Transfer and enrichment device and determination method for heavy metals in battery wastewater

Abstract

A transfer and enrichment device and determination method for heavy metals in battery wastewater, relating to the technical field of detection of heavy metals in battery wastewater. The device comprises an exchange column section A (1), an exchange column section B (2) is connected to the lower portion of the exchange column section A (1) by means of a connecting member (3), an outlet of the exchange column section B (2) is connected to an inlet of a storage tank (5), and the exchange column section A (1) and the exchange column section B (2) can be disassembled; an outlet of the storage tank (5) is connected to an inlet of the exchange column section A (1), and a pump (4) is provided on a connecting pipe between the outlet of the storage tank (5) and the inlet of the exchange column section A (1); the interior of the exchange column section A (1) is filled with an adsorption-type resin; and the interior of the exchange column section B (2) is filled with a gel-type ion exchange resin. The device is coupled with multiple functional materials, insoluble heavy metals in battery wastewater are adsorbed by virtue of the adsorption-type resin, and soluble heavy metals in the battery wastewater are selectively exchanged by virtue of the gel-type resin, achieving complete transfer of non-ionic heavy metals and ionic heavy metals; and by means of multiple cycles, efficient enrichment of heavy metals in wastewater is achieved.

Description

A device and method for the transfer and enrichment of heavy metals in battery wastewater

[0001] Cross-references to related applications

[0002] This application claims priority to Chinese Patent Application No. 202411033982.4, filed on July 30, 2024, entitled "A device and method for the transfer and enrichment of heavy metals in battery wastewater", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application belongs to the field of heavy metal detection technology in battery wastewater, specifically relating to a device for the transfer and enrichment of heavy metals in battery wastewater and a method for their determination. Background Technology

[0004] With the rapid development of the electronics and communications and new energy vehicle industries, the demand for batteries has increased accordingly. The manufacturing and improper disposal of calomel batteries, lead-acid batteries, nickel-cadmium batteries, and zinc-carbon batteries generate wastewater containing heavy metals such as mercury, lead, nickel, cadmium, and zinc, which is difficult to degrade and highly toxic, posing a serious threat to the ecological environment and human health.

[0005] Efficient and accurate determination of heavy metal content is crucial and serves as the data basis for the rational design of water treatment processes.

[0006] Commonly used detection methods include atomic absorption spectrometry (AAS) and inductively coupled plasma mass spectrometry (ICP). These instruments are precise, expensive, highly sensitive, and suitable for detecting low / small concentrations. However, battery wastewater has a complex and diverse composition, which can easily interfere with detection results and damage instrument components. The content of various heavy metals varies widely, requiring separate working curves to be plotted and the water sample to be diluted by different factors before measurement, which can easily amplify experimental errors. The solid content is high, and heavy metals are present in the solids. If separation and filtration are performed, only the content of soluble heavy metals can be measured. Acidification and digestion are required to determine the content of heavy metals, but this process is complex and carries certain operational hazards. Summary of the Invention

[0007] In order to overcome the shortcomings of the prior art, the purpose of this application is to provide a device and method for the transfer and enrichment of heavy metals in battery wastewater. The method is simple and efficient, and the test results are stable and reliable, which can solve the technical problems of the complex methods in the existing methods.

[0008] To achieve the above objectives, this application adopts the following technical solution:

[0009] This application provides a device for the transfer and enrichment of heavy metals in battery wastewater, including an exchange column A section, an exchange column B section connected to the lower part of the exchange column A section via a connector, the exchange column A section and the exchange column B section are detachable; the outlet of the exchange column B section is connected to the inlet of a storage tank, the outlet of the storage tank is connected to the inlet of the exchange column A section, and a pump is installed on the connecting pipe between the outlet of the storage tank and the inlet of the exchange column A section.

[0010] The interior of section A of the exchange column is filled with adsorption resin; the interior of section B of the exchange column is filled with gel-type ion exchange resin.

[0011] In specific implementation, the exchange column A section includes a detachable component and an exchange column A section housing; the detachable component is movably connected to the top of the exchange column A section housing.

[0012] In the specific implementation process, a first gasket is provided on the top of the connector, a first filter baffle is built into the top of the connector, and a second gasket is provided on the bottom of the connector.

