CN111233202A - Device and method for removing heavy metal ions in photovoltaic waste liquid in multistage selectivity mode - Google Patents
Device and method for removing heavy metal ions in photovoltaic waste liquid in multistage selectivity mode Download PDFInfo
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Abstract
The invention relates to a device and a method for removing heavy metal ions in photovoltaic waste liquid in a multistage selective manner, wherein the device adopts a metal adsorption mechanism arranged in multiple stages to selectively adsorb and remove the heavy metal ions in dialysate and cleaning liquid. Meanwhile, as the heavy metal is selectively adsorbed, the removal rate of the heavy metal is up to more than 90%, and the pH value of the wastewater is adjusted step by step, so that the treated wastewater can reach the discharge standard, and the sewage treatment cost of enterprises is greatly reduced.
Description
Technical Field
The invention relates to the technical field of environmental protection treatment, in particular to the technical field of waste liquid recovery treatment, and in particular relates to a device for performing multistage selective removal on heavy metal ions in silicon wool making wastewater.
Background
The wet black silicon technology adopts noble metal particles of gold, silver and the like randomly attached to the surface of a silicon wafer as a cathode, silicon as an anode, a micro electrochemical reaction channel is formed on the surface of the silicon simultaneously, and a silicon substrate is quickly etched below the metal particles to form a nano structure. KOH and HNO are also used for polishing, digging holes, desilvering and reaming in the production process3、H2O2Chemical solvents such as ammonia water and hydrofluoric acid, therefore, waste acid solution containing a large amount of silver ions and other heavy metal ions such as zinc, iron, manganese, copper, nickel, chromium, cadmium and the like is generated in the wet black silicon technology. The content of silver ions is the largest, and is about 98800ppb, the content of nitric acid is about 30% -35%, the content of hydrofluoric acid is 3% -4%, and the content of fluosilicic acid is 4% -5%, and if the silver ions are directly treated as hazardous waste, the method undoubtedly causes great resource waste. Therefore, the recycling of nitric acid, hydrofluoric acid and silver metal ions is required in consideration of the maximum utilization of resources.
The best technology for recovering the nitric acid and the hydrofluoric acid in the waste mixed acid is diffusion dialysis, and the method has the advantages that the recovery rate of the nitric acid and the hydrofluoric acid is high and can reach 80-90%, the recovery device is small in occupied area, simple to operate and almost free of energy consumption, but the method has the defect that dialysate with the same volume is generated, and the dialysate contains about 90% of metal ions and about 10-20% of acid in the stock solution. The dialyzate cannot be directly discharged due to its large metal ion content and small pH, and must be treated before being discharged to a factory, or else it causes environmental pollution, and the loss of noble metals contained in the dialyzate also causes economic loss.
Therefore, how to treat the waste acid solution containing the noble metal silver ions and other heavy metal ions is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a device for removing heavy metal ions in photovoltaic waste liquid in a multistage selective manner, which is simple in overall structure, can realize the collection of different metal ions step by step, improves the resource recovery and utilization rate, improves the environmental friendliness and can reduce the production and processing cost.
Furthermore, the invention also provides a method for removing heavy metal ions in photovoltaic waste liquid in a multistage selective manner, which combines the characteristics of dialyzate, realizes adsorption and separation of gold and silver, iron, zinc, copper, manganese and lead, chromium, nickel and cadmium different metal ions while gradually adjusting and improving the pH value, and improves the resource recovery rate.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a device for removing heavy metal ions in photovoltaic waste liquid in a multistage selective manner, which is used for treating dialyzate after diffusion dialysis treatment of the waste liquid generated by wet black silicon.
For the above technical solution, the applicant has further optimization measures.
Further, the first metal adsorption mechanism, the second metal adsorption mechanism and the third metal adsorption mechanism are basically the same in structure, wherein each metal adsorption mechanism comprises a buffer tank, a conveying pump and a resin adsorption column respectively, the buffer tanks are used for storing wastewater and adjusting the pH value of the wastewater, one ends of liquid inlet of the conveying pumps are connected with the buffer tanks, one ends of liquid outlet of the conveying pumps are connected with the lower portions of the resin adsorption columns, and the upper portions of the resin adsorption columns are communicated into the next-stage mechanism.
