CN109180548A - The method for improving ethylbenzene hydroperoxide stability - Google Patents
The method for improving ethylbenzene hydroperoxide stability Download PDFInfo
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- CN109180548A CN109180548A CN201811056643.2A CN201811056643A CN109180548A CN 109180548 A CN109180548 A CN 109180548A CN 201811056643 A CN201811056643 A CN 201811056643A CN 109180548 A CN109180548 A CN 109180548A
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- ethylbenzene
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
- C07C407/006—Stabilisation; Use of additives
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Abstract
The invention discloses a kind of methods for improving ethylbenzene hydroperoxide stability.The method includes malonate derivative and/or butanedioic acid derivative are added in the preparation process of ethylbenzene hydroperoxide.The ethylbenzene hydroperoxide that the method for the present invention can effectively inhibit oxidation to generate decomposes, and is particularly suitable for SMPO technique, conducive to the stability for improving the intermediate ethylbenzene hydroperoxide in the technique.The method of the present invention will not introduce metal cation sodium or potassium etc., can reduce scale problems caused by material clamp band etc., while reduce the discharge of phosphorus-containing wastewater, and the feature of environmental protection is good, and improve the selectivity and yield of reaction.
Description
Technical field
The present invention relates to petrochemical industries, more particularly, to a kind of method for improving ethylbenzene hydroperoxide stability.
Background technique
Ethylbenzene hydroperoxide is the intermediate in propylene oxide and styrene joint production process, propylene oxide and benzene second
The characteristics of alkene combined producing process is referred to as SMPO technique, SMPO co-production method is not need pyroreaction, can coproduction benzene simultaneously
Two kinds of important Organic chemical products of ethylene and propylene oxide.Ethylbenzene oxidation generates ethylbenzene hydroperoxide in SMPO technical process
It is a crucial step, Halcon company succeeds in developing and is most situated between early in United States Patent (USP) US3459810 and US3475498
It continues, and realized industrialized production for the first time in Spain in 1973.Possess the manufacturer of the method patent power of alienation in the world at present
Mainly there are Lyondell company, Shell company, Repsol company etc..
In the SMPO technique, in addition to ethylbenzene oxidation generates the main reaction of ethylbenzene hydroperoxide, it also occur that secondary anti-
Methyl phenyl carbinol and acetophenone etc. should be generated, main reaction and side reaction belong to exothermic reaction, and in reaction process not
It is that all ethylbenzene all reacts, unreacted ethylbenzene can be recycled in oxidation reactor.The oxidation reaction is in ethylbenzene
The concentration of total weight of the hydroperoxides based on the reaction mixture carries out under conditions of being lower than 20wt%, in general, at this
Concentration is higher than under the concentration, and the generation of side-products methyl phenyl methanol and acetophenone has been more than ethylbenzene hydroperoxide
Amount, causes the inefficiency loss of reactant ethylbenzene.
It is described in CN201510624458, the reaction that ethylbenzene oxidation generates ethylbenzene hydroperoxide is zero-order reaction, and second
Benzene hydroperoxides depth side reaction generates methyl phenyl carbinol and acetophenone close to 1 grade, and reactant concentration is to ethylbenzene
Oxidation influence smaller, but be affected to the decomposition of ethylbenzene hydroperoxide, plural serial stage reaction can make ethylbenzene hydroperoxidation
Object is unfavorable for improving the selectivity of ethylbenzene hydroperoxide, i.e. increase conversion of ethylbenzene and raising ethylbenzene in later period high accumulation
The selectivity of hydroperoxides is a pair of implacable contradiction.But the patent does not refer to how inhibiting second when improving ethylbenzene oxidation
Benzene hydroperoxides decomposable process.In patent US8017812, CN200780042092, Shell Co. Ltd is described about ethylbenzene liquid
The improvement of phase oxidation technique improves ethylbenzene oxidation by addition styrene and/or styrene derivative, realizes high oxidation speed
Rate.But do not refer to that addition auxiliary agent improves oxidation effectiveness.
