CN115253954B - Continuous reaction device and application - Google Patents

Continuous reaction device and application Download PDF

Info

Publication number
CN115253954B
CN115253954B CN202210940045.1A CN202210940045A CN115253954B CN 115253954 B CN115253954 B CN 115253954B CN 202210940045 A CN202210940045 A CN 202210940045A CN 115253954 B CN115253954 B CN 115253954B
Authority
CN
China
Prior art keywords
reaction
micro
unit
mixing
maleic anhydride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210940045.1A
Other languages
Chinese (zh)
Other versions
CN115253954A (en
Inventor
张英杰
杜斌
胡清
蔡玉东
陈商涛
石行波
荔栓红
何盛宝
高克京
张风波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN202210940045.1A priority Critical patent/CN115253954B/en
Publication of CN115253954A publication Critical patent/CN115253954A/en
Priority to PCT/CN2022/139174 priority patent/WO2024027074A1/en
Application granted granted Critical
Publication of CN115253954B publication Critical patent/CN115253954B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • B01F33/80—Mixing plants; Combinations of mixers
    • 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
    • B01J19/0006—Controlling or regulating processes
    • 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
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • 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
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a continuous reaction device and application, wherein the reaction device comprises a T-shaped micro-mixing unit, a channel switching unit and N mutually different micro-reaction units, wherein N is more than or equal to 2; the liquid phase outlets of the T-shaped micro-mixing units are communicated with the inlets of the channel switching units, and N outlets of the channel switching units are respectively communicated with the inlets of the N micro-reaction units one by one; the channel switching unit is used for guiding the liquid phase output through the liquid phase outlet into one micro-reaction unit. The continuous reaction device can effectively solve the problems of low utilization rate, poor safety and the like of common raw materials in chemical reaction, and greatly improves the production efficiency and reduces the production cost by providing more proper reaction environment and realizing continuous feeding for different types of raw materials.