Furthermore, the resin adsorption column in the first metal adsorption mechanism is a sulfhydryl chelate resin adsorption column or a carboxymethyl chitosan thiourea resin adsorption column, the resin adsorption column in the second metal adsorption mechanism is an iminodiacetic acid chelate resin adsorption column, and the resin adsorption column in the third metal adsorption mechanism is an amine chelate resin.
Further, the device is provided with first elution mechanism, second elution mechanism and third elution mechanism respectively corresponding to every metal adsorption mechanism, first elution mechanism, second elution mechanism and third elution mechanism's structure is the same basically, and wherein, every elution mechanism includes that high pressure sweeps gas circuit, eluant storage tank and recovery tank, the import that the gas circuit was swept to high pressure is located the top of resin adsorption column, the export of eluant storage tank links to each other with the eluant import on the resin adsorption column, the bottom of resin adsorption column is provided with the eluant export, the eluant export with the recovery tank passes through the pipeline and links to each other.
Furthermore, the buffer tanks in the first metal adsorption mechanism, the second metal adsorption mechanism and the third metal adsorption mechanism are all reaction kettles with jackets and electric stirring types.
Furthermore, a coagulating sedimentation tank is arranged at the rear end of the third metal adsorption mechanism, the wastewater treated by the third metal adsorption mechanism is discharged into the coagulating sedimentation tank, and the coagulating sedimentation tank is used for removing aluminum ions in the wastewater after a coagulating sedimentation agent is added into the coagulating sedimentation tank.
Particularly, the invention also provides a method for removing heavy metal ions in photovoltaic waste liquid in a multistage selective manner, which is used for treating dialyzate obtained after diffusion dialysis treatment of waste liquid generated by wet black silicon, and the treatment steps comprise:
conveying the dialyzate to a first buffer tank for pH adjustment, controlling the pH value to 2-4, conveying the dialyzate in the first buffer tank from the lower part of a first resin adsorption column through a first conveying pump, conveying the dialyzate subjected to adsorption treatment from the upper part of the first resin adsorption column, and flowing into a second buffer tank of the next stage;
sending the liquid flowing out of the first resin adsorption column to a second buffer tank for pH adjustment, controlling the pH value to 5-6, sending the dialysate in the second buffer tank from the lower part of the second resin adsorption column through a second conveying pump, and sending the dialysate subjected to adsorption treatment from the upper part of the second resin adsorption column into a third buffer tank of the next stage;
and (3) delivering the liquid flowing out of the second resin adsorption column to a third buffer tank for pH adjustment, controlling the pH value to 6-7, delivering the dialysate in the third buffer tank from the lower part of the third resin adsorption column through a third delivery pump, and delivering the dialysate subjected to adsorption treatment from the upper part of the third resin adsorption column.
And further, liquid flowing out of the upper part of the third resin adsorption column enters a coagulating sedimentation tank, the pH value of the liquid in the coagulating sedimentation tank is adjusted to 7-8, a coagulating sedimentation agent is added, stirring, sedimentation and filtration are carried out, and the supernatant in the coagulating sedimentation tank is treated after reaching the standard.
Further, the first buffer tank, the second buffer tank and the third buffer tank are all heatable stirring type reaction kettles with jackets, and the liquid temperature of the reaction kettles is controlled to be 15-20 ℃.
Further, when any one of the first resin adsorption column, the second resin adsorption column and the third resin adsorption column reaches adsorption saturation, dilute nitric acid or dilute hydrochloric acid is used as an eluent for the saturated resin adsorption column, and metal ions adsorbed on the surface of the resin are eluted and recovered.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the device for removing the heavy metal ions in the photovoltaic waste liquid in a multistage mode selectively adopts the metal adsorption mechanisms arranged in the multistage mode to selectively adsorb and remove the heavy metal ions in the dialyzate and the cleaning liquid, different metal ions are respectively removed through the resin adsorption columns of different types arranged in the metal adsorption mechanisms of each stage in a directional adsorption mode, after adsorption saturation, the resin surface for adsorption is eluted through the elution liquid, and the metal ions are recovered, so that metal recycling is achieved, and particularly, elements such as gold and silver and the like are recovered.
Furthermore, because the effect of removing aluminum ions by resin adsorption is not ideal, the coagulating sedimentation tank is adopted in the device to add the coagulating sedimentation agent into the dialyzate to remove the aluminum ions, so that the metal ions in the dialyzate are removed to the maximum extent, and the dialyzate can reach the discharge standard or be discharged to field service for recycling.
