Integrated production device for preparing composite I-COFs / TiO2 photocatalyst

Abstract

The utility model discloses an integrated production device for preparing a composite I-COFs / TiO2 photocatalyst, which belongs to the technical field of photocatalyst preparation, and adopts the technical scheme that the integrated production device comprises a high-pressure vacuum reaction kettle and an ultrasonic refining feeder positioned at the top of the high-pressure vacuum reaction kettle, the lower part of the high-pressure vacuum reaction kettle is connected with a cooling condensation pipe; a lower pipe opening of the cooling condensation pipe is connected with a Soxhlet refining extractor; and the lower part of the Soxhlet refining extractor is connected with a constant-temperature liquid storage bottle. According to the utility model, the integrated design is adopted, the operation process is simplified, and the ultrasonic refining contact area and time of reaction raw materials are effectively increased; treatment and emission of dangerous or harmful substances are better controlled in a closed system, and the risk of leakage and accidents is reduced. And meanwhile, a plurality of production steps are integrated in one system, so that transfer of materials among different production units is reduced, and the production efficiency is remarkably improved.

Description

TECHNICAL FIELD

[0001] The utility model relates to the field of catalyst preparation device, specifically relates to a kind of integrated production device for composite I-COFs / TiO2 photocatalyst preparation. BACKGROUND

[0002] With the development of global economy, the demand for energy is increasing. However, the consumption of traditional fossil energy not only may lead to energy crisis, but also will produce greenhouse gases, which hinders the realization of the goal of "double carbon plan". Hydrogen energy, as a clean renewable energy, through water splitting technology, using photocatalyst and renewable light source to decompose water to produce hydrogen, not only meets the sustainable development strategy, but also helps to achieve the goal of carbon peak and carbon neutral.

[0003] Currently, although a variety of inorganic semiconductor materials such as sulfur indium zinc, titanium dioxide, cadmium sulfide, etc. have been used for water splitting hydrogen production research, these materials have limitations such as difficulty in band gap control, structure not easy to adjust, poor visible light response, etc. Although porous materials such as metal organic framework (MOFs), covalent organic framework (COFs), reduced graphene oxide, etc. have been widely studied, they also have problems such as poor stability, high photo-generated electron-hole recombination rate, and band gap mismatch. Therefore, developing new photocatalysts with high-speed photo-generated carrier generation, low charge recombination rate and high stability has become the focus of research.

[0004] Covalent organic framework (COFs) has great potential in many fields due to its adjustable structure, large specific surface area, high stability and easy functionalization. In particular, ionic COFs are considered as a strong candidate material for water splitting hydrogen production due to their high electron transfer efficiency, easy band gap control and good stability with inorganic semiconductors.

[0005] Therefore, the inventors have developed a method for preparing a composite I-COFs / TiO2 photocatalyst, and have applied for an invention patent (application number 202410224565.1). The method constructs a covalent organic framework through Schiff base reaction and dehydration reaction between boronic acid groups, and then combines with titanium dioxide through polycondensation reaction to form a composite photocatalyst with excellent hydrogen production performance.

[0006] The present inventors have provided a special integrated COFs catalyst preparation device according to the previous photocatalyst preparation method, which integrates the catalyst synthesis steps and can be effectively used in industrial production to simplify the production process and improve the catalyst synthesis efficiency. CONTENT OF THE UTILITY MODEL

[0007] The utility model wants to solve the technical problem to provide a kind of integrated production device for composite I-COFs / TiO2 photocatalyst preparation, adaptation inventor research and development composite I-COFs / TiO2 photocatalyst's preparation method, can effectively improve the production efficiency of composite I-COFs / TiO2 photocatalyst, reduce equipment investment and reduce operating cost, significantly reduce production cost.

[0008] In order to realize above technical problem, the technical scheme that the utility model adopts provides a kind of integrated production device for composite I-COFs / TiO2 photocatalyst preparation, including high-pressure vacuum reactor and the ultrasonic refining feeder in the top of high-pressure vacuum reactor;Cooling condensation pipe is connected in the lower part of high-pressure vacuum reactor;In the lower pipe opening of cooling condensation pipe, connect the Soxhlet extractor;Constant temperature liquid storage bottle is connected in the lower part of the Soxhlet extractor.

[0009] Further, the cooling condensation pipe and the Soxhlet extractor and constant temperature liquid storage bottle are coaxially and longitudinally connected in sequence.

[0010] Further, the high-pressure vacuum reactor is provided with a high-pressure vacuum reactor lock pin, the ultrasonic refining feeder is provided with an ultrasonic refining feeder lock pin, the high-pressure vacuum reactor is airtight connected with the ultrasonic refining feeder, and positioning is carried out through the high-pressure vacuum reactor lock pin and the ultrasonic refining feeder lock pin.

[0011] Further, the high-pressure vacuum reactor is provided with an integrated heater, and a temperature and pressure display is arranged on the integrated heater;The high-pressure vacuum reactor is provided with a rotary stirrer support;The rotary stirrer support is connected with a rotary stirrer.

[0012] Further, the cooling condensation pipe is provided with two layers of inner and outer layers, the outer layer is a cooling condensation pipe outer wall, and the inner layer is a cooling condensation pipe spherical inner wall;The upper part of the cooling condensation pipe is provided with a water outlet, and the lower part of the cooling condensation pipe is provided with a water inlet;Cooling water enters the cooling water channel formed by the cooling condensation pipe outer wall and the cooling condensation pipe spherical inner wall from the water inlet, and flows out through the water outlet by external water pressure.

[0013] Further, the Soxhlet extractor is connected with a siphon tube at the bottom;The side wall of the Soxhlet extractor is connected with a steam pipe;The Soxhlet extractor is provided with an extractor discharge port, and the upper part of the Soxhlet extractor is provided with a Soxhlet extractor upper top cover.

[0014] Further, the high-pressure vacuum reaction kettle is provided with an evacuation port, which is connected with a vacuum pump through a high-pressure gas path pipe; the ultrasonic refining feeding instrument is provided with an upper sample inlet at the upper portion; the ultrasonic refining feeding instrument is provided with a lower sample inlet at the lower portion; the ultrasonic refining feeding instrument is loaded with a spiral ultrasonic pipeline; and the ultrasonic refining feeding instrument is filled with pure water as an ultrasonic carrier.

[0015] Further, the outer kettle wall of the high-pressure vacuum reaction kettle is provided with three support grooves and three electric telescopic supports connected with the support grooves; and the bottom of the electric telescopic support is provided with a support base.

[0016] Further, a temperature and pressure sensor is arranged at the top connection of the high-pressure vacuum reaction kettle, and a high-pressure valve is arranged at the evacuation port of the kettle wall of the high-pressure vacuum reaction kettle; the lower portion of the high-pressure vacuum reaction kettle is provided with a reaction kettle discharge port, which is in airtight connection with the upper port of a cooling condensation pipe, and the reaction kettle discharge port is provided with an airtight valve.

[0017] Compared with the distributed preparation technology, the novel production device has the following advantages and beneficial effects: the production device is designed in an integrated manner to simplify the operation process, and the overall production device has a clear structure; the spiral ultrasonic pipeline in the ultrasonic refining feeding instrument can effectively increase the contact area and time of the ultrasonic refining of the reaction raw materials, so as to avoid the insufficient refining degree of the reaction raw materials; in the closed and integrated system, the treatment and discharge of dangerous or harmful substances can be better controlled, and the risk of leakage and accidents can be reduced; the integrated production device for preparing the composite I-COFs / TiO2 photocatalyst integrates multiple production steps in one system, reduces the transfer time of materials between different production units, and significantly improves the overall production efficiency; and with the change of production demand, the integrated production device for preparing the composite I-COFs / TiO2 photocatalyst can more flexibly adjust the production scale or change the production process. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is a front view structural schematic diagram of the device of the utility model;

[0019] Figure 2 is a sectional view structural schematic diagram of the device of the utility model;

[0020] Figure 3 is a top view structural schematic diagram of the device of the utility model.

[0021] The labels in the diagram are as follows: High-pressure vacuum reactor—1; High-pressure vacuum reactor locking pin—11; Support slot—12; Evacuation port—13; Reactor outlet—14; Integrated heater—15; Temperature and pressure display—16; Rotary stirrer support—17; Rotary stirrer—18; Ultrasonic fine feeder—2; Ultrasonic fine feeder locking pin—21; Upper inlet—22; Lower inlet—23; Spiral ultrasonic pipe—24; Cooling condensate pipe—3; Water outlet—31; Water inlet—32; Spherical inner wall of cooling condensate pipe—33; Soxhlet refining extractor—4; Siphon pipe—41; Steam pipe—42; Extractor outlet—43; Top cover of Soxhlet refining extractor—44; Constant temperature storage bottle—5; Electric telescopic support—6; Support base—61; Detailed Implementation

[0022] The technical solutions of the present utility model will be clearly and completely described below with reference to the accompanying drawings of the embodiments, so as to provide a better understanding of the concept of the present utility model, the technical problem solved, the technical features constituting the technical solution, and the technical effects brought about. At the same time, the described embodiments are only some embodiments of the present utility model, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present utility model without creative effort are within the scope of protection of the present utility model.

[0023] like Figure 1 As shown, an integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts includes a high-pressure vacuum reactor 1 and an ultrasonic fine feeder 2 located at the top of the high-pressure vacuum reactor 1; a cooling condensation tube 3 is connected to the lower part of the high-pressure vacuum reactor 1; a Soxhlet extractor 4 is connected to the lower end of the cooling condensation tube 3; and a constant temperature storage bottle 5 is connected to the lower part of the Soxhlet extractor 4.

[0024] In a preferred embodiment, the cooling condensation tube 3 is coaxially and longitudinally connected in an airtight manner with the Soxhlet extractor 4 and the constant temperature storage bottle 5.

[0025] In this embodiment, the high-pressure vacuum reactor 1 is equipped with a high-pressure vacuum reactor locking pin 11, and the ultrasonic fine feeder 2 is equipped with an ultrasonic fine feeder locking pin 21. The high-pressure vacuum reactor 1 and the ultrasonic fine feeder 2 are airtightly connected. The high-pressure vacuum reactor locking pin 11 and the ultrasonic fine feeder locking pin 21 are used for positioning to ensure the normal operation of the high-pressure vacuum reaction.

[0026] As a preferred embodiment, the high-pressure vacuum reaction kettle 1 is provided with an integrated heater 15 for increasing the temperature of the high-pressure vacuum reaction kettle 1; a temperature and pressure display 16 is arranged on the integrated heater 15, which can display the temperature and pressure of the high-pressure vacuum reaction kettle 1 in real time.

[0027] In this embodiment, the high-pressure vacuum reaction kettle 1 is provided with a rotary stirrer support 17; the rotary stirrer support 17 is connected with a rotary stirrer 18 to accelerate the reaction rate in the high-pressure vacuum reaction kettle 1.

[0028] As a preferred embodiment, the cooling condensation pipe 3 is provided with an inner layer and an outer layer; the outer layer is the outer wall of the cooling condensation pipe 3, and the inner layer is the spherical inner wall 33 of the cooling condensation pipe; organic solvent vapor enters the solvent area inside the hollow cooling condensation pipe spherical inner wall 33 through the lower port; the spherical inner wall design can increase the contact area of the organic solvent vapor and the inner wall, and improve the heat exchange efficiency of the organic solvent and the condensed water; the upper part of the cooling condensation pipe 3 is provided with a water outlet 31, and the lower part of the cooling condensation pipe 3 is provided with a water inlet 32; cooling water enters the cooling water channel formed by the outer wall of the cooling condensation pipe 3 and the cooling condensation pipe spherical inner wall 33 through the water inlet 32, and flows out through the water outlet 31 by external water pressure;

[0029] The Soxhlet extractor 4 is connected with a siphon 41 at the bottom; the Soxhlet extractor 4 is connected with a steam pipe 42 at the side wall; the Soxhlet extractor 4 is provided with an extractor discharge port 43, and the upper part of the Soxhlet extractor 4 is provided with a Soxhlet extractor upper cover 44, which is airtight connected with the lower part of the cooling condensation pipe 3 to prevent organic solvent vapor leakage.

[0030] As shown in Figure 2 The high-pressure vacuum reaction kettle 1 is provided with an evacuation port 13 connected with a vacuum pump through a high-pressure gas path pipe to realize vacuum treatment; the ultrasonic refining feeder 2 is provided with an upper sample inlet 22 at the upper part; the ultrasonic refining feeder 2 is provided with a lower sample inlet 23 at the lower part; the ultrasonic refining feeder 2 is loaded with a spiral ultrasonic pipeline 24, and the ultrasonic refining feeder 2 is filled with pure water as an ultrasonic carrier.

[0031] The working principle of the device is that: in the ultrasonic refining feeding instrument 2, pure water is added, which is only used as a propagation medium of ultrasonic waves and is not directly mixed with the reactants. The required reactants are added to the upper sample inlet 22, and the ultrasonic vibration is turned on, and the frequency is set to 80 kHz. After forming a clear solution under ultrasonic vibration, the clear solution is added to the high-pressure vacuum reaction kettle 1 through the lower sample inlet 23. The external vacuum pump is turned on, and the high-pressure gas path pipe is connected with the evacuation port 13, so that the inside of the high-pressure vacuum reaction kettle 1 is vacuumized to 0.05 MPa (50 kPa) absolute pressure. The high-pressure vacuum reaction kettle 1 is heated to 130 degrees Celsius, and the reaction lasts for 72 hours. After the reaction is completed, it is cooled to room temperature, and the reaction product enters the soxhlet extractor 4 through the cooling condensation pipe 3. The soxhlet extractor 4 is attached with a glass fiber filter paper, which is used to collect the solid photocatalyst. The temperature of the constant-temperature liquid storage bottle 5 is set to make the solvent in the constant-temperature liquid storage bottle 5 evaporate stably. Pure organic solvent vapor enters the soxhlet extractor 4 through the vapor pipe 42, and then enters the internal solvent area of the cooling condensation pipe spherical inner wall 33 through the lower port of the cooling condensation pipe 3. Cooling water is supplied to the water inlet 32 at the lower part of the cooling condensation pipe 3 and is discharged through the water outlet 31. The gaseous organic solvent exchanges heat with the cooling water in the cooling water channel formed by the outer wall of the cooling condensation pipe 3 and the cooling condensation pipe spherical inner wall 33, and is condensed to form liquid organic solvent which naturally falls into the soxhlet extractor 4 and is extracted and purified with the reaction product on the glass fiber filter paper in the soxhlet extractor 4. In this process, the organic solvent dissolves and removes the soluble impurities in the solid photocatalyst. The cooling water is supplied to the water inlet 32 at the lower part of the cooling condensation pipe 3 and is discharged through the water outlet 31. The organic solvent continuously accumulates in the soxhlet extractor 4, and when the liquid level of the organic solvent in the soxhlet extractor 4 exceeds the upper edge of the siphon pipe 41, the organic solvent containing dissolved impurities in the soxhlet extractor 4 is sucked back into the constant-temperature liquid storage bottle 5 by siphon effect. In the constant-temperature liquid storage bottle 5, the organic solvent evaporates again to form pure vapor reflux, and the dissolved impurities are retained in the constant-temperature liquid storage bottle 5. This continuous circulation can effectively reduce the use of solvent, improve efficiency, reduce cost, and achieve the effect of continuous purification of the reaction product. Finally, high-purity photocatalyst is obtained on the glass fiber filter paper in the soxhlet extractor 4, and the photocatalyst is taken out from the extractor discharge port 43.

[0032] In the embodiment, the outer kettle wall of the high-pressure vacuum reaction kettle 1 is provided with three support grooves 12 and three electric telescopic supports 6 connected with the support grooves 12; the bottom of the electric telescopic support 6 is provided with a support base 61; the electric telescopic support 6 can freely control the height of the production device, which greatly improves the adaptability in different production environments.

[0033] As a preferred embodiment, a temperature and pressure sensor is arranged at the top connection of the high-pressure vacuum reaction kettle 1 to ensure that the high-pressure vacuum reaction kettle 1 works at normal temperature and pressure, and a high-pressure valve is arranged at the evacuation port 13 on the wall of the high-pressure vacuum reaction kettle 1 to ensure the operability of the high-pressure environment inside the high-pressure vacuum reaction kettle 1.

[0034] In the embodiment, a reaction kettle discharge port 14 is arranged at the lower part of the high-pressure vacuum reaction kettle 1, the reaction kettle discharge port 14 is in airtight connection with the upper port of the cooling condensation pipe 3, and the reaction kettle discharge port 14 is provided with an airtight valve, so that the material can be discharged through the upper port of the cooling condensation pipe 3 after the reaction is completed.

[0035] In the description of the utility model, the "connection", "setting" can be fixed connection, processing molding, welding, and can also be mechanical connection, and the specific case is understood as the specific meaning of the above terms in the utility model.