Description

Continuous reaction device and application
Technical Field
The invention relates to a continuous reaction device and application thereof, and belongs to the technical field of chemical industry.
Background
The C4-C10 alpha-monoolefin-maleic anhydride copolymer is a chemical product with wide application, and the application is different due to the different molecular weights and different functional groups (derivative products such as amide-ammonia type, imide type, crosslinking type, hydrolysis type, ionic type and the like). The isobutylene maleic anhydride copolymer with low molecular weight can be used as scale inhibitor, dispersant and water reducer of cement slurry, and the isobutylene maleic anhydride copolymer with medium and high molecular weight can be used as adhesive for wood and paper processing, emulsion polymerization stabilizer and the like. In addition, the anhydride groups in the isobutylene maleic anhydride copolymer can undergo esterification reaction, amidation reaction, imidization reaction and ionization reaction, so that the application range of the isobutylene maleic anhydride copolymer is further widened. For example, the isobutylene maleic anhydride copolymer can be used as an adhesive, a water-based paint and the like after being aminated, can be used as a polymerization stabilizer and an adhesive latex after being modified by imine, can be used as a water-absorbent resin after being crosslinked, has excellent performance and wide application, and has important application prospect.
At this stage, the C4-C10 alpha-monoolefin is generally introduced directly into a reaction vessel containing a maleic anhydride solution to prepare a C4-C10 alpha-monoolefin-maleic anhydride copolymer. The C4-C10 alpha-monoolefin in the mode has long dissolution time and is difficult to timely release heat generated by polymerization reaction, so that the raw material utilization efficiency is low and certain potential safety hazard is provided.
In addition, the properties, viscosity and other parameters of different mono-olefin raw materials are different, and the current reaction kettle has difficulty in giving a more proper reaction environment according to the raw material difference. And the mode efficiency of traditional reation kettle preparation chemical product is also not high, can only improve the output of unit time through increasing reation kettle's synchronous operation quantity, and not only area is big, has also consumed a large amount of equipment cost and human cost.
Disclosure of Invention
The invention provides a continuous reaction device which can effectively solve the problems of low utilization rate, poor safety and the like of common raw materials in chemical reaction, and greatly improves the production efficiency and reduces the production cost by providing more proper reaction environment for different types of raw materials and realizing continuous feeding.
The invention also provides an application of the continuous reaction device in polymer preparation. The continuous reaction device can improve the utilization rate of raw materials, realize the accurate control of the reaction temperature and the reaction degree, avoid the phenomenon of thermal runaway caused by uncontrollable polymerization reaction, and realize the stable production of target products. In addition, the continuous feeding advantage of the continuous reaction device also obviously improves the production efficiency and reduces the production cost.
The invention also provides a preparation method of the C4-C10 alpha-mono-olefin-maleic anhydride copolymer, which is prepared by adopting the continuous reaction device. Therefore, the method has the advantages of high safety, high yield, high product stability and low cost.
The invention provides a continuous reaction device, which comprises a T-shaped micro-mixing unit, a channel switching unit and N mutually different micro-reaction units, wherein N is more than or equal to 2;
The liquid phase outlets of the T-shaped micro-mixing units are communicated with the inlets of the channel switching units, and N outlets of the channel switching units are respectively communicated with the inlets of the N micro-reaction units one by one;
The channel switching unit is used for guiding the liquid phase output through the liquid phase outlet into one micro-reaction unit.
The continuous reaction apparatus as described above, further comprising an ultrasonic unit for ultrasonic treatment of at least one of the micro-reaction units.
The continuous reaction apparatus as described above, wherein further comprising a first pressure regulating unit and/or a second pressure regulating unit;
The first pressure regulating unit is positioned at the liquid phase outlet and is used for regulating the pressure in the T-shaped micro-mixing unit;
the second pressure regulating unit is positioned at the reaction liquid outlet of the micro-reaction unit and is used for regulating the pressure in the micro-reaction unit.
The continuous reaction apparatus as described above, wherein each of the N micro-reaction units is selected from one of a micro-channel reactor, a capillary micro-reactor, a falling film micro-reactor, and a film dispersion micro-reactor.
The continuous reaction apparatus as described above, wherein the T-shaped micro-mixing unit further comprises a first feedstock inlet, a second feedstock inlet, and a gas phase outlet;
The gas phase outlet communicates with the first feedstock inlet and/or the second feedstock inlet.
The invention also provides an application of the continuous reaction device in preparing polymers.
The invention also provides a preparation method of the C4-C10 alpha-mono-olefin-maleic anhydride copolymer, which is prepared by adopting the continuous reaction device.
The preparation method comprises the following steps:
1) Introducing a raw material comprising C4-C10 alpha-mono-olefin and maleic anhydride into the T-shaped micro-mixing unit for mixing treatment to obtain a mixed solution;
2) And controlling the channel switching unit to enable the mixed solution to enter one micro-reaction unit for polymerization reaction after being output from the liquid phase outlet, so as to obtain a reaction solution comprising C4-C10 alpha-mono-olefin-maleic anhydride copolymer.
The preparation method comprises the steps of reacting at the reaction pressure of 0.5-2MPa for 1-4s at 55-100 ℃;
and/or the number of the groups of groups,
The reaction pressure of the polymerization reaction is 0.2-2MPa, the time is 30-90min, and the temperature is 50-100 ℃.
The preparation method as described above, wherein in step 2), the flow rate of the mixed solution entering the micro-reaction unit is 20-40ml/min.
The implementation of the invention has at least the following advantages:
1. the continuous reaction device can promote the mass transfer speed of the raw materials and shorten the dissolution time of the raw materials, so that the utilization rate of the raw materials is obviously improved, the cost of the raw materials is saved, and the high yield of the product is realized;
2. the continuous reaction device can accurately control the reaction temperature, timely disperse the heat generated in the reaction process, avoid the thermal runaway phenomenon caused by heat aggregation, and lay a foundation for the safe operation of the reaction;
3. The continuous reaction device can accurately control the reaction time, particularly when the continuous reaction device is used for preparing polymers, the phenomenon of uncontrolled polymerization caused by uncontrollable polymerization reaction is avoided to a great extent, the consistency of products is ensured by accurately controlling reaction nodes, and the stability of the products in different batches is optimized;
4. The continuous reaction device can realize a continuous feeding production mode, can improve the product output per unit time on the basis of not increasing the reaction device, and has the advantages of small occupied area, low equipment cost and low labor cost;
5. in consideration of different reaction requirements of different raw materials, the continuous reaction device integrates proper reaction environments of various different raw materials, and forward propulsion of various different reactions is realized to the greatest extent with the lowest equipment cost and the smallest device volume.
Drawings
FIG. 1 is a schematic structural view of a continuous reaction apparatus in an embodiment of the present invention;
FIG. 2 is an infrared spectrum of a copolymer obtained at a copolymerization temperature of 55℃in example 5 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a continuous reaction device, which comprises a T-shaped micro-mixing unit, a channel switching unit and N mutually different micro-reaction units, wherein N is more than or equal to 2;
The liquid phase outlets of the T-shaped micro-mixing units are communicated with the inlets of the channel switching units, and N outlets of the channel switching units are respectively communicated with the inlets of the N micro-reaction units one by one;
