanones is original
Material prepares 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes.
Preferably, the temperature being evaporated under reduced pressure in the step (1) is 50~80 DEG C.
Preferably, the vacuum degree being evaporated under reduced pressure in the step (1) is -0.08~-0.1MPa.
Preferably, the time being evaporated under reduced pressure in the step (1) is 1~for 24 hours.
Preferably, the temperature mixed in the step (2) is 5~30 DEG C.
Preferably, 1,1- bis(t-butylperoxy)s -3,3 in the step (3), the preparation packet of 5- trimethyl-cyclohexanes
It includes：By tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones is mixed with sulfuric acid solution carries out addition reaction, obtains
To 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes.
Preferably, the temperature of the addition reaction is 5~30 DEG C, and the time of addition reaction is 2.5~5h.
Preferably, further include after the addition reaction：The product of the addition reaction is detached, it is bis- to obtain 1,1-
(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes crude product and water phase mother liquor；Contain sulfuric acid in the water phase mother liquor；
By the 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes crude product successively through alkali cleaning, washing, drying
And filtering, obtain 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes；The water phase mother liquor is made after being mixed with sulfuric acid
For sulfuric acid solution reuse.
Preferably, the tert-butyl hydroperoxide and tert-butyl hydroperoxide in the mixed liquor of 3,3,5- trimethylcyclohexanones
Molar ratio with 3,3,5- trimethylcyclohexanones is (2.05~3):1.
Preferably, the mixing of the sulfuric acid in the sulfuric acid solution and tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones
The molar ratio of 3,3,5- trimethylcyclohexanones is (1.010~2.164) in liquid:1.
The present invention provides a kind of recycling of 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters profits
With method, include the following steps：1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes soda-wash waters are subjected to decompression steaming
It evaporates, obtains fraction water and bottom liquid；Contain 3,3,5- trimethylcyclohexanones in the fraction water；The bottom liquid is tert-butyl hydroperoxide
The sodium salt of hydrogen；Water phase is removed after the fraction water is mixed with tert-butyl hydroperoxide, obtains tert-butyl hydroperoxide and 3,3,
The mixed liquor of 5- trimethylcyclohexanones；Using the mixed liquor of the tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones as raw material
Prepare 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes.The present invention by bis(t-butylperoxy) -3,3 1,1-,
5- trimethyl-cyclohexane soda-wash waters are evaporated under reduced pressure, and the fraction water containing 3,3,5- trimethylcyclohexanones and tertiary butyl mistake are obtained
The sodium salt of hydrogen oxide, will contain 3,3,5- trimethylcyclohexanones fraction water mixed with tert-butyl hydroperoxide after removal water phase i.e.
It can be used as the raw material reuse of 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes.The experimental results showed that the present invention carries
The recoverying and utilizing method of confession is simple and can realize the sodium salt of tert-butyl hydroperoxide and 3,3,5- 3-methyl cyclohexanols in soda-wash water
The abundant recycling of ketone.
Specific implementation mode
The present invention provides a kind of recycling of 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters profits
With method, include the following steps：
(1) by 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters are evaporated under reduced pressure, are evaporated
Fen Shui and bottom liquid；Contain 3,3,5- trimethylcyclohexanones in the fraction water；The bottom liquid is the sodium salt of tert-butyl hydroperoxide；
(2) the fraction water that the step (1) obtains is mixed with tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones
After remove water phase, obtain tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones；
(3) mixed liquor of the tert-butyl hydroperoxide obtained with the step (2) and 3,3,5- trimethylcyclohexanones is original
Material prepares 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes.
1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters are evaporated under reduced pressure, are obtained by the present invention
To fraction water and bottom liquid.In the present invention, contain 3,3,5- trimethylcyclohexanones in the fraction water；The bottom liquid is tertiary butyl
The sodium salt of hydrogen peroxide.
The present invention is to the source of the 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters without spy
Different restriction, using 1,1- bis(t-butylperoxy)s -3,3 well known to those skilled in the art, the production of 5- trimethyl-cyclohexanes
The soda-wash water generated in the process.In the present invention, 1, the 1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes
The mass concentration of the sodium salt of tert-butyl hydroperoxide is preferably that the quality of 2~7%, 3,3,5- trimethylcyclohexanones is dense in soda-wash water
Degree preferably 0.01~3%, the mass concentration of the tert-butyl alcohol is preferably 0.01~0.3%.
