CN106588734B - A kind of cumene oxidation prepares the method and device of cumyl hydroperoxide - Google Patents
A kind of cumene oxidation prepares the method and device of cumyl hydroperoxide Download PDFInfo
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- CN106588734B CN106588734B CN201611168755.8A CN201611168755A CN106588734B CN 106588734 B CN106588734 B CN 106588734B CN 201611168755 A CN201611168755 A CN 201611168755A CN 106588734 B CN106588734 B CN 106588734B
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Abstract
The present invention provides the method and devices that a kind of cumene oxidation prepares cumyl hydroperoxide.In the first microreactor group that one or more microreactors are connected in series, isopropylbenzene and initiator are passed through in first microreactor in the first microreactor group, second microreactor that the reaction product obtained after peroxidization flows into the first microreactor group carries out oxidation reaction, successively recursion carries out continuous flowing type oxidation reaction, until reaction product finally flows into the last one microreactor and carries out oxidation reaction, it is final to purify；In each oxidation reaction process, all microreactors are passed through oxygen, and the molar ratio of oxygen summation that the isopropylbenzene that is passed through of first microreactor and all microreactors are passed through is 0.1:5.The present invention solves the problems, such as that the fluctuation of traditional handicraft reaction temperature is big, production efficiency is low, low yield.
Description
Technical field
The present invention relates to chemical technology fields, and the side of cumyl hydroperoxide is prepared more particularly, to a kind of cumene oxidation
Method and device.
Background technique
Cumene method is that production phenol and the most important method of acetone, production capacity account for about Phenol at Home in the world at present
The 92% of total productive capacity.Cumene method is synthetically produced phenol and is specifically divided into three-step reaction:
First step reaction is to make propylene and benzene that the alkyl that addition reaction generates isopropylbenzene occur using vapor phase method or liquid phase method
Change reaction；Second step reaction is that cumene oxidation is generated to the oxidation reaction of cumyl hydroperoxide (CHP)；Third step is peroxide
Change the decomposition reaction that hydrogen isopropylbenzene is decomposed into phenol and acetone.
The oxidation reaction of second step is the key reaction in phenol production, it is therefore an objective to be generated reducing by-product to greatest extent
While so that isopropylbenzene is farthest converted to peroxidating oxygen isopropylbenzene (CHP), and guarantee safe operation as much as possible.Peroxide
The thermal stability for changing oxygen isopropylbenzene (CHP) is poor, can voluntarily decompose after heated, so under oxidative conditions it also occur that many secondary anti-
It answers.With the increase of peroxidating oxygen isopropylbenzene (CHP) content or the raising of temperature, major and minor reaction can increase simultaneously and make to react
Yield reduces, and generates a large amount of by-products, and the by-product of simultaneous oxidation reaction will accelerate the decomposition of peroxidating oxygen isopropylbenzene (CHP).
Currently, the oxidation of industrial isopropylbenzene produces since ambient oxygen partial is difficult to activate under the conditions of non-catalytic
The defects of technique is long, equipment requirement is high, safety is poor, working condition is harsh there are induction period belongs to the production of not environment friendly type
Technique.
Generally mostly use bubble tower or bubble column oxidizing tower as oxidation reactor in traditional cumene oxidation technique,
The technique dynamics Controlling is difficult, and reaction speed is slower, and the reaction time is also very long.Specifically, air is from bottom drum into isopropylbenzene
Also it is added from lower part, product and unreacted isopropylbenzene are constantly flowed out from liquid upper layer.Cumene oxidation reaction generally exists
80~120 DEG C, carry out under the conditions of normal pressure~1.0MPa, with product cumyl hydroperoxide (CHP) for reaction initiator, isopropyl
The chain self-catalyzed reaction of free radical occurs for benzene, obtains the cumyl hydroperoxide (CHP) that mass fraction is 10%~40%, dense
Cumyl hydroperoxide (CHP) mass fraction is 80%~90% after contracting, and unreacted isopropylbenzene recycles.
