Silver-containing electroplating wastewater recovery device and recovery method thereof

Abstract

The invention relates to a silver-containing electroplating wastewater recovery device and a recovery method thereof, and belongs to the technical field of silver-containing electroplating wastewater recovery. The silver-containing electroplating wastewater recovery device comprises a filter box and a recovery box, the filter box is communicated with a wastewater input pipe, and the filter box is communicated with a drainage pipe; a filter screen group and an activated carbon screen group are sequentially arranged in the filter box along the wastewater inlet direction; a clamping groove and a bearing net plate matched with the clamping groove are arranged in the recycling box, and a plurality of evenly-distributed hole channels are formed in the bearing net plate. The bearing net plate is detachably connected with the recycling box; and the load-bearing net plate is loaded with adsorption filler. The recovery equipment disclosed by the invention has the characteristics of simple structure and good application stability, and can effectively adsorb silver ions by virtue of strong interaction generated when the silver-containing wastewater flows through the adsorption medium, so that the separation and recovery of metals are realized, the risk of secondary pollution is remarkably reduced, the treatment speed is increased, the treatment cost is reduced, and the economic benefit is increased. And the method has good applicability and high practicability.

Description

Technical Field

[0001] The invention belongs to the technical field of silver-containing electroplating wastewater recovery, and relates to a silver-containing electroplating wastewater recovery device and a recovery method thereof. Background Art

[0002] As a precious metal resource, silver has excellent physical and chemical properties and is widely used in electronics, electroplating, photosensitive materials, chemicals and other industries. At the same time, silver also belongs to the category of highly toxic heavy metal pollutants. Wastewater containing silver ions has significant cytotoxicity. If it is discharged directly without proper treatment, it will not only seriously harm the ecological environment, but also cause resources to be wasted. Therefore, recovering precious metal silver from industrial wastewater is crucial to protecting the ecological environment, promoting resource recycling and reuse, and reducing economic costs.

[0003] At present, the technology for treating silver-containing wastewater generally faces problems such as high energy consumption, low recovery efficiency, unclear purification effect and easy to cause secondary pollution, making it difficult to achieve efficient recycling of resources. Recovering silver through electrolytic reduction has strict requirements on equipment and high operating costs.

[0004] In recent years, as a representative material of silicon-based mesoporous materials, silicon dioxide is a material with excellent adsorption performance. Its orderly pore structure, single and controllable pore size distribution, and diverse mesoporous shapes make it extremely important in the fields of adsorption separation, industrial catalysis, biomedicine, environmental protection, etc.

[0005] Covalent organic frameworks (COFs), as an emerging crystalline porous material composed of lightweight organic units connected by covalent bonds, have become a research frontier in the field of chemistry. Two-dimensional Schiff base COFs are particularly considered to be nearly ideal adsorption materials due to their good stability, high-density one-dimensional columnar channels, easy modification and adjustment, and easy stripping and processing. Summary of the invention

[0006] The purpose of the present invention is to provide a silver-containing electroplating wastewater recovery device and a recovery method thereof. The recovery equipment disclosed in the present invention has the characteristics of simple structure and good stability in use. It can effectively adsorb silver ions by virtue of the strong interaction generated when the silver-containing wastewater flows through the adsorption medium, thereby realizing the separation and recovery of metals, significantly reducing the risk of secondary pollution, improving the processing speed, reducing the processing cost, having good applicability and strong practicality.

[0007] The purpose of the present invention can be achieved through the following technical solutions: A silver-containing electroplating wastewater recovery device comprises a filter box and a recovery box, wherein the recovery box is connected to the filter box, a wastewater input pipe is connected to the filter box, and a drain pipe is connected to the filter box; a filter net group and an activated carbon net group are sequentially arranged in the filter box along the wastewater inlet direction.

[0008] As a preferred technical solution of the present invention, the filter screen group includes a plurality of filter screens connected in sequence, and a plurality of through holes are formed on the filter screens.

[0009] As a preferred technical solution of the present invention, the through holes on two adjacent filter screens are arranged in a staggered structure.

[0010] As a preferred technical solution of the present invention, the activated carbon net group includes a plurality of activated carbon nets connected in sequence.