Ethylbenzene hydroperoxidation is reduced using potassium pyrophosphate or sodium pyrophosphate solution to be injected into reactor on device at present
Object decomposition rate.But metal cation sodium or potassium etc. are introduced in potassium pyrophosphate or sodium pyrophosphate use process, it may be due to
Material clamp band, which is deposited in tower tray, causes fouling, it is necessary to be handled using other methods.And phosphor in sewage that treated member
Cellulose content is higher, is discharged into environment and easily causes water eutrophication, promotes the growth and breeding of bacterium algae, generates serious environment
Hidden danger.With the increasing of Environmental Protection in China dynamics, the requirement to P elements in the industrial wastewater of discharge is increasingly stringenter.
For relevant issues in the prior art, effective solution method is not yet proposed at present.
Summary of the invention
The application technical problems to be solved are to provide a kind of method for improving ethylbenzene hydroperoxide stability.This method
The ethylbenzene hydroperoxide that can effectively inhibit oxidation to generate decomposes, while metal cation sodium or potassium will not be introduced etc., it reduces
The discharge of phosphorus-containing wastewater, the feature of environmental protection are good.
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
A method of ethylbenzene hydroperoxide stability being improved, the method includes the preparations in ethylbenzene hydroperoxide
Malonate derivative and/or butanedioic acid derivative are added in the process.
As the further improvement of technical solution, the general formula of the butanedioic acid derivative is as follows:
Wherein, R1、R2The respectively linear chain or branched chain alkyl of hydrogen or C1-C8, R3、R4、R5、R6Respectively hydrogen, amino, hydroxyl
The linear chain or branched chain alkyl of base or C1-C5.
As the further improvement of technical solution, the general formula of the malonate derivative is as follows:
Wherein, R7、R8The respectively linear chain or branched chain alkyl of hydrogen or C1-C8；R9、R10Respectively hydrogen, amino or C1-C5
Linear chain or branched chain alkyl.
As the further improvement of technical solution, the method includes being feed oxygen metaplasia into ethylbenzene hydroperoxidation using ethylbenzene
Malonate derivative and/or butanedioic acid derivative are added during object.
As the further improvement of technical solution, in terms of raw material total amount, the malonate derivative and/or succinic acid are derivative
The addition concentration of object is 0.1~450mg/kg.
As the further improvement of technical solution, described method includes following steps:
Using single-stage or multi-stage oxidizing reactor, oxygen-containing gas is blasted in single-stage or multi-stage oxidizing reactor, by the third two
Acid derivative and/or butanedioic acid derivative mix with liquid phase ethylbenzene and followed by single-stage or multi-stage oxidizing reactors, gradually oxygen
Metaplasia is sent at the solution containing ethylbenzene hydroperoxide, solution through conduit line containing ethylbenzene hydroperoxide generated to next unit.
As the further improvement of technical solution, the addition manner of the malonate derivative and/or butanedioic acid derivative
Are as follows: it is uniformly mixed before liquid phase ethylbenzene enters first oxidation reactor with liquid phase ethylbenzene, or in each oxidation reactor
Increase before liquid phase ethylbenzene or ethylbenzene reactant entrance and pipeline addition is added.
As the further improvement of technical solution, the addition manner of the malonate derivative and/or butanedioic acid derivative
Are as follows: it is added at one time.
As the further improvement of technical solution, the oxidation reactor is bubbling column reactor, and number is 1~6.
As the further improvement of technical solution, the oxidation reactor reaction temperature is 125~185 DEG C.
As the further improvement of technical solution, the adjacent two-stage oxidation reaction device temperature difference is 0~10 DEG C.
As the further improvement of technical solution, the oxidation reactor reaction pressure is 0.1~1.2MPa.
Any range documented by the present invention includes any numerical value between end value and end value and end value or end value
Between any subrange for being constituted of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention
The conventional equipment in fields can be used or carried out referring to the prior art of fields.