[0013] In specific implementation, the exchange column B section includes an exchange column B section shell and a second filter baffle; the second filter baffle is disposed inside the exchange column B section shell.

[0014] In specific implementation, the adsorption resin is a macroporous adsorption resin; the gel-type ion exchange resin is one or more of the following: resin containing methyl mercaptan functional groups, resin containing iminodiacetic acid functional groups, and resin containing type I quaternary ammonium functional groups.

[0015] This application also provides a method for determining heavy metals in battery wastewater, comprising the following steps:

[0016] S1: Take an adsorption-type resin and fill it into section A of the exchange column, and take a gel-type ion exchange resin and fill it into section B of the exchange column;

[0017] S2: Take battery wastewater and adjust the pH value with acid. Then, the battery wastewater is transferred through the A section and B section of the exchange column at a set flow rate. The mixture is cycled multiple times to enrich the adsorption resin and gel ion exchange resin to be tested.

[0018] S3: After mixing the adsorption resin and the gel ion exchange resin to be tested, remove the water, compress the mixture into tablets, and obtain mixed resin tablets.

[0019] S4: Select a mixed standard solution of the metals corresponding to each heavy metal in the battery wastewater, repeat S1 to S3, prepare a standard pellet, analyze the standard pellet, and plot the standard working curve according to the X-ray fluorescence spectrometer operation method.

[0020] S5: Under the same conditions as the standard tablet analysis in S4, determine the fluorescence intensity of the mixed resin tablet, and calculate the content of each heavy metal in the battery wastewater by combining the standard working curve.

[0021] In the specific implementation process, in S1, the adsorption type resin and the gel type ion exchange resin are used in excess relative to the battery wastewater;

[0022] For every 1L of battery wastewater, use no less than 30g of adsorption resin and no less than 90g of gel-type ion exchange resin.

[0023] In the specific implementation process, in step S2, the pH value ranges from 2 to 4, the set flow rate is 1 to 3 mL / min, and the number of cycles is not less than two.

[0024] In step S3, the process of removing moisture from the mixed resin is as follows:

[0025] Centrifuge at 1800–2200 r / min for 5 min, then dry at 100–105 °C for 3 h.

[0026] In the specific implementation process, in S4, the metals corresponding to each heavy metal in the battery wastewater are one or more of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic; the concentration of the mixed standard solution is 0 mg / L to 10.00 mg / L; the vertical axis of the standard working curve is fluorescence intensity, and the horizontal axis of the standard working curve is the content of each heavy metal element.

[0027] In the specific implementation process, the formula used in S5 to calculate the content of each heavy metal in the battery wastewater is as follows:

[0028] Among them, Q i The content of each heavy metal i in battery wastewater is expressed in mg / L; q i m1 represents the content of each heavy metal i in the mixed resin tablets determined by X-ray fluorescence spectrometry, in ppm; m2 represents the mass of the adsorption resin, in g; m3 represents the mass of the mixed resin used for tableting, in g; and V represents the volume of battery wastewater, in L.

[0029] Compared with the prior art, this application has the following beneficial effects:

[0030] This application provides a device for the transfer and enrichment of heavy metals in battery wastewater, coupled with multiple functional materials. It utilizes adsorption resins to adsorb insoluble heavy metals from the wastewater and gel-type resins to selectively exchange soluble heavy metals, achieving complete transfer of both non-ionic and ionic heavy metals. The transfer and enrichment of heavy metals in battery wastewater are achieved through multiple cycles of two-stage exchange columns (Section A and Section B) filled with different types of resins. Battery wastewater flows first through the adsorption section and then through the exchange section, ensuring that the exchange process is not blocked by large molecules or particles, thus increasing the exchange capacity. The gel-type ion exchange resin in the exchange section selectively exchanges soluble heavy metal ions in the wastewater; this resin has high exchange capacity and selectivity, efficiently enriching heavy metal ions in the wastewater. Furthermore, the two-stage design of the exchange columns (Section A and Section B) makes the device more flexible and easier to operate. Both exchange columns can be disassembled separately, facilitating separate filling, material removal, and cleaning operations, reducing maintenance costs and time. The connectors ensure a stable connection between exchange columns A and B, guaranteeing smooth flow of wastewater between the two columns. A storage tank stores the treated wastewater, while a pump provides the power to circulate the wastewater within the unit. Together, the tank and pump form a circulation system, achieving efficient enrichment of heavy metals in the wastewater through multiple cycles.