In addition, the method for removing the heavy metal ions in the photovoltaic waste liquid in a multistage selective manner utilizes different acting forces between different metals and resin functional groups to enable different resin adsorption columns to selectively adsorb the heavy metal ions, so that the heavy metal is separated, and the method plays a vital role in subsequently recovering metals, particularly precious metals such as gold and silver. Meanwhile, as the heavy metal is selectively adsorbed, the removal rate of the heavy metal is up to more than 90%, and the pH value of the wastewater is adjusted step by step, so that the treated wastewater can reach the discharge standard, and the sewage treatment cost of enterprises is greatly reduced. Therefore, the popularization of the method can ensure higher economic benefit and environmental benefit.
Drawings
Some specific embodiments of the invention will be described in detail hereinafter, by way of illustration and not limitation, with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
fig. 1 is a schematic overall structure diagram of a device for multi-stage selective removal of heavy metal ions from photovoltaic waste liquid according to an embodiment of the present invention.
Wherein the reference numerals are as follows:
1. the device comprises a first buffer tank, 2, a first delivery pump, 3, a first resin adsorption column, 4, a second buffer tank, 5, a first delivery pump, 6, a second resin adsorption column, 7, a third buffer tank, 8, a third delivery pump, 9, a third resin adsorption column, 10, a coagulating sedimentation tank, 11, a medicine storage tank, 12, an output water pump, 13, a first recovery tank, 14, a second recovery tank, 15, a third recovery tank, 16, a first eluent storage tank, 17, a first elution pump, 18, a second eluent storage tank, 19 and a second elution pump.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first", "second", "third" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance, such as the first, second and third heating tubes, in order to be able to describe the product structure more clearly, without limiting its importance.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The adsorption resin refers to a high molecular polymer, and can be used for removing organic matters in wastewater, decoloring sugar liquor, separating and refining natural products and biochemical products and the like. The adsorption resin has a plurality of varieties, and the change of the monomer and the change of the functional group on the monomer can endow the resin with various special properties. High molecular weight polymers such as polystyrene resins and polyacrylate resins are commonly used. The adsorption resin is a resin adsorbent which has the characteristic of adsorption and has a porous three-dimensional structure. It is a new porous resin developed in the field of polymer in recent years, and is made up by using monomers of styrene and divinylbenzene, etc. and adopting suspension copolymerization process in the presence of organic solvent of toluene, etc. The resin adsorption column in the present application is constituted by carrying a specific adsorption resin in a columnar container.
Example 1:
this embodiment has described a device of heavy metal ion among photovoltaic waste liquid is got rid of to multistage selectivity for the dislysate after the diffusion dialysis treatment is handled to the produced waste liquid of wet process black silicon, including multistage first metal adsorption mechanism, second metal adsorption mechanism and the third metal adsorption mechanism of establishing ties, pass through respectively first metal adsorption mechanism, second metal adsorption mechanism and third metal adsorption mechanism carry out the absorption of different metal ions and get rid of, be provided with the resin adsorption column that is used for the selective adsorption of corresponding metal ion in first metal adsorption mechanism, second metal adsorption mechanism and the third metal adsorption mechanism respectively.
As shown in fig. 1, the first metal adsorption mechanism, the second metal adsorption mechanism and the third metal adsorption mechanism have substantially the same structure, wherein the first metal adsorption mechanism respectively comprises a first buffer tank 1, a first delivery pump 2 and a first resin adsorption column 3, the first buffer tank 1 is used for storing wastewater and adjusting the pH value therein, a liquid inlet end of the first delivery pump 2 is connected with the first buffer tank 1, a liquid outlet end of the first delivery pump 2 is connected with the lower part of the first resin adsorption column 3, and the upper part of the first resin adsorption column 3 is introduced into a next-stage mechanism, that is, a second buffer tank 4 of the second metal adsorption mechanism.
