CN213254326U - Device for preparing covalent organic framework based on automatic acid-base alternate spraying - Google Patents

Abstract

The utility model discloses a device for preparing covalent organic framework based on automatic acid-base alternating spraying, which comprises a covalent organic framework material preparation device, a spraying reaction device and a washing and drying device which are connected in sequence; the spray reaction device UNICOM is provided with the polymorphic type reagent device that sprays, the polymorphic type reagent device that sprays includes first reagent device that sprays, the second reagent device that sprays, the third reagent device that sprays, the polymorphic type reagent device that sprays still electric connection spray controlling means frame and spray the device of preparation covalence organic frame based on automatic acid-base is in turn. According to the utility model discloses the preparation facilities that realizes, the utility model provides a preparation facilities all carries out the reagent quantity of sculpture operation and the regulation and control of spraying time to each grade reaction, adopts a plurality of reagent devices to spray to switch and the volume of spraying to above-mentioned spray set control in order to realize that higher-quality result generation part filters pH.

Description

Device for preparing covalent organic framework based on automatic acid-base alternate spraying

Technical Field

The utility model belongs to covalence organic frame material preparation facilities field, concretely relates to frame sprays device of preparation covalence organic frame based on automatic acid-base is in turn.

Background

Covalent Organic Frameworks (COFs) are porous materials which are connected by building units through reversible covalent bonds, and are novel porous crystalline materials with ordered pore channel structures. The porous crystalline material has potential application value in the fields of gas storage, chemical sensing, drug release, heterogeneous catalysis and photoelectricity. In the past decade, many two-dimensional or three-dimensional COFs have been obtained by selecting various building blocks, and the structural synthesis thereof focuses on the selection of building elements and the design of structures, which are also important factors for determining the performance of COF materials. However, the structural units for synthesizing COFs are mainly concentrated on organic structural units, which limits the structural and functional diversity of COFs to some extent. Therefore, the development of the multi-metal composite construction unit has important significance for enriching the structure and the function of the COFs material.

At present, a silica-based COF carbon junction with a nanotube-decorated yolk-shell structure is a hot point of research, silicon dioxide (SiO2) becomes one of the most researched materials due to cost effectiveness, nontoxicity, high thermal stability and chemical stability, and when the silica-based COF carbon junction is applied to the preparation of a covalent organic framework material, a silica sphere is used as a core in a processing process, and carbon with different morphologies is formed after carbonization and etching.

Disclosure of Invention

To the above defect of prior art or improve the demand, the utility model provides a frame sprays the device of preparation covalence organic frame in turn based on automatic acid-base, uses this device to prepare out the covalence organic framework material that has yolk-shell structure, and this material surface multi-stage functionalization utensil high catalytic activity.

The invention provides a device for preparing a covalent organic framework based on automatic acid-base alternate spraying of the framework, which comprises a covalent organic framework material preparation device, a spraying reaction device and a washing and drying device which are sequentially connected; the spray reaction device is communicated with a plurality of types of spray reagent devices, each type of spray reagent device comprises a first spray reagent device, a second spray reagent device and a third spray reagent device, and the plurality of types of spray reagent devices are electrically connected with a spray control device.

Furthermore, a first washing and drying device is also arranged between the covalent organic framework material preparation device and the spraying reaction device.

Furthermore, a partial filtering membrane is arranged in the spraying reaction device and is used for performing partial filtering on the etching solution containing the solid phase in the reaction process.

Furthermore, a pH sensor is arranged in the spraying reaction device and used for acquiring the pH value of the etching reactant in the device in real time, and the value is used for feedback calculation and control of the spraying amount in the spraying reaction device.

Further, the preparation device also comprises a first waste liquid treatment collection tank and a second waste liquid treatment collection tank frame which are communicated with the spraying reaction device, and the pH value of the etching solution containing the solid phase is partially filtered by the device for preparing the covalent organic frame through automatic acid-base alternate spraying.

Further, stirrers are arranged in the covalent organic framework material preparation device and the spray reaction device.

Generally, through the utility model discloses above technical scheme who conceives compares with prior art, has following beneficial effect:

1. the utility model provides a frame is based on automatic acid-base alternative sprays device of preparation covalence organic frame can be suitable for large-scale production, adopts the computer to carry out the accurate control and the on-off control of timing quantity, makes the regulation and control of the reagent quantity of etching operation and spray time each time, and then makes the reaction product of final covalence organic frame material more abundant;

2. the utility model provides a device for preparing covalent organic frame based on automatic acid-base alternate spraying, which adopts alternate spraying process mode and sets partial filtering membrane in the spraying activation chamber, so that solid phase reaction product can be more fully reacted;

3. this reality is with novel device that provides a frame and spray preparation covalence organic frame based on automatic acid-base is in turn, sprays the indoor pH sensing device that sets up of activation, can monitor this completion condition of the process that sprays through sensing device to feedback process.