[0031] Furthermore, the adsorption resin is a macroporous adsorption resin. Macroporous adsorption resins have a large pore size and specific surface area, resulting in a three-dimensional pore structure inside. This helps to increase the contact area between the resin and the substances in the solution, thereby improving adsorption efficiency and adsorption capacity. Due to the advantages of macroporous structure and specific surface area, macroporous adsorption resins can adsorb more target substances and exhibit high selectivity for specific substances.

[0032] Furthermore, gel-type ion exchange resins contain specific functional groups that can undergo exchange or adsorption reactions with specific ions or molecules, achieving selective separation and enrichment. Among these, the methylthiol functional group exhibits highly selective reactivity with heavy metal ions such as mercury, platinum, and palladium. For example, the methylthiol functional group undergoes a complexation reaction with mercury ions to form a stable complex, thereby removing mercury ions. The iminodiacetic acid functional group has a strong adsorption capacity for heavy metal ions such as nickel, cobalt, and lead. For instance, the iminodiacetic acid functional group undergoes a chelation reaction with nickel ions to form a stable chelate, thereby removing nickel ions. Type I quaternary ammonium functional groups have a strong affinity for monovalent anions such as arsenates and arsenites. For example, the type I quaternary ammonium functional group undergoes an ion exchange reaction with arsenates, adsorbing the arsenates onto the resin, thereby removing arsenic.

[0033] This application also provides a method for determining heavy metals in battery wastewater. First, a combination of adsorption resin and gel-type ion exchange resin is used, respectively filling different sections of an exchange column. This effectively adsorbs and enriches heavy metals in the wastewater, including both non-ionic and ionic forms. The sequential passage of heavy metals through the adsorption resin and gel-type ion exchange resin provides effective adsorption and exchange for different types of heavy metals, improving the adaptability of the detection. The enriched resin is then mixed, dehydrated, and compressed into a pellet form that is easy to analyze. Subsequently, by comparing the results with mixed standard solutions corresponding to each heavy metal, a standard working curve is plotted according to the X-ray fluorescence spectrometer operation method, enabling accurate calculation of the heavy metal content in battery wastewater. This method, through the preparation of mixed standard solutions and the plotting of standard working curves, can simultaneously detect multiple heavy metal elements (such as mercury, platinum, palladium, nickel, cobalt, lead, arsenic, etc.) in battery wastewater without the need for separate working curve plotting and dilution by different factors, thus improving detection efficiency, reducing experimental errors, and enhancing detection accuracy. Furthermore, by combining the measured heavy metal content in the tablets, as well as parameters such as the mass of the resin and the volume of battery wastewater, the content of each heavy metal in the battery wastewater can be accurately calculated.

[0034] Furthermore, adjusting the pH value of the battery wastewater with acid not only creates a reaction environment for the exchange section composed of gel-type ion exchange resin, but also ionizes heavy metals, facilitating adsorption by the adsorption section composed of adsorption-type resin. The wastewater passes through the exchange column at a set flow rate, undergoing multiple cycles of enrichment to ensure that heavy metals are fully captured. Attached Figure Description

[0035] Figure 1 is a schematic diagram of the device for transferring and enriching heavy metals in battery wastewater according to this application;

[0036] Figure 2 is a schematic diagram of the structure of the exchange column A section and the exchange column B section in the heavy metal transfer and enrichment device in the battery wastewater of this application.

[0037] Figure 3 is a flowchart of the method for determining heavy metals in battery wastewater according to this application.

[0038] Wherein: 1-Exchange column A section; 2-Exchange column B section; 3-Connector; 4-Pump; 5-Storage tank; 6-First gasket; 7-Second gasket; 8-First filter baffle; 9-Second filter baffle; 10-Removable part; 11-Exchange column A section housing; 12-Exchange column B section housing. Detailed Implementation

[0039] In the following description, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments can be modified in various ways without departing from the spirit or scope of this application. Therefore, the drawings and description are considered to be exemplary in nature and not restrictive.