The channel switching unit is used for guiding the liquid phase output through the liquid phase outlet into one micro-reaction unit.
In the continuous reaction device, the T-shaped micro-mixing unit is used for providing a mixing and pre-reacting place for raw materials, and the micro-reaction unit is used for providing a deep reacting place for mixed liquid from the T-shaped micro-mixing unit. The continuous reaction device comprises N mutually different micro-reaction units, each micro-reaction unit has different structures or structural parameters, and the inlet of each micro-reaction unit is communicated with one outlet of the channel switching unit, namely N channels are arranged between the channel switching unit and the micro-reaction unit. In a specific application process, the channel switching unit needs to be controlled to close the channel between the inlet of the channel switching unit and the (N-1) outlets of the channel switching unit, and only the inlet of the closed channel switching unit and one outlet of the channel switching unit are conducted, so that the mixed liquid from the T-shaped micro-mixing unit can be efficiently guided into one micro-reaction unit for reaction.
Because the continuous reaction device integrates N different micro-reaction units and the channel switching units, the channel switching units can be simply controlled according to the property parameters of the real-time reaction raw materials, so that the micro-reaction units which are more suitable for the reaction of the current raw materials are selected, and the reaction efficiency is greatly improved by improving the suitability of the raw materials and the reaction environment.
The present invention is not limited to the specific form of the channel switching unit. For example, a dovetail having an inlet in communication with the liquid phase outlet of the T-shaped micro-mixing unit and N outlets in communication with a micro-reaction unit, respectively. When a proper and unique micro-reaction unit is required to be selected, the target micro-reaction unit is positioned below the dovetail pipe inlet only by rotating the dovetail pipe, and other micro-reaction units are positioned above the dovetail pipe inlet, so that the mixed liquid from the T-shaped micro-mixing unit can directly flow into the target micro-reaction unit for reaction under the action of gravity; or the channel switching unit can be an (N+1) through valve, one inlet is communicated with the liquid phase outlet of the T-shaped micro-mixing unit, and N outlets are respectively communicated with one micro-reaction unit. When a proper and unique micro-reaction unit is needed to be selected, only the opening and closing direction and the opening and closing angle of the valve are reasonably controlled, so that the inlet and one outlet are communicated to close the channel between the inlet and other outlets, and at the moment, the mixed liquid from the T-shaped micro-mixing unit directly flows into the target micro-reaction unit for reaction through the unique communicated channel in the (N+1) communication valve.
As previously described, the T-shaped micromixing unit is used to provide a mixing and pre-reaction locus for the feedstock. The T-shaped micro-mixing unit is provided with two opposite first raw material inlets and two opposite second raw material inlets, raw materials respectively enter the T-shaped micro-mixing unit through the first raw material inlets and the second raw material inlets and are in reverse contact and are mixed, and mixed raw material liquid can continuously flow to the liquid phase outlet along the direction perpendicular to the feeding direction. In the whole mixing process, the raw materials are reversely contacted and flow in a turning way, so that the mass transfer speed of the raw materials is increased, the mixing time is shortened, the dissolution speed of the raw materials is accelerated, and the utilization rate of the raw materials is improved. The T-shaped micro-mixer unit may be a T-shaped micro-mixer. The T-shaped micromixer is provided with a feeding channel and a mixing channel which are perpendicular to each other and are communicated, the feeding channel is provided with two opposite feeding inlets (a first raw material inlet and a second raw material inlet) which are positioned at two ends, one end of the mixing channel is communicated with the side wall of the feeding channel, and the other end of the mixing channel is a liquid phase outlet communicated with the inlet of the channel switching unit. Further, the T-shaped micro-mixing unit also comprises a gas phase outlet which is arranged on the side wall of the mixing channel and is used for returning insufficiently dissolved gas phase raw materials to the first raw material inlet and/or the second raw material inlet for mixing treatment again so as to improve the raw material utilization rate.
In one embodiment, the total length of the T-shaped micro-mixing unit (the total length of the feed channel and the mixing channel) is 2 to 5m, and the inner diameters of the feed channel and the mixing channel are 1 to 3mm, respectively.
The microreaction unit of the present invention refers to a reactor having a fluid channel of the order of micrometers or a dispersion scale inside. The micron-sized flow can effectively strengthen the mixing process, ensure the full mixing and uniform distribution of materials in the reactor, and further ensure the consistency of the reaction process. And the specific surface area of the fluid in the micro-reaction unit can reach the order of 104-106 m 2/m3, so that the fluid can be subjected to efficient heat exchange with the wall surface, and the reaction temperature can be effectively controlled. In addition, the channel type reactor structure can ensure that the reaction is operated under the condition of approaching plug flow, realize the accurate control of millisecond-level residence time and realize the reaction mode of continuous injection of raw materials. Therefore, the T-shaped micro-mixing unit and the micro-reaction unit are combined, and the safety and the reaction efficiency of the chemical reaction are obviously improved by improving the mixing degree of the raw materials, accurately controlling the reaction temperature and time of the raw materials and continuously injecting the raw materials.
The present invention is not limited to a specific choice of the N micro-reaction units, as long as the N micro-reaction units are different from each other. For example, one selected from the group consisting of a micro flow channel reactor, a capillary micro reactor, a falling film micro reactor, and a membrane dispersion micro reactor may be used.
Wherein the micro-channel reactor is a reactor with a linear hollow channel; the capillary microreactor is a reactor which is made of metal and has a hollow spiral tube structure; the falling film type micro-reactor is made of stainless steel and is provided with a plurality of linear hollow channels (the inlets and the outlets of the hollow channels are in parallel connection); the membrane-dispersed micro-reactor comprises a first stainless steel layer, a micro-filtration membrane layer and a second stainless steel layer, wherein the micro-filtration membrane layer is clamped between the first stainless steel layer and the second stainless steel layer, and the micro-filtration membrane layer consists of a micro-filtration membrane and a stainless steel gasket.
Further, the cross section of the linear hollow channel of the micro-channel reactor is square with the side length of 100 mu m, and the total length is 2-8 m; the total length of the capillary microreactor is 3-10 m, and the inner diameter is 10-1000 mu m; the size of the falling film type microreactor is 120mm multiplied by 76mm multiplied by 40mm, the number of channels is 64, the length of each channel section is 200-400 mu m, and the width is 50-200 mu m.
In a specific application process, a more suitable micro-reaction unit can be selected through the channel conversion unit according to the type of raw materials. Taking C4-C10 alpha-monoolefin as the raw material, gaseous C4 alpha-monoolefin is more suitable for a micro-channel reactor, C5-C6 alpha-monoolefin is more suitable for a capillary reactor, C7-C8 alpha-monoolefin is more suitable for a falling film microreactor, and C9-C10 alpha-monoolefin is more suitable for a film dispersion microreactor.
Based on the consideration of raw material diversity and production cost, a plurality of different micro-reaction units are integrated in one reaction device, so that more proper reaction environments can be provided for different raw materials, the device cost and the site cost can be reduced, and the preparation of chemical products with high yield and low cost is realized.
In one embodiment, the continuous reaction apparatus of the present invention further comprises an ultrasonic unit in order to further enhance the forward progress of the reaction. The ultrasonic unit may be disposed inside the micro-reaction unit to directly perform ultrasonic treatment on the raw material system, or the micro-reaction unit may be disposed inside the ultrasonic unit to perform ultrasonic treatment on the entire micro-reaction unit. The ultrasonic unit may be, for example, an ultrasonic reactor.