Compared with prior art, the invention has the following beneficial effects:
Method of the invention can effectively inhibit oxygen using malonate derivative and/or butanedioic acid derivative as stabilizer
Metaplasia at ethylbenzene hydroperoxide decompose, the generation of by-product is reduced, while this method will not introduce new impurity, without multiple
Miscellaneous post-processing.
Method of the invention is suitable for SMPO technique, conducive to the intermediate ethylbenzene hydroperoxide improved in the technique
Stability；By addition malonate derivative and/or butanedioic acid derivative, the ethylbenzene hydrogen peroxide that can effectively inhibit oxidation to generate
Compound is decomposed, and is reduced the generation of the by-products such as methyl phenyl carbinol, acetophenone in reaction system, is improved the selectivity of reaction
And yield.
Method of the invention will not introduce metal cation sodium compared with using antisludging agent sodium pyrophosphate or potassium pyrophosphate
Or potassium etc., scale problems caused by material clamp band etc. are reduced, subsequent processing is simplified.
Method of the invention, added stabilizer are no phosphorus compound, it is possible to reduce the discharge of phosphorus-containing wastewater, after reduction
The difficulty of continuous processing, good environmental protection.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
A kind of method for improving ethylbenzene hydroperoxide stability of the present invention, including the preparation in ethylbenzene hydroperoxide
Malonate derivative and/or butanedioic acid derivative are added in journey.
It has been investigated that can effectively inhibit oxidation to generate by addition malonate derivative and/or butanedioic acid derivative
Ethylbenzene hydroperoxide decompose, while metal cation sodium or potassium etc. will not be introduced in system, reduce the row of phosphorus-containing wastewater
It puts, simplifies post-processing, the feature of environmental protection is good.
According to the certain embodiments of the application, the general formula of the butanedioic acid derivative is as follows:
Wherein, R1、R2The respectively linear chain or branched chain alkyl of hydrogen or C1-C8, as hydrogen, methyl, ethyl, propyl, isopropyl,
N-hexyl, n-octyl etc., R1、R2It may be the same or different；R3、R4、R5、R6Respectively hydrogen, amino, hydroxyl or C1-
The linear chain or branched chain alkyl of C5, such as hydrogen, amino, methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl, n-pentyl, R3、
R4、R5、R6It may be the same or different.Applicant, using the derivative, can effectively inhibit oxygen by further investigation discovery
Metaplasia at ethylbenzene hydroperoxide decompose, while will not introduce metal cation sodium or potassium etc. in system, reduce phosphorous gives up
The discharge of water.
According to the certain embodiments of the application, the general formula of the malonate derivative is as follows:
Wherein, R7、R8The respectively linear chain or branched chain alkyl of hydrogen or C1-C8, as hydrogen, methyl, ethyl, propyl, isopropyl,
N-hexyl, n-octyl etc., R7、R8It may be the same or different；R9、R10Respectively the straight chain of hydrogen, amino or C1-C5 or
Branched hydrocarbyl, such as hydrogen, amino, hydroxyl, methyl, ethyl, propyl, isopropyl, normal-butyl, tert-butyl, n-pentyl, R9、R10It can
With identical, can also be different.Applicant can effectively inhibit oxidation to generate by further investigation discovery using the derivative
Ethylbenzene hydroperoxide decomposes, while metal cation sodium or potassium etc. will not be introduced in system, reduces the discharge of phosphorus-containing wastewater.
According to the certain embodiments of the application, the method includes being feed oxygen metaplasia into ethylbenzene hydroperoxidation using ethylbenzene
Malonate derivative and/or butanedioic acid derivative are added during object, especially using ethylbenzene as raw material Joint Production epoxy
Malonate derivative and/or butanedioic acid derivative are added in the technique of the SMPO of propane and styrene.