[0040] In the description of this application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc., indicating the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, are only for the convenience of describing this application and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this application.

[0041] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this application, "a plurality of" means two or more, unless otherwise explicitly specified.

[0042] In this application, unless otherwise expressly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a communication connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.

[0043] In this application, unless otherwise expressly specified and limited, "above" or "below" the second feature can include direct contact between the first and second features, or contact between the first and second features through another feature between them. Furthermore, "above," "over," and "on top" of the second feature includes the first feature being directly above or diagonally above the second feature, or simply indicates that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature includes the first feature being directly above or diagonally above the second feature, or simply indicates that the first feature is at a lower horizontal level than the second feature.

[0044] It should be understood that, when used in this specification and the appended claims, the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0045] It should also be understood that the terminology used in this application specification is for the purpose of describing particular embodiments only and is not intended to limit the application. As used in this application specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms unless the context clearly indicates otherwise.

[0046] It should also be further understood that the term “and / or” as used in this application specification and the appended claims means any combination of one or more of the associated listed items and all possible combinations, and includes such combinations.

[0047] The accompanying drawings illustrate various structural schematics according to embodiments disclosed in this application. These drawings are not to scale, and some details have been enlarged for clarity, and some details may have been omitted. The shapes of the various regions and layers shown in the drawings, as well as their relative sizes and positional relationships, are merely exemplary and may deviate from reality due to manufacturing tolerances or technical limitations. Furthermore, those skilled in the art can design regions / layers with different shapes, sizes, and relative positions as needed.

[0048] The embodiments of this application will now be described in detail with reference to the accompanying drawings.

[0049] As shown in Figure 1, this application provides a device for the transfer and enrichment of heavy metals in battery wastewater. The core of the device consists of two sequentially arranged exchange columns with different functions: an adsorption section (exchange column A section 1) and an ion exchange section (exchange column B section 2). The adsorption section is filled with adsorption-type resin, whose main function is to adsorb large particles and macromolecules in the battery wastewater, thereby transferring insoluble heavy metals. The ion exchange section is filled with gel-type ion exchange resin, which has high selectivity and can specifically target soluble heavy metals in the battery wastewater for ion exchange. Exchange column A section 1 and exchange column B section 2 are detachable and tightly connected by a connector 3. After preliminary purification in the adsorption section, the battery wastewater enters the ion exchange section for the enrichment and separation of heavy metals. Finally, the treated battery wastewater enters a storage tank 5 and is then pumped back into the adsorption and ion exchange sections by a pump 4, forming a cyclic treatment process to achieve efficient transfer and enrichment of heavy metals in the battery wastewater.

[0050] Specifically, the heavy metal transfer and enrichment device in the battery wastewater includes an exchange column A section 1, an exchange column B section 2, a connector 3, a pump 4, and a storage tank 5, as well as adsorption resin and gel-type ion exchange resin.

[0051] The lower part of exchange column A section 1 is connected to exchange column B section 2 via connector 3. The outlet of exchange column B section 2 is connected to the inlet of storage tank 5, and the outlet of storage tank 5 is connected to the inlet of exchange column A section 1. Additionally, pump 4 is installed on the connecting pipe between the outlet of storage tank 5 and the inlet of exchange column A section 1. Adsorption-type resin fills the interior of exchange column A section 1, and gel-type ion exchange resin fills the interior of exchange column B section 2.

[0052] As shown in Figure 2, in one embodiment, the A section 1 of the exchange column includes a detachable component 10 and an A section housing 11, and the B section 2 of the exchange column includes an B section housing 12 and a second filter baffle 9. The detachable component 10 is movably connected to the top of the A section housing 11, and the second filter baffle 9 is disposed inside the B section housing 12 and located at the bottom of the B section housing 12.

[0053] In one embodiment, a first gasket 6 is provided on the top of the connector 3, a first filter baffle 8 is built into the top of the connector 3, and a second gasket 7 is provided on the bottom of the connector 3.

[0054] In addition, the connector 3 is connected to the exchange column A section 1 and the exchange column B section 2 via threads. Specifically, the top of the connector 3 is provided with a first thread, which is connected to the thread at the bottom of the exchange column A section housing 11; the bottom of the connector 3 is provided with a second thread, which is connected to the thread at the top of the exchange column B section housing 12.

