CN114288949A - Device and method for preparing uniform particle resin - Google Patents
Device and method for preparing uniform particle resin Download PDFInfo
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Abstract
The invention relates to a device and a method for preparing uniform particle resin, which comprises a fluidized reactor, a head tank and a curing kettle, wherein the fluidized reactor comprises a reactor body and a reactor base, a resin nozzle is arranged on the reactor base, the resin nozzle comprises a first nozzle and a second nozzle, an oil phase is sprayed in the first nozzle, a continuous phase is sprayed in the second nozzle, a continuous phase flow channel and an oil phase flow channel are also arranged on the reactor base, the reactor body of the fluidized reactor is internally provided with the continuous phase, the continuous phase head tank is connected with the second nozzle through the continuous phase flow channel of the reactor base, the oil phase head tank is connected with the first nozzle through the oil phase flow channel of the reactor base to spray oil phase materials through a pinhole in a differential mode, and the oil phase materials are uniformly divided into oil drops with uniform sizes by utilizing the speed difference formed by two streams of fluid. The invention realizes the high-speed preparation of the homogeneous resin, greatly improves the production efficiency, and has mild production conditions and high reaction speed.
Description
Technical Field
The invention relates to the field of preparation of homogeneous resins, in particular to a device and a method for preparing homogeneous resins at a high speed by using circular shear flow.
Background
Ion exchange resin and macroporous adsorption resin are widely used in the fields of industrial production and scientific research such as water treatment, non-ferrous metal separation, synthetic chemistry, natural product separation and purification and the like, and the material skeleton of the ion exchange resin and the macroporous adsorption resin is mostly spheres polymerized from styrene-divinylbenzene, acrylic acid-divinylbenzene and the like, and the ion exchange resin and the macroporous adsorption resin are called resin white spheres in the industry. The traditional resin white ball polymerization process adopts suspension polymerization or emulsion polymerization, and in terms of size, the size of the white ball synthesized by the suspension polymerization process is larger than that of the emulsion polymerization process, so that the preparation of 100-2000 micron-sized resin can be realized, and the emulsion polymerization process can only reach the order of magnitude of 10-200 microns; regarding the size uniformity, the particle size distribution of the products prepared by the suspension polymerization process and the emulsion polymerization process is gaussian, and the Polydispersity Index (PDI) of the resin particles can only reach 1.3-1.8. Although the novel precipitation polymerization process can prepare products with dispersion coefficients reaching 1.03-1.2, the product granularity can only reach the specification of 5-50 microns. Therefore, the traditional polymerization process cannot realize specific large-size particle size and size uniformity at the same time, and the resin white balls generated by suspension polymerization need to be screened in different degrees to separate the resin with different particle size ranges, so that the resin white balls meet the requirement of uniformity, a large amount of waste materials are generated, and the cost of the uniform particle resin is greatly increased.
The suspension polymerization process is a commonly used process at present, and in view of the polymerization process, a certain proportion of monomer phase and an initiator are uniformly mixed, the monomer phase is dispersed in a continuous phase containing a proper stable dispersant or emulsifier to form oil droplets with a certain size under stirring or other conditions, and the monomer phase undergoes polymerization reaction under the action of the initiator to generate polymer particles along with the rise of temperature. The suspension polymerization mechanism shows that the polymerization reaction occurs in each oil drop, and the size of the oil drop stably existing in the continuous phase determines the size of the finally formed polymer particles, so that the whole process has two key points, namely, how to disperse the monomer phase into uniform-sized droplets and how to keep the oil drop obtained by dispersion stably existing in the dispersed phase without fragmentation and coalescence.
To solve the problem of the dispersion of the monomer phase into uniform droplets, patent US4444961A proposes an apparatus for achieving particle size control of resin particles by applying vibration interference, and by applying a mechanical vibration source to the raw material injection chamber, uniform droplet dispersion with adjustable size can be achieved. However, in the structure, external vibration is applied to the propelling rod of the raw material cavity, the vibration is indirectly applied to liquid, the vibration effect is poor, and meanwhile, the high-frequency vibration causes poor stability of the device and leakage of a sealing piece at a connecting part, so that the equipment maintenance frequency is high.
Patent CN106345367A proposes a piezoelectric vibration device which is arranged in the material cavity and can perform piezoelectric vibration on the material, and directly applies fluid through a piezoelectric ceramic vibration film to generate vibration interference, so as to obtain liquid drops with uniform size and height. The method has the advantages that a device is not needed to be stopped and disassembled, convenience and rapidness are realized, and the problem that vibration is indirectly applied to liquid and the vibration effect is poor in the prior art is solved. However, the method directly applies vibration to the oil phase material, and static electricity accumulation is easily generated in the high-frequency vibration process of the material, and if the static electricity accumulation cannot be timely removed, the production safety is seriously affected.
Patent No. cn113248772.a proposes a method for preparing a Polyhydroxyalkanoate (PHA) porous microsphere in a T-type microfluidic device. The continuous phase adopts polyvinyl alcohol which can be completely dissolved in water as a surface active polymer, and the polyvinyl alcohol and the water can form a uniform and stable solution system, and the system has great limitation because the physical and chemical properties of the polyvinyl alcohol determine that the polyvinyl alcohol can only be applied under the temperature condition of below 90 ℃. And because of the characteristics of the preparation process of the microfluidic chip, the diameter of a channel etched by the chip is mostly within 100 microns, an excessively narrow channel cannot be suitable for long-period operation of a high-temperature-resistant inorganic dispersion system, and blockage is easily caused, and due to the hydrophilic characteristic of a dispersion phase material, volume expansion under a microscale can be generated in the process that liquid drops are subjected to phase change from a liquid phase to a solid phase, so that the probability of congestion in the channel is increased, and the application of the high-temperature-resistant inorganic dispersion system is not facilitated.
Patent CN102086240A provides a method for preparing uniform particle ion exchange resin polymer beads by vibration injection, the core of which is that oil phase liquid is broken at a spray head by a vibration generating device to generate oil drops with uniform size, the oil drops are solidified by a fluidized polymerization reactor, and after curing in a curing tank, a product with the mass fraction of the target particle size of +/-0.5 mm which is not screened is greater than 95% is obtained, and the continuous phase can be recycled, thereby reducing the discharge of waste water. However, the long-time vibration generated by the method can cause a series of potential safety hazards such as mechanical fatigue of equipment connecting pieces, leakage of sealing pieces and the like, and is not beneficial to the industrial application of the method.
Disclosure of Invention
The invention aims to overcome the defect that the existing vibration jet technology causes vibration damage to chemical devices after long-term operation, and provides a device and a method for homogenizing resin for polymerizing large-particle homogenizing resin white balls.A crane pipe type design of a shell layer pipeline is adopted, and the speed of a two-phase fluid is regulated to form a speed difference at an outlet of a concentric pipe, so that a continuous phase wraps the surface of oil phase liquid drops, and the front and rear oil drops are physically separated, thereby obtaining the resin white balls with uniform height; the method does not generate equipment vibration and can not cause the loosening of the main device and the auxiliary parts thereof, thereby ensuring the long-term stable operation of the equipment.
To achieve the object of the present invention, the present invention provides an apparatus for preparing a pelletized resin comprising: fluidized reactor, elevated tank and curing kettle, fluidized reactor includes reactor body and reactor base, be equipped with the resin nozzle on the reactor base, the resin nozzle includes first nozzle and second nozzle, sprays the oil phase in the first nozzle, sprays the continuous phase in the second nozzle, still is equipped with continuous phase runner and oil phase runner on the reactor base, be the continuous phase in fluidized reactor's the reactor body, reactor body upper end is connected with curing kettle, the elevated tank divide into continuous phase elevated tank and oil phase elevated tank, wherein continuous phase runner and the second nozzle that the continuous phase elevated tank passes through the reactor base are connected, and the oil phase runner that the oil phase elevated tank passes through the reactor base is connected with first nozzle.
And dispersing the oil phase into liquid drops with uniform size by utilizing the speed difference of two phases, wherein the flow speed of the continuous phase ranges from 0.2ml/min to 50ml/min, the flow speed of the oil phase ranges from 0.05ml/min to 30ml/min, the speed difference of the two phases is adjusted to range from 0.15ml/min to 15ml/min, and preferably, the flow speed of the continuous phase is greater than the flow speed of the oil phase.
Preferably, the bottom of the curing kettle is connected with the fluidized reactor through a circulating pump to form internal circulation.
Preferably, the cross sections of the first nozzle and the second nozzle are concentric circles, and the concentricity can have a tolerance less than or equal to 3 per thousand.
Preferably, the outlet of the first nozzle is lower than the outlet of the second nozzle, and more preferably, the distance between the outlet of the first nozzle and the outlet of the second nozzle is 0.305-1.88 mm
Preferably, the diameter of the first nozzle is 0.108-0.423 mm, the diameter of the second nozzle is 0.337-2.5 mm, and the diameter of the first nozzle is smaller than that of the second nozzle.
The resin nozzle is equipped with a plurality ofly, and evenly distributed is on the reactor base, for example can establish 10 ~ 100, and the interval between is 2 ~ 10 mm. A buffer cavity is arranged between the oil phase flow channel and the first nozzle, the buffer area is used for reducing fluid fluctuation caused by pump pressure so as to stabilize the feeding frequency of the spray head and enable parameters at the spray head to be fixed and controllable, and a baffle plate is arranged in the buffer cavity so that the oil phase enters the cavity through the bent flow channel and is used for reducing pressure impact caused by flow velocity; so as to be beneficial to the volume, the speed and the pressure of the oil phase conveyed to each spray head to be uniform and consistent.
Preferably, the reactor body is a vertical stainless steel jacket pressure reaction tower, the volume can be 2-200L, the working temperature is 80-150 ℃, and the design pressure is 0-1.5 mPa;
preferably, the curing kettle is a stainless steel jacket pressure reaction kettle, the volume is 30-1000L, the working temperature is 80-150 ℃, and the design pressure is 0-1.5 mPa;
preferably, the head tank is connected to the fluidized reactor by means of a pressure pump.
The invention also provides a preparation method of the homogeneous particle resin, which comprises the following steps:
(A) preparing an oil phase: adding the components of the oil phase into an oil phase elevated tank, and stirring to fully mix the components, wherein the temperature in the oil phase elevated tank is 25-40 ℃;
(B) preparing a continuous phase: adding each component of the continuous phase into the elevated tank, the vulcanization reactor and the curing kettle, heating the elevated tank, the fluidized reactor and the curing kettle to 80-150 ℃, and starting the circulating pump to keep the total amount in the elevated tank of the continuous phase not more than 60% of the total volume.
(C) Setting the working pressure of a connecting pipeline between a fluidized reactor and a continuous phase elevated tank to be 0-1.5 mpa, setting the working pressure of the connecting pipeline between the fluidized reactor and an oil phase elevated tank to be 0-1.5 map, starting a pressure pump, spraying out the oil phase through a first nozzle, spraying out the continuous phase through a second nozzle, dispersing the oil phase into liquid drops with uniform size by utilizing the speed difference of the two phases, and floating up in a fluidized reactor body.
(D) The floating oil drops are subjected to phase change after passing through the fluidized reactor to form solid spherical particles with a net-shaped cross-linked structure, and flow into the curing kettle along with the circulating continuous phase.
(E) And after further reaction and curing of the liquid drops in the curing kettle, separating the solid balls to obtain a solid spherical product, and washing the product with water, washing with a solvent and drying to obtain the final product.
Preferably, the oil phase comprises the following components:
unsaturated monomer component: 47.5 to 99 wt.%, preferably 50 to 90 wt.%;
0 to 50 weight percent of cross-linking agent, preferably 2 to 15 weight percent;
0.1 to 2.5 wt%, preferably 0.4 to 1.0 wt% of an initiator
Preferably, the unsaturated monomer component comprises monomers such as styrene, acrylic, allyl, acrylate monomers, or mixtures thereof;
the cross-linking agent comprises monomers such as polyvinyl benzene, polyacrylic acid, polyallyl, polyacrylate and the like or a mixture thereof;
the initiator is selected from one or more of peroxide initiators and azo initiators;
based on the total mass of all the components as 100 percent.
Preferably, a solvent is further added into the oil phase, and the solvent comprises (cyclo) alkanes with high boiling points, aromatic hydrocarbons, halogenated alkanes, esters, alcohols and the like.
Preferably, the continuous phase comprises: water, surfactant, inorganic dispersant and assistant dispersant.
Wherein the mass content of each component is as follows based on the total mass of the continuous phase:
76 to 97.5 wt.% of water, preferably 82 to 92 wt.%;
0 to 0.03 wt%, preferably 0.005 to 0.02 wt% of a surfactant;
0.5-3 wt% of inorganic dispersant, preferably 1-2 wt%;
0-24 wt% of auxiliary dispersant, preferably 5-10%.
Preferably, the surfactant includes anionic surfactant, cationic surfactant, nonionic surfactant, etc., such as sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, PVA.
Preferably, the inorganic dispersant includes an inorganic polymer, an inorganic-organic polymer, etc., such as tricalcium phosphate or hydroxyapatite.
Preferred said co-dispersions include small molecular weight inorganic electrolytes such as sodium chloride, calcium chloride, magnesium chloride, potassium chloride, magnesium hydroxide and the like.
Preferably, in the step (C), the components of the continuous phase are firstly put into the continuous phase head tank, and after the components are stirred and mixed uniformly, the pipeline valve, the pressure pump and the circulating pump are opened to uniformly distribute the continuous phase in the continuous phase head tank, the fluidized reactor and the curing kettle.
Preheating the fluidized reactor before introducing the continuous phase, wherein the preheating temperature is 25-60 ℃, and the pressure is 0-1.5 mPa;
the elevated tank can be a 2-200L vertical stainless steel jacket pressure reaction kettle with the design pressure of 0-1.5 MPa.
A stainless steel jacket pressure reaction kettle with the volume of 30-1000L can be used as a prefabricated kettle to prepare a continuous phase solution in advance, for example, the stainless steel jacket pressure reaction kettle with the diameter of 40cm, the height of 56cm and the effective volume of 50L has the design pressure of 0-1.5 MPa.
The curing kettle can be a stainless steel jacket pressure reaction kettle with an effective volume of 30-1000L, for example, a stainless steel jacket pressure reaction kettle with a diameter of 40cm, a height of 56cm and an effective volume of 50L, and the design pressure is 0-1.5 MPa. The stainless steel filter screen with 80-150 meshes, preferably about 100 meshes, is arranged at the outlet of the connecting pipe of the circulating pump, so that the separation of the continuous phase and the solid particles is realized.
The method and the device can be used for preparing the uniform particle resin with the particle size of 500-1500 microns, the uniformity coefficient can reach 1.05-1.2, and the BET specific surface area is 50-700 m2(iv)/g, BET average pore diameter is 3.0 to 80 nm, and BET pore volume is 0.3 to 2.0 mL/g.
The device and the method for preparing the uniform particle resin can be used for preparing the macroporous adsorption resin of styrene-multivinyl benzene type, acrylic acid-multiacrylic acid type, styrene-multiacrylic acid type, allyl-multiacrylic acid type and acrylate-polyallyl type
The invention has the advantages that:
according to the invention, the first nozzle and the second nozzle are provided with special structures through the double-layer design of the nozzles, the speed of the two-phase fluid is adjusted to form a speed difference at the outlet of the concentric tube, so that the continuous phase wraps the surface of oil phase liquid drops, and the front and rear oil drop phases are physically separated, thereby obtaining the resin white balls with uniform height; the method does not generate equipment vibration and can not cause the loosening of the main device and the auxiliary parts thereof, thereby ensuring the long-term stable operation of the equipment.
Drawings
FIG. 1 is a schematic view of the overall structure of the apparatus of the present invention.
FIG. 2 is a schematic view of the structure of a fluidized reactor base resin nozzle of the present invention.
FIG. 3 is a photograph of white balls of a styrene-divinylbenzene skeleton monodisperse resin prepared in example 1.
FIG. 4 is a schematic view of a suspension polymerization apparatus of comparative example 1
Fig. 5 is a photograph of gel-type resin white balls prepared in comparative example 1.
FIG. 6 is a photograph of a resin prepared in comparative example 2.
Fig. 7 is a photograph of white balls of a divinylbenzene-methyl acrylate skeleton monodisperse resin prepared in example 2.
FIG. 8 is a photograph of white balls of a methyl acrylate-ethylene glycol dimethacrylate skeleton monodisperse resin prepared in example 3.
Reference numerals:
1-a fluidized reactor; 2-a pressure pump; 3-continuous phase head tank; 4-a curing kettle; 5-a circulating pump; 6-oil phase head tank; 101-a first nozzle; 102-a second nozzle; 103-continuous phase flow channel; 104-oil phase flow channel; 105-buffer chamber.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in fig. 1, the homogeneous resin apparatus of the present invention comprises: the fluidized reactor 1 comprises a reactor body and a reactor base, wherein 50 resin nozzles are arranged on the reactor base and comprise a first nozzle 101 and a second nozzle 102, an oil phase is sprayed in the first nozzle 101, a continuous phase is sprayed in the second nozzle 102, a continuous phase flow channel 103 and an oil phase flow channel 104 are further arranged on the reactor base, the continuous phase is arranged in the reactor body of the fluidized reactor, the upper end of the reactor body is connected with the curing kettle 4, the elevated tank is divided into a continuous phase elevated tank 3 and an oil phase elevated tank 6, the continuous phase elevated tank 3 is connected with the second nozzle 102 through the continuous phase flow channel 103 of the reactor base, and the oil phase elevated tank 6 is connected with the first nozzle through the oil phase flow channel of the reactor base. The first nozzle and the second nozzle are of two crane-pipe type concentric tubular structures, a buffer cavity 105 is further arranged between the oil phase flow channel 104 and the first nozzle, a baffle plate is further arranged in the buffer cavity, and the oil phase flow channel 104 is connected with the oil phase elevated tank 6, so that the volume, the speed and the pressure of oil phase conveyed to each spray head are uniform and consistent.
The continuous phase elevated tank 3 is provided with a feeding pipe which is connected with the fluidized reactor 1 and is conveyed into the fluidized reactor 1 through a high-precision pressure pump 2, the continuous phase elevated tank is directly connected with the curing kettle 4 through a circulating pipeline, and the continuous phase accumulated in the curing kettle can be supplemented back to the continuous phase elevated tank 3 through a circulating pump so as to keep the using volume of the continuous phase elevated tank not to exceed 60 percent of the effective volume. The temperature of the continuous phase is controlled between 80-150 ℃, and the pressure is controlled between 0-1.5 mpa.
The oil phase elevated tank 6 is provided with a feed pipe which is connected with the fluidized reactor 1 and is conveyed into the fluidized reactor 1 through the high-precision pressure pump 2. The temperature of the oil phase in the oil tank is controlled to be 25-40 ℃, and the pressure is controlled to be 0-1.5 mpa
The power of the nozzle jet comes from the pressure generated by the high-precision pressure pump 2. Meanwhile, the flow velocity of the oil phase and the flow velocity of the continuous phase are set to be different velocities, so that a velocity difference is formed, and uniform liquid drops are generated by means of the velocity difference of the two phases
The curing kettle 4 is provided with a circulating pipeline connected with the fluidized reactor 1, the built-in filter plate enables resin particles to be separated from the continuous phase, and then the resin particles flow back to the fluidized reactor 1 through the circulating pump 5 to form internal circulation, so that the resin particles continuously flow into the curing kettle.
Example 1
In this embodiment, the first nozzle has a diameter of 0.202mm and the second nozzle has a diameter of 0.370 mm. The outlet of the first nozzle is lower than the outlet of the second nozzle, and the distance between the outlet of the first nozzle and the outlet of the second nozzle is 0.505 mm.
The method for preparing the styrene-divinylbenzene framework homogeneous resin white ball comprises the following steps:
(A) 444.44g of styrene (polymerization monomer) with polymerization inhibitor removed and 55.56g of divinylbenzene (crosslinking agent) with the mass percent of 63 percent are added into an oil phase head tank 6, stirring is started, 5g of BPO (dibenzoyl peroxide) is added as an initiator, and the mixture is uniformly mixed for later use, wherein the temperature in the oil phase head tank is 25 ℃.
(B) Hydroxyapatite accounting for 2.0 percent of the mass of the continuous phase, tricalcium phosphate accounting for 1.5 percent of the mass of the continuous phase, sodium dodecyl benzene sulfonate accounting for 0.005 percent of the mass of the continuous phase and water accounting for 96.495 percent of the mass of the continuous phase are sequentially added into the high-level tank 3 and are uniformly mixed to form the continuous phase, and the total water content of the continuous phase does not exceed 60 percent of the total volume of the high-level tank 3 of the continuous phase. The stirring was started to keep the temperature of the continuous phase constant at 150 ℃ in the continuous phase head tank 3.
(C) Hydroxyapatite accounting for 2 percent of the mass of the continuous phase, tricalcium phosphate accounting for 1.5 percent of the mass of the continuous phase and sodium dodecyl benzene sulfonate accounting for 0.005 percent of the mass of the continuous phase are sequentially added into the curing kettle 4, 96.495 percent of water is added and uniformly mixed to form the continuous phase, and the total water content of the continuous phase is not more than 60 percent of the total volume of the curing kettle 4.
(D) The stirring was started to keep the temperature of the continuous phase constant at 150 ℃ in the continuous phase head tank 3. After the temperature is stable, starting a circulating pump 5, and sending the prepared continuous phase into a fluidized reactor 1 to keep the temperature stable and constant at 150 ℃; the continuous phase flow rate was 20.09 ml/min.
(E) And opening a connecting pipeline of the oil phase elevated tank 6 and the fluidized reactor 1, starting the pressure pump 2 on the pipeline, and setting the flow rate to be 10 ml/min.
Observing the shearing condition of the liquid drops at the outlet of the spray head to ensure that stable and continuous liquid drops are formed
Further reacting and curing the liquid drops in the curing kettle 4 at 150 ℃ for 5 hours, and then separating the liquid drops from the dispersed phase to obtain a solid spherical product.
After the product is washed by water, washed by a solvent and dried, the indexes of the tested product are shown in table 1:
TABLE 1 characterization of the resin white spheres
| Median particle diameter/mm | Coefficient of uniformity | Specific surface area/m2/g | Average pore diameter/nm | Pore volume/ml/g |
| 1.063 | 1.08 | 17 | —— | —— |
A photograph of the styrene-divinylbenzene skeleton monodisperse resin white beads thus prepared is shown in FIG. 3.
Comparative example 1
According to the conventional suspension polymerization method described in "ion exchange and adsorption resin" (Shanghai science and technology Press, Yougenham, Huangwen Qiang Shui Co., Ltd., P20-P37), as shown in FIG. 4, a premixed continuous phase was added to a 3L four-necked flask at room temperature in the same formulation as described in example 1, and the premixed continuous phase was composed of 20.4g of hydroxyapatite 2.0 mass%, 15.18g of tricalcium phosphate 1.5 mass%, 0.005 mass% of sodium dodecylbenzenesulfonate 0.506g, and 96.495 mass% of water was added thereto and mixed uniformly to obtain 976.53g of a continuous phase. The stirring was started and the temperature was raised to 40 ℃. Turning off stirring, adding oil phase premixed at normal temperature, adding 444.44g of styrene with polymerization inhibitor removed and 55.56g of divinylbenzene (cross-linking agent) with the mass percent of 63% into a beaker, uniformly mixing, adding 5g of BPO (dibenzoyl peroxide) serving as an initiator into the beaker, and adding into a four-mouth bottle after complete dissolution. Starting stirring, and adjusting the rotating speed according to the required particle size. Heating to 80 ℃, and keeping the temperature for 9 hours to obtain the copolymer beads.
And (3) after the copolymer beads are washed, drying in an oven to obtain the resin white balls. The results of the sample measurements are shown in the following table:
TABLE 2 characterization results of white spheres in suspension polymerization
| Median particle diameter/mm | Coefficient of uniformity | Specific surface area/m2/g | Average pore diameter/nm | Pore volume/ml/g |
| 0.58 | 1.42 | 13 | —— | —— |
The photograph of the prepared gel-type resin white ball is shown in FIG. 5. Comparing the data in tables 1 and 2 with the pictures of example 1 and comparative example 1, it can be seen that the uniformity coefficient of the product prepared by the method is obviously superior to the index of the traditional process, and the service performance of the product is greatly improved.
Comparative example 2
A gel-type resin white ball was prepared in the same manner and formulation as in example 1, except that the distance between the first nozzle outlet and the second nozzle outlet was 0, i.e., the first nozzle outlet was flush with the second nozzle outlet.
The particle size of the white resin spheres prepared by the device is shown in Table 3
TABLE 3 characterization of the resin white spheres
| Median particle diameter/mm | Coefficient of uniformity | Specific surface area/m2/g | Average pore diameter/nm | Pore volume/ml/g |
| 0.92 | 1.32 | 15 | —— | —— |
A photograph of the styrene-divinylbenzene skeleton monodisperse resin white beads thus prepared is shown in FIG. 6. Since the continuous phase cannot ensure continuous cutting of the oil phase, the uniformity coefficient of the droplet size becomes wide, and the uniformity is lost.
Example 2
In this embodiment, the first nozzle has an aperture of 0.135mm and the second nozzle has a diameter of 0.348 mm. The outlet of the first nozzle is lower than the outlet of the second nozzle, and the distance between the outlet of the first nozzle and the outlet of the second nozzle is 0.410 mm.
The method for preparing the divinylbenzene-methyl acrylate skeleton monodisperse resin white ball comprises the following steps:
(A) 300g of divinylbenzene with the polymerization inhibitor removed and 45g of methyl acrylate are added into an oil phase head tank 6, 3.45g of BPO (dibenzoyl peroxide) is added as an initiator, 172.5g of toluene and 172.5g of cyclohexanol are respectively added and uniformly mixed for later use, and the temperature in the oil phase head tank is 25 ℃.
(B) Hydroxyapatite accounting for 2 percent of the mass of the continuous phase, tricalcium phosphate accounting for 1.5 percent of the mass of the continuous phase, sodium dodecyl benzene sulfonate accounting for 0.005 percent of the mass of the sodium chloride accounting for 10 percent of the mass of the sodium chloride are sequentially added into the continuous phase elevated tank 3, 86.495 percent of water is added and uniformly mixed to serve as the continuous phase, and the total water amount of the continuous phase does not exceed 60 percent of the total volume of the continuous phase elevated tank 3. The stirring was started to keep the temperature of the continuous phase constant at 120 ℃ in the continuous phase head tank 3.
(C) 2 mass percent of hydroxyapatite, 1.5 mass percent of tricalcium phosphate, 0.005 mass percent of sodium dodecyl benzene sulfonate and 10 mass percent of sodium chloride are sequentially added into a curing kettle 4, 86.495 mass percent of water is added and uniformly mixed to be used as a continuous phase, and the total water content of the continuous phase is not more than 60 percent of the total volume. The stirring was started to keep the temperature of the continuous phase constant at 120 ℃ in the continuous phase head tank 3. After the temperature is stable, starting a circulating pump 5, and sending the prepared continuous phase into the fluidized reactor 1 to keep the temperature stable and constant at 120 ℃; the continuous phase flow rate was 13.21 ml/min.
(D) And opening a connecting pipeline between the oil phase head tank 6 and the fluidized reactor 1, starting the pressure pump 2 on the pipeline, and setting the flow rate to be 5.3 ml/min.
And observing the shearing condition of the liquid drops at the outlet of the spray head to ensure that stable and continuous liquid drops are formed.
Further reacting and curing the liquid drops in the curing kettle 4 at 120 ℃ for 5 hours, and then separating the liquid drops from the dispersed phase to obtain a solid spherical product.
After the product is washed by water, washed by solvent and dried, the indexes of the tested product are shown in table 4.
TABLE 4 characterization of the resin white spheres
| Median particle diameter/mm | Coefficient of uniformity | Specific surface area/m2/g | Average pore diameter/nm | Pore volume/ml/g |
| 0.78 | 1.12 | 427 | 5.3 | 0.9 |
A photograph of the prepared divinylbenzene-methyl acrylate skeleton monodisperse resin white spheres is shown in FIG. 7.
Example 3
In this embodiment, the first nozzle has a diameter of 0.400mm and the second nozzle has a diameter of 1.21 mm. The outlet of the first nozzle is lower than the outlet of the second nozzle, and the distance between the outlet of the first nozzle and the outlet of the second nozzle is 1.21 mm.
The method for preparing the methyl acrylate-ethylene glycol dimethacrylate skeleton monodisperse resin white ball comprises the following steps:
(A) adding 400g of methyl acrylate and 100g of ethylene glycol dimethacrylate into an oil phase head tank 6, starting stirring, adding 2.5g of dibenzoyl peroxide, 2.5g of azobisisobutyronitrile as an initiator, and 125g of toluene and ethyl acetate respectively, uniformly mixing for later use, wherein the temperature in the oil phase head tank is 25 ℃.
(B) 2 percent by mass of hydroxyapatite, 1.5 percent by mass of tricalcium phosphate, 0.005 percent by mass of sodium dodecyl benzene sulfonate and 10 percent by mass of sodium chloride are sequentially added into the continuous phase elevated tank 3, 86.495 percent by mass of water is added and uniformly mixed to form a continuous phase, and the total water content of the continuous phase is not more than 60 percent of the total volume of the continuous phase elevated tank 3. The stirring was started to keep the temperature of the continuous phase constant at 120 ℃ in the continuous phase head tank 3.
(C) 2 percent by mass of hydroxyapatite, 1.5 percent by mass of tricalcium phosphate, 0.005 percent by mass of sodium dodecyl benzene sulfonate and 10 percent by mass of sodium chloride are sequentially added into a curing kettle 4, 86.495 percent by mass of water is added and uniformly mixed to form a continuous phase, and the total water content of the continuous phase is not more than 60 percent of the total volume.
(D) The stirring was started to keep the temperature of the continuous phase constant at 120 ℃ in the continuous phase head tank 3. After the temperature is stable, starting a circulating pump 5, and feeding the prepared continuous phase into the fluidized reactor 1 to keep the temperature stable and constant at 120 ℃; the continuous phase flow rate was 2.14 ml/min.
(E) The connecting pipeline between the elevated tank 6 and the fluidized reactor 1 is opened, the pressure pump 2 on the pipeline is started, and the flow rate is set to be 0.822ml/min
Observing the shearing condition of the liquid drops at the outlet of the spray head to ensure that stable and continuous liquid drops are formed
Further reacting and curing the liquid drops in the curing kettle 4 at 120 ℃ for 5 hours, and then separating the liquid drops from the dispersed phase to obtain a solid spherical product.
After the product is washed by water, washed by solvent and dried, the indexes of the tested product are shown in table 5.
TABLE 5 characterization of the resin white spheres
| Median particle diameter/mm | Coefficient of uniformity | Specific surface area/m2/g | Average pore diameter/nm | Pore volume/ml/g |
| 1.603 | 1.10 | 334 | 3.8 | 1.7 |
A photograph of the prepared methyl acrylate-ethylene glycol dimethacrylate skeleton monodisperse resin white sphere is shown in FIG. 8.
Claims (9)
1. An apparatus for preparing a pelletized resin comprising: the fluidized reactor comprises a reactor body and a reactor base, wherein a resin nozzle is arranged on the reactor base and comprises a first nozzle and a second nozzle, an oil phase is sprayed in the first nozzle, a continuous phase is sprayed in the second nozzle, a continuous phase runner and an oil phase runner are also arranged on the reactor base, the continuous phase is arranged in the reactor body of the fluidized reactor, the upper end of the reactor body is connected with the curing kettle, the elevated tank is divided into a continuous phase elevated tank and an oil phase elevated tank, the continuous phase elevated tank is connected with the second nozzle through the continuous phase runner of the reactor base, and the oil phase elevated tank is connected with the first nozzle through the oil phase runner of the reactor base;
preferably, the bottom of the curing kettle is connected with the fluidized reactor through a circulating pump to form internal circulation.
2. The apparatus of claim 1, wherein the continuous phase flow rate ranges from 0.2ml/min to 50ml/min, the oil phase flow rate ranges from 0.05ml/min to 30ml/min, and wherein the two phases have a velocity difference ranging from 0.15ml/min to 15 ml/min;
preferably, the continuous phase flow rate is greater than the oil phase flow rate;
preferably, the cross sections of the first nozzle and the second nozzle are concentric circles;
preferably, the outlet of the first nozzle is lower than the outlet of the second nozzle, and more preferably, the distance between the outlet of the first nozzle and the outlet of the second nozzle is 0.305-1.88 mm.
3. The apparatus according to claim 1 or 2, wherein the first nozzle has a diameter of 0.108 to 0.423mm, the second nozzle has a diameter of 0.337 to 2.5mm, and the first nozzle diameter is smaller than the second nozzle diameter.
4. The apparatus according to any one of claims 1 to 3, wherein the resin injection nozzle is provided in plurality and uniformly distributed on the reactor base;
preferably, a buffer cavity is further arranged between the oil phase flow channel and the first nozzle.
5. The device according to any one of claims 1 to 4, wherein the reactor body is a vertical stainless steel jacket pressure reaction tower, the volume of the reactor can be 2-200L, the working temperature is 80-150 ℃, and the design pressure is 0-1.5 mPa;
preferably, the curing kettle is a stainless steel jacket pressure reaction kettle, the volume is 30-1000L, the working temperature is 80-150 ℃, and the design pressure is 0-1.5 mPa;
preferably, the head tank is connected to the fluidized reactor by means of a pressure pump.
6. A method for preparing a pelletized resin using the apparatus according to any one of claims 1 to 5, comprising the steps of:
(A) preparing an oil phase: adding the components of the oil phase into an oil phase elevated tank, and stirring to fully mix the components, wherein the temperature in the oil phase elevated tank is 25-40 ℃;
(B) preparing a continuous phase: adding each component of the continuous phase into the elevated tank, the vulcanization reactor and the curing kettle, heating the elevated tank, the fluidized reactor and the curing kettle to 80-150 ℃, starting a circulating pump, and keeping the total amount in the elevated tank of the continuous phase not more than 60% of the total volume;
(C) setting the working pressure of a connecting pipeline between a fluidized reactor and a continuous phase elevated tank to be 0-1.5 mpa, setting the working pressure of the connecting pipeline between the fluidized reactor and an oil phase elevated tank to be 0-1.5 map, starting a pressure pump, spraying out the oil phase through a first nozzle, spraying out the continuous phase through a second nozzle, dispersing the oil phase into liquid drops with uniform size by utilizing the speed difference of the two phases, and floating up in a fluidized reactor body;
(D) the floating oil drops are subjected to phase change after passing through a fluidized reactor to form solid spherical particles with a net-shaped cross-linked structure, and flow into a curing kettle along with a circulating continuous phase;
(E) and after the liquid drops are further reacted and cured in the curing kettle, separating the solid balls to obtain solid spherical products, and washing and drying the products to obtain the final products.
7. The method of claim 6, wherein the oil phase comprises the following components:
unsaturated monomer component: 47.5 to 99 wt.%, preferably 50 to 90 wt.%;
0 to 50 weight percent of cross-linking agent, preferably 2 to 15 weight percent;
0.1-2.5 wt% of initiator, preferably 0.4-1.0 wt%;
calculated by taking the total mass of all the components as 100 percent;
preferably, the unsaturated monomer component comprises a styrenic, acrylic, allylic, acrylate monomer or a mixture thereof;
the cross-linking agent comprises polyvinyl benzene, polyacrylic acid, polyallyl monomer, polyacrylate monomer or their mixture;
the initiator is selected from one or more of peroxide initiators and azo initiators;
preferably, a solvent can be added into the oil phase, and the solvent comprises (cyclo) alkanes with high boiling points, aromatic hydrocarbons, halogenated alkanes, esters and alcohols.
8. The method of claim 6 or 7, wherein the continuous phase comprises: water, surfactant, inorganic dispersant and auxiliary dispersant;
preferably, the mass content of each component is as follows based on the total mass of the continuous phase:
76 to 97.5 wt.% of water, preferably 82 to 92 wt.%;
0 to 0.03 wt%, preferably 0.005 to 0.02 wt% of a surfactant;
0.5-3 wt% of inorganic dispersant, preferably 1-2 wt%;
0-24 wt% of auxiliary dispersant, preferably 5-10%.
9. The method according to any one of claims 6 to 8, wherein in the step (C), the components of the continuous phase are firstly put into the continuous phase elevated tank, and after the components are stirred and mixed uniformly, the pipeline valve, the pressure pump and the circulating pump are opened to ensure that the continuous phase is uniformly distributed in the continuous phase elevated tank, the fluidized reactor and the curing kettle;
preferably, the fluidized reactor is preheated before being introduced into the continuous phase, wherein the preheating temperature is 25-60 ℃, and the pressure is 0-1.5 mPa.
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| CN102086240A (en) * | 2010-12-22 | 2011-06-08 | 天津大学 | Equipment and method for producing uniform particle ion exchange resin beads |
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| CN112920309A (en) * | 2021-04-17 | 2021-06-08 | 江苏国创新材料研究中心有限公司 | Synthesis device and method of polymer with uniform particle size |
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| CN102086240A (en) * | 2010-12-22 | 2011-06-08 | 天津大学 | Equipment and method for producing uniform particle ion exchange resin beads |
| CN102697731A (en) * | 2012-05-10 | 2012-10-03 | 华东医院 | 5-aminolevulinic acid nano particle as well as preparation method and device thereof |
| CN109351443A (en) * | 2018-12-02 | 2019-02-19 | 北京协同创新食品科技有限公司 | A kind of high-pressure jet spray head and the high-pressure jet grinding device using the spray head |
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