Ethylbenzene hydroperoxide is the intermediate in propylene oxide and styrene joint production process, propylene oxide and benzene second
Alkene combined producing process is referred to as SMPO technique.Ethylbenzene is first generated in Liquid-phase reactor with dioxygen oxidation in SMPO technical process
Ethylbenzene peroxide carries out further conversion reaction again later.It is crucial that wherein ethylbenzene oxidation, which generates ethylbenzene hydroperoxide,
One step, usually because the impurity in system leads to the decomposition of ethylbenzene hydroperoxide.And present inventor is through a large amount of practical studies
It was found that can effectively eliminate the influence of system impurity, to press down by addition malonate derivative and/or butanedioic acid derivative
The ethylbenzene hydroperoxide that oxygenerating generates decomposes, and reduces the generation of by-product, improves the yield of SMPO technique.
According to the certain embodiments of the application, in terms of raw material total amount, the malonate derivative and/or succinic acid are derivative
The addition concentration of object be 0.1~450mg/kg, preferably 0.5~250mg/kg, be specifically as follows 0.5mg/kg, 3mg/kg,
18mg/kg, 60.5mg/kg, 120mg/kg, 186mg/kg, 225mg/kg, 255mg/kg etc., to guarantee effectively to inhibit oxidation
The ethylbenzene hydroperoxide of generation decomposes.
According to the certain embodiments of the application, described method includes following steps:
Using single-stage or multi-stage oxidizing reactor, oxygen-containing gas is blasted in single-stage or multi-stage oxidizing reactor, by the third two
Acid derivative and/or butanedioic acid derivative mix with liquid phase ethylbenzene and followed by single-stage or multi-stage oxidizing reactors, gradually oxygen
Metaplasia is sent at the solution containing ethylbenzene hydroperoxide, solution through conduit line containing ethylbenzene hydroperoxide generated to next unit.
Using the technology, number of reactors required for random selection can according to need.
According to the certain embodiments of the application, the addition manner of the malonate derivative and/or butanedioic acid derivative
Are as follows: it is uniformly mixed before liquid phase ethylbenzene enters first oxidation reactor with liquid phase ethylbenzene, or in each oxidation reactor
Increase before liquid phase ethylbenzene or ethylbenzene reactant entrance and pipeline addition is added.And the malonate derivative and/or succinic acid are derivative
Object opposite liquid phase ethylbenzene concentration in each oxidation reactor is 0.1~450mg/kg, preferably 0.5~250mg/kg, specifically
It can be 0.5mg/kg, 3mg/kg, 18mg/kg, 60.5mg/kg, 120mg/kg, 186mg/kg, 225mg/kg, 255mg/kg
Deng to effectively inhibit the decomposition of ethylbenzene hydroperoxide.
According to the certain embodiments of the application, the addition manner of the malonate derivative and/or butanedioic acid derivative
Are as follows: it is added at one time；And auxiliary agent need not be recycled, auxiliary agent can be expelled directly out with subsequent processing.It is followed to reduce auxiliary agent
The problems such as ring is increased using bring equipment investment.
According to the certain embodiments of the application, the oxidation reactor is bubbling column reactor, and number is 1~6, excellent
3~5 are selected, concretely 3,4,5.Usually number can be determined according to real reaction effect and practice in factory.
According to the certain embodiments of the application, the oxidation reactor reaction temperature be 125~185 DEG C, preferably 140~
160 DEG C, concretely 140 DEG C, 145 DEG C, 150.5 DEG C, 160 DEG C.To guarantee the conversion ratio of ethylbenzene, and it can be reduced ethylbenzene hydrogen mistake
Peroxide breaks down.
According to the certain embodiments of the application, the adjacent two-stage oxidation reaction device temperature difference be 0~10 DEG C, preferably 0~5 DEG C,
Concretely 0 DEG C, 0.6 DEG C, 1 DEG C, 4 DEG C, 5 DEG C.It is poor using suitable reaction temperature, it is ensured that ethylbenzene hydrogen in subsequent reactor
Peroxide concentrations further increase.
According to the certain embodiments of the application, the oxidation reactor reaction pressure be 0.1~1.2MPa, preferably 0.1
~0.5MPa, concretely 0.1MPa, 0.16MPa, 0.25MPa, 0.4MPa, 0.5MPa.It, can be with using suitable reaction pressure
Guarantee the raising of ethylbenzene hydroperoxide concentration.