[0036] In the description of the utility model, the terms "upper", "lower", "coaxial", "inner", "outer" and the like are only for the convenience of describing the utility model and simplifying the description, and do not indicate or imply that the indicated device or element must have a specific orientation, so it cannot be understood as a limitation on the utility model.

[0037] Finally, it should be pointed out that: the above embodiments are only used to illustrate the technical scheme of the utility model, and are not limited to them; although the utility model has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: it can still modify the technical scheme described in the foregoing embodiments, or make equivalent replacement to part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical scheme deviate from the scope of the technical scheme of the embodiments of the utility model.

Claims

1. An integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts, characterized in that, It includes a high-pressure vacuum reactor (1) and an ultrasonic fine feeder (2) located at the top of the high-pressure vacuum reactor (1); a cooling condensation tube (3) is connected to the lower part of the high-pressure vacuum reactor (1); a Soxhlet extractor (4) is connected to the lower end of the cooling condensation tube (3); and a constant temperature storage bottle (5) is connected to the lower part of the Soxhlet extractor (4).

2. The integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts according to claim 1, characterized in that, The cooling condensation tube (3), the Soxhlet refining extractor (4), and the constant temperature storage bottle (5) are coaxially and longitudinally connected in an airtight manner.

3. The integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts according to claim 1, characterized in that, The high-pressure vacuum reactor (1) is equipped with a high-pressure vacuum reactor locking pin (11), and the ultrasonic fine feeder (2) is equipped with an ultrasonic fine feeder locking pin (21). The high-pressure vacuum reactor (1) and the ultrasonic fine feeder (2) are airtightly connected and positioned by the high-pressure vacuum reactor locking pin (11) and the ultrasonic fine feeder locking pin (21).

4. The integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts according to claim 1, characterized in that, The high-pressure vacuum reactor (1) is equipped with an integrated heater (15), and a temperature and pressure display (16) is installed on the integrated heater (15); the high-pressure vacuum reactor (1) is equipped with a rotary stirrer support (17); the rotary stirrer support (17) is connected to a rotary stirrer (18).

5. An integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts according to claim 1, characterized in that, The cooling condensation pipe (3) is provided with two layers, an outer layer being the outer wall of the cooling condensation pipe (3) and an inner layer being the spherical inner wall (33) of the cooling condensation pipe; the upper part of the cooling condensation pipe (3) is provided with an outlet (31) and the lower part of the cooling condensation pipe (3) is provided with an inlet (32); the cooling water enters the cooling water channel formed by the outer wall of the cooling condensation pipe and the spherical inner wall (33) of the cooling condensation pipe through the inlet (32), and the cooling wastewater flows out through the outlet (31) by relying on the external water pressure.

6. An integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts according to claim 1, characterized in that, The bottom of the Soxhlet refining extractor (4) is connected to a siphon pipe (41); the side wall of the Soxhlet refining extractor (4) is connected to a steam pipe (42); the Soxhlet refining extractor (4) is provided with an extractor outlet (43); and the top of the Soxhlet refining extractor (4) is provided with a top cover (44).

7. An integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts according to claim 1, characterized in that, The high-pressure vacuum reactor (1) is provided with an evacuation port (13), which is connected to a vacuum pump through a high-pressure gas pipeline; the ultrasonic fine feeder (2) is provided with an upper sample inlet (22) at the top; the ultrasonic fine feeder (2) is provided with a lower sample inlet (23) at the bottom; the ultrasonic fine feeder (2) is loaded with a spiral ultrasonic pipeline (24), and the ultrasonic fine feeder (2) is filled with pure water as an ultrasonic carrier.

8. An integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts according to claim 1, characterized in that, The outer wall of the high-pressure vacuum reactor (1) is provided with three support slots (12) and three electric telescopic brackets (6) connected to the support slots (12); the bottom of the electric telescopic brackets (6) is provided with a bracket base (61).

9. An integrated production apparatus for preparing composite I-COFs / TiO2 photocatalysts according to claim 1, characterized in that, A temperature and pressure sensor is installed at the top connection of the high-pressure vacuum reactor (1), and a high-pressure valve is installed on the evacuation port on the wall of the high-pressure vacuum reactor (1); a reactor outlet (14) is installed at the bottom of the high-pressure vacuum reactor (1), and the reactor outlet (14) is airtightly connected to the upper port of the cooling condensation pipe (3), and an airtight valve is installed on the reactor outlet (14).

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