In the present invention, the temperature of the vacuum distillation is preferably 50~80 DEG C；The vacuum degree of the vacuum distillation is preferred
For -0.08~-0.1MPa；The time of the vacuum distillation is preferably 1~for 24 hours.In the present invention, the vacuum distillation can incite somebody to action
The sodium salt of tert-butyl hydroperoxide and the aqueous phase separation for containing 3,3,5- trimethylcyclohexanones and the tert-butyl alcohol, obtain containing 3,3,5-
The sodium salt bottom liquid of the fraction water and tert-butyl hydroperoxide of trimethylcyclohexanone and the tert-butyl alcohol, convenient for being separately recovered.
In the present invention, the fraction water for containing 3,3,5- trimethylcyclohexanones and the tert-butyl alcohol is after processing as preparation
The raw material reuse of 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes；The sodium salt of the tert-butyl hydroperoxide is used
In the raw material for synthesizing other peroxide, such as peroxidized t-butyl perbenzoate.
After obtaining fraction water, for the present invention by the fraction water and tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones are mixed
Water phase is removed after conjunction, obtains tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones.
In the present invention, the mass concentration of the tert-butyl hydroperoxide is preferably 68~85%, more preferably 75~
80%.
The present invention is not special to the fraction water and tert-butyl hydroperoxide and the ratio of 3,3,5- trimethylcyclohexanones
Restriction, to ensure tert-butyl hydroperoxide and 3, tert-butyl hydroperoxide and 3,3 in the mixed liquor of 3,5- trimethylcyclohexanones,
The ratio of 5- trimethylcyclohexanones in claimed range subject to, according in fraction water 3,3,5- trimethylcyclohexanones content determine
.In the present invention, the tert-butyl hydroperoxide and tert-butyl hydroperoxide in the mixed liquor of 3,3,5- trimethylcyclohexanones
The molar ratio of hydrogen and 3,3,5- trimethylcyclohexanones is preferably (2.05~3):1, more preferably (2.2~2.6):1.
In the present invention, the temperature that the fraction water is mixed with tert-butyl hydroperoxide is preferably 5~30 DEG C, more preferably
10~25 DEG C, more preferably 15~20 DEG C.In the present invention, the mixing of the fraction water and tert-butyl hydroperoxide 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 stirring can promote 3,3,5- in fraction water
The mixing of trimethylcyclohexanone and tert-butyl hydroperoxide and the separation of water phase.
After the completion of mixing, the present invention preferably stands the product of the mixing, obtains upper organic phase and lower layer's water phase, so
Water phase is removed afterwards, obtains tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones.In the present invention, described quiet
The time set is preferably 15min or more, more preferably 20~30min.
In the present invention, the tert-butyl hydroperoxide preferably further includes with the mixed liquor of 3,3,5- trimethylcyclohexanones
The tert-butyl alcohol.In the present invention, the presence of the tert-butyl alcohol is for tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones it is anti-
Should be without influence, the mixed liquor of tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones can be directly as raw material reuse.
Obtain tert-butyl hydroperoxide and 3, after the mixed liquor of 3,5- trimethylcyclohexanones, the present invention is with the tertiary butyl mistake
The mixed liquor of hydrogen oxide and 3,3,5- trimethylcyclohexanones is that raw material prepares 1,1- bis(t-butylperoxy) -3,3,5- trimethyls
Hexamethylene.
In the present invention, 1, the 1- bis(t-butylperoxy)s -3,3, the preparation of 5- trimethyl-cyclohexanes preferably include：
By tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones is mixed with sulfuric acid solution carries out addition reaction, obtains 1,
1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes.
The present invention preferably mixes tert-butyl hydroperoxide with the mixed liquor of 3,3,5- trimethylcyclohexanones with sulfuric acid solution
Carry out addition reaction.In the present invention, the sulfuric acid in the sulfuric acid solution and tert-butyl hydroperoxide and 3,3,5- front three basic rings
The molar ratio of 3,3,5- trimethylcyclohexanones is preferably (1.010~2.164) in the mixed liquor of hexanone:1, more preferably (1.5~
2):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 by the concentrated sulfuric acid after dilution；The dilution is preferably water and/or 1,1- bis- with diluent
The water phase mother liquor generated in (t-butylperoxy) -3,3,5- trimethyl-cyclohexane production processes.