The invention will be further described for the following examples.
Embodiment 1
A method of ethylbenzene hydroperoxide stability is improved, is included the following steps:
In tool there are three in identical bubble column oxidation reactor device, ethylbenzene and butanedioic acid derivative are mixed through mixer
After conjunction, into the first oxidation reactor, the nitrogen and oxygen mixed gas of the oxygen containing 23v% enter from reactor bottom, go forward side by side
Row reaction, wherein the general formula of butanedioic acid derivative used is as follows:
Wherein, R1For ethyl, R2For ethyl, R3For n-propyl, R4For n-propyl, R5 is normal-butyl, R6For normal-butyl.First
In oxidation reactor, ethylbenzene feed amount 1kg/h, controlling butanedioic acid derivative content in ethylbenzene feed is 70mg/kg, reaction temperature
It is 156 DEG C, reaction pressure 0.20MPa, the reaction liquid phase residence time is 45min, enters second reactor, reaction temperature later
It is 154 DEG C, reaction pressure 0.20MPa, the reaction liquid phase residence time is 45min, finally enters third reactor, reaction temperature
It is 152 DEG C, reaction pressure 0.20MPa, the reaction liquid phase residence time is 45min, and after the reaction was completed, ethylbenzene hydroperoxide is dense
Degree is 6.87%, in addition, side-products methyl phenyl methanol concentration is 0.66%, acetophenone concentration is 0.92%.
Embodiment 2
A method of ethylbenzene hydroperoxide stability is improved, is included the following steps:
In tool there are four being tested in identical bubble column oxidation reactor device, ethylbenzene and butanedioic acid derivative are passed through
After mixer mixing, into the first oxidation reactor, the nitrogen and oxygen mixed gas of the oxygen containing 23v% from reactor bottom into
Enter, and is reacted, wherein the general formula of butanedioic acid derivative used is as follows:
Wherein, R1For methyl, R2For methyl, R3For hydrogen, R4For hydrogen, R5For normal-butyl, R6For normal-butyl.First oxidation reaction
In device, ethylbenzene feed amount is 1kg/h, and controlling butanedioic acid derivative content in ethylbenzene feed is 85mg/kg, reaction temperature 160
DEG C, reaction pressure 0.20MPa, the reaction liquid phase residence time is 40min, enters second reactor, reaction temperature 158 later
DEG C, reaction pressure 0.20MPa, the reaction liquid phase residence time is 40min, enters third reactor, reaction temperature 156 later
DEG C, reaction pressure 0.20MPa, the reaction liquid phase residence time is 40min, finally enters the 4th reactor, reaction temperature 154
DEG C, reaction pressure 0.20MPa, the reaction liquid phase residence time is 40min, and after the reaction was completed, ethylbenzene hydroperoxide concentration is
7.55%, in addition, side-products methyl phenyl methanol concentration is 0.87%, acetophenone concentration is 0.98%.
Embodiment 3
A method of ethylbenzene hydroperoxide stability is improved, is included the following steps:
In tool there are three being tested in identical bubble column oxidation reactor device, ethylbenzene and malonate derivative are passed through
After mixer mixing, into the first oxidation reactor, the nitrogen and oxygen mixed gas of the oxygen containing 23v% from reactor bottom into
Enter, and is reacted, wherein the general formula of malonate derivative used is as follows:
Wherein, R7For normal-butyl, R8For normal-butyl, R9For methyl, R10For methyl.In first oxidation reactor, ethylbenzene feed
Amount is 1kg/h, and controlling malonate derivative content in ethylbenzene feed is 65mg/kg, and reaction temperature is 162 DEG C, and reaction pressure is
0.20MPa, reaction liquid phase residence time are 45min, enter second reactor later, and reaction temperature is 161 DEG C, and reaction pressure is
0.20MPa, reaction liquid phase residence time are 45min, finally enter third reactor, and reaction temperature is 160 DEG C, and reaction pressure is
0.20MPa, reaction liquid phase residence time are 45min, after the reaction was completed, ethylbenzene hydroperoxide concentration 7.55%, in addition, by-product
Object methyl phenyl carbinol concentration is 0.70%, and acetophenone concentration is 0.99%.
