CN106977379A - High-grade p-t-Butylbenzaldehyde preparation method and preparation facilities - Google Patents
High-grade p-t-Butylbenzaldehyde preparation method and preparation facilities Download PDFInfo
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- CN106977379A CN106977379A CN201710179771.5A CN201710179771A CN106977379A CN 106977379 A CN106977379 A CN 106977379A CN 201710179771 A CN201710179771 A CN 201710179771A CN 106977379 A CN106977379 A CN 106977379A
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- butylbenzaldehyde
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- 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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
Abstract
The invention discloses a kind of high-grade p-t-Butylbenzaldehyde preparation method and high-grade p-t-Butylbenzaldehyde preparation facilities.The high-grade p-t-Butylbenzaldehyde preparation method comprises the following steps：A）P-tert-butyltoluene, water and the catalyst for not containing halogen are mixed in micron bubble reactor and carries out oxidation reaction, to obtain reaction material liquid；B）Water-oil separating is carried out to the reaction material liquid, to obtain aqueous phase and oil phase, the aqueous phase contains catalyst, and the oil phase contains p-t-Butylbenzaldehyde and impurity；And C）The p-t-Butylbenzaldehyde and the impurity is separated to obtain high-grade p-t-Butylbenzaldehyde.The p-t-Butylbenzaldehyde prepared using high-grade p-t-Butylbenzaldehyde preparation method according to embodiments of the present invention does not contain halogen, can be used for the fields such as food, medicine, spices.
Description
Technical field
The present invention relates to chemical field, in particular to high-grade p-t-Butylbenzaldehyde preparation method, height is further related to
Grade p-t-Butylbenzaldehyde preparation facilities.
Background technology
High-grade p-t-Butylbenzaldehyde refers to not halogen-containing p-t-Butylbenzaldehyde.High-grade p-t-Butylbenzaldehyde
Available for fields such as medicine, food, spices.Domestic p-t-Butylbenzaldehyde production is main to use p-tert-butyltoluene chlorinated hydrolysis
Technique, the technique is seriously polluted because causing production procedure lengthy and tedious using chlorine, and the chlorine element remained in product can not be removed completely
Go and be difficult to use in food and field of medicaments.By solvent of acetic acid, Co/Mn/Br be catalyst oxidation p-tert-butyltoluene
It is one of study hotspot of p-t-Butylbenzaldehyde synthesis technique, this method can improve p-t-Butylbenzaldehyde selectivity, still
A small amount of bromo element is inevitably remained in bromide, product due to using, also limit makes in the fields such as its medicine, food
With next is solvent using acetic acid, and the operation cost of investment of equipment greatly improved.
At present, domestic high-grade p-t-Butylbenzaldehyde prepares the accessory substance of p-tert-butyl benzoic acid from liquid phase oxidation
（Yield is less than 5%）And external import, its price is common aromatic aldehyde more than twice, but its demand increases year by year.
The liquid phase oxidation of p-tert-butyltoluene is carried out in bubble stirring reactor, and oxygen source is used as using pressure-air.But should
There is the pollution that limited gas liquid interfacial area, reaction time length, reaction temperature are high, oxygen utilization rate is low, exhaust emissions is formed in method
The problems such as.Therefore, exploiting economy environmental protection high-grade p-t-Butylbenzaldehyde new preparation process have important researching value and
Economic implications.
The content of the invention
It is contemplated that at least solving one of technical problem present in prior art.Therefore, one object of the present invention
The high-grade p-t-Butylbenzaldehyde preparation method for not containing halogen can be prepared by being that proposition is a kind of.
It is another object of the present invention to propose a kind of high-grade p-t-Butylbenzaldehyde preparation facilities.
The high-grade p-t-Butylbenzaldehyde preparation method of embodiment comprises the following steps according to a first aspect of the present invention：A）
P-tert-butyltoluene, water and the catalyst for not containing halogen are mixed in micron bubble reactor and carries out oxidation reaction, with
Just reaction material liquid is obtained；B）Water-oil separating is carried out to the reaction material liquid, to obtain aqueous phase and oil phase, the aqueous phase, which contains, urges
Agent, the oil phase contains p-t-Butylbenzaldehyde and impurity；And C）Separate the p-t-Butylbenzaldehyde and the impurity with
Just high-grade p-t-Butylbenzaldehyde is obtained.
Using high-grade p-t-Butylbenzaldehyde preparation method according to embodiments of the present invention prepare to the tert-butyl group
Benzaldehyde does not contain halogen, can be used for the fields such as food, medicine, spices.
In addition, high-grade p-t-Butylbenzaldehyde preparation method according to embodiments of the present invention can also have following add
Technical characteristic：
According to one embodiment of present invention, the impurity includes p-tert-butyltoluene, water, catalyst and benzoic acid, the step
Rapid C）Including：C-1）Rectifying is carried out to the p-t-Butylbenzaldehyde and the impurity, so as to obtain p-tert-butyltoluene, water with
And tower bottoms, the tower bottoms include the p-t-Butylbenzaldehyde, catalyst and benzoic acid；C-2）The tower bottoms is carried out
Rectifying, to make the p-t-Butylbenzaldehyde be separated with catalyst and benzoic acid；And C-3）Successively to described to tert-butyl benzene
Formaldehyde carries out anion exchange and cation exchange.
According to one embodiment of present invention, the reaction temperature of the oxidation reaction is 50 DEG C -90 DEG C, the micron bubble
Pressure in reactor is 0.2MPa-0.4MPa, and the reaction time of the oxidation reaction is -2 hours 0.1 hour.
According to one embodiment of present invention, the micron bubble reactor by swiftly flowing liquid cutting gas with
Just bubble is produced, the bubble size distribution of generation is in the range of 50 μm -1000 μm.
According to one embodiment of present invention, the oxidation reaction carried out in the micron bubble reactor is successive reaction,
Feed liquid in the micron bubble reactor is circulated 10 ~ 200 times per hour, after the oxidation reaction is carried out -2 hours 0.1 hour,
From the micron bubble reactor continuous discharge, while to the micron bubble reactor continuous feed.