In the present invention, the mixed liquor of the tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones and sulfuric acid solution
Mixing preferably carries out under agitation；The rate of the stirring is preferably 50~150r/min, more preferably 100r/min；Institute
The time for stating stirring is preferably 10min or more, more preferably 15~20min.
In the present invention, the temperature of the addition reaction is preferably 5~30 DEG C, more preferably 10~25 DEG C, most preferably
15~20 DEG C；The time of the addition reaction is preferably 2.5~5h, more preferably 3~4h.In the present invention, the addition 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, preferably further include after the addition reaction：
The product of the addition reaction is detached, 1,1- bis(t-butylperoxy)s -3,3,5- front three basic rings are obtained
Hexane crude product and water phase mother liquor；Contain sulfuric acid in the water phase mother liquor；
By the 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes crude product successively through alkali cleaning, washing, drying
And filtering, obtain 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes；The water phase mother liquor is made after being mixed with sulfuric acid
For sulfuric acid solution reuse.
Product of the present invention preferably by the addition reaction detaches, and obtains 1,1- bis(t-butylperoxy)s -3,3,
5- trimethyl-cyclohexanes crude product and water phase mother liquor；Contain sulfuric acid in the water phase mother liquor.The present invention is preferably by the addition reaction
Product introduce layering slot be layered, obtain upper layer 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane crude products
With lower layer's water phase mother liquor, then detach.
Obtain 1,1- bis(t-butylperoxy)s -3,3, after 5- trimethyl-cyclohexanes crude product and water phase mother liquor, the present invention is excellent
Choosing is by the 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes crude product successively through alkali cleaning, washing, drying and mistake
Filter, obtains 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes；The water phase mother liquor is used as sulphur after being mixed with sulfuric acid
Acid solution reuse.
The not special restriction of operation of the present invention to the alkali cleaning, washing, drying and filtering, using people in the art
The technical solution of 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexane crude products purification known to member.
In order to further illustrate the present invention, with reference to embodiment to the bis- (t-butyl peroxies of 1,1- provided by the invention
Base) recoverying and utilizing methods of -3,3,5- trimethyl-cyclohexane soda-wash waters is described in detail, but cannot be interpreted as them pair
The restriction of the scope of the present invention.
Embodiment 1:
In a kettle input 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexane soda-wash waters 1000kg (3,
3,5- trimethylcyclohexanones：0.081%, the tert-butyl alcohol：0.12%) it is evaporated under reduced pressure, vacuum degree control is -0.85MPa, temperature 60
DEG C, it is evaporated under reduced pressure 6h, obtains fraction water 60kg (3,3,5- trimethylcyclohexanones：1.3%, the tert-butyl alcohol：1.95%), bottom liquid is uncle
Butyl peroxy hydrogen sodium salt；
613.9kg tert-butyl hydroperoxide (mass concentration 85%) and 400kg3,3,5- trimethylcyclohexanones are added into (matter
Measure it is a concentration of 99%) enter into mixing kettle, fraction water 60kg is added, is stirred under the conditions of 5 DEG C of temperature control, rotating speed 120r/min,
It is stood after mixing 10min and separates lower layer's water phase, obtain tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones
974.09kg；
114.78kg sulfuric acid (mass concentration 98%) and 885.22kg mother liquors (h 2 so 4 concentration 55.1%) are added
Enter into complex acid kettle, under the conditions of 5 DEG C of temperature control, 120r/min is stirred 30min, obtains the sulfuric acid solution 1000kg of catalysis；
Mixed liquor and the 1000kg catalysis of 974.09kg tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones are used
Sulfuric acid solution be added in synthesis reactor and be stirred to react, and control and reacted at 5 DEG C, rotating speed 120r/min reacts 5h, obtains anti-
Answer product；
Reaction product is introduced into layering slot and stands 1h layerings, obtains upper layer 1,1- bis(t-butylperoxy)s -3,3,5- tri-
The mother liquor 1089.46kg of hexahydrotoluene crude product and lower layer's water phase sulfur acid, and by the mother liquor of lower layer's water phase sulfur acid
885.22kg is mixed to get sulfuric acid solution reuse with sulfuric acid, by upper layer 1,1- bis(t-butylperoxy)s -3,3,5- front three basic rings
Hexane crude product 882.1kg is imported in post-processing kettle；
1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes the crude product in kettle will be post-processed and pass through alkali successively
After washing, wash, dry and filtering, 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane finished products 858.2kg are obtained.