Further, the continuous reaction device of the invention further comprises a first pressure regulating unit and/or a second pressure regulating unit; the first pressure regulating unit is positioned at the liquid phase outlet and is used for regulating the pressure in the T-shaped micro-mixing unit; the second pressure regulating unit is positioned at the reaction liquid outlet of the micro-reaction unit and is used for regulating the pressure in the micro-reaction unit. For example, the first pressure unit and the second pressure unit may be pressure regulating valves.
The working flow of the continuous reaction apparatus of the present invention will be described below.
The method comprises the steps that raw materials enter a T-shaped micro-mixing unit through a first raw material inlet and a second raw material inlet of the T-shaped micro-mixing unit respectively, the pressure in the T-shaped micro-mixing unit is controlled through adjusting a first pressure unit, and the raw materials are mixed and pre-reacted under the first pressure to obtain mixed liquid; the mixed liquid is output through a liquid phase outlet of the T-shaped micro-mixing unit, enters a micro-reaction unit which is controlled by a channel switching unit and is only conducted, and the second pressure regulating unit is synchronously regulated, so that the mixed liquid entering the micro-reaction unit reacts under the second pressure, and the obtained reaction liquid is output through an outlet of the micro-reaction unit, so that a target product is obtained.
In order to control the reaction more precisely, metering units may be provided at the first and second feed inlets to precisely control the amount of feed to the T-shaped micromixing unit. In addition, a buffer unit and a metering unit are sequentially arranged between the liquid phase outlet and the channel switching unit, wherein the buffer unit is used as a transfer accommodating unit and used for receiving the mixed liquid from the T-shaped micro-mixing unit, and the metering unit is used for inputting the mixed liquid accommodated in the buffer unit into the micro-reaction unit through the channel switching unit for reaction in a more accurate dosage. The metering unit can be a metering pump, and the buffer unit can be a buffer tank.
Further, in order to ensure efficient utilization of the raw materials, when a gas phase raw material is included, the micro-reaction unit may also include a gas phase outlet, which is in communication with the first raw material inlet and/or the second raw material inlet, for returning the unreacted complete gas phase raw material to the T-type micro-mixing unit for recycling.
In a second aspect the invention provides the use of a continuous reaction apparatus as described in any one of the preceding claims in the preparation of a polymer.
Since the polymerization reaction is generally carried out under high pressure conditions, and as the molecular weight of the product increases, the more pronounced the heat generation of the system and the poorer the thermal conductivity of the high-viscosity system are, the reaction safety is poor. The continuous reaction device can effectively dredge the heat of the system, further improves the efficiency of the polymerization reaction by controlling the reaction time, the reaction temperature and the concentration distribution of the reactants, shortens the reaction time of the further polymerization, reduces the reaction cost, improves the generation rate of the reactants and provides a more feasible method for efficiently producing the polymer.
In a third aspect, the invention provides a method for preparing a C4-C10 alpha-monoolefin-maleic anhydride copolymer, which is prepared by adopting the continuous reaction device.
The C4-C10 alpha-mono-olefins may be blended and initially reacted with the maleic anhydride solution containing the initiator in a T-type micro-mixing unit. The T-shaped micro-mixing unit can fully and quickly mutually dissolve C4-C10 alpha-mono-olefin and maleic anhydride solution containing an initiator, and complete the preliminary polar copolymerization reaction. The C4-C10 alpha-mono-olefin referred to in the present invention means at least one of C4-C10 alpha-mono-olefins.
Besides the T-shaped micro-mixing units, the channel switching units and the N micro-reaction units in the continuous reaction device can select and switch more proper micro-reaction units among the N micro-reaction units to react according to the difference of raw materials (especially the difference between C4-C10 alpha-mono-olefins), so that the raw materials can be utilized more efficiently.
In addition, compared with a common reaction kettle, the micro-reaction unit used in the invention can effectively remove the polymerization heat of the copolymerization reaction and well control the polymerization reaction temperature; providing the necessary residence time of the reaction mass; providing necessary material mixing conditions, and ensuring that the concentration distribution in the reaction unit is relatively uniform; and the production cost is lower.
In one embodiment, the method of preparation comprises the steps of:
1) Introducing a raw material comprising C4-C10 alpha-mono-olefin and maleic anhydride into the T-shaped micro-mixing unit for mixing to obtain a mixed solution;
2) And controlling the channel switching unit to enable the mixed solution to enter one micro-reaction unit for polymerization reaction after being output from the liquid phase outlet, so as to obtain a reaction solution comprising C4-C10 alpha-mono-olefin-maleic anhydride copolymer.
In the step 1), a raw material comprising C4-C10 alpha-mono-olefin can enter a T-shaped micro-mixing unit from a first raw material inlet, a raw material comprising maleic anhydride can enter the T-shaped micro-mixing unit from a second raw material inlet, and the raw material and the mixed liquid are mixed in the T-shaped micro-mixing unit to obtain a mixed liquid. Wherein the raw material comprising maleic anhydride refers to a maleic anhydride solution containing an initiator.
In one embodiment, the volume ratio of C4 alpha-mono-olefin to maleic anhydride solution containing initiator is (50-500): 1, or the mass ratio of C4-C10 alpha-monoolefin to maleic anhydride is (0.2-5): 1, preferably, the mass ratio is (0.5-3): 1.
Further, the mass of the initiator is 1-20% of the mass of the maleic anhydride, and the initiator is a thermal decomposition type initiator and comprises at least one of dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, terbutyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile.
The maleic anhydride solution refers to an amide-based solution in which maleic anhydride is dissolved. Wherein the mass percentage of the maleic anhydride in the maleic anhydride solution containing the initiator is 3-25 wt%.
In order to ensure that the mixing treatment is carried out efficiently, the C4-C10 alpha-monoolefin and the maleic anhydride solution containing the initiator can be heated separately and then injected into the T-shaped micro-mixing unit. For example, the heating temperature is 55-100 ℃.
In the step 2), a more suitable micro-reaction unit is determined according to the specific type of the raw materials, and the channel switching unit is controlled to enable the channel switching unit to be provided with only one passage communicated with the target micro-reaction unit, so that the mixed solution from the T-shaped micro-mixing unit is guided into the target micro-reaction unit to carry out polymerization reaction, and the reaction solution comprising the C4-C10 alpha-mono-olefin-maleic anhydride copolymer is obtained.
Further, the mixing pressure of the mixing treatment is 0.5-2MPa, the time is 1-4s, and the temperature is 55-100 ℃; and/or the reaction pressure of the polymerization reaction is 0.2-2MPa, the time is 30-90min, and the temperature is 50-100 ℃.
Further, the flow rate of the mixed solution entering the micro-reaction unit is 20-40ml/min, which is helpful for further improving the monomer conversion rate and avoiding the phenomenon of blocking the micro-reaction unit.
It will be appreciated that the reaction solution comprising the C4-C10 alpha-mono-olefin-maleic anhydride copolymer may also need to be post-treated after being output through the outlet of the target micro-reaction unit to obtain the C4-C10 alpha-mono-olefin-maleic anhydride copolymer. In one embodiment, the post-treatment comprises sequentially precipitation treatment, solid-liquid separation treatment, washing and drying to finally obtain the C4-C10 alpha-mono-olefin-maleic anhydride copolymer.
Wherein the precipitation treatment is to add poor solvents of alcohols and/or alkanes into the reaction solution containing the C4-C10 alpha-monoolefin-maleic anhydride copolymer so as to separate out solid precipitate from the reaction solution containing the C4-C10 alpha-monoolefin-maleic anhydride copolymer. In addition, the solid-liquid separation treatment may be carried out by filtration or centrifugation, followed by washing the separated solid precipitate with an alcohol liquid as a washing liquid.