Drawings

Fig. 1 is a schematic view of the structure of the device for preparing the covalent organic framework based on automatic acid-base alternate spraying according to the utility model.

The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:

the device comprises a covalent organic framework material preparation device-1, a first washing and drying device-2, a spraying reaction device-3, a first reagent spraying device-4, a second reagent spraying device-5, a third reagent spraying device-6, a spraying control device-7, a washing and drying device-8, a first waste liquid treatment and collection tank-9 and a second waste liquid treatment and collection tank-10.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

It should be noted that the term "first \ second" referred to in the present invention is only used for distinguishing similar objects, and does not represent a specific ordering for the objects, and it should be understood that "first \ second" may be interchanged in a specific order or sequence, if allowed. It should be understood that "first \ second" distinct objects may be interchanged under appropriate circumstances such that embodiments of the invention described herein may be practiced in sequences other than those described or illustrated herein.

The utility model discloses a frame sprays device of preparation covalence organic frame in turn based on automatic acid-base for the preparation needs carry out the covalence organic framework material of acid/alkali sculpture, the preferred covalence organic framework material who is used for preparing yolk-shell structure, this material use silica as the core, the covalent organic framework material of cladding, rethread weak acid or weak base carry out the sculpture, form the covalent organic framework material of yolk-shell structure. Therefore, the process flow using the device comprises the following steps: firstly, preparing a covalent organic framework material taking silicon dioxide as a core, extracting weak acid or weak base to carry out spray etching on the material, and then washing and drying to obtain a corresponding product.

As shown in fig. 1, the device comprises a covalent organic framework material preparation device 1, a spraying reaction device 3 and a washing and drying device 8 which are connected in sequence; the spray reaction device 3 communicates and is provided with a plurality of types of spray reagent devices, the plurality of types of spray reagent devices comprise a first spray reagent device 4, a second spray reagent device 5 and a third spray reagent device 6, and the plurality of types of spray reagent devices are electrically connected with a spray control device 7.

The method comprises the following steps of washing a product obtained from a covalent organic framework material preparation device 1 through a first washing and drying device 2, and enabling the product to reach a spraying reaction device 3, wherein the covalent organic framework material preparation device 1 is used for preparing a core-shell structure with a covalent organic framework coated by silicon dioxide, a metal source solution, a ligand and a solvent are input through a feed inlet, and the reaction is carried out in the covalent organic framework material preparation device 1, the covalent organic framework material preparation device 1 is of a reaction kettle structure, and is provided with a heating device and a pressure regulation and control device, so that the reaction can be set at the optimal reaction condition. After the reaction is finished, the reaction product enters a spraying reaction device 3 to be alternately sprayed with acid and alkali.

Further, the covalent organic framework material production apparatus 1 is provided with a stirrer, and the raw materials can be sufficiently reacted.

Further, the covalent organic skeleton may be prepared by including two kinds of ligands, and the first ligand may include at least one of trimesic aldehyde, terephthalaldehyde, tetrakis (4-formylbenzene) methane, tetraaldehyde phenylporphyrin, 3',5,5' -tetraaldehyde biphenyl, 2 '-bipyridine-5, 5' -dicarboxaldehyde, 2, 5-dihydroxyterephthalaldehyde, 2, 5-dimethoxybenzene-1, 4-dicarboxaldehyde, 2, 5-diformylfuran, 1,3, 5-trialdehyde phloroglucinol, and the like, but is not limited thereto. The second ligand includes, but is not limited to, at least one of p-phenylenediamine, melem, biphenyldiamine, 5,15- (aminophenyl) -10, 20-phenylporphyrin, tetrakis (4-aminophenyl) methane, tris (4-aminophenyl) amine, 5 '-diamino-2, 2' -bipyridine, 2,4, 6-tris (4-aminophenoxy) -1,3, 5-triazine, 1,3, 5-tris (4-aminophenyl) benzene, and the like. The spray reaction device 3 is used for receiving the spray reagents from the first spray reagent device 4, the second spray reagent device 5 and the third spray reagent device 6, so as to correspondingly spray and wash the reactants, and thus, wash the silicon dioxide;

wherein, the first reagent spraying device 4 is loaded with acid spraying reagent, wherein the acid spraying reagent comprises: hydrobromic acid, hydrogen iodide, hydrofluoric acid, polyphosphoric acid, phosphorous acid, phosphoric acid, phosphomolybdic acid, hypophosphorous acid, iodic acid, dilute hydrochloric acid, dilute sulfuric acid, boric acid, tungstic acid, metaphosphoric acid, perrhenic acid, silicotungstic acid, hydrate sulfonic acid, phosphotungstic acid, selenic acid, iodoacetic anhydride, hydrogen bromide, and acetic acid.

Wherein, the second reagent spraying device 5 is loaded with a washing solvent, wherein the washing solvent comprises: one or more of absolute ethyl alcohol, absolute methanol, water, ethyl acetate, acetone, petroleum ether, dichloromethane, trichloromethane, tetrachloromethane, acetonitrile, N, N-dimethylformamide, N, N-diethylformamide and the like.

Wherein, the third sprays and holds in the data set 6 that alkaline sprays the reagent, and wherein alkaline sprays the reagent including: sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium bicarbonate, sodium phenolate, potassium bicarbonate, sodium hydroxide, potassium hydrogen phosphate, potassium dihydrogen phosphate, trimethyl ammonium hydroxide, triethyl ammonium hydroxide, triethylamine or a mixture thereof.

The preparation device also comprises a spray pipeline arranged in the multistage device, mainly comprising an acidic spray pipeline, an alkaline spray pipeline and a washing solvent spray pipeline, wherein the pipelines can be communicated with the spray reaction device 3 in an integrated mode through a plurality of channel ports as shown in figure 1, and can also be integrated in a mode of being respectively communicated with the spray reaction device 3, so that the conveying of the spray reagent is realized.

The first reagent spraying device 4, the second reagent spraying device 5 and the third reagent spraying device 6 are provided with a spraying control device 7, wherein the spraying control device 7 is used for controlling the on-off and the dosage of the devices, the specific calculation control method can be a timing and quantitative alternative mode, or a corresponding pH sensing device is arranged in the spraying reaction device 3, so that the pH value in the reaction process is collected in real time and fed back to a computer for carrying out the on-off and adjustment of the dosage of the washing reagent, and the on-off control and the dosage can be realized.

Further, a partial filtering membrane is arranged inside the spraying reaction device 3 and is used for further partially filtering the solid-phase product of the reaction, so that the reagent sprayed by the spraying device can be fully contacted with the product, and the etching of the silicon dioxide core is completed.

Furthermore, the spraying reaction device 3 is internally provided with a stirrer, so that the product can be more fully contacted with the sprayed reagent, and preferably, the filtering speed and the spraying flow rate of the spraying reaction device 3 are kept consistent, so that the product in the spraying reaction device 3 is always kept in a solid-liquid mixed suspension state, and then can enter the washing and drying device 8 through a pipeline device.

Further, the spraying mode of the spraying reagent can be an alternate spraying mode, namely after the acid spraying is finished, the spraying of the washing reagent is finished, and then the alkaline spraying is carried out, so that the multistage alternate spraying is finished.

Further, the inside of spraying reaction unit 3 is provided with agitating unit to have along with agitating unit's work, can regulate and control the stirring and spray the ground shower head, agitating unit makes reaction product solid phase solvent can be more abundant and this acid basicity or be that the washing solvent contacts, makes can accomplish more abundant washing.

Partial filtration and partial filtration further, inside the spray reaction device 3, a pH sensor is further provided, which can sense the pH value of the solvent during the washing and spraying process so that the amount of the reagent sprayed during the subsequent washing process can be effectively controlled.

In order to influence the environment of the etching process in large-scale production, the rear of the spraying device is communicated with the corresponding waste liquid collector, and in one embodiment, two stages of waste liquid collecting tanks are adopted, but multi-stage setting can be performed as required, and details are not repeated.

It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (6)

1. The device for preparing the covalent organic framework based on automatic acid-base alternate spraying is characterized by comprising a covalent organic framework material preparation device (1), a spraying reaction device (3) and a washing and drying device (8) which are sequentially connected; spray reaction unit (3) intercommunication and be provided with the polymorphic type and spray reagent device, the polymorphic type sprays reagent device and includes that first sprays reagent device (4), and the second sprays reagent device (5), and the third sprays reagent device (6), the polymorphic type sprays reagent device and still the electricity connection and sprays controlling means (7).

2. The apparatus for preparing covalent organic frameworks based on automatic acid-base alternating spraying as claimed in claim 1, characterized in that a first washing and drying device (2) is further included between the apparatus for preparing covalent organic framework materials (1) and the spraying reaction device (3).

3. The device for preparing covalent organic frameworks based on automatic acid-base alternating spraying as claimed in claim 1, characterized in that a partial filtration membrane is arranged in the spraying reaction device (3) for performing partial filtration of the etching solution containing the solid phase during the reaction.

4. The device for preparing covalent organic frameworks based on automatic acid-base alternating spraying as claimed in claim 1, wherein a pH sensor is further arranged inside the spraying reaction device (3) for real-time acquisition of the pH value of the etching reactant inside the device, and the value is used for feedback calculation and control of the spraying amount inside the spraying reaction device (3).

5. The apparatus for the preparation of covalent organic frameworks based on automatic acid-base alternating spraying according to claim 1, characterized in that it further comprises a first waste treatment collection tank (9) and a second waste treatment collection tank (10) in communication with said spraying reaction device (3).

6. The apparatus for preparing covalent organic frameworks based on automatic acid-base alternating spraying as claimed in claim 1, wherein stirrers are provided in the apparatus for preparing covalent organic framework material (1) and the spray reaction apparatus (3).

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