Embodiment 2:
In a kettle input 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexane soda-wash waters 1000kg (3,
3,5- trimethylcyclohexanones：0.121%, the tert-butyl alcohol：0.23%) it is evaporated under reduced pressure, vacuum degree control is -0.095MPa, and temperature is
70 DEG C, it is evaporated under reduced pressure 12h, obtains fraction water 96kg (3,3,5- trimethylcyclohexanones：1.25%, the tert-butyl alcohol：2.36%), bottom liquid
For t-butyl peroxy hydrogen sodium salt；
700kg tert-butyl hydroperoxide (mass concentration 80%) and 399kg3,3,5- trimethylcyclohexanones are added into (quality
It is a concentration of 99%) to enter into mixing kettle, fraction water 96kg is added, is stirred under the conditions of 10 DEG C of temperature control, rotating speed 80r/min, mixes
Standing separates lower layer's water phase after closing 20min, obtains tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones
1057.3kg；
205.08kg sulfuric acid (mass concentration 98%) and 654.92kg mother liquors (h 2 so 4 concentration 50.7%) are added
Enter into complex acid kettle, under the conditions of 10 DEG C of temperature control, 80r/min is stirred 30min, obtains the sulfuric acid solution 860kg of catalysis；
By the mixed liquor and 860kg catalysis of 1057.3kg tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones
Sulfuric acid solution is added in synthesis reactor and is stirred to react, and controls and reacted at 10 DEG C, and rotating speed 80r/min reacts 5h, is reacted
Product；
Reaction product is introduced into layering slot and stands 1h layerings, obtains upper layer 1,1- bis(t-butylperoxy)s -3,3,5- tri-
The mother liquor 1051.12kg of hexahydrotoluene crude product and lower layer's water phase sulfur acid, and by the mother liquor of lower layer's water phase sulfur acid
654.92kg is mixed to get sulfuric acid solution reuse with sulfuric acid, by upper layer 1,1- bis(t-butylperoxy)s -3,3,5- front three basic rings
Hexane crude product 863.75kg is imported in post-processing kettle；
1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes the crude product in kettle will be post-processed and pass through alkali successively
After washing, wash, dry and filtering, 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane finished products 841.47kg are obtained.
Embodiment 3:
In a kettle input 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexane soda-wash waters 1000kg (3,
3,5- trimethylcyclohexanones：0.02%, the tert-butyl alcohol：0.19%) it is evaporated under reduced pressure, vacuum degree control is -0.095MPa, temperature 70
DEG C, it is evaporated under reduced pressure 20h, obtains fraction water 15.6kg (3,3,5- trimethylcyclohexanones：1.28%, the tert-butyl alcohol：12.01%), bottom
Liquid is t-butyl peroxy hydrogen sodium salt；
814.6kg tert-butyl hydroperoxide (mass concentration 75%) and 400kg3,3,5- trimethylcyclohexanones are added into (matter
Measure it is a concentration of 99%) enter into mixing kettle, fraction water 15.6kg is added, is stirred under the conditions of 15 DEG C of temperature control, rotating speed 50r/
Min, standing separates lower layer's water phase after mixing 20min, obtains tert-butyl hydroperoxide and 3, the mixing of 3,5- trimethylcyclohexanones
Liquid 1169.01kg；
255.96kg sulfuric acid (mass concentration 98%) and 474.04kg mother liquors (h 2 so 4 concentration 45.6%) are added
Enter into complex acid kettle, under the conditions of 15 DEG C of temperature control, 50r/min is stirred 30min, obtains the sulfuric acid solution 730kg of catalysis；
Mixed liquor and the 730kg catalysis of 1169.01kg tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones are used
Sulfuric acid solution be added in synthesis reactor and be stirred to react, and control and reacted at 15 DEG C, rotating speed 50r/min reacts 4.5h, obtains
Reaction product；
Reaction product is introduced into layering slot and stands 1h layerings, obtains upper layer 1,1- bis(t-butylperoxy)s -3,3,5- tri-
The mother liquor 1023.63kg of hexahydrotoluene crude product and lower layer's water phase sulfur acid, and by the mother liquor of lower layer's water phase sulfur acid
474.04kg is mixed to get sulfuric acid solution reuse with sulfuric acid, by upper layer 1,1- bis(t-butylperoxy)s -3,3,5- front three basic rings
Hexane crude product 872.88kg is imported in post-processing kettle；
1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes the crude product in kettle will be post-processed and pass through alkali successively
After washing, wash, dry and filtering, 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane finished products 849.34kg are obtained.