Hereinafter, the present invention will be described in more detail by way of specific examples.
The continuous reaction apparatus in the example is shown in FIG. 1, and comprises an olefin storage unit 11 after heat exchange, a storage tank 12 for a maleic anhydride solution containing an initiator after heat exchange, a first metering pump 21, a second metering pump 22, a T-shaped micromixer 3, a buffer tank 4, a third metering pump 23, a channel switching unit 5, and 4 micro reactors (a micro channel reactor 61, a membrane dispersion type micro reactor 62, a falling film type micro reactor 63, and a capillary micro reactor 64 connected to an ultrasonic reactor 7). The outlets of the first metering pump 21 and the second metering pump 22 are respectively communicated with the first raw material inlet and the second raw material inlet of the T-shaped micro-mixer 3, and the gas phase outlet of the T-shaped micro-mixer 3 is communicated with the olefin storage unit 11 after heat exchange (the gas phase outlet is controlled to open and close by a valve). The liquid phase outlet of the T-shaped micromixer 3 is communicated with the inlet of the buffer tank 4, the outlet of the buffer tank 4 is communicated with the inlet of the third metering pump 23, and the outlet of the third metering pump 23 is communicated with the inlet of the channel switching unit 5. The channel switching unit 5 in this embodiment is a dovetail pipe having 4 outlets.
Example 1
After purging the T-type microreactor with nitrogen, heat exchanging a 1.1l solution of n, n-dimethylformamide containing 2.5g of azobisisobutyronitrile and 157g of maleic anhydride to 60 ℃, and entering the T-type micromixer via a first metering pump; isobutene enters a T-shaped micromixer through a second metering pump after heat exchange to 60 ℃, and gas and liquid are fully mixed in the T-shaped micromixer and undergo primary reaction; wherein, the gas-liquid ratio in the T-shaped micromixer is 400:1 (v/v, volume ratio of isobutene to maleic anhydride solution containing initiator) at an operating pressure of 0.6MPa.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to flow into a micro-channel reactor through a channel switching unit to continuously carry out copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.6MPa, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 1 shows the yields and molecular weights of the final copolymers obtained at various residence times of the gas and liquid in the T-micromixer.
TABLE 1
Example 2
After purging the super T-shaped micromixer with nitrogen, heat exchanging a 1.1L solution of N, N-dimethylformamide containing 2.5g of azobisisobutyronitrile and 157g of maleic anhydride to 60 ℃, and entering the T-shaped micromixer via a first metering pump; isobutene enters a T-shaped micromixer through a second metering pump after heat exchange to 60 ℃, and gas and liquid are fully mixed in the T-shaped micromixer and undergo primary reaction; wherein the operating pressure in the T-type micromixer was 0.6MPa and the gas-liquid residence time was 2.5 seconds.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to flow into a capillary microreactor through a channel switching unit to continuously carry out copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.6MPa, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 2 shows the yields and molecular weights of the copolymers finally obtained at different gas-liquid ratios (volume ratio of isobutene to maleic anhydride solution containing initiator) in T-micromixers.
TABLE 2
Sequence number Ratio of gas to liquid Copolymer mass Copolymer number average molecular weight
1 100 197g 53000
2 300 224g 58000
3 400 217g 51000
4 500 210g 55000
Example 3
After purging the super T-shaped micromixer by nitrogen, carrying out heat exchange on a 1.1L N, N-dimethylformamide solution containing 2.5g of benzoyl peroxide and 157g of maleic anhydride to 60 ℃, feeding the solution into the T-shaped micromixer through a first metering pump, carrying out heat exchange on isobutene to 60 ℃, feeding the solution into the T-shaped micromixer through a second metering pump, fully mixing gas and liquid in the T-shaped micromixer, and carrying out primary reaction; wherein, the gas-liquid ratio in the T-shaped micromixer is 300:1 (v/v), and the gas-liquid residence time was 2.5s.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to flow into a falling film type micro-reactor through a channel switching unit to continuously carry out copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.6MPa, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 3 shows the yields and molecular weights of the final copolymers obtained at different operating pressures of the T-micromixer.
TABLE 3 Table 3
Example 4
After purging the super T-shaped micromixer by nitrogen, carrying out heat exchange on 1.1L of N, N-dimethylformamide solution containing 2.5g of benzoyl peroxide and 157g of maleic anhydride, then, entering the T-shaped micromixer through a first metering pump, and after carrying out heat exchange on isobutene, entering the T-shaped micromixer through a second metering pump, fully mixing gas and liquid in the T-shaped micromixer, and carrying out primary reaction; wherein, the gas-liquid ratio in the T-shaped micromixer is 300:1 (v/v), operating pressure 0.6MPa, residence time 2.5s.
And (3) after passing the liquid phase product obtained by the T-shaped micromixer through a buffer tank and a third metering pump, introducing the liquid phase product into a membrane dispersion type microreactor through a channel switching unit to continuously carry out copolymerization reaction of isobutene and maleic anhydride, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.6MPa, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 4 shows the yields and molecular weights of the final copolymers obtained under different conditions of T-type micromixer inlet temperature (heat exchange temperature of the feedstock).
TABLE 4 Table 4
Example 5
After purging the T-micromixer with nitrogen, heat exchanging a 1.1l n, n-dimethylformamide solution containing 2.5g of azobisisobutyronitrile and 157g of maleic anhydride to 70 ℃, entering the T-micromixer via a first metering pump; the isobutene is subjected to heat exchange to 70 ℃, enters a T-shaped micromixer through a second metering pump, and the gas and the liquid are fully mixed in the T-shaped micromixer and undergo primary reaction; wherein, the gas-liquid ratio in the T-shaped micromixer is 300:1 (v/v), operating pressure 0.6MPa, residence time 2.5s.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to flow into a capillary microreactor positioned in the ultrasonic reactor through a channel switching unit to continuously carry out copolymerization reaction of isobutene and maleic anhydride. The reaction pressure was 0.6MPa, the liquid phase inlet flow rate was 30ml/min, and the reaction time was 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, performing centrifugal separation, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 5 shows the yields and molecular weights of the copolymers finally obtained at different copolymerization temperatures.
TABLE 5
Sequence number Microreactor temperature Copolymer mass Copolymer number average molecular weight
1 55℃ 220g 65000
2 70℃ 241g 51000
3 90℃ 232g 45000
FIG. 2 is an infrared spectrum of a copolymer obtained at a copolymerization temperature of 55℃in example 5 of the present invention, 1771cm -1 and 1852cm -1 being C=O stretching vibration absorption peaks of acid anhydride, and 3000cm-1 being stretching vibration absorption peaks of methyl and methylene.
Example 6
After purging the T-type micromixer with nitrogen, a 1.1L solution of N, N-dimethylformamide containing 2.5g of dicyclohexyl peroxydicarbonate and 157g of maleic anhydride is subjected to heat exchange to 70 ℃, the solution enters the T-type micromixer through a first metering pump, 1-pentene is subjected to heat exchange to 70 ℃ and then enters the T-type micromixer through a second metering pump, and the mass ratio of the 1-pentene to the solution of maleic anhydride containing the initiator in the T-type micromixer is 5:1, fully mixing and carrying out primary reaction in a T-shaped micromixer, wherein the operation pressure is 0.6Mpa, and the residence time is 2.5s.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to a capillary microreactor positioned in an ultrasonic reactor through a channel switching unit to continuously carry out copolymerization reaction of 1-pentene and maleic anhydride, wherein the reaction temperature is 70 ℃, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, performing centrifugal separation, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 6 shows the final copolymer yields and molecular weights for the microreactors at different operating pressures.
TABLE 6
Sequence number Microreactor pressure Copolymer mass Copolymer number average molecular weight
1 0.2Mpa 210g 39000
2 0.6Mpa 222g 41000
3 2Mpa 201g 43000
Example 7