That is to say, the second metal adsorption mechanism includes second buffer tank 4, second delivery pump 5 and second resin adsorption column 6 respectively, and second buffer tank 4 receives the waste water that comes out from first resin adsorption column 3 and adjusts pH value wherein, the feed liquor one end of second delivery pump 5 is connected second buffer tank 4, the play liquid one end of second delivery pump 5 with the lower part of second resin adsorption column 6 links to each other, the upper portion of second resin adsorption column 6 lets in next stage mechanism, namely goes in third buffer tank 7 of third metal adsorption mechanism. Third metal adsorption mechanism includes third buffer tank 7, third delivery pump 8 and third resin adsorption column 9 respectively, and third buffer tank 7 receives the waste water that comes out from second resin adsorption column 6 and adjusts pH value wherein, the feed liquor one end of third delivery pump 8 is connected third buffer tank 7, the play liquid one end of third delivery pump 8 with the lower part of third resin adsorption column 9 links to each other, the upper portion of third resin adsorption column 9 lets in next level mechanism district and handles, for example discharges or carries out other processings.
In order to ensure the temperature of the dialysate during treatment and complete reaction, buffer tanks in the first metal adsorption mechanism, the second metal adsorption mechanism and the third metal adsorption mechanism are reaction kettles with clamping sleeves and electric stirring types, and the heating and stirring of the dialysate can be realized.
Specifically, the resin adsorption column in the first metal adsorption mechanism adopts a mercapto-type chelate resin adsorption column or a carboxymethyl chitosan thiourea resin adsorption column, and the selected mercapto-type chelate resin adsorption column or carboxymethyl chitosan thiourea resin has high selective adsorption performance on gold ions and silver ions, high elution rate (> 90%), good reusability, no obvious reduction in adsorption capacity after 5 times of reuse observed at present, and the two types of resins can effectively separate and recover precious metals from mixed metal wastewater to obtain high purity and recovery rate.
The resin adsorption column in the second metal adsorption mechanism adopts an imino oxalic acid type chelating resin adsorption column, the selected imino oxalic acid type chelating resin is mostly Amberlite IRC-718 type and Lewatit TP-207 type, and the two types of chelating resin show higher adsorption effect on iron ions, zinc ions and manganese ions.
The resin adsorption column in the third metal adsorption mechanism adopts amine chelating resin, such as Dowex M-4195, Purolite S-985, Diaion CR-20 and other types of amine chelating resin can be selected, and copper ions, nickel ions, chromium ions, cadmium ions, lead ions and other ions can be selectively adsorbed.
Because above resin adsorption column is unsatisfactory to the aluminium ion adsorption effect, consequently handle behind most metal ion waste liquid and can carry to coagulating sedimentation jar 10 through above-mentioned step the rear end of third metal adsorption mechanism sets up coagulating sedimentation jar 10, the upper end liquid outlet of third resin adsorption column 9 with coagulating sedimentation jar 10 links to each other, waste water after the third metal adsorption mechanism handles is discharged into in coagulating sedimentation jar 10, coagulating sedimentation jar 10 is used for getting rid of the aluminium ion in the waste water after adding coagulating sedimentation agent. Adding coagulating precipitant to remove Al ions directionally. Stirring for 15-30 minutes, precipitating for 30-60 minutes, taking the supernatant, analyzing, determining the content of each component, discharging the supernatant after reaching the standard or performing centralized treatment in factories, taking out the precipitate at the lower part, evaporating, drying and performing centralized treatment.
In order to effectively elute metal ions in the metal adsorption mechanism, the device is provided with a first elution mechanism, a second elution mechanism and a third elution mechanism corresponding to the first metal adsorption mechanism, the second metal adsorption mechanism and the third metal adsorption mechanism respectively, the structures of the first elution mechanism, the second elution mechanism and the third elution mechanism are basically the same, wherein each elution mechanism comprises a high-pressure purging gas circuit, an eluent storage tank 16 and 18 and a recovery tank 13 and 14, an inlet of the high-pressure purging gas circuit is positioned at the top end of the resin adsorption column, outlets of the eluent storage tanks 16 and 18 are connected with eluent inlets on the corresponding resin adsorption column respectively, an eluent outlet is arranged at the bottom end of the resin adsorption column, and the eluent outlet is connected with the corresponding recovery tanks 13 and 14 through pipelines.
Example 2:
the invention also provides a method for removing heavy metal ions in photovoltaic waste liquid in a multistage selective manner, which is based on the device in example 1 and is used for treating dialyzate obtained by performing diffusion dialysis on waste liquid generated by wet black silicon, wherein the treatment steps comprise:
the dialysis fluid is conveyed to a first buffer tank 1 for pH adjustment, the first buffer tank 1 is a heatable stirring type reaction kettle with a clamping sleeve, the temperature of the solution in the reaction kettle is adjusted to be 15-20 ℃, a sample is taken from a sample port below the first buffer tank 1, the concentration of H & lt + & gt is measured, the amount of alkali liquor such as NaOH or KOH which needs to be added is calculated, the pH is adjusted to be about 2-4, if the pH is larger than the range, dilute nitric acid can be added for adjustment, and the adsorption rate of the first resin adsorption column 3 is higher under the pH value. Then the dialysate in the first buffer tank 1 is fed from the lower part of the first resin adsorption column 3 through the first delivery pump 2, and the dialysate after adsorption treatment is fed from the upper part of the first resin adsorption column 3 and flows into the second buffer tank 4 of the next stage. The first resin adsorption column 3 is a resin type for selectively adsorbing gold and silver ions, such as a mercapto chelate resin adsorption column and carboxymethyl chitosan thiourea resin;
and (2) sending the liquid flowing out of the first resin adsorption column 3 to a second buffer tank 4 for pH adjustment, wherein the second buffer tank 4 is a heatable stirring reaction kettle with a clamping sleeve, the temperature of the solution in the reaction kettle is adjusted to be 15-20 ℃, a sampling opening below the second buffer tank 4 is used for sampling, the H + concentration is measured, the amount of alkali liquor such as NaOH or KOH required to be added is calculated, the pH value is adjusted to be about 2-4, if the pH value is larger than the range, dilute nitric acid can be added for adjustment, and the adsorption rate of the first resin adsorption column 3 is higher at the pH value. Then the dialysate in the second buffer tank 4 is fed from the lower part of the second resin adsorption column 6 through the second delivery pump 5, and the dialysate after adsorption treatment is fed from the upper part of the second resin adsorption column 6 and flows into the third buffer tank 7 of the next stage. The second resin adsorption column 6 is a resin type for selectively adsorbing metal ions such as iron, zinc, copper, manganese and the like, and can select iminodiacetic acid chelating resin, such as Amberlite IRC-718 type and Lewatit TP-207 type which are applied more;
and (2) sending the liquid flowing out of the second resin adsorption column 6 to a third buffer tank 7 for pH adjustment, wherein the third buffer tank 7 is a heatable stirring reaction kettle with a clamping sleeve, the temperature of the solution in the reaction kettle is adjusted to be 15-20 ℃, a sampling port below the third buffer tank 7 is used for sampling, the concentration of H & lt + & gt is measured, the amount of alkali liquor such as NaOH or KOH required to be added is calculated, the pH is adjusted to be about 2-4, if the pH is larger than the range, dilute nitric acid can be added for adjustment, and the adsorption rate of the first resin adsorption column 3 is higher at the pH value. Then the dialysate in the third buffer tank 7 is fed from the lower part of the third resin adsorption column 9 through the third delivery pump 8, and the dialysate after adsorption treatment is fed from the upper part of the third resin adsorption column 9. The third resin adsorption column 9 is of resin type for selectively adsorbing copper ion, nickel ion, chromium ion, cadmium ion, and lead ion, and can be amine chelating resin such as Dowex M-4195, Purolite S-985, Diaion CR-20.
And (2) allowing the liquid flowing out of the upper part of the third resin adsorption column 9 to enter a coagulating sedimentation tank 10, adjusting the temperature of the solution in the coagulating sedimentation tank 10 to be 15-20 ℃, sampling at a sampling port at the upper part to measure the content of each component, adjusting the pH to be 7-8, adding a coagulating sedimentation agent such as polyaluminium chloride, polyaluminium sulfate, polyaluminium phosphate, polyferric sulfate, polyferric chloride, polyferric phosphate, polyferric iron and anionic polymeric silicic acid into the coagulating sedimentation tank 10 through a medicine storage tank 11, stirring, filtering and precipitating, taking supernatant to measure the content of each component, and discharging or serving to a factory through an output water pump 12 after the supernatant reaches the standard.
In addition, the contents of the components are measured by sampling at the outlets above the first, second and third resin adsorption columns 9 at regular intervals, and if the contents of the components in the effluent water are found to be increased, the adsorption is saturated and elution is needed. When any one of the first resin adsorption column 3, the second resin adsorption column 6 and the third resin adsorption column 9 reaches adsorption saturation, dilute nitric acid or dilute hydrochloric acid is used as an eluent for the saturated resin adsorption column, and metal ions adsorbed on the surface of the resin are eluted and recovered.
Take the example that the first resin adsorption column 3 needs to be eluted. During elution, compressed air is firstly blown in from the upper part of the first resin adsorption column 3, the remaining liquid is blown out from the lower part, the remaining liquid is conveyed to the first buffer tank 1 connected with the first resin adsorption column 3, and then diluted nitric acid is used for elution. Here, the eluent of the first resin adsorption column 3 is diluted nitric acid, and hydrochloric acid is not used, because if diluted hydrochloric acid is used, silver chloride precipitation is generated by reaction with silver ions and is easily adhered to resin particles, when the second resin adsorption column 6 or the third resin adsorption column 9 is eluted, the diluted nitric acid and the diluted hydrochloric acid can be used for elution, and in order to save cost, the same eluent storage tank can be used for the second resin adsorption column 6 or the third resin adsorption column 9. Therefore, in the present embodiment, the eluent of the first resin adsorption column 3 is supplied from the first eluent storage tank 16 through the first elution pump 17, and the eluents of the second resin adsorption column 6 and the third resin adsorption column 9 are supplied from the second eluent storage tank 18 through the second elution pump 19.
When the first resin adsorption column 3 is eluted, the eluent enters from the upper part of the first resin adsorption column 3 and flows out of the first resin adsorption column 3 from the lower part, the flow is adjusted in a proper range in the process, the outflow eluent is collected in the first recovery tank 13, relatively, the outflow eluent enters the second recovery tank 14 when the second resin adsorption column 6 is eluted, and the outflow eluent enters the third recovery tank 15 when the third resin adsorption column 9 is eluted. The first recovery tank 13 contains silver ions and gold ions with relatively high concentrations, and can directionally carry out subsequent treatment to recover gold and silver simple substances, and by analogy, the second recovery tank 14 contains metal ions with relatively high concentrations such as iron, zinc, copper, manganese and the like, and the second recovery tank 14 contains copper ions, nickel ions, chromium ions, cadmium ions, lead ions and the like with relatively high concentrations.
And after the elution is finished, blowing the residual eluent in the resin adsorption column to a corresponding recovery tank by using compressed air for 3-5 minutes, and then performing the resin adsorption process of the next period.
Namely, the adsorption, blowing, elution, blowing and adsorption processes are circularly carried out, so that the effects of recovering different types of metal ions, particularly gold and silver ions and removing other ions are achieved, the treated water metal ions reach the national first-level sewage discharge standard, and the operation is convenient.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. The utility model provides a device of heavy metal ion among photovoltaic waste liquid is got rid of to multistage selectivity for the dislysate after the produced waste liquid of wet process black silicon is handled through diffusion dialysis, its characterized in that, the device includes first metal adsorption mechanism, second metal adsorption mechanism and the third metal adsorption mechanism of multistage series connection, passes through respectively first metal adsorption mechanism, second metal adsorption mechanism and third metal adsorption mechanism carry out the absorption of different metal ions and get rid of, be provided with the resin adsorption column that is used for the selective adsorption of corresponding metal ion in first metal adsorption mechanism, second metal adsorption mechanism and the third metal adsorption mechanism respectively.
2. The device of claim 1, wherein the first metal adsorption mechanism, the second metal adsorption mechanism and the third metal adsorption mechanism are substantially the same in structure, wherein each metal adsorption mechanism comprises a buffer tank, a delivery pump and a resin adsorption column, the buffer tank is used for storing wastewater and adjusting the pH value of the wastewater, the liquid inlet end of the delivery pump is connected with the buffer tank, the liquid outlet end of the delivery pump is connected with the lower part of the resin adsorption column, and the upper part of the resin adsorption column is communicated with the next-stage mechanism.
3. The device according to claim 2, wherein the resin adsorption column in the first metal adsorption mechanism is a mercapto chelate resin adsorption column or a carboxymethyl chitosan thiourea resin adsorption column, the resin adsorption column in the second metal adsorption mechanism is an iminodiacetic acid chelate resin adsorption column, and the resin adsorption column in the third metal adsorption mechanism is an amine chelate resin.
4. The device according to claim 2 or 3, wherein a first elution mechanism, a second elution mechanism and a third elution mechanism are respectively arranged corresponding to each metal adsorption mechanism, the structures of the first elution mechanism, the second elution mechanism and the third elution mechanism are basically the same, each elution mechanism comprises a high-pressure purging gas circuit, an eluent storage tank and a recovery tank, an inlet of the high-pressure purging gas circuit is located at the top end of the resin adsorption column, an outlet of the eluent storage tank is connected with an eluent inlet on the resin adsorption column, an eluent outlet is arranged at the bottom end of the resin adsorption column, and the eluent outlet is connected with the recovery tank through a pipeline.
5. The apparatus according to claim 2 or 3, wherein the buffer tanks of the first metal adsorption mechanism, the second metal adsorption mechanism and the third metal adsorption mechanism are all jacketed reaction kettles with electric stirrers.
6. The device as claimed in claim 1, wherein a coagulating sedimentation tank is arranged at the rear end of the third metal adsorption mechanism, the wastewater treated by the third metal adsorption mechanism is discharged into the coagulating sedimentation tank, and the coagulating sedimentation tank is used for removing aluminum ions in the wastewater after a coagulating sedimentation agent is added.
7. A method for removing heavy metal ions in photovoltaic waste liquid in a multistage selective manner is used for treating dialyzate obtained after diffusion dialysis treatment of waste liquid generated by wet black silicon, and is characterized by comprising the following treatment steps:
conveying the dialyzate to a first buffer tank for pH adjustment, controlling the pH value to 2-4, conveying the dialyzate in the first buffer tank from the lower part of a first resin adsorption column through a first conveying pump, conveying the dialyzate subjected to adsorption treatment from the upper part of the first resin adsorption column, and flowing into a second buffer tank of the next stage;
sending the liquid flowing out of the first resin adsorption column to a second buffer tank for pH adjustment, controlling the pH value to 5-6, sending the dialysate in the second buffer tank from the lower part of the second resin adsorption column through a second conveying pump, and sending the dialysate subjected to adsorption treatment from the upper part of the second resin adsorption column into a third buffer tank of the next stage;
and (3) delivering the liquid flowing out of the second resin adsorption column to a third buffer tank for pH adjustment, controlling the pH value to 6-7, delivering the dialysate in the third buffer tank from the lower part of the third resin adsorption column through a third delivery pump, and delivering the dialysate subjected to adsorption treatment from the upper part of the third resin adsorption column.
8. The method according to claim 7, wherein the liquid flowing out of the upper part of the third resin adsorption column enters a coagulating sedimentation tank, the pH value of the liquid in the coagulating sedimentation tank is adjusted to 7-8, a coagulating sedimentation agent is added, then stirring, sedimentation and filtration are carried out, and the liquid is treated after the supernatant in the coagulating sedimentation tank reaches the standard.
9. The method according to claim 7, wherein the first buffer tank, the second buffer tank and the third buffer tank are all heatable stirrable reaction kettles with jackets, and the liquid temperature of the reaction kettles is controlled to be 15-20 ℃.
10. The method according to any one of claims 7 to 9, wherein when any one of the first resin adsorption column, the second resin adsorption column and the third resin adsorption column reaches adsorption saturation, dilute nitric acid or dilute hydrochloric acid is used as an eluent for the saturated resin adsorption column, and metal ions adsorbed on the surface of the resin are eluted and recovered.
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| CN202010119857.0A CN111233202A (en) | 2020-02-26 | 2020-02-26 | Device and method for removing heavy metal ions in photovoltaic waste liquid in multistage selectivity mode |
| PCT/CN2020/135178 WO2021169482A1 (en) | 2020-02-26 | 2020-12-10 | Device and method for multistage selective removal of heavy metal ions in photovoltaic waste liquid |
| PCT/CN2020/135218 WO2021169483A1 (en) | 2020-02-26 | 2020-12-10 | Device and method for removing heavy metal ions in photovoltaic waste liquid |
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| WO2021169483A1 (en) * | 2020-02-26 | 2021-09-02 | 苏州晶洲装备科技有限公司 | Device and method for removing heavy metal ions in photovoltaic waste liquid |
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