As can be seen from the above embodiments, method provided by the invention can 1,1- bis(t-butylperoxy)s -3,3,5-
The recoverying and utilizing method of trimethyl-cyclohexane soda-wash water it is simple and can realize in soda-wash water the sodium salt of tert-butyl hydroperoxide and
The abundant recycling of 3,3,5- trimethylcyclohexanones.
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should
It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. one kind 1,1- bis(t-butylperoxy)s -3,3, the recoverying and utilizing method of 5- trimethyl-cyclohexane soda-wash waters, including with
Lower step：
(1) by 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexane soda-wash waters are evaporated under reduced pressure, and fraction water is obtained
With bottom liquid；Contain 3,3,5- trimethylcyclohexanones in the fraction water；The bottom liquid is the sodium salt of tert-butyl hydroperoxide；
(2) it is gone after mixing the fraction water that the step (1) obtains with tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones
Except water phase, tert-butyl hydroperoxide and 3, the mixed liquor of 3,5- trimethylcyclohexanones are obtained；
(3) mixed liquor of the tert-butyl hydroperoxide obtained using the step (2) and 3,3,5- trimethylcyclohexanones is raw material system
Standby 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexanes.
2. recoverying and utilizing method according to claim 1, which is characterized in that the temperature being evaporated under reduced pressure in the step (1)
It is 50~80 DEG C.
3. recoverying and utilizing method according to claim 2, which is characterized in that the vacuum being evaporated under reduced pressure in the step (1)
Degree is -0.08~-0.1MPa.
4. according to the recoverying and utilizing method described in claims 1 to 3 any one, which is characterized in that decompression in the step (1)
The time of distillation be 1~for 24 hours.
5. recoverying and utilizing method according to claim 1, which is characterized in that the temperature mixed in the step (2) is 5~
30℃。
6. recoverying and utilizing method according to claim 1, which is characterized in that bis- (the tertiary butyl mistakes of 1,1- in the step (3)
Oxygroup) preparations of -3,3,5- trimethyl-cyclohexanes includes：By the mixing of tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones
Liquid is mixed with sulfuric acid solution carries out addition reaction, obtains 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes.
7. recoverying and utilizing method according to claim 6, which is characterized in that the temperature of the addition reaction is 5~30 DEG C,
The time of addition reaction is 2.5~5h.
8. recoverying and utilizing method according to claim 6, which is characterized in that further include after the addition reaction：It will be described
The product of addition reaction is detached, and 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes crude product and water phase are obtained
Mother liquor；Contain sulfuric acid in the water phase mother liquor；
By the 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes crude product successively through alkali cleaning, washing, drying and mistake
Filter, obtains 1,1- bis(t-butylperoxy)s -3,3,5- trimethyl-cyclohexanes；The water phase mother liquor is used as sulphur after being mixed with sulfuric acid
Acid solution reuse.