After purging the T-type micromixer with nitrogen, a 1.1L solution of N, N-dimethylformamide containing 2.5g of azobisisobutyronitrile and 157g of maleic anhydride was subjected to heat exchange to 70℃and fed into the T-type micromixer via a first metering pump, and 1-hexene was subjected to heat exchange to 70℃and fed into the T-type micromixer via a second metering pump, the mass ratio of 1-hexene to the maleic anhydride solution containing the initiator in the T-type micromixer being 4:1, fully mixing and carrying out primary reaction in a T-shaped micromixer, wherein the operation pressure is 0.6Mpa, and the residence time is 2.5s.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to a capillary microreactor positioned in an ultrasonic reactor through a channel switching unit to continuously carry out copolymerization reaction of 1-hexene and maleic anhydride, wherein the reaction temperature is 70 ℃, and the reaction pressure is 0.6MPa.
And adding ethanol into the obtained liquid phase product to separate out solid, performing centrifugal separation, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 7 shows the final copolymer yields and molecular weights at different microreactor liquid inlet flow rates and reaction times.
TABLE 7
Example 8
After purging the T-type micromixer with nitrogen, a 1.1L solution of N, N-dimethylformamide containing a certain amount of azobisisobutyronitrile and 157g of maleic anhydride is subjected to heat exchange to 70 ℃, the solution enters the T-type micromixer through a first metering pump, 1-heptene is subjected to heat exchange to 70 ℃ and then enters the T-type micromixer through a second metering pump, and the mass ratio of the 1-heptene to the solution of maleic anhydride containing an initiator in the T-type micromixer is 3:1, fully mixing and carrying out primary reaction in a T-shaped micromixer, wherein the operation pressure is 0.6Mpa, and the residence time is 2.5s.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to a capillary microreactor positioned in an ultrasonic reactor through a channel switching unit to continuously carry out copolymerization reaction of 1-heptene and maleic anhydride, wherein the reaction temperature is 70 ℃, the reaction pressure is 0.6MPa, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 8 shows the yields and molecular weights of the copolymers finally obtained at various initiator levels.
TABLE 8
Sequence number Mass of initiator Copolymer mass Copolymer number average molecular weight
1 2.5g 201g 44000
2 12.5g 213g 35000
3 25g 225g 29000
Example 9
After purging the super T-type micromixer with nitrogen, heat-exchanging 1.1L of N, N-dimethylformamide solution containing 2.5g of azodiisobutyronitrile and a certain amount of maleic anhydride to 70 ℃, feeding the solution into the T-type micromixer through a first metering pump, heat-exchanging 1-octene to 70 ℃ and feeding the solution into the T-type micromixer through a second metering pump, wherein the mass ratio of the 1-octene to the maleic anhydride solution containing an initiator in the T-type micromixer is 2:1, fully mixing and carrying out primary reaction in a T-shaped micromixer, wherein the operation pressure is 0.6Mpa, and the residence time is 2.5s.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to a capillary microreactor positioned in an ultrasonic reactor through a channel switching unit to continuously carry out the polar copolymerization reaction of 1-octene and maleic anhydride, wherein the reaction temperature is 70 ℃, the reaction pressure is 0.6MPa, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 9 shows the yields and molecular weights of the final copolymers obtained at various mass fractions of the maleic anhydride solutions.
TABLE 9
Example 10
After purging the T-type micromixer with nitrogen, a 1.1L solution of N, N-dimethylformamide containing a certain amount of azobisisobutyronitrile and 157g of maleic anhydride is subjected to heat exchange to 70 ℃, enters the T-type micromixer via a first metering pump, 1-nonene is subjected to heat exchange to 70 ℃ and enters the T-type micromixer via a second metering pump, and the mass ratio of the 1-nonene to the solution of maleic anhydride containing an initiator in the T-type micromixer is 1:1, fully mixing and carrying out primary reaction in a T-shaped micromixer, wherein the operation pressure is 0.6Mpa, and the residence time is 2.5s.
And after passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to a capillary microreactor positioned in an ultrasonic reactor through a channel switching unit to continuously carry out copolymerization reaction of 1-nonene and maleic anhydride, wherein the reaction temperature is 70 ℃, the reaction pressure is 0.6MPa, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min.
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 10 shows the yields and molecular weights of the copolymers finally obtained at various initiator levels.
Table 10
Sequence number Mass of initiator Copolymer mass Copolymer number average molecular weight
1 2.5g 198g 45000
2 12.5g 215g 37000
3 25g 229g 31000
Example 11
After purging the super T-type micromixer with nitrogen, heat exchanging 1.1L of N, N-dimethylformamide solution containing 2.5g of azobisisobutyronitrile and a certain amount of maleic anhydride to 70 ℃, entering the T-type micromixer through a first metering pump, and entering the T-type micromixer through a second metering pump after heat exchanging 1-decene to 70 ℃, wherein the mass ratio of the 1-decene to the maleic anhydride solution containing an initiator in the T-type micromixer is 0.5:1, fully mixing and carrying out primary reaction in a T-shaped micromixer, wherein the operation pressure is 0.6Mpa, and the residence time is 2.5s.
After passing through a buffer tank and a third metering pump, the liquid phase product obtained by the T-shaped micromixer is led to a capillary microreactor positioned in an ultrasonic reactor through a channel switching unit to continuously carry out the polar copolymerization reaction of 1-decene and maleic anhydride, wherein the reaction temperature is 70 ℃, the reaction pressure is 0.6MPa, the liquid phase inlet flow rate is 30ml/min, and the reaction time is 60min;
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 11 shows the yields and molecular weights of the final copolymers obtained at various mass fractions of the maleic anhydride solutions.
TABLE 11
Comparative example 1
The device of this comparative example does not include a T-shaped micromixer. Namely, 1.1L of N, N-dimethylformamide solution containing 2.5g of azodiisobutyronitrile and 157g of maleic anhydride is subjected to heat exchange to 70 ℃, 1-hexene is subjected to heat exchange to 70 ℃, and then is directly introduced into a micro-channel reactor through a buffer tank and a metering pump to carry out copolymerization reaction of 1-hexene and maleic anhydride, wherein the mass ratio of 1-hexene to the maleic anhydride solution containing an initiator is 4:1, the reaction temperature is 70 ℃, and the reaction pressure is 0.6MPa.
And adding ethanol into the obtained liquid phase product to separate out solid, filtering and separating, and washing and drying the solid phase product by using ethanol to obtain white isobutylene maleic anhydride copolymer powder.
Table 12 shows the yields of the final copolymers obtained at different microreactor flow rates and reaction times.
Table 12
Compared with the condition of a T-shaped micro-mixer (the gas-liquid ratio is 300:1 (v/v), the operating pressure is 0.6 Mpa), if the isobutylene maleic anhydride copolymer powder with almost the same mass difference is obtained, the flow rate of a liquid phase in the micro-reactor needs to be greatly reduced, and the reaction time needs to be increased by more than 1 time.
Comparative example 2
This comparative example is substantially identical to example 5, with the only difference that: this comparative example uses a reaction vessel instead of the microreactor in example 5 and does not contain an ultrasonic reactor.
Table 13 shows the yields of isobutylene maleic anhydride copolymers under the same experimental conditions and the same reaction time in the external field enhanced microreactor and the reaction vessel.
TABLE 13
As can be seen from table 13: compared with a reaction kettle, the micro-reactor has the advantage that the yield of the isobutylene maleic anhydride copolymer powder can be remarkably improved under the same experimental conditions and the same reaction time.
In describing embodiments of the present application, it should be noted that, unless explicitly stated and limited otherwise, the terms "mounted," "connected," and "coupled" should be interpreted broadly, as for example, whether fixedly coupled, indirectly coupled through intermediaries, in communication with each other, or in an interaction relationship between two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
The terms "first," "second," "third," "fourth" and the like in the description and in the claims and in the above drawings, if any, are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the application described herein may be implemented, for example, in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (9)

