CN204952873U - Millimeter passageway formula serialization preparation system - Google Patents

Abstract

The utility model provides a millimeter channel type continuous preparation system, comprising a raw material tank (1), a peristaltic pump (2), a channel type reaction tube (3), a condensation tube (5), a buffer tank (7), a peristaltic pump (8) and ultrafiltration device (9); the output end of raw material tank (1) is connected with the input end of peristaltic pump (2) through pipeline, and the output end of peristaltic pump (2) is through pipeline and channel type reaction tube ( 3) is connected to the input end; the output end of the channel reaction tube (3) is connected to the input end of the condensing pipe (5) through the pipeline; the output end of the condensing pipe (5) is connected to the input of the buffer tank (7) through the pipeline The output end of the buffer tank (7) is connected with the input end of the peristaltic pump (8) through the pipeline, and the output end of the peristaltic pump (8) is connected with the input end of the ultrafiltration device (9) through the pipeline. The utility model promotes turbulent flow in the channel, effectively promotes heat and mass transfer in the channel; realizes continuous preparation of products; and realizes channel-type heating reaction under an inert atmosphere.

Description

A millimeter channel continuous preparation system

technical field

The utility model relates to the technical field of a pilot-scale reaction preparation system for continuous preparation of nanocrystals or polymers, in particular to a millimeter channel continuous preparation system.

Background technique

The molecular weight or size distribution of semiconductor nanocrystals and organic polymers has an important influence on the physical and chemical properties of materials. The traditional reactor has the problem of poor heat and mass transfer in the process of large-capacity preparation, and cannot effectively control the molecular weight or size distribution of materials. In order to further improve the synthesis efficiency and quality of materials, the use of microchannel reactors has become the focus of attention. Internationally renowned companies and research institutions, such as DuPont, Massachusetts Institute of Technology, Mainz Institute of Microtechnology, BASF, Merck, Schering, Bayer, etc., are actively engaged in research on micro-reaction technology. The use of microchannel reactors can effectively overcome many shortcomings of traditional reactors. In the process of large-capacity preparation, it shows many advantages such as high specific surface area, small footprint, good mass and heat transfer effects, and continuous production. However, the processing cost of the microchannel reactor is very expensive, the product flow rate is very low, and the pipeline is easy to block, which will face many problems in practical application.

Utility model content

Aiming at the above problems, the utility model proposes a millimeter-channel continuous preparation system for nanocrystals or polymers, which is combined with an internal thread in the channel to promote the formation of turbulent flow and strengthen the heat and mass transfer process in the channel. While ensuring that the reaction process has excellent mass and heat transfer performance, it prevents the clogging of the reaction channel. In addition, an ultrafiltration purification device is used to filter out incompletely reacted raw material molecules or ions in the reaction mixture to realize continuous preparation of products such as nanocrystals or polymers.

In order to achieve the above object, the utility model has taken the following technical solutions:

A millimeter channel type continuous preparation system, comprising a raw material tank 1, a peristaltic pump 2, a channel reaction tube 3, a condenser tube 5, a buffer tank 7, a peristaltic pump 8 and an ultrafiltration device 9; the output end of the raw material tank 1 passes through the tube The road is connected to the input end of the peristaltic pump 2 (the raw material tank 1 has a feeding port besides the output end, which is used to add raw materials), and the output end of the peristaltic pump 2 is connected to the input end of the channel type reaction tube 3 through a pipeline; The inner diameter of the channel-type reaction tube 3 is 1-10 mm. If the hole diameter is greater than 10 mm, the temperature control will be uneven, and if it is less than 1 mm, the temperature will be easily blocked; the length of the channel-type reaction tube 3 is not limited, and it depends on the reaction needs; An internal thread is provided, and the pitch is preferably 1-5 mm, which can promote uniform mass transfer; if the reaction temperature needs to be controlled and adjusted, the channel-type reaction tube 3 can be placed in a temperature control device, such as a water bath device, an oil bath device, etc.; The output end of the channel-type reaction tube 3 is connected to the input end of the condenser tube 5 through a pipeline, and the purpose of terminating the reaction is achieved by cooling the reactants in the condenser tube; for general reactions, tap water can be directly passed into the condenser tube For cooling, a circulating water bath cooling device can also be used to obtain a specific condensation temperature; the output end of the condensation pipe 5 is connected with the input end of the buffer tank 7 through a pipeline, and the output end of the buffer tank 7 is connected with the input of the peristaltic pump 8 through a pipeline end connection; the output end of peristaltic pump 8 is connected with the input end of ultrafiltration device 9 by pipeline; Not the same, so the reaction solution needs to enter the buffer tank to stay first, and then input into the ultrafiltration device 9 through the peristaltic pump 8 . The ultrafiltration device 9 can adopt the hollow tube type, after the reaction solution is passed into the ultrafiltration device 9, under the pressure provided by the peristaltic pump 8, small molecules are discharged through the filter membrane in the device, and the product remains in the reaction solution; for example, it can The following structure is adopted: comprising an inner tube 901, an outer tube 902 and a filter membrane 903, the filter membrane 903 is arranged between the inner tube 901 and the outer tube 902, the outer tube 902 contains a solvent, when the reaction solution flows through the inner tube 901, in Under the pressure provided by the peristaltic pump 8, ions and molecules with a size smaller than the aperture of the filter membrane 903 permeate the filter membrane 903 and enter the outer tube 902, while semiconductor nanocrystals or polymer particles remain in the reaction liquid in the inner tube 901, and are discharged from the ultrafiltration device. The output end of 9 flows out to serve the purpose of ultrafiltration and purification, so as to realize the continuous preparation of nanocrystals or polymers. The pore diameter of the filter membrane in the ultrafiltration device 9 is selected according to the size of the nanocrystal synthesized by the target, whichever is smaller than the size of the synthesized nanocrystal, generally 1nm to 10nm can be used to ensure that the unreacted inorganic ions are permeated and removed, and the semiconductor is retained. products such as nanocrystals.

It can be applied to different reaction conditions by further improving the raw material tank. One of the improvements is as follows: the raw material tank 1 includes a tank body 11, a heater 12, an agitator 13, an air suction pump 14, and an air storage tank 15, and the top of the tank body 11 is provided with an air inlet 16, an air extraction port 17, a temperature measuring port 18 and The feeding port 19 and the air extraction port 17 are connected with the air pump 14, and the air inlet 16 is connected with the air storage tank 15. The temperature measuring device measures the temperature in the tank through the temperature measuring port 18 and controls the heater 12. Wherein, the heater 12, the temperature measuring port 18 and the temperature measuring device are used to monitor the temperature of the raw material tank, and can be removed if no temperature monitoring is required. And if the reaction conditions do not require an inert atmosphere, then the air pump 14, the gas storage tank 15, the air inlet 16, and the air inlet 17 can be removed. Optimized, the raw material tank can also be equipped with a pressure control device to prevent the internal pressure of the tank from exceeding the set value; for example, a gas outlet can be set, and the gas outlet is connected to the oil seal through a pipeline. When the pressure in the tank exceeds 1 atmosphere, the gas Overflow through the oil seal device to prevent overpressure.

The channel-type reaction tube 3 can adopt a conventional shape, such as a spiral tube type or a straight tube type. The choice of the shape mainly depends on the occupation of the device space. The area occupied by the spiral tube type is relatively small and is more commonly used, but the straight tube type can also be used. , has no effect on the effect of the present utility model; the material of the channel type reaction tube 3 is not particularly limited, and can be selected from commonly used materials such as metal, glass, quartz or temperature-resistant and solvent-resistant plastics (such as polytetrafluoroethylene or polytetrahydrofuran), generally according to The reaction conditions or the nature of the product select the appropriate material.

Furthermore, the continuous multi-step reaction can be realized by sequentially connecting several preparation systems of the present invention in series.

Wherein a kind of feasible series connection method is, the output end of the ultrafiltration device 9 of the first preparation system can be directly connected with the raw material tank of the second preparation system through pipeline, the product that the first preparation system obtains is connected with the second After the raw materials in the raw material tank of the system are mixed, the second step of reaction is carried out.

Several preparation systems of the present invention can also be connected in parallel to improve the efficiency of the reaction, and can also realize simultaneous reactions under different reaction conditions.

One of the feasible parallel connection methods is: multiple preparation systems use the same raw material tank 1, and multiple pipelines leading out from the raw material tank 1 are respectively connected to the peristaltic pumps 2 of each system.

The millimeter channel type continuous preparation system of the utility model can be used to prepare various inorganic non-metallic nanocrystals (such as oxides, sulfides, etc.) at a certain reaction temperature. It can be used in the pilot-scale preparation of nanocrystals and high molecular polymers to effectively control the size or molecular weight distribution of materials. Compared with the prior art, the utility model has the following advantages:

1. The millimeter-scale channel-type reaction tube is adopted, and internal threads are set to promote turbulent flow in the channel, and effectively promote heat and mass transfer in the channel;

2. Use an ultrafiltration purification device to filter out incompletely reacted raw material molecules or ions in the reaction mixture to realize continuous preparation of products;

3. If the raw material tank is further improved, nitrogen gas can be introduced to isolate the raw material from oxygen at room temperature and realize channel heating reaction under an inert atmosphere.

Description of drawings

Fig. 1 is the structural representation of the utility model;

Fig. 2 is the structural representation of embodiment 1;

Fig. 3 is the schematic diagram of the sectional structure of channel type reaction tube;

Fig. 4 is the structural representation of ultrafiltration device;

Fig. 5 is the structural representation of raw material tank after improvement;

Fig. 6 is the transmission electron micrograph of embodiment _1CuInS2 nanocrystal;

Fig. 7 is the transmission electron micrograph of embodiment 2CuInS ₂ /ZnS nanocrystal;

Fig. 8 is the transmission electron micrograph of comparative example _1CuInS2 nanocrystal;

Fig. 9 is a transmission electron micrograph of the comparative example 2CuInS ₂ nanocrystal.

Among them: 1, raw material tank; 2, peristaltic pump; 3, channel reaction tube; 4, oil bath device; 5, condenser; 6, circulating water bath cooling device; 7, buffer tank; 8, peristaltic pump; 9, super filter device; 11, raw material tank body; 12, heater; 13, agitator; 14, air pump; 15, air storage tank; 16, air inlet; Feeding port; 901, inner tube; 902, outer tube; 903, filter membrane.

detailed description

The content of the present utility model will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.

Example 1

The preparation system used in this embodiment is as shown in Figure 2, specifically as follows:

The output end of the raw material tank 1 is connected to the input end of the peristaltic pump 2 through a pipeline, and the output end of the peristaltic pump 2 is connected to the input end of the channel reaction tube 3 through a pipeline; the channel reaction tube 3 is arranged in the oil bath device 4 , the effect of oil bath device 4 is to control channel type reaction tube 3 at the reaction temperature of setting; Channel type reaction tube 3 is spiral tube type, and internal diameter is 6mm, and length is 27m, and inner wall is provided with internal thread (as shown in Figure 3 ), the screw pitch is 1mm, which can promote uniform mass transfer; the output end of the channel reaction tube 3 is connected with the input end of the condenser tube 5 through a pipeline, and the reactant in the condenser tube is cooled by a circulating water bath cooling device 6 to reach the termination reaction purpose; the output end of the condensation pipe 5 is connected with the input end of the buffer tank 7 through the pipeline, the output end of the buffer tank 7 is connected with the input end of the peristaltic pump 8 through the pipeline, and the output end of the peristaltic pump 8 is connected with the supercharger through the pipeline. The input terminal of filter device 9 is connected. The structure of ultrafiltration device 9 is as shown in Figure 4, comprises inner tube 901, outer tube 902 and filter membrane 903, and filter membrane 903 is arranged between inner tube 901 and outer tube 902, and filter membrane aperture is 2nm; White arrow represents reaction The flow direction of the liquid, the black arrow indicates the direction of small molecules passing through the filter membrane; the outer tube 902 contains a solvent, and after the reaction solution comes out of the peristaltic pump 8, it enters the inner tube 901 through the input end of the ultrafiltration device 9, and is provided by the peristaltic pump 8. Under pressure, the ions and molecules whose size is smaller than the pore diameter of the filter membrane 903 permeate the filter membrane 903 and enter the outer tube 902, while the product whose size is larger than the pore size of the filter membrane 903 remains in the reaction solution in the inner tube 901, and passes through the ultrafiltration device 9 out of the output terminal.

The raw material tank of this device is improved as follows, so that the device is used for material synthesis under an inert atmosphere: as shown in Figure 5, the improved raw material tank includes a tank body 11, a heater 12, an agitator 13, an air pump 14, a storage tank Air tank 15, air inlet 16, air extraction port 17, temperature measuring port 18 and feeding port 19 are arranged on the top of tank body 11 (there is also an output port on the tank body 11, but not shown in Fig. 5), air extraction port 17 is connected with the extraction The air pump 14 is connected, the air inlet 16 is connected with the air storage tank 15, and the temperature measuring device measures the temperature in the tank through the temperature measuring port 18 and controls the heater 12. Further, a pressure control device may also be provided to prevent the internal pressure of the tank from exceeding a set value.

Preparation of _CuInS2 nanocrystals:

1. Add 19.1g of cuprous iodide, 29.2g of indium acetate, and 1000ml of n-dodecanethiol into the tank body 11 of the raw material tank 1 from the feeding port 19, then start the air pump 14 to vacuumize for 5 minutes, and after stopping the air extraction, start the The gas storage tank 15 was fed with nitrogen for 5 minutes, and the operation was repeated 3 times. Then, the temperature in the tank 11 was raised to 100° C. by the heater 12, and the mixed solution was stirred at 100° C. until clarification;

2. Set the flow rate of the peristaltic pump 2 to 33ml/min, and set the temperature of the oil bath device 4 to 220°C. When the temperature of the oil bath device 4 reaches the set temperature, start the peristaltic pump 2, and input the reaction solution of 1 in the raw material tank Reaction is carried out in the channel reaction tube 3, and the product flows out from the channel reaction tube 3 after about 10 minutes;

3. The product from the passage reaction tube 3 is cooled by the condenser tube 5 and flows into the buffer tank 7 to terminate the reaction;

4. Set the flow rate of the peristaltic pump 8 to 5ml/min, the reaction solution is pumped into the ultrafiltration device 9 through the peristaltic pump 8, and the effluent is the purified CuInS ₂ nanocrystal solution.

The prepared CuInS ₂ nanocrystals have uniform size distribution and good dispersion. Figure 6 is a transmission electron microscope photograph of the prepared CuInS ₂ nanocrystals, with an average particle size of about 2.5nm.

Example 2

The difference from Example 1 is that in this example, two millimeter-channel continuous preparation systems are used in series, which can be used for the synthesis of core-shell structure nanocrystals. In this example, the preparation of CuInS ₂ /ZnS nanocrystals is specifically described:

The first preparation system is the same as in Example 1; the difference between the second preparation system and the first preparation system is that the inner diameter of the channel reaction tube 3 is 6mm, the length is 81m, and the internal thread pitch is 5mm.

Steps 1-4 of the preparation process of this example use the first preparation system, and the specific operations are the same as steps 1-4 of Example 1.

5. Directly add the CuInS2 nanocrystal solution obtained by the first preparation system into the raw material tank of the _second preparation system (afterwards in the description of this embodiment, all components refer to the components of the second preparation system), and Add 202.4g of zinc myristate and 800ml of octadecene, then start the air pump 14 to evacuate for 5min, after stopping the evacuation, feed nitrogen gas from the gas storage tank 15 for 5min, repeat the operation 3 times, then, pass the heater 12 The temperature in the tank body 11 rises to 100°C, and the mixed solution is stirred at 100°C until clear;

6. Set the flow rate of the peristaltic pump 2 to 33ml/min, and set the temperature of the oil bath device 4 to 230°C. When the temperature of the oil bath device 4 reaches the set temperature, start the peristaltic pump 2, and the reaction of 1 in the raw material tank Liquid input channel reaction tube 3 for reaction, about 30min after the product flows out from the channel reaction tube 3;

7. The product from the passage reaction tube 3 is cooled by the condenser tube 5 and flows into the buffer tank 7 to terminate the reaction;

8. Set the flow rate of the peristaltic pump 8 to 5ml/min, the reaction solution is pumped into the ultrafiltration device 9 through the peristaltic pump 8, and the effluent is the purified CuInS ₂ /ZnS nanocrystal solution.

The prepared CuInS ₂ /ZnS nanocrystals have uniform size distribution and good dispersibility. Fig. 7 is a transmission electron micrograph of the prepared CuInS ₂ /ZnS nanocrystals, with an average particle size of about 3.7nm.

Example 3

The difference from Example 1 is that the inner diameter of the channel reaction tube 3 is 10 mm. The size, uniformity, and dispersibility of the resulting product are the same as in Example 1.

Example 4

The difference from Example 1 is that the inner diameter of the channel reaction tube 3 is 1 mm. The size, uniformity, and dispersibility of the resulting product are the same as in Example 1.

Comparative example 1

Compared with Example 1, the difference lies in that the inner diameter of the channel reaction tube is 10 mm, and no internal thread is used. The size distribution of the as _- prepared CuInS2 nanocrystals is not uniform. Fig. 8 is a transmission electron micrograph of the prepared CuInS ₂ nanocrystals.

Comparative example 2

Compared with Example 1, the inner diameter of the channel reaction tube is 0.5mm. During the preparation process, the pipeline was blocked and the prepared nanoparticles were agglomerated. Figure 9 is a transmission electron microscope photo of the prepared CuInS ₂ nanocrystals.

Claims (4)

1. A millimeter channel type continuous preparation system is characterized in that it comprises a raw material tank (1), a peristaltic pump (2), a channel type reaction tube (3), a condenser tube (5), a buffer tank (7), a peristaltic pump (8) and ultrafiltration device (9); the output end of the raw material tank (1) is connected to the input end of the peristaltic pump (2) through the pipeline, and the output end of the peristaltic pump (2) is connected to the channel reaction tube through the pipeline The input end of (3) is connected; the inner diameter of channel type reaction tube (3) is 1～10mm, and inner wall is provided with internal thread; the output end of channel type reaction tube (3) passes through pipeline and the input end of condenser Connection; the output end of the condensation pipe (5) is connected with the input end of the buffer tank (7) through the pipeline, the output end of the buffer tank (7) is connected with the input end of the peristaltic pump (8) through the pipeline, and the peristaltic pump (8) ) output end is connected with the input end of ultrafiltration device (9) through pipeline. 2. The millimeter channel type continuous preparation system according to claim 1, characterized in that the pitch of the internal thread is 1-5 mm. 3. The millimeter channel type continuous preparation system as claimed in claim 1 or 2, characterized in that, the raw material tank (1) comprises a tank body (11), a heater (12), an agitator (13), a pump Air pump (14), air storage tank (15), air inlet (16), air extraction port (17), temperature measuring port (18) and feeding port (19), air extraction port (17) are arranged on the top of the tank body (11) It is connected with air pump (14), and air inlet (16) is connected with air storage tank (15). 4. The millimeter channel type continuous production system according to claim 1 or 2, characterized in that, the channel type reaction tube (3) is a spiral tube type or a straight tube type.