Embodiment 4
A method of ethylbenzene hydroperoxide stability is improved, is included the following steps:
In tool there are four being tested in identical bubble column oxidation reactor device, ethylbenzene and malonate derivative are passed through
After mixer mixing, into the first oxidation reactor, the nitrogen and oxygen mixed gas of the oxygen containing 23v% from reactor bottom into
Enter, and is reacted, wherein the general formula of malonate derivative used is as follows:
Wherein, R7For n-pentyl, R8For n-pentyl, R9For amino, R10For amino.In first oxidation reactor, ethylbenzene feed
Amount is 1kg/h, and controlling malonate derivative content in ethylbenzene feed is 35mg/kg, and reaction temperature is 168 DEG C, and reaction pressure is
0.20MPa, reaction liquid phase residence time are 40min, enter second reactor later, and reaction temperature is 166 DEG C, and reaction pressure is
0.20MPa, reaction liquid phase residence time are 40min, enter third reactor later, and reaction temperature is 164 DEG C, and reaction pressure is
0.20MPa, reaction liquid phase residence time are 40min, finally enter the 4th reactor, and reaction temperature is 162 DEG C, and reaction pressure is
0.20MPa, reaction liquid phase residence time are 40min, and after the reaction was completed, ethylbenzene hydroperoxide concentration is 7.90%, in addition, secondary
Product methyl phenyl carbinol concentration is 0.75%, and acetophenone concentration is 1.05%.
Comparative example 1
A method of ethylbenzene hydroperoxide stability is improved, is included the following steps:
In tool there are three in identical bubble column oxidation reactor device, by ethylbenzene and auxiliary agent after mixer mixes, into
Entering the first oxidation reactor, the nitrogen and oxygen mixed gas of the oxygen containing 23v% enter from reactor bottom, and are reacted,
Wherein adjuvant used is commercial product sodium pyrophosphate.In first oxidation reactor, ethylbenzene feed amount 1kg/h controls ethylbenzene feed
Middle auxiliary agent content be 90mg/kg, reaction temperature be 156 DEG C, reaction pressure 0.20MPa, reaction the liquid phase residence time be
45min, later enter second reactor, reaction temperature be 154 DEG C, reaction pressure 0.20MPa, reaction the liquid phase residence time be
45min, finally enters third reactor, and reaction temperature is 152 DEG C, reaction pressure 0.20MPa, and the reaction liquid phase residence time is
45min, after the reaction was completed, ethylbenzene hydroperoxide concentration are 6.32%, in addition, side-products methyl phenyl methanol concentration is
0.99%, acetophenone concentration is 1.66%.
Comparative example 2
A method of ethylbenzene hydroperoxide stability is improved, is included the following steps:
In tool there are four being tested in identical bubble column oxidation reactor device, ethylbenzene and auxiliary agent are mixed through mixer
After conjunction, into the first oxidation reactor, the nitrogen and oxygen mixed gas of the oxygen containing 23v% enter from reactor bottom, go forward side by side
Row reaction, wherein adjuvant used is commercial product sodium pyrophosphate.In first oxidation reactor, ethylbenzene feed amount is 1kg/h, control
Auxiliary agent content is 110mg/kg in ethylbenzene feed, and reaction temperature is 160 DEG C, reaction pressure 0.20MPa, when reaction liquid phase stops
Between be 40min, later enter second reactor, reaction temperature be 158 DEG C, reaction pressure 0.20MPa, reaction liquid phase stop when
Between be 40min, later enter third reactor, reaction temperature be 156 DEG C, reaction pressure 0.20MPa, reaction liquid phase stop when
Between be 40min, finally enter the 4th reactor, reaction temperature is 154 DEG C, reaction pressure 0.20MPa, when reaction liquid phase stops
Between be 40min, after the reaction was completed, ethylbenzene hydroperoxide concentration be 7.09%, in addition, side-products methyl phenyl methanol concentration is
1.02%, acetophenone concentration is 1.44%.
