CN106914203B - Cyclobutanetetracarboxylic dianhydride continuous preparation device and method based on micro-mixer - Google Patents
Cyclobutanetetracarboxylic dianhydride continuous preparation device and method based on micro-mixer Download PDFInfo
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- CN106914203B CN106914203B CN201710096206.2A CN201710096206A CN106914203B CN 106914203 B CN106914203 B CN 106914203B CN 201710096206 A CN201710096206 A CN 201710096206A CN 106914203 B CN106914203 B CN 106914203B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultra-violet light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/30—Micromixers
- B01F33/3034—Micromixers using induced convection or movement in the mixture to mix or move the fluids without mechanical means, e.g. thermodynamic instability, strong gradients, etc.
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/2204—Mixing chemical components in generals in order to improve chemical treatment or reactions, independently from the specific application
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00851—Additional features
- B01J2219/00858—Aspects relating to the size of the reactor
- B01J2219/0086—Dimensions of the flow channels
Abstract
A kind of cyclobutanetetracarboxylic dianhydride continuous preparation device and method based on micro-mixer, it include: T-type micro-mixer, the gas source being connected respectively with two input terminal and micro syringe and the capillary microchannels being connected with its output end, in which: capillary microchannels are set in the cooling device with ultraviolet light.The present invention with nitrogen as gas phase, using maleic anhydride solution as liquid phase, after being mixed to form two phase flow by T-type micro-mixer, reacted in capillary microchannels through ultraviolet source irradiation, reaction product obtains cyclobutanetetracarboxylic dianhydride after being separated by filtration.
Description
Technical field
The present invention relates to a kind of technology of chemical field, specifically a kind of cyclobutanetetracarboxylic based on micro-mixer
Dianhydride continuous preparation device and method.
Background technique
Polyimides because its excellent heat-resisting quantity, mechanical strength and insulation performance be widely used in aviation, automobile and
Microelectronic field.Traditional aromatic polyimide film is due to intermolecular and Intramolecular charge transfer complex formation, face
Color is lower compared with deep and optical clarity, greatly limits it in the application of photoelectric field.
The polyimides of cyclobutanetetracarboxylic dianhydride and diamine monomer polymerization, introduces aliphatic monomer in strand, breaks
It is broken the formation of charge transfer complex, visible light transmittance with higher, excellent optically and electrically characteristic, is to prepare
The ideal material of transparent polyimide.Traditional still reaction prepares cyclobutanetetracarboxylic dianhydride by maleic anhydride strong purple
Cyclization is carried out under the irradiation of outer light, but yield is very low, only less than 10% or so, and can generate a large amount of byproducts,
It makes troubles for later purification, while the intermittent reaction operation cycle is long, energy consumption is high.
Micro-mixer is the three-dimensional structure element that can be used for chemically reacting manufactured by precision processing technology, channel size
Generally in micron to submillimeter magnitude.Compared to traditional mixer, micro-mixer due to size significantly reduction, in it
Distance is extremely short between portion's thin layer of fluid, and specific surface area is larger, and reaction mass can be rapidly uniformly mixed, and there is efficient heat/matter to pass
Pass performance；And internal mixer can obtain uniform illumination, reaction (stop) time can accurately be controlled by the flow velocity of material.By
In above-mentioned advantage, micro-mixer is widely used in by heat transfer/mass transfer limited fast reaction system or photochemical reaction system,
Reaction selectivity obtained and yield are commonly greater than traditional mixer, and the reaction time is greatly reduced.Meanwhile for relating to
And the reaction process to high-risk chemical, it is small that micro-mixer using the mode that continuously flows, in internal mixer deposits liquid holdup, easily
In control reaction process, the safety of reaction process is substantially increased.Micro-mixer technology is in organic synthesis, polymerization reaction, extraction
The fields such as separation are taken to obtain local industrial applications.
Summary of the invention
The present invention prepares that conversion ratio caused by cyclobutanetetracarboxylic dianhydride is low, the reaction time is long, energy for traditional mixer
The defects of consumption is big, discontinuous and reaction is uneven, by-product, proposes a kind of cyclobutanetetracarboxylic dianhydride based on micro-mixer
Continuous preparation device and method.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of devices continuously prepared for cyclobutanetetracarboxylic dianhydride, comprising: T-type micro-mixer divides
The gas source and micro syringe that are not connected with two input terminal and the capillary microchannels being connected with its output end, in which:
Capillary microchannels are set in the cooling device with ultraviolet light.