9. recoverying and utilizing method according to claim 1 or 6, which is characterized in that the tert-butyl hydroperoxide and 3,3,
In the mixed liquor of 5- trimethylcyclohexanones the molar ratio of tert-butyl hydroperoxide and 3,3,5- trimethylcyclohexanones be (2.05~
3):1。
10. recoverying and utilizing method according to claim 6, which is characterized in that the sulfuric acid in the sulfuric acid solution and tertiary fourth
In the mixed liquor of base hydrogen peroxide and 3,3,5- trimethylcyclohexanones the molar ratio of 3,3,5- trimethylcyclohexanones be (1.010~
2.164):1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810403134.6A CN108373435A (en) | 2018-04-28 | 2018-04-28 | A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of -3,3,5- trimethyl-cyclohexane soda-wash waters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810403134.6A CN108373435A (en) | 2018-04-28 | 2018-04-28 | A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of -3,3,5- trimethyl-cyclohexane soda-wash waters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108373435A true CN108373435A (en) | 2018-08-07 |
Family
ID=63033031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810403134.6A Pending CN108373435A (en) | 2018-04-28 | 2018-04-28 | A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of -3,3,5- trimethyl-cyclohexane soda-wash waters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108373435A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232347A (en) * | 2018-10-29 | 2019-01-18 | 常熟市滨江化工有限公司 | A kind of recoverying and utilizing method of 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexane soda-wash water |
| CN113387859A (en) * | 2021-06-18 | 2021-09-14 | 常熟市滨江化工有限公司 | Recycling treatment method of 1, 1-bis (tert-butyl peroxy) -3,3, 5-trimethylcyclohexane waste material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850249A (en) * | 2012-09-21 | 2013-01-02 | 江苏强盛功能化学股份有限公司 | Preparation method of 1, 1-bis(t-butyl peroxy)-3, 3, 5-trimethylcyclohexane |
-
2018
- 2018-04-28 CN CN201810403134.6A patent/CN108373435A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850249A (en) * | 2012-09-21 | 2013-01-02 | 江苏强盛功能化学股份有限公司 | Preparation method of 1, 1-bis(t-butyl peroxy)-3, 3, 5-trimethylcyclohexane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232347A (en) * | 2018-10-29 | 2019-01-18 | 常熟市滨江化工有限公司 | A kind of recoverying and utilizing method of 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexane soda-wash water |
| CN113387859A (en) * | 2021-06-18 | 2021-09-14 | 常熟市滨江化工有限公司 | Recycling treatment method of 1, 1-bis (tert-butyl peroxy) -3,3, 5-trimethylcyclohexane waste material |
| CN113387859B (en) * | 2021-06-18 | 2022-04-26 | 常熟市滨江化工有限公司 | Recycling treatment method of 1, 1-bis (tert-butyl peroxy) -3,3, 5-trimethylcyclohexane waste material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108373435A (en) | A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of -3,3,5- trimethyl-cyclohexane soda-wash waters | |
| CN110028542A (en) | The clean preparation method of canrenone | |
| CN112830867A (en) | Preparation method of energy-saving environment-friendly flame retardant tetrabromo double-part A | |
| CN106187877A (en) | A kind of production method of quinolinic acid | |
| CN106554480B (en) | A kind of preparation method of bisphenol A type epoxy resin | |
| CN106478438A (en) | A kind of preparation method of magnesium glycinate chelate | |
| CN103086959A (en) | Novel process for producing 3,5,6-sodium trichloropyrindinol | |
| CN106044730B (en) | Utilize the method for high-grade phosphorus ore production phosphoric acid by wet process | |
| CN107032981A (en) | A kind of method recycled containing sodium formate and sodium chloride mixing solid wastes recycling | |
| CN101955233A (en) | Method for producing ferrous sulphate monohydrate | |
| CN103979503B (en) | A kind of method preparing telluric acid | |
| CN105330545B (en) | The method that triazine ring cyclization mother liquid bits mesoxalic acid is recycled using stannic chloride as catalyst | |
| CN106866399A (en) | Tetrachloroquinone and preparation method thereof | |
| CN104086393B (en) | A kind of preparation method of the 3,6-dichlorosalicylic acid of improvement | |
| CN108409624A (en) | A kind of 1,1- is bis-（T-butylperoxy）The recoverying and utilizing method of hexamethylene soda-wash water | |
| US3773838A (en) | Method of preparing dimethylsulphoxide | |
| CN109232347A (en) | A kind of recoverying and utilizing method of 1,1- bis(t-butylperoxy) -3,3,5- trimethyl-cyclohexane soda-wash water | |
| CN112939764A (en) | Production process of 2-hydroxy-3-naphthoic acid | |
| CN103641793A (en) | Treatment method of AE (Active Ester) residual liquid | |
| JPH05112728A (en) | Refining of indigo | |
| CN106854161A (en) | The synthetic method of the nitrobenzoic acid of 3,4 dimethoxy 6 | |
| CN112225720A (en) | Production method of thiophene-2-acetyl chloride | |
| CN108516556B (en) | Method for preparing high-purity silicon dioxide by using silicon slag | |
| CN106966934B (en) | A kind of preparation method of dialkyl dithio amino formate | |
| CN106673015B (en) | The method for producing high-purity ammonium fluoride using sodium bifluoride waste residue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180807 |
|
| RJ01 | Rejection of invention patent application after publication |