According to one embodiment of present invention, the reaction material liquid is cooled to 15 DEG C -30 DEG C, then will in phase-splitter
The reaction material liquid after cooling stands -0.5 hour 0.1 hour, to obtain aqueous phase and oil phase.
According to one embodiment of present invention, the single transformation rate of p-tert-butyltoluene is 10% ~ 65%, to tert-butyl benzene first
The single reaction selectivity of aldehyde is more than 99%.
The high-grade p-t-Butylbenzaldehyde preparation facilities of embodiment includes according to a second aspect of the present invention：Micron bubble is anti-
Device is answered, the micron bubble reactor has charging aperture, loop exit, circulation import, oxidant inlet and discharging opening, described to follow
Ring is exported and the circulation inlet communication；Phase-splitter, the phase-splitter has charging aperture, aqueous phase discharging opening and oil phase discharging opening,
The charging aperture of the phase-splitter is connected with the discharging opening of the micron bubble reactor；First rectifying column, the first rectifying column
With charging aperture, tower top discharging opening, side discharging opening and bottom of towe discharging opening, the charging aperture of the first rectifying column and the phase-splitter
Oil phase discharging opening connection；Second distillation column, the Second distillation column has charging aperture, tower top discharging opening and bottom of towe discharging opening,
The charging aperture of the Second distillation column is connected with the bottom of towe discharging opening of the first rectifying column；Anion-exchange column, it is described it is cloudy from
Sub- exchange column has charging aperture and discharging opening, and the tower top of the charging aperture of the anion-exchange column and the Second distillation column discharges
Mouth connection；And cation exchange column, the cation exchange column has charging aperture and discharging opening, the cation exchange column
Charging aperture is connected with the discharging opening of the anion-exchange column.
According to one embodiment of present invention, the aqueous phase discharging opening of the phase-splitter and entering for the micron bubble reactor
Material mouth is connected, each in the tower top discharging opening and side discharging opening of the first rectifying column with the micron bubble reactor
Charging aperture connection, it is preferable that the high-grade p-t-Butylbenzaldehyde preparation facilities further comprises heat exchanger, the heat exchange
Utensil has charging aperture and discharging opening, and the charging aperture of the heat exchanger is connected with the discharging opening of the micron bubble reactor, described
The discharging opening of heat exchanger is connected with the charging aperture of the phase-splitter.
According to one embodiment of present invention, the micron bubble reactor includes：There is reaction in body, the body
Chamber, the wall of the reaction chamber is provided with charging aperture, discharging opening, circulating air outlet and loop exit；Injector, the injector
A part is through the body and extend into the reaction chamber, wherein the injector has circulation import, oxidant inlet
And jet, the circulation import connects with the loop exit, the oxidant inlet and the circulating air outlet；With
Bubble generator, the bubble generator has charging aperture and discharging opening, the charging aperture of the bubble generator and the injection
Mouth connection, it is preferable that the bubble generator includes：Connecting tube, the first end of the connecting tube is connected with the jet；With
Housing, has accommodating chamber in the housing, and the wall of the accommodating chamber is provided with charging aperture and discharging opening, the accommodating chamber at it
On axial direction discharging opening, the second end of the connecting tube and the charging of the accommodating chamber are equipped with relative first end and the second end
Mouth is connected, and the length direction of the connecting tube and the circumference of the accommodating chamber are tangent, it is further preferred that the accommodating chamber is revolution
Body shape, the revolution bus of the accommodating chamber be a circular arc line or one with the straight line of the diameter parallel of the accommodating chamber and
The curve or a song constituted with the straight line of the diameter parallel of the accommodating chamber and two circular arc lines of two rectilinear(-al)s
Line, it is preferable that with the straight line of the diameter parallel of the accommodating chamber and two circular arc lines they intersection it is tangent.
P-t-Butylbenzaldehyde micron bubble reactor
High-grade p-t-Butylbenzaldehyde preparation facilities according to embodiments of the present invention has that gas liquid interfacial area is big, the reaction time
Short, oxidant utilization rate is high, the advantage that reaction temperature is low, energy consumption is low.
Brief description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become from description of the accompanying drawings below to embodiment is combined
Substantially and be readily appreciated that, wherein：
Fig. 1 is the structural representation of high-grade p-t-Butylbenzaldehyde preparation facilities according to embodiments of the present invention；
Fig. 2 is the structure of the micron bubble reactor of high-grade p-t-Butylbenzaldehyde preparation facilities according to embodiments of the present invention
Schematic diagram；
Fig. 3 is the part of the micron bubble reactor of high-grade p-t-Butylbenzaldehyde preparation facilities according to embodiments of the present invention
Structural representation.
Embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
The embodiment of figure description is exemplary, is only used for explaining the present invention, and is not considered as limiting the invention.
In the description of the invention, it is to be understood that term " " center ", " longitudinal direction ", " transverse direction ", " on ", " under ",
The orientation or position relationship of the instruction such as "front", "rear", "left", "right", " vertical ", " level ", " top ", " bottom ", " interior ", " outer " are
Based on orientation shown in the drawings or position relationship, it is for only for ease of the description present invention and simplifies description, rather than indicate or dark
Specific orientation must be had, with specific azimuth configuration and operation by showing the device or element of meaning, therefore it is not intended that right
The limitation of the present invention.In addition, term " first ", " second " are only used for describing purpose, and it is not intended that indicating or implying and be relative
Importance or the implicit quantity for indicating indicated technical characteristic.Thus, define " first ", the feature of " second " can be with bright
Show or implicitly include one or more this feature.In the description of the invention, unless otherwise indicated, " multiple " contain
Justice is two or more.
In the description of the invention, it is necessary to illustrate, unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " should be interpreted broadly, for example, it may be being fixedly connected or being detachably connected, or be integrally connected；Can
To be mechanical connection or electrical connection；Can be joined directly together, can also be indirectly connected to by intermediary, Ke Yishi
The connection of two element internals.For the ordinary skill in the art, with concrete condition above-mentioned term can be understood at this
Concrete meaning in invention.
The invention provides high-grade p-t-Butylbenzaldehyde preparation method.According to embodiments of the present invention is high-grade to uncle
Butyl benzaldehyde preparation method comprises the following steps：
A）P-tert-butyltoluene, water and the catalyst for not containing halogen are mixed in micron bubble reactor and aoxidize anti-
Should, to obtain reaction material liquid；
B）Water-oil separating is carried out to the reaction material liquid, to obtain aqueous phase and oil phase, the aqueous phase contains catalyst, and the oil phase contains
P-t-Butylbenzaldehyde and impurity；With
C）The p-t-Butylbenzaldehyde and the impurity is separated to obtain high-grade p-t-Butylbenzaldehyde.
Because high-grade p-t-Butylbenzaldehyde preparation method according to embodiments of the present invention is not using containing halogen
Catalyst, thus high-grade p-t-Butylbenzaldehyde preparation method according to embodiments of the present invention prepare to tert-butyl benzene
Formaldehyde does not contain halogen.
Moreover, by carrying out the oxidation reaction in micron bubble reactor, so as to so that p-tert-butyltoluene, water,
Oxidation reaction occurs in micron bubble reactor 5 for catalyst and oxidant, to react generation p-t-Butylbenzaldehyde, so that
Gas liquid interfacial area, the utilization rate for shortening the reaction time, improving oxidant, reduction reaction temperature, reduction can be greatly enhanced
Energy consumption, greatly reduce exhaust emissions.
Under the same reaction conditions, compared with the existing progress reaction using bubble stirring reactor, according to of the invention real
Apply the high-grade p-t-Butylbenzaldehyde preparation method of example the reaction time can be shortened 2-5 times and by energy consumption reduction by 50% with
On.Therefore, high-grade p-t-Butylbenzaldehyde preparation method according to embodiments of the present invention has that gas liquid interfacial area is big, reaction
The advantages of time is short, oxidant utilization rate is high, reaction temperature is low, energy consumption is low, exhaust emissions is few.
The p-t-Butylbenzaldehyde of high-grade p-t-Butylbenzaldehyde preparation method synthesis according to embodiments of the present invention
Single selectively up to 99.0%, product quality fraction are more than 99.0%, and the p-t-Butylbenzaldehyde prepared does not contain halogen
Race's element, can be used for the fields such as food, medicine, spices.
High-grade p-t-Butylbenzaldehyde preparation facilities 100 according to embodiments of the present invention is described below with reference to Fig. 1.As schemed
Shown in 1, high-grade p-t-Butylbenzaldehyde preparation facilities 100 according to embodiments of the present invention includes micron bubble reactor 5, divided
Phase device 21, first rectifying column 25, Second distillation column 28, anion-exchange column 29 and cation exchange column 31.
Micron bubble reactor 5 has charging aperture 104, loop exit 108, circulation import 1021, oxidant inlet 1022
With discharging opening 107, the loop exit of micron bubble reactor 5 and the circulation inlet communication of micron bubble reactor 5.Phase-splitter 21
With charging aperture, aqueous phase discharging opening and oil phase discharging opening, the charging aperture of phase-splitter 21 connects with the discharging opening of micron bubble reactor 5
It is logical.
First rectifying column 25 has charging aperture, tower top discharging opening, side discharging opening and bottom of towe discharging opening, first rectifying column 25
Charging aperture is connected with the oil phase discharging opening of phase-splitter 21.Second distillation column 28 has charging aperture, tower top discharging opening and bottom of towe discharging
Mouthful, the charging aperture of Second distillation column 28 is connected with the bottom of towe discharging opening of first rectifying column 25.
Anion-exchange column 29 has charging aperture and discharging opening, charging aperture and the Second distillation column 28 of anion-exchange column 29
Tower top discharging opening connection.Cation exchange column 31 has charging aperture and a discharging opening, the charging aperture of cation exchange column 31 with
The discharging opening connection of anion-exchange column 29.
Existing liquid phase oxidation prepares the reaction of benzoic acid（As described in the background section, p-t-Butylbenzaldehyde is this
The accessory substance of reaction）Carried out in bubble stirring reactor, oxygen source is used as using pressure-air.But there is gas-liquid and connect in the preparation method
The problems such as touching the pollution that limited area, reaction time length, reaction temperature are high, oxygen utilization rate is low, exhaust emissions is formed.
High-grade p-t-Butylbenzaldehyde preparation facilities 100 according to embodiments of the present invention is by setting micron bubble to react
Device 5, so as to so that oxidation reaction occurs in the micron bubble reactor 5 for p-tert-butyltoluene, water, catalyst and oxidant,
To react generation p-t-Butylbenzaldehyde, so as to be greatly enhanced gas liquid interfacial area, shorten reaction time, raising oxygen
The utilization rate of agent, reduction reaction temperature, reduction energy consumption, greatly reduce exhaust emissions.
Specifically, the oxidant of high-grade p-t-Butylbenzaldehyde preparation facilities 100 according to embodiments of the present invention can
To be oxygen-containing gas, the oxygen-containing gas closed cycle, the unreacted oxygen-containing gas at the top of micron bubble reactor 5 passes through valve
Pipeline where door 8 enters micron bubble reactor 5 by volume inspiration again.And in traditional bubble stirring reactor, unreacted
Oxygen-containing gas reach reactor top after, it is necessary to be vented, the process of emptying can take away the reaction material liquid of high temperature, and this can be caused
Reaction material liquid is lost, while will also result in tail gas pollution.
Under the same reaction conditions, compared with the existing progress reaction using bubble stirring reactor, according to of the invention real
2-5 times can be shortened the reaction time and energy consumption is reduced into 50% by applying the high-grade p-t-Butylbenzaldehyde preparation facilities 100 of example
More than.Therefore, high-grade p-t-Butylbenzaldehyde preparation facilities 100 according to embodiments of the present invention has gas liquid interfacial area
Greatly, the advantages of reaction time is short, oxidant utilization rate is high, reaction temperature is low, energy consumption is low, exhaust emissions is few.
High-grade p-t-Butylbenzaldehyde preparation side according to embodiments of the present invention is described more fully below with reference to Fig. 1
Method and high-grade p-t-Butylbenzaldehyde preparation facilities 100.
As shown in figure 1, can be provided for store water water tank 2 and for store p-tert-butyltoluene to the tert-butyl group
Toluene tank 4, water tank 2 and p-tert-butyltoluene storage tank 4 are connected by pipeline with micron bubble reactor 5 respectively, with facility
The water in water tank 2 is transported in micron bubble reactor 5 with pump 1, and using pump 3 by p-tert-butyltoluene storage tank 4
P-tert-butyltoluene is transported in micron bubble reactor 5.Wherein, catalyst can be separately added to micron bubble reactor 5
It is interior, it can also be dissolved in the water in water tank 2, be transported to together with water in micron bubble reactor 5.
Advantageously, oxidant can be oxygen-containing gas, such as air.Air can be by being provided with valve 8 and valve 9
Pipeline transport is in micron bubble reactor 5.
After p-tert-butyltoluene, water and catalyst are added into micron bubble reactor 5, open valve 9 so as to
Conveying air in micron bubble reactor 5, valve 8 can control the gas interior circulation in micron bubble reactor 5.Open simultaneously
Pump 14,（Pump 14 is opened,）Because the loop exit of micron bubble reactor 5 passes through with the circulation import of micron bubble reactor 5
Pipeline is connected, therefore can circulate the feed liquid in micron bubble reactor 5.Wherein, following in connection micron bubble reactor 5
Ring, which is exported and circulated, sets valve 13, pump 14, flowmeter 12 and heat exchanger 11 on the pipeline of import.By setting flowmeter 12,
The circular flow of the feed liquid in micron bubble reactor 5 can be adjusted, by setting heat exchanger 11, the feed liquid of circulation can be added
Heat arrives preset temperature.
In some embodiments of the invention, p-tert-butyltoluene, water and catalyst are carried out in micron bubble reactor 5
Oxidation reaction, the reaction temperature of the oxidation reaction is that the pressure in 50 DEG C -90 DEG C, micron bubble reactor 5 is 0.2MPa-
0.4MPa, the reaction time of the oxidation reaction is -2 hours 0.1 hour.Advantageously, micron bubble reactor 5 passes through high velocity stream
Dynamic liquid cutting gas is to produce bubble, and the particle diameter distribution for the bubble that micron bubble reactor 5 is produced is at 50 μm -500 μm
In the range of.
As shown in Fig. 2 micron bubble reactor 5 includes body 10, injector 102 and bubble generator 103.In body 10
With reaction chamber 101, the wall of reaction chamber 101 is provided with charging aperture 104, discharging opening 107, circulating air outlet 106 and loop exit
108.A part for injector 102 is through body 10 and extend into reaction chamber 101.Wherein, injector 102 has circulation import
1021st, oxidant inlet 1022 and jet, loop exit 108 are connected with circulation import 1021, and oxidant inlet 1022 is with following
Ring gas outlet 106 is connected.Bubble generator 103 has charging aperture and discharging opening, the charging aperture and injector of bubble generator 103
102 jet connection.
The course of work of micron bubble reactor 5 according to embodiments of the present invention is described below with reference to Fig. 1 and Fig. 2.To uncle
Butyl toluene, water and catalyst are added in reaction chamber 101 from charging aperture 104, oxidant（Oxygen-containing gas）From oxidant inlet
1022 are added in reaction chamber 101 until reaching required pressure in reaction chamber 101.Feed liquid in reaction chamber 101 is from recycling
Mouth 108 is extracted out, is entered under the driving of pump in injector 102.Advantageously, it is entered in injector 102 in circulation feed liquid
Before, feed liquid can be exchanged heat.
Simultaneously as the circulation feed liquid of high speed forms negative pressure in injector 102, therefore the circulation feed liquid of high speed will be oxygen-containing
Gas and recyclegas, which are brought into injector 102 and mix shearing, produces a large amount of bubbles, to form gas-liquid mixture.It is specific and
Speech, recyclegas leaves reaction chamber 101 by circulating air outlet 106, and is entered by oxidant inlet 1022 in injector 102.
The gas-liquid mixture is sprayed and entered in bubble generator 103 by the jet 1028 of injector 102, the gas-liquid
Mixture rotates at a high speed in bubble generator 103, and due to density variation, air accumulation is attached in the axis of bubble generator 103
Closely, substantial amounts of particle diameter distribution bubble in the range of 50 μm -500 μm is produced by liquid compression shearing, and by bubble generator
103 discharging opening sprays, into reaction chamber 101.Because bubble diameter is smaller, the rate of climb of bubble in a liquid is smaller.
Therefore, substantial amounts of bubble can be full of in reaction chamber 101, to form emulsion, so as to so that reaction can be carried out rapidly.
Moreover, the diameter of bubble is smaller, the mass tranfer coefficient of bubble is higher, so as to increase substantially micron bubble reaction
The reaction efficiency of device 5.
As shown in Fig. 2 micron bubble reactor 5 further comprises overflow baffle 109, overflow baffle 109 is located at reaction chamber
On 101 wall and adjacent to discharging opening 107, the upper edge of overflow baffle 109 is located at the top of discharging opening 107.It is possible thereby to make micron
The structure of bubble reactor 5 is more reasonable.
Specifically, overflow baffle 109 includes level board and vertical plate, and the level board is welded on the wall of reaction chamber 101,
The lower edge of the vertical plate is welded on the level board, and the upper edge of the vertical plate is located at the top that circulation fluid exports 107.
As shown in figure 3, bubble generator 103 includes connecting tube 1031 and housing 1032.The first end of connecting tube 1031 with
Jet 1028 is connected.There is accommodating chamber 1033, the wall of accommodating chamber 1033 is provided with charging aperture and discharging opening in housing 1032.
Discharging opening is equipped with the first end relative in its axial direction of accommodating chamber 1033 and the second end.In other words, accommodate
The first end of chamber 1033 relative, first end of accommodating chamber 1033 in the axial direction of accommodating chamber 1033 with the second end of accommodating chamber 1033
Discharging opening is equipped with the second end.Wherein, the second end of connecting tube 1031 is connected with the charging aperture, the length of connecting tube 1031
Direction and the circumference of accommodating chamber 1033 are tangent.
Because the length direction and the circumference of accommodating chamber 1033 of connecting tube 1031 are tangent, therefore ejected from injector 102
The gas-liquid mixture come is tangentially entered in accommodating chamber 1033 by connecting tube 1031, it is possible thereby to make the gas-liquid mixture in appearance
Chamber 1033 of receiving is interior to be rotated at a high speed.Due to density variation, air accumulation is sheared in the near axis of accommodating chamber 1033 by liquid compression
Substantial amounts of particle diameter distribution is produced in 100 bubbles in the range of nm-500 μm.Liquid containing the bubble is by the two of accommodating chamber 1033
The discharging opening at end sprays, into reaction chamber 101.Because bubble diameter is smaller, the rate of climb of bubble in a liquid is smaller, therefore
Substantial amounts of bubble can be full of in reaction chamber 101, emulsion is formed, so that reaction can be carried out quickly.
In the example of the present invention, accommodating chamber 1033 can be rotational-like.It is possible thereby to make bubble generator 103
Structure it is more reasonable.The revolution bus of accommodating chamber 1033 can be a circular arc line, and the revolution bus of accommodating chamber 1033 may be used also
To be one and the straight line of the diameter parallel of accommodating chamber 1033 and the curve of two rectilinear(-al)s.In addition, time of accommodating chamber 1033
It can also be the curve that one and the straight line of the diameter parallel of accommodating chamber 1033 and two circular arc lines are constituted to turn bus,.Advantageously,
The straight line with the diameter parallel of accommodating chamber 1033 and two circular arc lines they with straight line intersection at it is tangent.
The charging aperture is at the middle part for being located axially at accommodating chamber 1033 of accommodating chamber 1033, the cross-sectional area of accommodating chamber 1033
Reduce from the middle part of accommodating chamber 1033 to the end of accommodating chamber 1033.Specifically, the cross-sectional area of accommodating chamber 1033 is by accommodating
First end from the middle part of chamber 1033 to accommodating chamber 1033 reduce, and accommodating chamber 1033 cross-sectional area by the middle part of accommodating chamber 1033
Reduce to the second end of accommodating chamber 1033.It is possible thereby to make the structure of bubble generator 103 more reasonable.
Advantageously, the cross section at the relative axial center Jing Guo accommodating chamber 1033 of accommodating chamber 1033 is symmetrical.It is possible thereby to
Make the structure of bubble generator 103 more reasonable.
Specifically, the oxidation reaction carried out in micron bubble reactor 5 is in successive reaction, micron bubble reactor 5
Feed liquid circulate per hour 10 ~ 200 times, the oxidation reaction carry out -2 hours 0.1 hour after, it is continuous from micron bubble reactor 5
Discharging, while to the continuous feed of micron bubble reactor 5, that is, opening pump 1 and pump 3 to convey into micron bubble reactor 5
P-tert-butyltoluene, water and catalyst.Wherein, the single transformation rate of p-tert-butyltoluene is 10% ~ 65%, p-t-Butylbenzaldehyde
Single reaction selectivity be more than 99%.
After the oxidation reaction terminates, the feed liquid in micron bubble reactor 5 is properly termed as reaction material liquid.Open valve 15 and
Close valve 13（At least one opening in valve 6 and valve 7）, using pump 14 by the reaction material in micron bubble reactor 5
Liquid is transported in phase-splitter 21, to carry out water-oil separating to the reaction material liquid in phase-splitter 21, and obtains aqueous phase and oil phase.
Wherein, the aqueous phase contains catalyst, and the oil phase contains p-t-Butylbenzaldehyde and impurity.
Specifically, set on the discharging opening and the pipeline of the charging aperture of phase-splitter 21 for connecting micron bubble reactor 5
Pump 14, valve 15, flowmeter 16 and heat exchanger 17., can be defeated to phase-splitter 21 according to preset flow by setting flowmeter 16
The reaction material liquid is given, by setting heat exchanger 17, the reaction material liquid preset temperature can be cooled to.
In one embodiment of the invention, the reaction material liquid is cooled to 15 DEG C -30 DEG C, Ran Hou using heat exchanger 17
The reaction material liquid after cooling is stood -0.5 hour 0.1 hour in phase-splitter 21, to obtain the aqueous phase and the oil phase.
The aqueous phase discharging opening of phase-splitter 21 is connected by pipeline with water tank 2, and the pipeline is provided with pump 20, valve 19 and stream
Gauge 18, using pump 20 by the water conveying to water tank 2, to recycle the catalyst in the aqueous phase.
As shown in figure 1, the oil phase discharging opening of phase-splitter 21 is connected by pipeline with the charging aperture of first rectifying column 25, the pipe
Road is provided with pump 24, valve 23 and flowmeter 22.The oil phase is transported in first rectifying column 25 using pump 24.
The oil phase carries out rectification under vacuum separation in first rectifying column 25.Wherein, from the side discharging opening of first rectifying column 25
（Side line）Water outlet, and water is returned into water tank 2, from the tower top discharging opening of first rectifying column 25（Tower top）Extraction is to tert-butyl group first
Benzene, and p-tert-butyltoluene is returned into p-tert-butyltoluene storage tank 4.Thus unreacted raw material p-tert-butyltoluene, solvent
Water and catalyst can be recycled, so as to so that whole technical process green non-pollution, can be continuously produced.From the first essence
Evaporate the bottom of towe discharging opening of tower 25（Bottom of towe）Tower bottoms is produced, the tower bottoms includes p-t-Butylbenzaldehyde, catalyst and benzoic acid.
In some examples of the present invention, as shown in figure 1, the bottom of towe discharging opening of first rectifying column 25 passes through pipeline and second
The charging aperture of rectifying column 28 is connected, and the pipeline is provided with pump 27 and valve 26.The tower bottoms is transported to the second essence using pump 27
Evaporate in tower 28.The tower bottoms carries out rectification under vacuum separation in Second distillation column 28, to make p-t-Butylbenzaldehyde and catalysis
Agent and benzoic acid separation.Wherein, from the bottom of towe discharging opening of Second distillation column 28（Tower reactor）Benzoic acid and catalyst etc. are produced, and is transported
To the processing of specified place, from the tower top discharging opening of Second distillation column 28（Tower top）Produce p-t-Butylbenzaldehyde.
As shown in figure 1, charging aperture phase of the tower top discharging opening of Second distillation column 28 by pipeline and anion-exchange column 29
Even, anion exchange is carried out so as to which p-t-Butylbenzaldehyde is transported in anion-exchange column 29.Anion-exchange column 29
Discharging opening is connected by pipeline with the charging aperture of cation exchange column 31, to pass through anion-exchange column 29 using pump 30
P-t-Butylbenzaldehyde, which is transported in cation exchange column 31, carries out cation exchange.By carrying out anion exchange and cation
Exchange, metal ion can be removed, be further purified.
Embodiment 1
Catalyst is dissolved in aqueous solvent, and mass fraction is 1%, and p-tert-butyltoluene and aqueous solvent are according to mass ratio 1：1 respectively by pump
3 and pump 1 be delivered in 100L micron bubble reactor 5.When adding 60 kg feed liquid, i.e., p-tert-butyltoluene, water and urge
When the gross weight of agent is 60 kilograms, stop charging, open pump 14, the flow for making the feed liquid of circulation is 1000L/h, micron bubble
The Air Bubble Size that reactor 5 is produced is 500nm-500 μm, and the feed liquid by heat exchanger 11 to circulation is heated, when being warming up to 50 DEG C,
It is passed through oxygen into micron bubble reactor 5 to make the pressure in micron bubble reactor 5 rise to 0.2MPa simultaneously（Gauge pressure）.
After reaction 1.6 hours, valve 15, pump 1 and pump 3 are opened, flowmeter 16 is adjusted, according to 10L/h flow velocity to split-phase
Device 21 conveys reaction material liquid so that pump 1 and pump 3 convey p-tert-butyltoluene and solvent according to 5L/h to micron bubble reactor 5
Water.Reaction material liquid is cooled to 15 DEG C using heat exchanger 17, after phase-splitter stands 0.1h, aqueous phase is back to water tank by pump 20
2, oil phase is delivered to rectification under vacuum in first rectifying column 25 by pump 24 and separated.
The tower diameter of first rectifying column 25 be 1.5 m, theoretical tray be 80 pieces, tower top pressure be 15.2 kPa, tower reactor pressure
For 23.5 kPa.The side line water outlet of first rectifying column 25, overhead extraction p-tert-butyltoluene, water and p-tert-butyltoluene are distinguished again
It is back to water tank 2 and p-tert-butyltoluene storage tank 4.The tower bottoms of first rectifying column 25 is delivered in Second distillation column 28 by pump 27
Rectification under vacuum is separated.The tower diameter of Second distillation column 28 be 0.8 m, theoretical tray be 85 pieces, tower top pressure be 10.2 kPa, tower top
Pressure is 17.3 kPa.Benzoic acid, catalyst of tower reactor extraction of Second distillation column 28 etc. transport to specified place processing, the second essence
The p-t-Butylbenzaldehyde for evaporating the overhead extraction of tower 28 is delivered to anion-exchange column 29.
D301 macroreticular weakly base styrene series anion exchange resins are filled with anion-exchange column 29, to tert-butyl benzene
Formaldehyde carries out anion exchange in anion-exchange column 29.Finally, p-t-Butylbenzaldehyde is transported to cation exchange column
31, cation exchange column 31 is interior to be filled with D113 macroporous type acidulous acrylic acid's cation exchanger resins, to tert-butyl benzene first
Aldehyde carries out cation exchange in cation exchange column 31, to obtain high-purity p-t-Butylbenzaldehyde.
Embodiment 2
Catalyst is dissolved in aqueous solvent, and mass fraction is 1.2%, and p-tert-butyltoluene and aqueous solvent are according to mass ratio 1：1.5 respectively
It is delivered to by pump 3 and pump 1 in 100L micron bubble reactor 5.When adding 60kg feed liquid, i.e. p-tert-butyltoluene, water
When gross weight with catalyst is 60 kilograms, stop charging, open pump 14, the flow for making the feed liquid of circulation is 20000L/h, micro-
The Air Bubble Size that rice bubble reactor 5 is produced is 50 μm -1000 μm, and the feed liquid by heat exchanger 11 to circulation is heated, heating
During to 90 DEG C, while being passed through oxygen into micron bubble reactor 5 to rise to the pressure in micron bubble reactor 5
0.3MPa（Gauge pressure）.
After reaction 0.1 hour, valve 15, pump 1 and pump 3 are opened, flowmeter 16 is adjusted, according to 100L/h flow velocity to split-phase
Device 21 conveys reaction material liquid so that pump 1 and pump 3 convey p-tert-butyltoluene and solvent according to 50L/h to micron bubble reactor 5
Water.Reaction material liquid is cooled to 30 DEG C using heat exchanger 17, after phase-splitter stands 0.3h, aqueous phase is back to water tank by pump 20
2, oil phase is delivered to rectification under vacuum in first rectifying column 25 by pump 24 and separated.
The tower diameter of first rectifying column 25 be 1.1m, theoretical tray be 70 pieces, tower top pressure be that 13.6 kPa, tower reactor pressure are
21.1 kPa.The side line water outlet of first rectifying column 25, overhead extraction p-tert-butyltoluene, water and p-tert-butyltoluene are returned respectively again
To water tank 2 and p-tert-butyltoluene storage tank 4.The tower bottoms of first rectifying column 25 is delivered in Second distillation column 28 by pump 27 to be subtracted
Press rectifying separation.The tower diameter of Second distillation column 28 be 0.9 m, theoretical tray be 80 pieces, tower top pressure be 11.2kPa, tower top pressure
Power is 18.4kPa.Benzoic acid, catalyst of tower reactor extraction of Second distillation column 28 etc. transport to specified place processing, the second rectifying
The p-t-Butylbenzaldehyde of the overhead extraction of tower 28 is delivered to anion-exchange column 29.
D001 strong-basicity styrene series anion exchange resins, p-t-Butylbenzaldehyde are filled with anion-exchange column 29
Anion exchange is carried out in anion-exchange column 29.Finally, p-t-Butylbenzaldehyde is transported to cation exchange column 31, sun
Be filled with D001 large hole strong acid styrene system cation exchange resins in ion exchange column 31, p-t-Butylbenzaldehyde sun from
Cation exchange is carried out in sub- exchange column 31, to obtain high-purity p-t-Butylbenzaldehyde.
Embodiment 3
Catalyst is dissolved in aqueous solvent, and mass fraction is 1.5%, and p-tert-butyltoluene and aqueous solvent are according to mass ratio 1：2 respectively by
Pump 3 and pump 1 are delivered in 100L micron bubble reactor 5.When add 60kg feed liquid when, i.e., p-tert-butyltoluene, water and
When the gross weight of catalyst is 60 kilograms, stop charging, open pump 14, the flow for making the feed liquid of circulation is 10000L/h, micron
The Air Bubble Size that bubble reactor 5 is produced is 50 μm -1000 μm, and the feed liquid by heat exchanger 11 to circulation is heated, and is warming up to
At 70 DEG C, while being passed through oxygen into micron bubble reactor 5 to rise to the pressure in micron bubble reactor 5
0.38MPa（Gauge pressure）.
After reaction 2 hours, valve 15, pump 1 and pump 3 are opened, flowmeter 16 is adjusted, according to 200L/h flow velocity to phase-splitter
21 conveying reaction material liquids so that pump 1 and pump 3 are conveyed to the tert-butyl group according to 120L/h and 80L/h to micron bubble reactor 5 respectively
Toluene and aqueous solvent.Reaction material liquid is cooled to 20 DEG C using heat exchanger 17, after phase-splitter stands 0.5h, aqueous phase is returned by pump 20
Water tank 2 is back to, oil phase is delivered to rectification under vacuum in first rectifying column 25 by pump 24 and separated.
The tower diameter of first rectifying column 25 be 1.7m, theoretical tray be 73 pieces, tower top pressure be that 15.6 kPa, tower reactor pressure are
23.1 kPa.The side line water outlet of first rectifying column 25, overhead extraction p-tert-butyltoluene, water and p-tert-butyltoluene are returned respectively again
To water tank 2 and p-tert-butyltoluene storage tank 4.The tower bottoms of first rectifying column 25 is delivered in Second distillation column 28 by pump 27 to be subtracted
Press rectifying separation.The tower diameter of Second distillation column 28 be 1.1 m, theoretical tray be 82 pieces, tower top pressure be 14.2kPa, tower top pressure
Power is 25.4kPa.Benzoic acid, catalyst of tower reactor extraction of Second distillation column 28 etc. transport to specified place processing, the second rectifying
The p-t-Butylbenzaldehyde of the overhead extraction of tower 28 is delivered to anion-exchange column 29.
D301 macroreticular weakly base styrene series anion exchange resins are filled with anion-exchange column 29, to tert-butyl benzene
Formaldehyde carries out anion exchange in anion-exchange column 29.Finally, p-t-Butylbenzaldehyde is transported to cation exchange column
31, cation exchange column 31 is interior to be filled with D113 macroporous type acidulous acrylic acid's cation exchanger resins, to tert-butyl benzene first
Aldehyde carries out cation exchange in cation exchange column 31, to obtain high-purity p-t-Butylbenzaldehyde.According to food security
National standard（GB-28320-2012）The p-t-Butylbenzaldehyde product that the detection method detection of announcement is obtained, wherein to tertiary fourth
Benzaldehyde content is 99.1%, and acid number is 3.0%, and relative density is 1.042, and chlorination analyte detection shows negative reaction.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " illustrative examples ",
The description of " example ", " specific example " or " some examples " etc. means to combine specific features, the knot that the embodiment or example are described
Structure, material or feature are contained at least one embodiment of the present invention or example.In this manual, to above-mentioned term
Schematic representation is not necessarily referring to identical embodiment or example.Moreover, specific features, structure, material or the spy of description
Point can in an appropriate manner be combined in any one or more embodiments or example.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that：Not
In the case of departing from the principle and objective of the present invention a variety of change, modification, replacement and modification can be carried out to these embodiments, this
The scope of invention is limited by claim and its equivalent.
Claims (10)
1. a kind of high-grade p-t-Butylbenzaldehyde preparation method, it is characterised in that comprise the following steps：
A）P-tert-butyltoluene, water and the catalyst for not containing halogen are mixed in micron bubble reactor and aoxidize anti-
Should, to obtain reaction material liquid；
B）Water-oil separating is carried out to the reaction material liquid, to obtain aqueous phase and oil phase, the aqueous phase contains catalyst, the oil
Mutually contain p-t-Butylbenzaldehyde and impurity；With
C）The p-t-Butylbenzaldehyde and the impurity is separated to obtain high-grade p-t-Butylbenzaldehyde.
2. high-grade p-t-Butylbenzaldehyde preparation method according to claim 1, it is characterised in that the impurity includes
P-tert-butyltoluene, water, catalyst and benzoic acid, the step C）Including：
C-1）Rectifying is carried out to the p-t-Butylbenzaldehyde and the impurity, to obtain p-tert-butyltoluene, water and tower
Kettle liquid, the tower bottoms includes the p-t-Butylbenzaldehyde, catalyst and benzoic acid；
C-2）Rectifying is carried out to the tower bottoms, to make the p-t-Butylbenzaldehyde be separated with catalyst and benzoic acid；With
C-3）Anion exchange and cation exchange are carried out to the p-t-Butylbenzaldehyde successively.
3. high-grade p-t-Butylbenzaldehyde preparation method according to claim 2, it is characterised in that the oxidation reaction
Reaction temperature be 50 DEG C -90 DEG C, the pressure in the micron bubble reactor is 0.2MPa-0.4MPa, the oxidation reaction
Reaction time be -2 hours 0.1 hour.
4. high-grade p-t-Butylbenzaldehyde preparation method according to claim 3, it is characterised in that the micron bubble
Reactor is by swiftly flowing liquid cutting gas to produce bubble, and the bubble size distribution of generation is at 50 μm -1000 μm
In the range of.
5. high-grade p-t-Butylbenzaldehyde preparation method according to claim 3, it is characterised in that the micron bubble
The oxidation reaction carried out in reactor is that the feed liquid in successive reaction, the micron bubble reactor circulates 10 ~ 200 per hour
It is secondary, after the oxidation reaction is carried out -2 hours 0.1 hour, from the micron bubble reactor continuous discharge, while to described micro-
Rice bubble reactor continuous feed.
6. high-grade p-t-Butylbenzaldehyde preparation method according to claim 2, it is characterised in that by the reaction material
Liquid is cooled to 15 DEG C -30 DEG C, and the reaction material liquid after cooling then is stood into -0.5 hour 0.1 hour in phase-splitter, with
Just aqueous phase and oil phase are obtained.
7. high-grade p-t-Butylbenzaldehyde preparation method according to claim 1, it is characterised in that p-tert-butyltoluene
Single transformation rate be 10% ~ 65%, the single reaction selectivity of p-t-Butylbenzaldehyde is more than 99%.
8. a kind of high-grade p-t-Butylbenzaldehyde preparation facilities, it is characterised in that including：
Micron bubble reactor, the micron bubble reactor has charging aperture, loop exit, circulation import, oxidant inlet
And discharging opening, the loop exit and the circulation inlet communication；
Phase-splitter, the phase-splitter has charging aperture, aqueous phase discharging opening and oil phase discharging opening, the charging aperture of the phase-splitter and institute
State the discharging opening connection of micron bubble reactor；
First rectifying column, the first rectifying column has charging aperture, tower top discharging opening, side discharging opening and bottom of towe discharging opening, described
The charging aperture of first rectifying column is connected with the oil phase discharging opening of the phase-splitter；
Second distillation column, the Second distillation column has charging aperture, tower top discharging opening and bottom of towe discharging opening, the Second distillation column
Charging aperture connected with the bottom of towe discharging opening of the first rectifying column；
Anion-exchange column, the anion-exchange column has charging aperture and discharging opening, the charging aperture of the anion-exchange column
Connected with the tower top discharging opening of the Second distillation column；With
Cation exchange column, the cation exchange column has charging aperture and discharging opening, the charging of the cation exchange column
Mouth is connected with the discharging opening of the anion-exchange column.
9. high-grade p-t-Butylbenzaldehyde preparation facilities according to claim 8, it is characterised in that the phase-splitter
Aqueous phase discharging opening is connected with the charging aperture of the micron bubble reactor, the tower top discharging opening of the first rectifying column and side discharging
Each charging aperture with the micron bubble reactor in mouthful is connected, it is preferable that described high-grade to tert-butyl benzene first
Aldehyde preparation facilities further comprises heat exchanger, and the heat exchanger has a charging aperture and discharging opening, the charging aperture of the heat exchanger with
The discharging opening connection of the micron bubble reactor, the discharging opening of the heat exchanger is connected with the charging aperture of the phase-splitter.
10. high-grade p-t-Butylbenzaldehyde preparation facilities according to claim 1, it is characterised in that the micron gas
Bubble reactor includes：
Body, has reaction chamber in the body, the wall of the reaction chamber provided with charging aperture, discharging opening, circulating air outlet and
Loop exit；
Injector a, part for the injector passes through the body and extend into the reaction chamber, wherein the injector
With circulation import, oxidant inlet and jet, the circulation import is connected with the loop exit, the oxidant inlet
With the circulating air outlet；With
Bubble generator, the bubble generator has a charging aperture and discharging opening, the charging aperture of the bubble generator with it is described
Jet is connected, it is preferable that the bubble generator includes：
Connecting tube, the first end of the connecting tube is connected with the jet；With
There is accommodating chamber, the wall of the accommodating chamber is provided with charging aperture and discharging opening, the accommodating chamber in housing, the housing
In its axial direction discharging opening, the second end and the accommodating chamber of the connecting tube are equipped with relative first end and the second end
Charging aperture is connected, and the length direction of the connecting tube and the circumference of the accommodating chamber are tangent, it is further preferred that the accommodating chamber is
Rotational-like, it is straight with the diameter parallel of the accommodating chamber that the revolution bus of the accommodating chamber is a circular arc line or one
The curve of line and two rectilinear(-al)s or one and the straight line of the diameter parallel of the accommodating chamber and two circular arc lines compositions
Curve, it is preferable that with the straight line of the diameter parallel of the accommodating chamber and two circular arc lines in their intersection phase
Cut.
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Cited By (1)
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