The internal diameter of the T-type micro-mixer is 0.2mm-2mm.
The channel interior diameter of the capillary microchannels is 0.5~3mm, and capillary microchannels length is 1m-20m,
It is preferred that being made of the high fluorinated ethylene propylene copolymer of uv transmittance.
The ultraviolet source is preferably high-pressure sodium lamp light source, and wavelength is greater than 280nm, and power is 100~500W.
The high-boron-silicon glass that the cooling device preferably uses UV Absorption small is made.
The present invention relates to the continuous preparation methods of cyclobutanetetracarboxylic dianhydride of above-mentioned apparatus, with nitrogen as gas phase, with horse
Carry out anhydride solution as liquid phase, after being mixed to form two phase flow by T-type micro-mixer, through ultraviolet source in capillary microchannels
Irradiation reaction, reaction product obtain cyclobutanetetracarboxylic dianhydride after being separated by filtration.
The liquid phase, preferably maleic anhydride are dissolved in ethyl acetate and obtain, further preferred maleic anhydride quality
Concentration range is 4~40%.
The vapor-liquid two phases volume flow rate ratio is 1:1~4.
The irradiation reaction, preferable reaction temperature are lower than 15 DEG C, and the reaction time is 5min~120min.
Technical effect
Compared with prior art, the reaction time of the invention foreshortens to 5-120min, and 90% or more products pure, solvent is through steaming
It can be recycled after evaporating.
Detailed description of the invention
Fig. 1 is apparatus of the present invention schematic diagram；
In figure: 1 gas bomb, 2 pressure reducing valves, 3 gas mass flow meters, 4 gas pipelines, 5 micro-injection pumps, 6 syringes,
7T type micro-mixer, 8 cooling devices, 9 ultraviolet sources, 10 capillary microchannels；
Fig. 2 is T-type micro-mixer structure schematic diagram；
In figure: 11 liquid phase streams, 12 mixed flows, 13 gas phase streams, 14 screw threads；
Fig. 3 is that cyclobutanetetracarboxylic dianhydride infrared spectrum is prepared in embodiment；
Fig. 4 is that cyclobutanetetracarboxylic dianhydride liquid chromatogram is prepared in embodiment.
Specific embodiment
The continuous preparation of cyclobutanetetracarboxylic dianhydride is accomplished by the following way in the present embodiment:
One, the maleic anhydride solution that mass concentration is 4% in organic solvent by maleic anhydride dissolution, is prepared as liquid
Phase；
Two, nitrogen is as gas phase, and the feed volume speed ratio of gas phase and liquid phase is that 1:3 enters T-type micro-mixer and mixes shape
At vapor-liquid two phases fluid；
Three, fluid is that photopolymerization reaction occurs through ultraviolet source irradiation in the microchannel 0.5mm in diameter, and fluid is in ultraviolet light
In residence time be 20min, reaction temperature be -5 DEG C；
Four, white solid is obtained after being separated by filtration, then washed, dry cyclobutanetetracarboxylic dianhydride.
As shown in Fig. 2, the T-type micro-mixer is connected through a screw thread with capillary microchannels, gas phase and liquid phase are flowed to
In 180 ° of convection current collision shearings to form Secondary Flow and increase disturbance and mixed effect, realized by the structure of T-type micro-mixer
The mixing of head-on collision mode, and such head-on collision mode mixture effect is best.
The present embodiment is prepared into cyclobutanetetracarboxylic dianhydride and makees examination of infrared spectrum.3013cm as shown in Figure 2-1It is stretched for C-H
Contracting vibration peak, 1850cm-1、1780cm-1For C=O absorption peak, 1208cm-1、1096cm-1、964cm-1、938cm-1For C-O-C suction
Receive peak.
The present embodiment is prepared into cyclobutanetetracarboxylic dianhydride with commercialization, pure cyclobutanetetracarboxylic dianhydride using liquid
The test of phase chromatography: the strength of fluid for using pure cyclobutanetetracarboxylic dianhydride to prepare is 1.14g/L, using synthesized by this method
The solution concentration that cyclobutanetetracarboxylic dianhydride is prepared is 1.00g/L, obtains the ring fourth of this method preparation by liquid chromatogram map analysis
Alkane tetracarboxylic acid dianhydride purity is 97.2%.
Comparative example 1: the mass concentration of maleic anhydride is 8% in solution described in step 1.Other and specific embodiment party
Formula one is identical, its role is to: mass concentration increases, and yield improves.
Comparative example 2: dispersed phase described in step 2 and the feed volume speed ratio of continuous phase are 1:2.It is other with it is specific
Embodiment one is identical, its role is to: content of dispersed phase increases, and reaction time changes, and yield changes.
Comparative example 3: microchannel described in step 3 is directly 1mm.It is other same as the specific embodiment one, effect
Be: microchannel diameter increases, and reaction amplification, the residence time reduces, and yield reduces.
Comparative example 4: residence time of the fluid described in step 3 in micro-mixer is 30min.Other and specific reality
It is identical to apply mode one, its role is to: the residence time increases, and yield improves.
Comparative example 5: reaction temperature described in step 3 is 0 DEG C.It is other same as the specific embodiment one, it acts on
In: temperature increases, and reaction conversion ratio changes.
Above-mentioned specific implementation can by those skilled in the art under the premise of without departing substantially from the principle of the invention and objective with difference
Mode carry out local directed complete set to it, protection scope of the present invention is subject to claims and not by above-mentioned specific implementation institute
Limit, each implementation within its scope is by the constraint of the present invention.
Claims (4)
1. a kind of continuous preparation method of cyclobutanetetracarboxylic dianhydride of reaction unit based on T-type micro-mixer, which is characterized in that
The reaction unit includes: the T-type micro-mixer that internal diameter is 0.2mm-2mm, the gas source being connected respectively with two input terminal
With micro syringe and the channel interior diameter being connected with its output end is 0.5~1mm and length is 1m-20m capillary
Microchannel, in which: capillary microchannels are set in the cooling device with ultraviolet light, the gas phase in the T-type micro-mixer with
Liquid phase flow direction is in 180 ° of convection current collision shearings to form Secondary Flow and increase disturbance and mixed effect；
The continuous preparation method, with nitrogen as gas phase, i.e. dispersed phase, using maleic anhydride solution as liquid phase, i.e., continuously
Phase is reacted in capillary microchannels through ultraviolet source irradiation after being mixed to form two phase flow by T-type micro-mixer, and reaction produces
Object obtains cyclobutanetetracarboxylic dianhydride after being separated by filtration；
The dispersed phase and continuous phase volume flow rate ratio is 1:1~4.
2. according to the method described in claim 1, it is characterized in that, the wavelength of the ultraviolet source is greater than 280nm.
3. according to the method described in claim 1, it is characterized in that, the continuous phase is dissolved in ethyl acetate for maleic anhydride
In obtain, maleic anhydride mass concentration range be 4~40%.
4. according to the method described in claim 1, it is characterized in that, the described irradiation reaction, reaction temperature is lower than 15 DEG C, when reaction
Between be 5min~120min.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110694566A (en) * | 2018-07-09 | 2020-01-17 | 中国科学院上海有机化学研究所 | Flow type photochemical reaction device |
| CN109111460B (en) * | 2018-09-18 | 2021-04-30 | 山东德晨能源科技有限公司 | Preparation device of cyclobutane tetracarboxylic dianhydride |
| CN110845513B (en) * | 2019-12-02 | 2021-04-27 | 青岛科技大学 | Synthetic method of aliphatic pentacyclic dianhydride |
| CN114163045B (en) * | 2021-12-09 | 2024-02-20 | 潍坊科技学院 | Process for continuously treating nickel-containing wastewater by utilizing micromixer |
| CN114177815B (en) * | 2021-12-09 | 2024-02-02 | 潍坊科技学院 | Micromixer and device for continuously treating nickel-containing wastewater by utilizing micromixer |
| CN114195620A (en) * | 2021-12-23 | 2022-03-18 | 上海交通大学 | Method for synthesizing phenol by photo-oxidation benzene continuous flow based on micro-reactor |
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