1. A continuous reaction device is characterized by comprising a T-shaped micro-mixing unit, a channel switching unit and N micro-reaction units which are different from each other, wherein N is more than or equal to 2;
The liquid phase outlets of the T-shaped micro-mixing units are communicated with the inlets of the channel switching units, and N outlets of the channel switching units are respectively communicated with the inlets of the N micro-reaction units one by one;
The channel switching unit is used for guiding the liquid phase output through the liquid phase outlet into one micro-reaction unit;
The T-shaped micro-mixing unit further comprises a first raw material inlet, a second raw material inlet and a gas phase outlet;
The gas phase outlet communicates with the first feedstock inlet and/or the second feedstock inlet.
2. The continuous reaction apparatus of claim 1, further comprising an ultrasonic unit for ultrasonically treating at least one of the micro-reaction units.
3. The continuous reaction apparatus according to claim 1 or 2, further comprising a first pressure regulating unit and/or a second pressure regulating unit;
The first pressure regulating unit is positioned at the liquid phase outlet and is used for regulating the pressure in the T-shaped micro-mixing unit;
the second pressure regulating unit is positioned at the reaction liquid outlet of the micro-reaction unit and is used for regulating the pressure in the micro-reaction unit.
4. The continuous reaction apparatus according to claim 1, wherein each of the N micro-reaction units is selected from one of a micro-channel reactor, a capillary micro-reactor, a falling film micro-reactor, and a membrane dispersion micro-reactor.
5. Use of a continuous reaction apparatus according to any one of claims 1 to 4 for the preparation of polymers.
6. A process for preparing a C4-C10 alpha-monoolefin-maleic anhydride copolymer, characterized in that it is carried out using the continuous reaction apparatus as claimed in any one of claims 1 to 4.
7. The method of manufacturing according to claim 6, comprising the steps of:
1) Introducing a raw material comprising C4-C10 alpha-mono-olefin and maleic anhydride into the T-shaped micro-mixing unit for mixing treatment to obtain a mixed solution;
2) And controlling the channel switching unit to enable the mixed solution to enter one micro-reaction unit for polymerization reaction after being output from the liquid phase outlet, so as to obtain a reaction solution comprising C4-C10 alpha-mono-olefin-maleic anhydride copolymer.
8. The preparation method according to claim 7, wherein the mixing pressure of the mixing treatment is 0.5-2MPa, the time is 1-4s, and the temperature is 55-100 ℃;
and/or the number of the groups of groups,
The reaction pressure of the polymerization reaction is 0.2-2MPa, the time is 30-90min, and the temperature is 50-100 ℃.
9. The method according to claim 7 or 8, wherein in step 2), the flow rate of the mixed solution into the micro-reaction unit is 20-40ml/min.
CN202210940045.1A 2022-08-05 2022-08-05 Continuous reaction device and application Active CN115253954B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202210940045.1A CN115253954B (en) 2022-08-05 2022-08-05 Continuous reaction device and application
PCT/CN2022/139174 WO2024027074A1 (en) 2022-08-05 2022-12-15 Continuous reaction device and use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210940045.1A CN115253954B (en) 2022-08-05 2022-08-05 Continuous reaction device and application