At present, the reactor of traditional reaction process has that inlet oxygen concentration is relatively low, as reaction is along tower height direction
It carries out, air is largely consumed, and device supplies oxygen total amount wretched insufficiency.From the point of view of thermodynamics, which is exothermic reaction, is
Ensuring oxidation reactor safety operation, the concentration for timely removing oxidation reaction heat and accurately controlling in reactor is critically important,
It therefore, must be plus cooling equipment in this oxidation technology.In addition, reaction palpus strict control reaction temperature, so, reaction
Device should select the material of good heat-transfer, and since reaction temperature is up to 100 DEG C, reactor also needs matched heating and attemperator,
And temperature measuring point appropriate should be selected on reactor, reached needed for reaction with the temperature accurately controlled in reactor.
CN103052618A discloses a kind of method for producing phenol of Exxon.Mobil chemical patents Corp: being to produce
It include cyclohexyl -1- phenyl -1- with production comprising being charging by oxidation with cyclohexyl benzene in the method for phenol and cyclohexanone
The oxidation reaction product of hydroperoxides.Then at least part of the oxidation reaction product is cleaved, include benzene with production
The cleavage reaction product of phenol, cyclohexanone and at least one pollutant.At least part of the cleavage reaction product and acid material
Material is contacted to convert at least part of at least one pollutant into the pollutant of converter, and thus produces the anti-of modification
Answer product.The technique is extremely complex.
CN101100415A discloses a kind of green synthesis method of phenol by directly hydroxylating benzene: being a kind of direct hydroxyl of benzene
Changing the green synthesis method of phenol processed, i.e., application DC high voltage 10-30kV generates corona discharge in plasma reactor,
Maintaining plasma reactor temperature is 50-80 DEG C, is passed through the unstripped gas containing benzene and oxidant in reactor, the oxidation
The molar ratio of agent and benzene is 16:1, stop 5~after ten minutes benzene phenol is oxidized to by highly selective.The inventive method is suitable for
Prepare phenol.
There is following disadvantages for traditional technique: (1) initial stage of cumene oxidation reaction, there are longer induction periods
(i.e. self-catalyzed reaction), reaction rate is slower, and the time is long；(2) more difficult activation under the conditions of non-catalytic due to oxygen molecule, must adopt
With higher reaction temperatures, easily leads to side reaction generation and the fierce of cumyl hydroperoxide decomposes, careless manipulation may cause quick-fried
It is fried；(3) tar growing amount is larger, by-product species more (such as acetophenone, dimethylphenylcarbinol, α-methylstyrene and polyisocyanates third
Benzene peroxide etc.), process flow is complicated, and pretreatment and postprocessing working procedures are various；(4) when using air oxidant, tail is aoxidized
The isopropylbenzene taken away in gas by inert gas is more, to prevent pollution atmosphere, it is necessary to be recycled with absorption tower, increase equipment investment.
Reaction rate can be improved with oxygen-enriched air, but safety problem must be taken into consideration.(5) bubble tower used at present or bubble column oxidation
For tower as oxidation reactor, reaction temperature fluctuation is big, about fluctuates between 80-120 DEG C, significantly affects containing for impurity in product
Amount.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of method that cumene oxidation prepares cumyl hydroperoxide, described
Method solves the problems, such as that the fluctuation of traditional handicraft reaction temperature is big, production efficiency is low, low yield.
The second object of the present invention is to provide the device that a kind of cumene oxidation prepares cumyl hydroperoxide, described
Device solves the problems, such as that the fluctuation of conventional apparatus reaction temperature is big, production efficiency is low, low yield, equipment investment are big.
In order to reach the goals above, the present invention provides following technical schemes:
A kind of method that cumene oxidation prepares cumyl hydroperoxide, comprising the following steps:
Using the first microreactor group being connected in series by one or more microreactors as reaction unit, by isopropylbenzene and draw
Hair agent is passed through in first microreactor in the first microreactor group, the reacting product stream obtained after peroxidization
Second microreactor entered in the first microreactor group carries out oxidation reaction, and successively recursion carries out continuous flowing type oxidation
Reaction, until reaction product finally flows into the last one microreactor in the first microreactor group and carries out oxidation reaction,
The purifying hydrogen peroxide isopropylbenzene from finally obtained reaction product；
Wherein, the residence time of reactant is 0.1-1.0h in each microreactor, reaction temperature is 90~130
DEG C, reaction pressure be 0.1~1.0MPa；
In each oxidation reaction process, all microreactors are passed through oxygen, and in the microreactor group
The molar ratio for the oxygen summation that the isopropylbenzene and all microreactors that first microreactor is passed through are passed through is 0.1:0.2-
5, preferably 0.1:0.2-1.