[0011] As a preferred technical solution of the present invention, a card slot and a load-bearing mesh plate matched with the card slot are provided on the inner wall of the recycling box, and the load-bearing mesh plate is provided with a plurality of evenly distributed holes; the load-bearing mesh plate and the recycling box are detachably connected; the load-bearing mesh plate is loaded with adsorption filler; the thickness of the adsorption filler is 50 mm.

[0012] As a preferred technical solution of the present invention, the preparation method of the adsorption filler comprises the following steps: Step 1, placing silicon dioxide in anhydrous ethanol, mixing and then ultrasonically treating, adding a silane coupling agent after preheating and stirring at a constant temperature, filtering and taking out a solid, washing with ethanol, and vacuum drying to constant weight to obtain prefabricated silicon dioxide; Step 2: After prefabricated silica, anhydrous ethanol and unsaturated monomers are stirred and mixed, an initiator is added, the mixture is heated and stirred, centrifuged, washed with ethanol, and vacuum dried to constant weight to obtain an intermediate compound; Step 3: ultrasonically mix the intermediate compound, anhydrous ethanol and dimethyl sulfoxide, add benzidine monomer and stir at room temperature, filter out the solid, and vacuum dry to constant weight to obtain the product.

[0013] As a preferred technical solution of the present invention, in step one, the ultrasonic treatment is ultrasonic treatment at a power of 300-400W for 30-40min; the preheating is heating to 40°C; the constant temperature stirring is stirring at a temperature of 45-50°C for 8-9h; the number of cleanings is three times; the temperature of the vacuum drying is 80°C; the mass ratio of the silicon dioxide, anhydrous ethanol and silane coupling agent is 10-12:30-40:4-5; and the silane coupling agent is vinyl triethoxysilane.

[0014] As a preferred technical solution of the present invention, in step 2, the stirring and mixing is stirring at a speed of 300-400r / min for 20-30min; the heating stirring is stirring at a temperature of 62-70°C for 6-8h; the number of cleanings is four times; the temperature of the vacuum drying is 80°C; the mass ratio of the prefabricated silica, anhydrous ethanol, unsaturated monomer and initiator is 13-15:40-50:2.4-2.8:0.06-0.07; the unsaturated monomer is 3-(3,4-dihydroxyphenyl)acrolein; and the initiator is a free radical initiator.

[0015] As a preferred technical solution of the present invention, in step three, the ultrasonic mixing is performed at a power of 150-200W for 8-10 minutes; the stirring is performed at a speed of 400-500r / min for 8-10 hours; the vacuum drying temperature is 70°C; the mass ratio of the intermediate compound, anhydrous ethanol, dimethyl sulfoxide and benzidine monomer is 15-16:24-30:30-40:2.7-3.0; and the benzidine monomer is 3,3'-dimercaptobenzidine.

[0016] The invention discloses a recovery method using the above-mentioned silver-containing electroplating wastewater recovery device.

[0017] Beneficial effects of the present invention: (1) The recovery equipment disclosed in the present invention has the characteristics of simple structure and good stability in operation. It can effectively adsorb silver ions by virtue of the strong interaction generated when silver-containing wastewater flows through the adsorption medium, thereby realizing the separation and recovery of metals, significantly reducing the risk of secondary pollution, improving the processing speed, reducing the processing cost, having good applicability and strong practicality.

[0018] (2) The materials used in this preparation method have a simple preparation process and controllable costs. They do not require a harsh high-temperature and high-pressure reaction environment and are easy to implement. The materials have excellent performance and a stable structure. They are effective in removing silver ions. Their adsorption capacity exceeds that of traditional adsorption materials. After a simple desorption process, they can be recycled many times. DETAILED DESCRIPTION

[0019] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0020] A silver-containing electroplating wastewater recovery device comprises a filter box and a recovery box, the recovery box is connected to the filter box, a wastewater input pipe is connected to the filter box, and a drain pipe is connected to the filter box; a filter mesh group and an activated carbon mesh group are arranged in sequence along the wastewater inlet direction in the filter box, the filter mesh group comprises a plurality of filter meshes connected in sequence, a plurality of through holes are opened on the filter mesh, and the through holes on two adjacent filter meshes are arranged in a staggered structure; the activated carbon mesh group comprises a plurality of activated carbon meshes connected in sequence; The inner wall of the recycling box is provided with a card slot and a load-bearing mesh plate adapted to the card slot, and the load-bearing mesh plate is provided with a plurality of evenly distributed holes; the load-bearing mesh plate and the recycling box are detachably connected; the load-bearing mesh plate is loaded with adsorption filler; the thickness of the adsorption filler is 50mm. Example 1