Publications (2)

Publication Number Publication Date
CN115253954A CN115253954A (en) 2022-11-01
CN115253954B true CN115253954B (en) 2024-04-16

Family

ID=83748124

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210940045.1A Active CN115253954B (en) 2022-08-05 2022-08-05 Continuous reaction device and application

Country Status (2)

Country Link
CN (1) CN115253954B (en)
WO (1) WO2024027074A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115253954B (en) * 2022-08-05 2024-04-16 中国石油天然气股份有限公司 Continuous reaction device and application

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007098193A (en) * 2005-09-30 2007-04-19 Yokogawa Electric Corp Chemical reaction evaluation device and chemical reaction evaluation method
CN108380150A (en) * 2018-03-21 2018-08-10 上海交通大学 Prepare the multichannel microreactor system and method for low-molecular-weight polystyrene
WO2020044359A1 (en) * 2018-08-25 2020-03-05 Ganapati Dadasaheb Yadav Dual function multiphase microreactor
CN111617710A (en) * 2020-06-08 2020-09-04 山东微井化工科技股份有限公司 Industrial multifunctional micro-channel reactor production system
CN113045518A (en) * 2021-02-05 2021-06-29 上海昶法新材料有限公司 Method for continuously preparing alkenyl succinic anhydride by using microchannel reactor
CN114426639A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Alpha-olefin-maleic anhydride copolymer and preparation method and application thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008080306A (en) * 2006-09-29 2008-04-10 Hitachi Ltd Chemical synthesizer
JP4449997B2 (en) * 2007-03-12 2010-04-14 株式会社日立製作所 Microreactor system
JP2014051543A (en) * 2012-09-05 2014-03-20 Kaneka Corp Continuous production method of polymer
JP6086250B2 (en) * 2014-04-25 2017-03-01 大陽日酸株式会社 Gas-liquid reaction method and aminosilane production method
CN104844748B (en) * 2015-05-12 2017-04-05 清华大学 A kind of preparation method of butyl rubber
CN109293858B (en) * 2018-09-27 2022-04-29 南京工业大学 Method for preparing functionalized polyolefin by continuous flow polymerization-polymerization coupling
CN111777700B (en) * 2019-04-03 2021-10-12 中国科学院化学研究所 Method for preparing polyolefin by coordination polymerization in microreactor
CN112206727B (en) * 2019-07-10 2024-01-05 中国石油化工股份有限公司 Microchannel gas-liquid reaction device and method for strengthening gas-liquid reaction and method for preparing adipic acid
CN112851588B (en) * 2021-01-28 2023-04-21 复旦大学 Micro-reaction system and method for continuously preparing 2-methyl-4-amino-5-cyanopyrimidine by using same
CN113264845B (en) * 2021-04-26 2022-05-20 复旦大学 Method for continuously preparing chloramphenicol by using micro-reaction system
CN115253954B (en) * 2022-08-05 2024-04-16 中国石油天然气股份有限公司 Continuous reaction device and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007098193A (en) * 2005-09-30 2007-04-19 Yokogawa Electric Corp Chemical reaction evaluation device and chemical reaction evaluation method
CN108380150A (en) * 2018-03-21 2018-08-10 上海交通大学 Prepare the multichannel microreactor system and method for low-molecular-weight polystyrene
WO2020044359A1 (en) * 2018-08-25 2020-03-05 Ganapati Dadasaheb Yadav Dual function multiphase microreactor
CN111617710A (en) * 2020-06-08 2020-09-04 山东微井化工科技股份有限公司 Industrial multifunctional micro-channel reactor production system
CN114426639A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Alpha-olefin-maleic anhydride copolymer and preparation method and application thereof
CN113045518A (en) * 2021-02-05 2021-06-29 上海昶法新材料有限公司 Method for continuously preparing alkenyl succinic anhydride by using microchannel reactor

Also Published As

Publication number Publication date
CN115253954A (en) 2022-11-01
WO2024027074A1 (en) 2024-02-08

Similar Documents

Publication Publication Date Title
KR100526914B1 (en) Method and device for continuous production of polymers
CN101754987B (en) System and process for production of polyethylene and polypropylene
CN115253954B (en) Continuous reaction device and application
US9481742B2 (en) Continuous process for the manufacture of highly-branched polymers
CN109651539B (en) Micro-reaction system for producing polyvinyl chloride and polyvinyl chloride production method based on micro-reaction system
EP3495039A1 (en) Method for preparing polyisobutylene products
CN111690089B (en) High-solid weather-resistant and appearance acrylic resin
CN108690155A (en) The method that polyacrylamide is prepared by acrylamide using microreactor
JP4718185B2 (en) Taylor reactor for mass conversion
Méndez-Portillo et al. Free-radical polymerization of styrene using a split-and-recombination (SAR) and multilamination microreactors
CN212142558U (en) Continuous production system
DE19960389B4 (en) Process for the polymerization of olefinically unsaturated monomers by means of a Taylor reactor
US7651670B2 (en) Method for continuously polymerizing in mass quantities and taylor reactor for carrying out this method
CN101671417A (en) Acrylonitrile polymerized loop reactor for carbon fibers
CN114672012A (en) Method for preparing polyether polyol based on micro mixer and micro-channel reactor
CN213506693U (en) Preparation system of vinyl chloride polymer
CN114716358A (en) Method for continuously synthesizing peroxyacetic acid by using microreactor
CN115181201B (en) Copolymerization method of C4-C8 alpha-mono-olefin and maleic anhydride
WO2021047049A1 (en) System and process for strengthening ethylene polymerization
CN115197356B (en) Copolymerization method of C4-C6 alpha-mono-olefin and maleic anhydride
CN111298752A (en) Continuous production equipment for free radical polymerization and use method thereof
CN219377104U (en) Blade reactor with ultrasonic assistance suitable for high molecular polymerization
CN115181200B (en) Preparation method of C4-C8 alpha-mono-olefin-maleic anhydride copolymer
CN118063651B (en) Autoclave type polymerization process
CN114591459B (en) Tubular solution polymerization device with ultrasonic device and method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant