An apparatus for preparing a micro-mesoporous adsorbent material

Abstract

The present invention discloses a device for preparing a micro-mesoporous adsorption material, including: a raw material tank which is a storage tank for the adsorption material before treatment; a preparation system including a high-voltage pulse source, an array-type pulse reactor, a flow meter and a gas source connected in sequence; the array-type pulse reactor includes a reactor housing, a high-voltage electrode array, a low-voltage electrode array and a grounding electrode; the high-voltage electrode array is connected to the high-voltage pulse source, and the low-voltage electrode array is connected to the ground electrode; the array-type pulse reactor is connected to the flow meter and the gas source; a sampling system includes a sampling window and a sampling tank; the sampling window is connected to the array-type pulse reactor; a vacuum feeding system includes a vacuum pump, a vacuum feeder and a product tank; the vacuum pump evacuates the vacuum feeder to a low-pressure environment, and the outlet of the vacuum feeder is connected to the product tank. The device of the present invention is used for the preparation of micro-mesoporous adsorption materials, which can improve the preparation efficiency and simplify the process steps.

Description

Technical Field

[0001] The present invention relates to the technical field of production equipment, and particularly relates to a device for preparing a micro-mesoporous adsorption material. Background Art

[0002] Micro-mesoporous adsorption materials have the properties of large specific surface area, rich porosity, stable structure, and abundant unsaturated groups on the surface, and have broad application prospects in the fields of pollutant treatment, material enrichment and purification, biomedicine, functional materials, etc. And relevant research shows that the adsorbent structure with coexistence of micropores and mesopores has stronger advantages in organic matter adsorption, and micropores can also have a high adsorption capacity for organic pollutants at low concentrations. According to the IUPAC definition, materials with pore diameters between 2 - 50 nm are mesoporous materials, and materials with pore diameters between 0 - 2 nm are microporous materials. Relevant research shows that adsorbents with coexistence of micro and mesopores have stronger advantages in the field of pollutant treatment. Currently, the commonly used methods for preparing micro and mesoporous materials in industry are deposition method, acid-base modification method, and sintering method. Among them, in the process of preparing micro-mesoporous adsorption materials by using the deposition method, acid-base modification method, and sintering method, the performance of the original matrix material is damaged to varying degrees, damaging the intrinsic properties of the original material. The deposition process is complex and time-consuming. The use of chemical reagents in the acid-base modification method is likely to cause secondary pollution, and the use of the sintering method consumes a high amount of energy. Therefore, it is necessary to develop an economical, fast, efficient, and harmless method for preparing micro-mesoporous adsorption materials.

[0003] In recent years, the plasma modification method has gradually become a research hotspot in the field of material modification and preparation. The plasma only acts on the nanoscale surface of the material without damaging the matrix properties of the material. The plasma contains a large number of high-energy electrons and strongly oxidizing species, which can undergo physical and chemical reactions on the material surface, endowing it with new pore structures and surface chemical characteristics without damaging the material's own properties. Document ZL201910631360.4 discloses a method for preparing a micro-mesoporous XAD-2 material, which introduces that a micro-mesoporous resin adsorbent was successfully prepared by using the plasma method based on a macroporous adsorption material, and its adsorption capacity for organic pollutants was greatly improved. However, the plasma treatment device in this document cannot efficiently process a large number of samples in industry. Therefore, it is necessary to develop a plasma generating device that can produce uniform plasma to be suitable for industrial equipment capable of mass-producing micro-mesoporous adsorption materials.

[0004] The present invention mainly uses a high-voltage pulse source to drive an array of electrodes to generate a large-area uniform discharge plasma, and cooperates with a vacuum feeding system to realize a device for automatically preparing micro-mesoporous adsorption materials. Summary of the Invention

[0005] The object of the present invention is to provide a device for preparing a micro-mesoporous adsorption material. The high-voltage power supply excites the array-type pulse reactor to generate a large-area uniform discharge plasma, which processes and treats a large quantity of adsorption materials in the pulse reactor to prepare an adsorption material rich in micro-mesopores. The combined use of the pulse reactor and the vacuum feeder can reduce the air pressure in the pulse reactor to achieve large-area uniform discharge under low air pressure. At the same time, the low air pressure environment can realize the automatic discharging of the prepared adsorption material, meeting the industrial production requirements for the large-scale preparation of micro-mesoporous adsorption materials.

[0006] To achieve the above object, the following technical solution is adopted:

[0007] A device for preparing a micro-mesoporous adsorption material includes a raw material tank, a preparation system, a sampling system, and a vacuum feeding system.

[0008] The raw material tank is a storage tank for the adsorption material before treatment;

[0009] The preparation system includes a high-voltage pulse source, an array-type pulse reactor, a flow meter, and a gas source connected in sequence;

[0010] The high-voltage pulse source generates a pulsed high voltage, and the peak value of the pulse voltage and the pulse repetition frequency are adjustable;

[0011] The array-type pulse reactor includes a reactor housing, a high-voltage electrode array, a low-voltage electrode array, and a grounding electrode;

[0012] The high-voltage electrode array is composed of a plurality of mace-shaped high-voltage electrode rods and high-voltage insulating dielectric tubes. The high-voltage electrode rods are inserted into the high-voltage insulating dielectric tubes to form a high-voltage electrode group, and the high-voltage electrode groups are placed side by side to form the high-voltage electrode array; the low-voltage electrode array is composed of a plurality of mace-shaped low-voltage electrode rods and low-voltage insulating dielectric tubes. The low-voltage electrode rods are inserted into the low-voltage insulating dielectric tubes to form a low-voltage electrode group, and the low-voltage electrode groups are placed side by side to form the low-voltage electrode array.

[0013] Both the high-voltage electrode rod and the grounding electrode rod are mace-shaped, making it easy for discharge to occur at the tips, and there is a discharge channel at each tip, which can greatly increase the volume of the discharge plasma.

[0014] The high-voltage electrode array is connected to the high-voltage pulse source, and the low-voltage electrode array is connected to the grounding electrode;

[0015] The high-voltage electrode array and the low-voltage electrode array are alternately placed inside the reactor housing.

[0016] The array-type pulse reactor is connected to the flow meter and the gas source. The gas source provides various gas environments such as nitrogen, oxygen, air, and argon for the array-type pulse reactor, and the flow meter controls the gas flow rate entering the inside of the array-type pulse reactor.

[0017] The sampling system includes a sampling window and a sampling box;

[0018] The sampling window is connected to the array pulse reactor, and is used to take out the samples in the array pulse reactor in real time for monitoring and inspection. After being taken out, the samples automatically enter the sampling box;

[0019] The vacuum feeding system includes a vacuum pump, a vacuum feeder and a product box;

[0020] The vacuum pump evacuates the vacuum feeder to a low-pressure environment, and the outlet of the vacuum feeder is connected to the product box.

[0021] The vacuum feeder is connected to the sampling window and the array pulse reactor, and the air pressures of the three are the same. During the working process, they can all maintain a gas environment below one atmosphere.

[0022] Under this low-pressure environment, the discharge in the array pulse reactor can maintain a uniform large-area state, and the sampler and the product box can respectively achieve automatic sampling and automatic collection of materials under the action of the pressure difference. Description of the Drawings

[0023] Figure 1 It is a schematic diagram of the device for preparing the micro-mesoporous adsorption material of the present invention;

[0024] In the figure: 1 - raw material box, 2 - preparation system, 3 - sampling system, 4 - vacuum feeding system, 2.1 - high-voltage pulse source, 2.2 - array pulse reactor, 2.3 - flowmeter, 2.4 - gas source, 3.1 - sampling window, 3.2 - sampling box, 4.1 - vacuum pump, 4.2 - vacuum feeder, 4.3 - product box;

[0025] Figure 2 It is a schematic diagram of the arrangement of the high-voltage electrode array and the low-voltage electrode array inside the array pulse reactor;

[0026] In the figure: 2.2.1 - reactor shell, 2.2.2 - high-voltage electrode array, 2.2.3 - low-voltage electrode array, 2.2.4 - grounding electrode;

[0027] Figure 3 It is a schematic diagram of the structure of the high-voltage electrode group and the low-voltage electrode group;

[0028] In the figure: 2.2.2.1 - high-voltage electrode rod, 2.2.2.2 - high-voltage insulating dielectric tube, 2.2.3.1 - low-voltage electrode rod, 2.2.3.2 - low-voltage insulating dielectric tube.

[0029] Figure 4a It is a scanning electron microscope image of the matrix resin (magnification: 200,000 times);

[0030] Figure 4bScanning electron micrograph of the micro-mesoporous resin prepared according to the present invention (magnification: 200,000 times);

[0031] Figure 5 Schematic diagrams for comparison of N2 adsorption-desorption isotherms and pore size distributions of the matrix resin (a, b) and the micro-mesoporous resin (c, d) prepared according to the present invention. Detailed implementation manners

[0032] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0033] As Figure 1 shown, the embodiment of the present invention provides a device for preparing a micro-mesoporous adsorption material, including a raw material tank 1, a preparation system 2, a sampling system 3, and a vacuum feeding system 4;

[0034] The raw material tank 1 is a storage tank for the adsorption material before treatment;

[0035] As Figure 2 shown, the preparation system 2 includes a high-voltage pulse source 2.1, an array-type pulse reactor 2.2, a flowmeter 2.3, and a gas source 2.4 connected in sequence;

[0036] The high-voltage pulse source 2.1 generates pulsed high voltage, and the peak value of the pulse voltage and the pulse repetition frequency are adjustable;

[0037] As Figure 3 shown, the array-type pulse reactor 2.2 includes a reactor housing 2.2.1, a high-voltage electrode array 2.2.2, a low-voltage electrode array 2.2.3, and a grounding electrode 2.2.4;

[0038] The high-voltage electrode array 2.2.2 includes a plurality of high-voltage electrode rods 2.2.2.1 and a high-voltage insulating dielectric tube 2.2.2.2. The high-voltage electrode rods 2.2.2.1 are inserted into the high-voltage insulating dielectric tube 2.2.2.2 to form a high-voltage electrode group, and the high-voltage electrode groups are arranged side by side to form the high-voltage electrode array 2.2.2; the low-voltage electrode array 2.2.3 is composed of a plurality of low-voltage electrode rods 2.2.3.1 and a low-voltage insulating dielectric tube 2.2.3.2. The low-voltage electrode rods 2.2.3.1 are inserted into the low-voltage insulating dielectric tube 2.2.3.2 to form a low-voltage electrode group, and the low-voltage electrode groups are arranged side by side to form the low-voltage electrode array 2.2.3;

[0039] The high-voltage electrode array 2.2.2 is connected to the high-voltage pulse source 2.1, and the low-voltage electrode array 2.2.3 is connected to the grounding electrode 2.2.4;

[0040] The high-voltage electrode array 2.2.2 and the low-voltage electrode array 2.2.3 are alternately placed inside the reactor housing 2.2.1;

[0041] The array-type pulsed reactor 2.2 is connected to a flowmeter 2.3 and a gas source 2.4. The gas source 2.4 provides various gas environments such as nitrogen, oxygen, air, and argon for the array-type pulsed reactor 2.2, and the flowmeter 2.3 controls the gas flow rate entering the interior of the array-type pulsed reactor 2.2;

[0042] The sampling system 3 includes a sampling window 3.1 and a sampling box 3.2;

[0043] The sampling window 3.1 is connected to the array-type pulsed reactor 2.2 and is used to take out the samples inside the array-type pulsed reactor 2.2 in real time for monitoring and inspection. The taken-out samples automatically enter the sampling box 3.2;

[0044] The vacuum feeding system 4 includes a vacuum pump 4.1, a vacuum feeder 4.2, and a product box 4.3;

[0045] The vacuum pump 4.1 evacuates the vacuum feeder 4.2 to a low-pressure environment, and the outlet of the vacuum feeder 4.2 is connected to the product box 4.3.

[0046] In the process of preparing the micro-mesoporous resin, the matrix resin is a macroporous resin (MaPR). Its high-voltage pulse source 2.1 uses a pulse-modulated microwave source with a power of 500 W. The selected array-type pulsed reactor 2.2 is made of stainless steel, the insulating dielectric tube is made of plexiglass, and the gap between the dielectric tubes is 1.5 mm. The used gas source is a mixture of 80% nitrogen and 20% oxygen introduced, and the gas flowmeter is set to 500 mL / min. The whole equipment is evacuated by a vacuum pump to a vacuum pressure of 100 Pa. Under these conditions, after treatment for 30 minutes, the prepared micro-mesoporous resin (Mi-MePR) is taken out from the sampling box 3.2 and analyzed:

[0047] (1) Morphology analysis

[0048] Figure 4a are the scanning electron microscope images of the matrix resin and the micro-mesoporous resin prepared by the present invention shown in Figure 4b. Through the characterization of the surface morphology of the samples before and after plasma treatment by scanning electron microscopy, it can be seen that there are a large number of particulate matters on the surface of the matrix resin MaPR resin, and the pore diameter is blocked, and the pore structure is not developed. After plasma modification treatment, the larger particulate matters of the micro-mesoporous resin are removed, the surface becomes smooth, and there are a large number of pore diameters of different sizes on the surface, and the pore channels are distributed in a complex and intricate network structure.

[0049] (2) Pore structure analysis

[0050] The pore structures of the matrix macroporous resin MaPR and the micro-mesoporous resin Mi-MePR prepared in the present invention were analyzed by a N2 adsorption-desorption instrument to obtain corresponding specific surface area, pore size distribution, pore volume and other information, as shown in Table 1.

[0051] Table 1 Specific surface area and pore size distribution

[0052]

[0053] Figure 5 a and Figure 5 c are the N2 adsorption-desorption isotherms of the matrix macroporous resin MaPR and the micro-mesoporous resin Mi-MePR prepared in the present invention, Figure 5 b and Figure 5 d are the pore size distribution diagrams of the matrix macroporous resin MaPR and the micro-mesoporous resin Mi-MePR prepared in the present invention. Analysis shows that the prepared micro-mesoporous resin Mi-MePR has a stronger adsorption capacity for N2, and the specific surface area is greatly improved, increasing from the original 480.6 m 2 g -1 to 685.5 m 2 g -1 , and the pore size of the original matrix macroporous resin MaPR is mainly distributed at 57.6 nm. After plasma treatment, the resin material newly adds micropores in the range of 0.69 - 1.2 nm and mesopores distributed at 40.2 nm, successfully preparing the micro-mesoporous resin Mi-MePR material.

Claims

1. An apparatus for preparing a micro-mesoporous adsorption material, characterized in that, It includes a raw material tank (1), a preparation system (2), a sampling system (3), and a vacuum feeding system (4); The raw material tank (1) is a storage tank for the adsorption material before treatment; The preparation system (2) includes a high-voltage pulse source (2.1), an array-type pulse reactor (2.2), a flowmeter (2.3), and a gas source (2.4) connected in sequence; The high-voltage pulse source (2.1) generates pulsed high voltage, and the peak pulse voltage and the pulse repetition frequency are adjustable; The array-type pulse reactor (2.2) includes a reactor housing (2.2.1), a high-voltage electrode array (2.2.2), a low-voltage electrode array (2.2.3), and a grounding electrode (2.2.4); The high-voltage electrode array (2.2.2) is connected to the high-voltage pulse source (2.1), and the low-voltage electrode array (2.2.3) is connected to the grounding electrode (2.2.4); The high-voltage electrode array (2.2.2) and the low-voltage electrode array (2.2.3) are alternately placed inside the reactor housing (2.2.1); The array-type pulse reactor (2.2) is connected to the flowmeter (2.3) and the gas source (2.4). The gas source (2.4) provides a gas environment for the array-type pulse reactor (2.2), and the flowmeter (2.3) controls the gas flow rate entering the interior of the array-type pulse reactor (2.2); The sampling system (3) includes a sampling window (3.1) and a sampling box (3.2); The sampling window (3.1) is connected to the array-type pulse reactor (2.2) for taking out the samples inside the array-type pulse reactor (2.2) in real time for monitoring and inspection, and the taken-out samples automatically enter the sampling box (3.2); The vacuum feeding system (4) includes a vacuum pump (4.1), a vacuum feeder (4.2), and a product box (4.3); The vacuum pump (4.1) evacuates the vacuum feeder (4.2) into a low-pressure environment. The vacuum feeder (4.2) is connected to the sampling window (3.1) and the array-type pulse reactor (2.2), and the outlet of the vacuum feeder (4.2) is connected to the product box (4.3).

2. The device for preparing the micro-mesoporous adsorption material according to claim 1, characterized in that, The described high-voltage electrode array (2.2.2) includes a plurality of high-voltage electrode rods (2.2.2.1) and high-voltage insulating dielectric tubes (2.2.2.2). The high-voltage electrode rods (2.2.2.1) are inserted into the high-voltage insulating dielectric tubes (2.2.2.2) to form a high-voltage electrode group, and the high-voltage electrode groups are placed side by side to form the high-voltage electrode array (2.2.2); the low-voltage electrode array (2.2.3) is composed of a plurality of low-voltage electrode rods (2.2.3.1) and low-voltage insulating dielectric tubes (2.2.3.2). The low-voltage electrode rods (2.2.3.1) are inserted into the low-voltage insulating dielectric tubes (2.2.3.2) to form a low-voltage electrode group, and the low-voltage electrode groups are placed side by side to form the low-voltage electrode array (2.2.3).

3. The apparatus for preparing the micro-mesoporous adsorption material according to claim 2, wherein, The described high-voltage electrode rods (2.2.2.1) and low-voltage electrode rods (2.2.3.1) are both in the shape of mace.

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