[0021] The preparation method of the adsorption filler comprises the following steps: Step 1, placing silicon dioxide in anhydrous ethanol and mixing it, then performing ultrasonic treatment, adding a silane coupling agent after preheating and stirring at a constant temperature, filtering and taking out the solid, washing it with ethanol, and vacuum drying it to constant weight to obtain prefabricated silicon dioxide; the ultrasonic treatment is ultrasonic treatment at a power of 300 W for 30 minutes; the preheating is heating to 40° C.; the constant temperature stirring is stirring at a temperature of 45° C. for 8 hours; the number of washing is three times; the temperature of the vacuum drying is 80° C.; the mass ratio of the silicon dioxide, anhydrous ethanol and the silane coupling agent is 10:30:4; the silane coupling agent is vinyl triethoxysilane; Step 2: After prefabricated silica, anhydrous ethanol and unsaturated monomers are stirred and mixed, an initiator is added, the mixture is heated and stirred, centrifuged, washed with ethanol, and vacuum dried to constant weight to obtain an intermediate compound; the stirring and mixing is stirring at a speed of 300 r / min for 20 minutes; the heating and stirring is stirring at a temperature of 62° C. for 6 hours; the washing is performed four times; the vacuum drying temperature is 80° C.; the mass ratio of the prefabricated silica, anhydrous ethanol, unsaturated monomer and initiator is 13:40:2.4:0.06; the unsaturated monomer is 3-(3,4-dihydroxyphenyl)acrolein; the initiator is initiator AIBN; Step 3: ultrasonically mix the intermediate compound, anhydrous ethanol and dimethyl sulfoxide, add benzidine monomer and stir at room temperature, filter out the solid, and vacuum dry to constant weight to obtain the product; the ultrasonic mixing is performed at a power of 150 W for 8 minutes; the stirring is performed at a speed of 400 r / min for 8 hours; the vacuum drying temperature is 70°C; the mass ratio of the intermediate compound, anhydrous ethanol, dimethyl sulfoxide and benzidine monomer is 15:24:30:2.7; the benzidine monomer is 3,3'-dimercaptobenzidine. Example 2

[0022] The preparation method of the adsorption filler comprises the following steps: Step 1, placing silicon dioxide in anhydrous ethanol and mixing it, then performing ultrasonic treatment, adding a silane coupling agent after preheating and stirring at a constant temperature, filtering and taking the solid, washing it with ethanol, and vacuum drying it to constant weight to obtain prefabricated silicon dioxide; the ultrasonic treatment is ultrasonic treatment at a power of 350W for 35 minutes; the preheating is heating to 40°C; the constant temperature stirring is stirring at a temperature of 48°C for 8.5 hours; the number of washing is three times; the temperature of the vacuum drying is 80°C; the mass ratio of the silicon dioxide, anhydrous ethanol and the silane coupling agent is 11:35:4.5; the silane coupling agent is vinyl triethoxysilane; Step 2: After prefabricated silica, anhydrous ethanol and unsaturated monomers are stirred and mixed, an initiator is added, the mixture is heated and stirred, centrifuged, washed with ethanol, and vacuum dried to constant weight to obtain an intermediate compound; the stirring and mixing is stirring at a speed of 350r / min for 25min; the heating and stirring is stirring at a temperature of 65°C for 7h; the washing is performed four times; the vacuum drying temperature is 80°C; the mass ratio of the prefabricated silica, anhydrous ethanol, unsaturated monomer and initiator is 14:45:2.6:0.065; the unsaturated monomer is 3-(3,4-dihydroxyphenyl)acrolein; the initiator is initiator AIBN; Step 3: ultrasonically mix the intermediate compound, anhydrous ethanol and dimethyl sulfoxide, add benzidine monomer and stir at room temperature, filter out the solid, and vacuum dry to constant weight to obtain the product; the ultrasonic mixing is performed at a power of 175 W for 9 minutes; the stirring is performed at a speed of 450 r / min for 9 hours; the vacuum drying temperature is 70°C; the mass ratio of the intermediate compound, anhydrous ethanol, dimethyl sulfoxide and benzidine monomer is 15.5:27:35:2.8; the benzidine monomer is 3,3'-dimercaptobenzidine. Example 3

[0023] The preparation method of the adsorption filler comprises the following steps: Step 1, placing silicon dioxide in anhydrous ethanol and mixing it, then performing ultrasonic treatment, adding a silane coupling agent after preheating and stirring at a constant temperature, filtering and taking out the solid, washing it with ethanol, and vacuum drying it to constant weight to obtain prefabricated silicon dioxide; the ultrasonic treatment is ultrasonic treatment at a power of 400 W for 40 minutes; the preheating is heating to 40° C.; the constant temperature stirring is stirring at a temperature of 50° C. for 9 hours; the number of washing is three times; the temperature of the vacuum drying is 80° C.; the mass ratio of the silicon dioxide, anhydrous ethanol and the silane coupling agent is 12:40:5; the silane coupling agent is vinyl triethoxysilane; Step 2: After prefabricated silica, anhydrous ethanol and unsaturated monomers are stirred and mixed, an initiator is added, the mixture is heated and stirred, centrifuged, washed with ethanol, and vacuum dried to constant weight to obtain an intermediate compound; the stirring and mixing is stirring at a speed of 400 r / min for 30 minutes; the heating and stirring is stirring at a temperature of 70°C for 8 hours; the washing is performed four times; the vacuum drying temperature is 80°C; the mass ratio of the prefabricated silica, anhydrous ethanol, unsaturated monomer and initiator is 15:50:2.8:0.07; the unsaturated monomer is 3-(3,4-dihydroxyphenyl)acrolein; the initiator is initiator AIBN; Step 3: ultrasonically mix the intermediate compound, anhydrous ethanol and dimethyl sulfoxide, add benzidine monomer and stir at room temperature, filter out the solid, and vacuum dry to constant weight to obtain; the ultrasonic mixing is ultrasonic at 200 W power for 10 minutes; the stirring is stirring at 500 r / min speed for 10 hours; the vacuum drying temperature is 70°C; the mass ratio of the intermediate compound, anhydrous ethanol, dimethyl sulfoxide and benzidine monomer is 16:30:40:3.0; the benzidine monomer is 3,3'-dimercaptobenzidine.

[0024] Comparative Example 1 Compared with Example 3, the difference between Comparative Example 1 is that no silane coupling agent is used in step 1 of Comparative Example 1, and the other components, preparation steps and parameters are the same.

[0025] Comparative Example 2 Compared with Example 3, the difference of Comparative Example 2 is that the unsaturated monomer of Comparative Example 2 is B-phenylacrolein, and the other components, preparation steps and parameters are the same.

[0026] Comparative Example 3 Compared with Example 3, the difference of Comparative Example 3 is that the benzidine monomer of Comparative Example 3 is benzidine, and the other components, preparation steps and parameters are the same.

[0027] Comparative Example 4 Compared with Example 3, Comparative Example 4 is different in that step 3 of Comparative Example 4 does not use benzidine monomer, and the remaining components, preparation steps and parameters are the same.

[0028] The adsorption fillers prepared in Examples 1-3 and Comparative Examples 1-4 were tested for the following properties, and the test results are shown in Table 1.

[0029] Adsorption test: Weigh 10 mg of adsorption filler into 7 50 mL centrifuge tubes, add 10 mL of silver ion solution (500 ppm), and place the centrifuge tubes in a constant temperature oscillator at 25 ° C for 24 hours. After the adsorption is completed, filter the solution, measure the concentration with an atomic absorption spectrometer, and calculate the adsorption rate; Adsorption rate (%) = (C0-C1) / C0×100%; C0: solution concentration before adsorption, ppm; C1: solution concentration after adsorption, ppm; Table 1 Adsorption rate (%) Example 1 92.7 Example 2 92.8 Example 3 93.1 Comparative Example 1 74.8 Comparative Example 2 81.4 Comparative Example 3 78.8 Comparative Example 4 63.6 From the test results in Table 1, it can be seen that compared with Comparative Examples 1-4, the adsorption fillers prepared in Examples 1-3 of the present invention have excellent adsorption capacity for silver ions.

[0030] Through comparative analysis, it can be seen that this is because the present invention modifies silica by using a silane coupling agent, so that the surface of the silica is changed from hydrophilic to hydrophobic, and an unprotected carbon-carbon double bond is introduced. The introduction of hydrophobicity and carbon-carbon double bonds significantly promotes the grafting of unsaturated monomers. The catechol group of the unsaturated monomer has an excellent adsorption effect on silver ions. Then, the aldehyde group of the unsaturated monomer is used to form a covalent bond with the amino group of the benzidine monomer, and multiple thiol groups, Schiff base structures and biphenyl structures are introduced, which further significantly improves the adsorption effect on silver ions.

[0031] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any indirect modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A silver-containing electroplating wastewater recovery device, characterized in that: It includes a filter box and a recovery box, the recovery box is connected to the filter box, the filter box is connected to a wastewater input pipe, and the filter box is connected to a drain pipe; a filter net group and an activated carbon net group are arranged in sequence in the filter box along the wastewater inlet direction.

2. A silver-containing electroplating wastewater recovery device according to claim 1, characterized in that: The filter screen group includes a plurality of filter screens connected in sequence, and a plurality of through holes are formed on the filter screens.

3. A silver-containing electroplating wastewater recovery device according to claim 2, characterized in that: The through holes on two adjacent filter screens are arranged in a staggered structure.

4. A silver-containing electroplating wastewater recovery device according to claim 1, characterized in that: The activated carbon net group includes a plurality of activated carbon nets connected in sequence.

5. The silver-containing electroplating wastewater recovery device according to claim 1, characterized in that: The inner wall of the recycling box is provided with a card slot and a load-bearing mesh plate matched with the card slot, and the load-bearing mesh plate is provided with a plurality of evenly distributed holes; the load-bearing mesh plate and the recycling box are detachably connected; the load-bearing mesh plate is loaded with adsorption filler; the thickness of the adsorption filler is 50mm.

6. A silver-containing electroplating wastewater recovery device according to claim 5, characterized in that: The preparation method of the adsorption filler comprises the following steps: Step 1, placing silicon dioxide in anhydrous ethanol, mixing and then ultrasonically treating, adding a silane coupling agent after preheating and stirring at a constant temperature, filtering and taking out a solid, washing with ethanol, and vacuum drying to constant weight to obtain prefabricated silicon dioxide; Step 2: After prefabricated silica, anhydrous ethanol and unsaturated monomers are stirred and mixed, an initiator is added, the mixture is heated and stirred, centrifuged, washed with ethanol, and vacuum dried to constant weight to obtain an intermediate compound; Step 3: ultrasonically mix the intermediate compound, anhydrous ethanol and dimethyl sulfoxide, add benzidine monomer and stir at room temperature, filter out the solid, and vacuum dry to constant weight to obtain the product.

7. A silver-containing electroplating wastewater recovery device according to claim 6, characterized in that: In step one, the ultrasonic treatment is performed at a power of 300-400W for 30-40 minutes; the preheating is performed to raise the temperature to 40°C; the constant temperature stirring is performed at a temperature of 45-50°C for 8-9 hours; the number of cleanings is three times; the vacuum drying temperature is 80°C; the mass ratio of the silicon dioxide, anhydrous ethanol and silane coupling agent is 10-12:30-40:4-5; and the silane coupling agent is vinyl triethoxysilane.

8. The silver-containing electroplating wastewater recovery device according to claim 6, characterized in that: In step 2, the stirring and mixing is stirring at a speed of 300-400 r / min for 20-30 minutes; the heating stirring is stirring at a temperature of 62-70°C for 6-8 hours; the number of cleanings is four times; the temperature of the vacuum drying is 80°C; the mass ratio of the prefabricated silica, anhydrous ethanol, unsaturated monomer and initiator is 13-15:40-50:2.4-2.8:0.06-0.07; and the unsaturated monomer is 3-(3,4-dihydroxyphenyl)acrolein.

9. The silver-containing electroplating wastewater recovery device according to claim 6, characterized in that: In step three, the ultrasonic mixing is performed at a power of 150-200W for 8-10 minutes; the stirring is performed at a speed of 400-500r / min for 8-10 hours; the vacuum drying temperature is 70°C; the mass ratio of the intermediate compound, anhydrous ethanol, dimethyl sulfoxide and benzidine monomer is 15-16:24-30:30-40:2.7-3.0; and the benzidine monomer is 3,3'-dimercaptobenzidine.

10. A recycling method using the silver-containing electroplating wastewater recycling device as described in any one of claims 1 to 9.