Compared with prior art, mainly there are two innovative points for the above method of the invention:
One, continuous flowing type production is realized using concatenated multiple microreactors, reach high production efficiency, yield height (reaches
To 30% or more), the small purpose of temperature fluctuation.
Specifically, first in microreactor group multiple microreactors reaction can carry out simultaneously, therefore eliminate charging,
The overhead times such as filler, and the large specific surface area of microreactor, reaction rate is fast, shortens the reaction time, to sum up, this
Invention thoroughly solves the problems, such as that traditional batch caldron process production efficiency is low in terms of two.
It is added portionwise from multiple microreactors secondly, oxygen needed for each oxidation reaction process is divided by the present invention,
The oxidation reaction in each microreactor is mored easily guarantee in this way close to dynamics and thermodynamical equilibrium, therefore, reaction rate and production
Rate greatly improves.
It is conducted batch-wise further, since each oxidation reaction process is divided into multiple microreactors, therefore, integrated oxidation is anti-
The total amount of heat that should be released is dispersed in different reactors, is easier to exchange heat in this way, and thus bring temperature fluctuation also reduces,
It can control in ± 2 DEG C, at the same time, the impurity content in product also further decreases.And it is of the present invention micro- anti-
It is high to answer device heat exchange efficiency, thus the amount of heat released in reaction can be quickly moved out to keep reaction temperature homogeneous constant.It is comprehensive
On, the present invention at least solves cumene oxidation production cumyl hydroperoxide (CHP) this strong exothermal reaction in terms of two and asks
Topic.However, since mixing rate and heat exchange efficiency are lower, usually will appear hot-spot phenomenon in traditional handicraft, and it is local
Overheat often leads to by-product generation, to make yield and the selectivity decline of reaction.
The second, the non-air of the invention using oxygen, had both improved the selectivity of reaction speed and reaction process, and had avoided pair
The generation of reaction in turn avoids the more problem of the isopropylbenzene taken away in oxidized tail gas by inert gas, and it is big to avoid its pollution
Gas must be recycled with absorption tower, increase the problem of equipment investment.
In addition, method of the invention can also carry out following improve:
Preferably, the initiator is cumyl hydroperoxide and/or diisopropyl benzene hydrogen peroxide, preferably diisopropyl
Base benzene hydrogen peroxide；
Preferably, diisopropyl benzene hydrogen peroxide is dissolved in the isopropylbenzene and then is passed through first microreactor.
Cumyl hydroperoxide will not introduce sundries as initiator, but its chemical property is extremely unstable, encounter acid,
Heavy explosion can occur for alkali, heat and variable valent metal ion etc., and the requirement of storage and transportation condition is extremely stringent, and dosage is big.
And diisopropyl benzene hydrogen peroxide property is relatively stable and is solid-state, is easier to storage and transportation, improves safety；Simultaneously
It is passed through again after being dissolved in isopropylbenzene, solves the problems, such as to introduce solvent impurity；And diisopropyl benzene hydrogen peroxide is urged
Change high-efficient, dosage is few.
Preferably, initiator used in every 100mL isopropylbenzene is 0.2-0.5g, more preferable 0.2-0.25g.
Multiple microreactor groups identical with the first microreactor group can be set in the present invention, and between group and group
Parallel connection avoids the problem of expanding reactor volume to improve the reaction scale of construction.
For example, the first microreactor group is parallel with multiple second microreactor groups, and it is each described second micro- anti-
Device group is answered to be connected in series by multiple microreactors, the oxidation reaction method and described first of each second microreactor group
Microreactor group is identical.
Preferably, the quantity of microreactor is selected from the positive integer between 2-50, preferably 2-5 in the first microreactor group
Between positive integer, the positive integer between more preferable 3-5；
In each group of microreactor group, the oxygen allocation proportion of each microreactor is flat to approach oxidation reaction thermodynamics
Subject to weighing apparatus and kinetic balance.
Preferably, when the first microreactor group contains 2 microreactors, in each oxidation reaction process, first
The amount of oxygen that microreactor and second microreactor are passed through is respectively 40%, the 60% of required amount of oxygen；
Preferably, when the first microreactor group contains 3 microreactors, in each oxidation reaction process, first
The amount of oxygen that microreactor to the last one microreactor is passed through is respectively 30%, 30%, the 40% of required amount of oxygen.
Preferably, the residence time of reactant is 0.2-1.0h in each microreactor, reaction time and anti-
Temperature is answered to have certain relationship.
Preferably, the oxidation pressure of each microreactor is 0.1~0.5MPa.
As described above, the present invention due to by-product it is few, reaction selectivity is high, and yield is high, can be with so purification difficulty is low
Using following method of purification: successively passing through gas-liquid separation, flash separation, concentration.The hydrogen peroxide that the method for purification finally obtains
The purity of isopropylbenzene at least can achieve 80%~90%.
In addition, in order to improve reactant utilization rate, it is preferable that the last one microreactor in the first microreactor group
Reaction product in unreacted reactant return first microreactor in carry out oxidation reaction.
Apparatus structure corresponding with method as discussed above is as follows:
Including the first microreactor group and purifying plant；The first microreactor group include a microreactor or by
Multiple microreactors are connected in series, the last one microreactor in the first microreactor group connects the purifying plant；
All microreactors are connected with oxygen and are passed through pipeline and heat exchange pipeline；First in the first microreactor group is micro- anti-
Device is answered to be connected with the pipeline for being passed through isopropylbenzene and initiator.
Utilize the process of above-mentioned apparatus production cumyl hydroperoxide are as follows:
Reaction raw materials isopropylbenzene mixed with initiator (can be arranged before the first microreactor group mixing tube for both mix
Close), enter in first microreactor in the first microreactor group carry out hybrid reaction with a certain amount of oxygen together, passes through
The reaction of a period of time, oxygen consumption is larger, and the mixtures such as reactants and products and oxygen enter back into second microreactor, together
When supplement a certain amount of oxygen, accelerate the progress of oxidation reaction；Third microreactor is entered back into later, is supplemented a certain amount of
Oxygen makes oxidation reaction close to thermodynamical equilibrium as far as possible, and successively recursion promotes row continuous flowing type oxidation reaction, until reaction
Product finally flows into the last one microreactor in the first microreactor group and carries out oxidation reaction, finally, microreactor
Reactant, the product mixtures of group enter purifying plant by pipeline and purify.
If purifying plant is preflashing steaming pot interconnected, flash tank, reaction product enters in preflashing steaming pot and is divided
From each substance after entering back into flash tank concentration and separation is passed through different equipment by different pipelines, wherein goal response produces
Logistics enters cumyl hydroperoxide (CHP) storage tank, and unreacted reactant returns to microreactor group and re-starts reaction.The company of realization
Continuous metaplasia produces, high-efficient, and whole process is discharged without waste, energy conservation and environmental protection.
In addition identical as Method And Principle above, which can also make following improve:
Preferably, the first microreactor group is parallel with multiple second microreactor groups, the second microreactor group
It is connected in series by multiple microreactors.
Preferably, the quantity of microreactor is selected from the positive integer between 2-50, preferably 2-5 in the first microreactor group
Between positive integer, the positive integer between more preferable 3-5.
To sum up, compared with prior art, invention achieves following technical effects:
(1) high production efficiency: multiple microreactors reaction in microreactor group can carry out simultaneously, therefore eliminate dress
The overhead times such as material, filler, and the large specific surface area of microreactor, reaction rate is fast, shortens the reaction time.It can
See, the present invention thoroughly solves the problems, such as that traditional batch caldron process production efficiency is low in terms of two.
(2) yield of cumyl hydroperoxide is high: oxygen needed for each oxidation reaction process is divided into from more by the present invention
It is added portionwise in a microreactor, the oxidation reaction mored easily guarantee in each microreactor in this way is flat close to dynamics and thermodynamics
Weighing apparatus, therefore, reaction rate and yield greatly improves.Secondly, being improved using oxygen raising reaction selectivity and reaction speed
Yield.
(3) reaction temperature fluctuates small, Yi Huanre: since each oxidation reaction process is divided into multiple microreactors in batches
It carries out, therefore, the total amount of heat that integrated oxidation reaction is released is dispersed in different reactors, is easier to exchange heat in this way, thus
Bring temperature fluctuation also reduces, and can control in ± 2 DEG C, and at the same time, the impurity content in product also further decreases.And
And microreactor heat exchange efficiency of the present invention is high, thus the amount of heat released in reaction can be quickly moved out to keep
Reaction temperature homogeneous constant.To sum up, the present invention at least solves cumene oxidation production cumyl hydroperoxide in terms of two
(CHP) this strong exothermal reaction problem.
(4) environmentally friendly: the pollutants such as isopropylbenzene that will not be taken out of to environmental emission by inert gas.
(5) safe operation: since oxygen disperses to be added, reduce oxygen explosion phenomenon；Secondly, initiator is changed to
Diisopropyl benzene hydrogen peroxide, decreases explosion phenomenon.
(6) device provided by realizes the purpose that temperature accurately controls, and takes up little area.
(7) it avoids the volume for expanding single equipment: multiple microreactor groups is set, improve the reaction scale of construction, reduce and expand life
The difficulty of production.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the main view for the device that cumene oxidation provided in an embodiment of the present invention prepares cumyl hydroperoxide.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the drawings and specific embodiments, but
Be it will be understood to those of skill in the art that it is following described embodiments are some of the embodiments of the present invention, rather than it is whole
Embodiment is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, ability
Domain those of ordinary skill every other embodiment obtained without making creative work, belongs to guarantor of the present invention
The range of shield.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same
Or production firm person is not specified in instrument, is the conventional products that can be obtained by commercially available purchase.
Embodiment 1
Cumene oxidation produces cumyl hydroperoxide (CHP) method, and steps are as follows:
The microreactor system assembled using two microreactor tandem compound modes opens the heat exchange of microreactor system
System, control microreactor temperature are 90 DEG C ± 2, reaction pressure 0.5MPa；It is 0.5% diisopropyl by isopropylbenzene and containing concentration
After the cumene solution mixing of benzene hydrogen peroxide (DCP), it is passed through in first microreactor, while the amount for being passed through oxygen is required
The 40% of amount of oxygen, the total amount of oxygen are on year-on-year basis into 2 times of isopropylbenzene molal quantity in reactor, when control reactant stops
Between be 1.0h；In first microreactor outlet series connection, second microreactor, second microreactor have an oxygen into
Entrance, oxygen required for supplement is reacted, the amount of supplemental oxygen are the 60% of required amount of oxygen, to promote reaction to carry out, are mentioned
The conversion ratio of high isopropylbenzene, the product separation after reaction, respectively obtains goal response product, unreacted reactant；Unreacted
Reactant can directly return in first microreactor that the reaction was continued.
Embodiment 2
For operating method with embodiment 1, the concentration for changing diisopropyl benzene hydrogen peroxide (DCP) cumene solution is 0.4%,
The reaction temperature for adjusting microreactor is 100 DEG C ± 2, reaction pressure 0.4MPa；Control reaction time is 0.8h；After reaction
Product separation, respectively obtain goal response product, unreacted reactant.
Embodiment 3
For operating method with embodiment 1, the concentration for changing diisopropyl benzene hydrogen peroxide (DCP) cumene solution is 0.4%,
The reaction temperature for adjusting microreactor is 110 DEG C ± 2, reaction pressure 0.4MPa；Control reaction time is 0.5h；After reaction
Product separation, respectively obtain goal response product, unreacted reactant.
Embodiment 4
For operating method with embodiment 1, the concentration for changing diisopropyl benzene hydrogen peroxide (DCP) cumene solution is 0.2%,
The reaction temperature for adjusting microreactor is 120 DEG C ± 2, reaction pressure 0.5MPa；Control reaction time is 0.2h；After reaction
Product separation, respectively obtain goal response product, unreacted reactant.
Embodiment 5
For operating method with embodiment 1, the concentration for changing diisopropyl benzene hydrogen peroxide (DCP) cumene solution is 0.1%,
The reaction temperature for adjusting microreactor is 130 DEG C ± 2, reaction pressure 0.2MPa；Control reaction time is 0.1h；After reaction
Product separation, respectively obtain goal response product, unreacted reactant.
Embodiment 6
The microreactor system assembled using three microreactor tandem compound modes, structure are as shown in Figure 1.It opens micro- anti-
The heat-exchange system of device system is answered, the temperature of reactor of the first microreactor 3, the second microreactor 4, third microreactor 5 is controlled
It is 90 DEG C ± 2, reaction pressure 0.5MPa；DCP is stored in storage tank 1, and isopropylbenzene is mixed in blending tank 2 with DCP, is made and is contained
Concentration is the cumene solution of 0.5% diisopropyl benzene hydrogen peroxide (DCP), is then passed in the first microreactor 3, is led to simultaneously
The amount for entering oxygen is the 30% of required amount of oxygen, and the total amount of oxygen is 2 times for entering isopropylbenzene molal quantity in reactor on year-on-year basis,
Control reactant residence time is 1.0h；The second microreactor 4 of series connection is exported in the first microreactor 3, in the second microreactor 4
Oxygen required for having an oxygen inlet port, supplement to react, the amount of supplemental oxygen are the 30% of required amount of oxygen；Second
Series connection third microreactor 5 in the outlet of microreactor 4 equally has an oxygen inlet port, supplement reaction institute in third microreactor 5
The oxygen needed, the amount of supplemental oxygen are the 40% of required amount of oxygen, further reaction are promoted to carry out, and improve turning for isopropylbenzene
Rate, the product separation after reaction, respectively obtains goal response product, unreacted reactant；Unreacted reactant can be with
Directly the reaction was continued in return microreactor.After goal response product enters mitigation tank 6, then enter preflashing steaming pot 7, flash distillation in batches
By purification, obtained product hydrogen peroxide isopropylbenzene flows into holding vessel 9 tank 8.
Embodiment 7
For operating method with embodiment 6, the concentration for changing diisopropyl benzene hydrogen peroxide (DCP) cumene solution is 0.3%,
The reaction temperature for adjusting microreactor is 100 DEG C ± 2, reaction pressure 0.4MPa；Control reaction time is 0.8h；After reaction
Product separation, respectively obtain goal response product, unreacted reactant.
Embodiment 8
For operating method with embodiment 6, the concentration for changing diisopropyl benzene hydrogen peroxide (DCP) cumene solution is 0.4%,
The reaction temperature for adjusting microreactor is 110 DEG C ± 2, reaction pressure 0.4MPa；Control reaction time is 0.4h；After reaction
Product separation, respectively obtain goal response product, unreacted reactant.
Embodiment 9
For operating method with embodiment 6, the concentration for changing diisopropyl benzene hydrogen peroxide (DCP) cumene solution is 0.2%,
The reaction temperature for adjusting microreactor is 120 DEG C ± 2, reaction pressure 0.5MPa；Control reaction time is 0.5h；After reaction
Product separation, respectively obtain goal response product, unreacted reactant.
Embodiment 10
Operating method uses the concentration of cumene hydroperoxide hydrogen (CHP) cumene solution for 6%, adjustment with embodiment 6
The reaction temperature of microreactor is 130 DEG C ± 2, reaction pressure 0.2MPa；Control reaction time is 0.5h；Production after reaction
Object separation, respectively obtains goal response product, unreacted reactant.
Embodiment 11
The microreactor system assembled using 50 microreactor tandem compound modes.Open the heat exchange of microreactor system
System, the temperature of reactor for controlling all microreactors is 90 DEG C ± 2, reaction pressure 0.5MPa；DCP is stored in storage tank, will
Isopropylbenzene mixes in blending tank with DCP, is made molten containing the isopropylbenzene that concentration is 0.5% diisopropyl benzene hydrogen peroxide (DCP)
Liquid then passes in first microreactor, while the amount for being passed through oxygen is the 2% of required amount of oxygen, and the total amount of oxygen is
On year-on-year basis into 50 times of isopropylbenzene molal quantity in reactor, control reactant residence time is 0.1h；With the process phase of embodiment 6
Together, reaction product passes sequentially through concatenated all microreactors, until the 50th microreactor, constantly promotes reaction to carry out, mention
The conversion ratio of high isopropylbenzene, the product separation after reaction, respectively obtains goal response product, unreacted reactant；Unreacted
Reactant can directly return in microreactor that the reaction was continued.Wherein, the oxygen-supply quantity of the 2nd to 50 microreactor is requisite oxygen
The 2% of gas total amount.
Comparative example 1
In bubbling column reactor, using C H P as initiator, concentration is 6% or so, reaction pressure 0.30MPa,
It is passed through air to be aoxidized, oxygen volume space velocity is 9.0h-1, it is 85-125 DEG C, after reacting 6 hours in range of reaction temperature, C
H P concentration reaches 14.81%.Acetophenone is selectively 2.5%
Comparative example 2
It is tested with circulation flow reactor, using C H P as initiator, concentration is 0.8% or so, is passed through air progress
Oxidation, oxygen volume space velocity are 9.0h-1, it is 85-110 DEG C, after reacting 6 hours in range of reaction temperature, 0.20MPa C H P
Concentration reaches 17.6%.Acetophenone is selectively 1.5%.
The reaction effect of all of above technique is compared, as a result such as table 1.
The reaction effect of the invention of table 1
Note: the initiator of embodiment 10 and comparative example 1,2 is to replace with CHP in table 1, the hundred of the additional amount of all initiators
Dividing ratio is relative to isopropylbenzene, and " % " meaning refers to the weight g for the initiator that every 100mL is added.
To sum up, cumene oxidation provided by the invention produces cumyl hydroperoxide (CHP) method, in microreactor into
Row reaction, the heave amplitude of the control range of reaction temperature become 0.5-4 DEG C from 40-60 DEG C of Traditional Method, and stable reaction is quick,
Reaction becomes continuous flowing type from autoclave batch-type rotary, improves operation condition, the reaction time greatly shortens, hydrogen peroxide
Isopropylbenzene yield is greatly improved, and improves production efficiency, while using purity oxygen as oxidant, both improves anti-
The selectivity for answering speed and reaction process avoids the generation of side reaction, avoid in oxidized tail gas taken away by inert gas it is different
Propyl benzene is more, for prevent pollution atmosphere, it is necessary to recycled with absorption tower, increase equipment investment the problems such as.It is unreacted after reaction
Reactant can be reused without separation, reduce equipment investment, and the dosage of initiator greatly reduces, and entire reaction process connects
Continuous metaplasia produces, and no waste generates, energy conservation and environmental protection.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (15)
1. a kind of method that cumene oxidation prepares cumyl hydroperoxide, which comprises the following steps:
Using the first microreactor group being connected in series by one or more microreactors as reaction unit, by isopropylbenzene and initiator
It is passed through in first microreactor in the first microreactor group, the reaction product obtained after peroxidization flows into institute
Second microreactor stated in the first microreactor group carries out oxidation reaction, and successively it is anti-to carry out continuous flowing type oxidation for recursion
It answers, until reaction product finally flows into the last one microreactor in the first microreactor group and carries out oxidation reaction, from
Purifying hydrogen peroxide isopropylbenzene in finally obtained reaction product；The first microreactor group is parallel with multiple second micro- reactions
Device group, and each second microreactor group is connected in series by multiple microreactors, each second microreactor
The oxidation reaction method of group is identical as the first microreactor group；
Wherein, the residence time of reactant is 0.1-1.0h in each microreactor, reaction temperature is 90~130 DEG C, anti-
Answering pressure is 0.1~1.0MPa；
In each oxidation reaction process, all microreactors are passed through oxygen, and first in the microreactor group
The molar ratio for the oxygen summation that the isopropylbenzene and all microreactors that a microreactor is passed through are passed through is 0.1:0.2-5.
2. the method according to claim 1, wherein the initiator is that cumyl hydroperoxide and/or two are different
Propylbenzene hydrogen peroxide.
3. the method according to claim 1, wherein the initiator is diisopropyl benzene hydrogen peroxide.
4. according to the method in claim 2 or 3, which is characterized in that contain diisopropyl benzene peroxidating in the initiator
When hydrogen, diisopropyl benzene hydrogen peroxide is dissolved in the isopropylbenzene and then is passed through first microreactor.
5. the method according to claim 1, wherein initiator used in every 100mL isopropylbenzene is 0.2-0.5g.
6. the method according to claim 1, wherein initiator used in every 100mL isopropylbenzene is 0.2-
0.25g。
7. the method according to claim 1, wherein the quantity of microreactor is selected in the first microreactor group
From the positive integer between 2-50.
8. the method according to claim 1, wherein the quantity of microreactor is selected in the first microreactor group
From the positive integer between 2-5.
9. the method according to claim 1, wherein the quantity of microreactor is selected in the first microreactor group
From the positive integer between 3-5.
10. the method according to claim 1, wherein the first microreactor group contain 2 microreactors when,
In each oxidation reaction process, the amount of oxygen that first microreactor and second microreactor are passed through is respectively required oxygen
40%, the 60% of total amount.
11. the method according to claim 1, wherein the first microreactor group contain 3 microreactors when,
In each oxidation reaction process, first microreactor to the amount of oxygen that the last one microreactor is passed through is respectively requisite oxygen
30%, 30%, the 40% of gas total amount.
12. the method according to claim 1, wherein in each microreactor reactant residence time
For 0.2-1.0h.
13. the method according to claim 1, wherein the oxidation pressure of each microreactor is 0.1
~0.5MPa.
14. the method according to claim 1, wherein the method for the purification are as follows: successively by gas-liquid separation,
Flash separation, concentration.
15. the method according to claim 1, wherein the last one micro- reaction in the first microreactor group
Unreacted reactant returns in first microreactor and carries out oxidation reaction in the reaction product of device.
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| CN113511429B (en) * | 2020-04-10 | 2023-01-13 | 中国石油化工股份有限公司 | Cumene hydroperoxide storage device and storage environment adjusting method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101479239A (en) * | 2006-04-27 | 2009-07-08 | 阿克马法国公司 | Process for synthesizing selected organic peroxides |
| CN101980773A (en) * | 2008-04-07 | 2011-02-23 | 维罗西股份有限公司 | Microchannel apparatus comprising structured walls, chemical processes, methods of making formaldehyde |
| CN103372370A (en) * | 2012-04-23 | 2013-10-30 | 中国科学院大连化学物理研究所 | Method for absorbing carbon dioxide in multistage microchannel reaction system |
| CN104876845A (en) * | 2015-05-28 | 2015-09-02 | 南京红宝丽股份有限公司 | Preparation method of peroxide hydroxyl isopropyl benzene |
| CN105061129A (en) * | 2015-09-18 | 2015-11-18 | 中石化炼化工程（集团）股份有限公司 | Isoalkane/olefin alkylation method and device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP2019818B1 (en) * | 2006-05-23 | 2020-03-18 | DPx Holdings B.V. | Process for the production of compounds via hazardous intermediates in a series of microreactors |
-
2016
- 2016-12-16 CN CN201611168755.8A patent/CN106588734B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101479239A (en) * | 2006-04-27 | 2009-07-08 | 阿克马法国公司 | Process for synthesizing selected organic peroxides |
| CN101980773A (en) * | 2008-04-07 | 2011-02-23 | 维罗西股份有限公司 | Microchannel apparatus comprising structured walls, chemical processes, methods of making formaldehyde |
| CN103372370A (en) * | 2012-04-23 | 2013-10-30 | 中国科学院大连化学物理研究所 | Method for absorbing carbon dioxide in multistage microchannel reaction system |
| CN104876845A (en) * | 2015-05-28 | 2015-09-02 | 南京红宝丽股份有限公司 | Preparation method of peroxide hydroxyl isopropyl benzene |
| CN105061129A (en) * | 2015-09-18 | 2015-11-18 | 中石化炼化工程（集团）股份有限公司 | Isoalkane/olefin alkylation method and device |
Non-Patent Citations (1)
| Title |
|---|
| 微化工技术在化学反应中的应用进展;赵玉潮 等;《中国科技论文在线》;20080331;第3卷(第3期);第157-169页 |
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