Comparative example 3
A method of ethylbenzene hydroperoxide stability is improved, is included the following steps:
In tool there are three being tested in identical bubble column oxidation reactor device, ethylbenzene and auxiliary agent are mixed through mixer
After conjunction, into the first oxidation reactor, the nitrogen and oxygen mixed gas of the oxygen containing 23v% enter from reactor bottom, go forward side by side
Row reaction, wherein adjuvant used is commercial product potassium pyrophosphate.In first oxidation reactor, ethylbenzene feed amount is 1kg/h, control
Auxiliary agent content is 150mg/kg in ethylbenzene feed, and reaction temperature is 162 DEG C, reaction pressure 0.20MPa, when reaction liquid phase stops
Between be 45min, later enter second reactor, reaction temperature be 161 DEG C, reaction pressure 0.20MPa, reaction liquid phase stop when
Between be 45min, finally enter third reactor, reaction temperature is 160 DEG C, reaction pressure 0.20MPa, when reaction liquid phase stops
Between be 45min, after the reaction was completed, ethylbenzene hydroperoxide concentration 7.43%, in addition, side-products methyl phenyl methanol concentration is
0.83%, acetophenone concentration is 1.46%.
Comparative example 4
A method of ethylbenzene hydroperoxide stability is improved, is included the following steps:
In tool there are four being tested in identical bubble column oxidation reactor device, ethylbenzene and auxiliary agent are mixed through mixer
After conjunction, into the first oxidation reactor, the nitrogen and oxygen mixed gas of the oxygen containing 23v% enter from reactor bottom, go forward side by side
Row reaction, wherein adjuvant used is commercial product sodium pyrophosphate.In first oxidation reactor, ethylbenzene feed amount is 1kg/h, control
Auxiliary agent content is 150mg/kg in ethylbenzene feed, and reaction temperature is 168 DEG C, reaction pressure 0.20MPa, when reaction liquid phase stops
Between be 40min, later enter second reactor, reaction temperature be 166 DEG C, reaction pressure 0.20MPa, reaction liquid phase stop when
Between be 40min, later enter third reactor, reaction temperature be 164 DEG C, reaction pressure 0.20MPa, reaction liquid phase stop when
Between be 40min, finally enter the 4th reactor, reaction temperature is 162 DEG C, reaction pressure 0.20MPa, when reaction liquid phase stops
Between be 40min, after the reaction was completed, ethylbenzene hydroperoxide concentration be 7.68%, in addition, side-products methyl phenyl methanol concentration is
1.02%, acetophenone concentration is 1.67%.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (10)
1. a kind of method for improving ethylbenzene hydroperoxide stability, it is characterised in that: the method includes in ethylbenzene hydrogen peroxide
Malonate derivative and/or butanedioic acid derivative are added in the preparation process of compound.
2. the method according to claim 1 for improving ethylbenzene hydroperoxide stability, which is characterized in that the succinic acid
The general formula of derivative is as follows:
Wherein, R1、R2The respectively linear chain or branched chain alkyl of hydrogen or C1-C8, R3、R4、R5、R6Respectively hydrogen, amino, hydroxyl or
The linear chain or branched chain alkyl of person C1-C5.
3. the method according to claim 1 for improving ethylbenzene hydroperoxide stability, which is characterized in that the malonic acid
The general formula of derivative is as follows:
Wherein, R7、R8The respectively linear chain or branched chain alkyl of hydrogen or C1-C8；R9、R10Respectively hydrogen, amino or C1-C5's is straight
Chain or branched hydrocarbyl.
4. the method according to claim 1 for improving ethylbenzene hydroperoxide stability, which is characterized in that the method packet
Include using ethylbenzene as feed oxygen metaplasia at ethylbenzene hydroperoxide during to add malonate derivative and/or succinic acid derivative
Object.
5. the method according to claim 1 or 4 for improving ethylbenzene hydroperoxide stability, which is characterized in that with raw material
The addition concentration of total amount meter, the malonate derivative and/or butanedioic acid derivative is 0.1~450mg/kg.
6. the method according to claim 4 for improving ethylbenzene hydroperoxide stability, which is characterized in that the method packet
Include following steps:
Using single-stage or multi-stage oxidizing reactor, oxygen-containing gas is blasted in single-stage or multi-stage oxidizing reactor, malonic acid is spread out
Biology and/or butanedioic acid derivative mix with liquid phase ethylbenzene and followed by single-stage or multi-stage oxidizing reactor, gradually oxidation lifes
At the solution containing ethylbenzene hydroperoxide, solution through conduit line containing ethylbenzene hydroperoxide generated is sent to next unit.
7. the method according to claim 4 for improving ethylbenzene hydroperoxide stability, which is characterized in that the malonic acid
The addition manner of derivative and/or butanedioic acid derivative are as follows: before liquid phase ethylbenzene enters first oxidation reactor with liquid phase second
Benzene is uniformly mixed, or increases before the liquid phase ethylbenzene of each oxidation reactor or ethylbenzene reactant entrance and pipeline addition is added.
8. the method according to claim 4 for improving ethylbenzene hydroperoxide stability, which is characterized in that the malonic acid
The addition manner of derivative and/or butanedioic acid derivative are as follows: be added at one time.
9. the method according to claim 4 for improving ethylbenzene hydroperoxide stability, which is characterized in that the oxidation is anti-
Answering device is bubbling column reactor, and number is 1~6.
10. the method according to claim 4 for improving ethylbenzene hydroperoxide stability, which is characterized in that the oxidation
Reactor reaction temperature is 125~185 DEG C；The adjacent two-stage oxidation reaction device temperature difference is 0~10 DEG C；The oxidation reactor reaction
Pressure is 0.1~1.2MPa.
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| CN (1) | CN109180548A (en) |
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|---|---|---|---|---|
| US2674629A (en) * | 1952-04-11 | 1954-04-06 | Rhone Poulenc Sa | Production of hydroperoxides using beta-ketonic esters as oxidation initiators |
| US2792425A (en) * | 1954-10-14 | 1957-05-14 | Monsanto Chemicals | Production of hydroperoxides using malonic esters as oxidation initiators |
| US2861107A (en) * | 1955-08-22 | 1958-11-18 | Edogawa Kagaku Kogyo Kabushiki | Process for the production of cumene hydroperoxide |
| US4602118A (en) * | 1984-11-09 | 1986-07-22 | Exxon Research And Engineering Co. | Liquid phase oxidation of organic compounds to their hydroperoxides |
| CN106554298A (en) * | 2015-09-28 | 2017-04-05 | 万华化学集团股份有限公司 | A kind of method that ethylbenzene oxidation prepares ethylbenzene hydroperoxide |
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2018
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2674629A (en) * | 1952-04-11 | 1954-04-06 | Rhone Poulenc Sa | Production of hydroperoxides using beta-ketonic esters as oxidation initiators |
| US2792425A (en) * | 1954-10-14 | 1957-05-14 | Monsanto Chemicals | Production of hydroperoxides using malonic esters as oxidation initiators |
| US2861107A (en) * | 1955-08-22 | 1958-11-18 | Edogawa Kagaku Kogyo Kabushiki | Process for the production of cumene hydroperoxide |
| US4602118A (en) * | 1984-11-09 | 1986-07-22 | Exxon Research And Engineering Co. | Liquid phase oxidation of organic compounds to their hydroperoxides |
| CN106554298A (en) * | 2015-09-28 | 2017-04-05 | 万华化学集团股份有限公司 | A kind of method that ethylbenzene oxidation prepares ethylbenzene hydroperoxide |
Non-Patent Citations (2)
| Title |
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| 北京化工研究院乙苯共氧化组: "乙苯氧化制过氧化氢乙苯", 《石油化工》 * |
| 杨成德 等: "环氧丙烷 / 苯乙烯联产法生产工艺综述", 《武汉职业技术学院学报》 * |
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