[0055] In one embodiment, the adsorption resin is a macroporous adsorption resin. The gel-type ion exchange resin is one or more of the following: resins containing methyl mercaptan functional groups, resins containing iminodiacetic acid functional groups, and resins containing type I quaternary ammonium functional groups.

[0056] As shown in Figure 3, another aspect of this application provides a method for determining heavy metals in battery wastewater, comprising the following steps:

[0057] S1: Take adsorption resin and fill section A1 of the exchange column, and take gel-type ion exchange resin and fill section B2 of the exchange column. Among them, the adsorption resin and gel-type ion exchange resin are used in excess relative to the battery wastewater; no less than 30g of adsorption resin and no less than 90g of gel-type ion exchange resin are used per 1L of battery wastewater.

[0058] S2: Collect battery wastewater and adjust the pH value with acid. Then, transfer the battery wastewater sequentially through section A1 and section B2 of the exchange column at a set flow rate. Repeat the cycle multiple times to enrich the wastewater and obtain the adsorption resin and gel ion exchange resin to be tested. The pH value range is 2-4, the set flow rate is 1-3 mL / min, and the number of cycles is no less than two.

[0059] S3: After mixing the adsorbent resin and the gel ion exchange resin to be tested, remove the water, compress the mixture into tablets, and obtain mixed resin tablets. The specific process for removing water from the mixed resin is as follows: the mixed resin is centrifuged at 1800-2200 r / min for 5 min, and then dried at 100-105℃ for 3 h.

[0060] S4: Select a mixed standard solution of metals corresponding to each heavy metal in the battery wastewater. Repeat S1 to S3, and prepare standard pellets according to the X-ray fluorescence spectrometer operation method. Analyze the standard pellets and plot a standard working curve. The metals corresponding to each heavy metal in the battery wastewater are one or more of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic; the concentration of the mixed standard solution is 0 mg / L to 10.00 mg / L; the vertical axis of the standard working curve is fluorescence intensity, and the horizontal axis is the content of each heavy metal element.

[0061] S5: Under the same conditions as the standard tablet analysis in S4, determine the fluorescence intensity of the mixed resin tablet, and calculate the content of each heavy metal in the battery wastewater by combining the standard working curve.

[0062] The formulas used to calculate the content of various heavy metals in battery wastewater are as follows:

[0063] Among them, Q i The content of each heavy metal i in battery wastewater is expressed in mg / L; q i m1 represents the content of each heavy metal i in the mixed resin tablets determined by X-ray fluorescence spectrometry, in ppm; m2 represents the mass of the adsorption resin, in g; m3 represents the mass of the mixed resin used for tableting, in g; and V represents the volume of battery wastewater, in L.

[0064] In the specific implementation process, the heavy metal transfer and enrichment device in battery wastewater includes: exchange column A section 1, exchange column B section 2, connector 3, pump 4, storage tank 5, gaskets, and baffles. Exchange column A section 1 and exchange column B section 2 are connected by connector 3. Specifically, connector 3 and exchange column A section 1 and exchange column B section 2 all have built-in threaded sections, which can be manually tightened to connect them, facilitating the disassembly of exchange column A section 1 and exchange column B section 2.

[0065] The separator includes a first filter separator 8 and a second filter separator 9. The first filter separator 8 is installed inside the connector 3 to ensure the flow of battery wastewater and prevent the leakage of resin particles in the A section 1 of the exchange column; the second filter separator 9 is installed inside the B section 2 of the exchange column to ensure the flow of battery wastewater and prevent the leakage of resin particles in the B section 2 of the exchange column; the detachable part 10 at the top of the A section 1 of the exchange column can be disassembled and reassembled.

[0066] The gasket includes a first gasket 6 and a second gasket 7. The first gasket 6 is provided at the top of the connector 3, and the second gasket 7 is provided at the bottom of the connector 3.

[0067] The installation and use sequence of the above-mentioned heavy metal transfer and enrichment device in battery wastewater is as follows: a perforated partition, i.e., the second filter partition 9, is built into the bottom of the shell 12 of section B of the exchange column, and gel-type ion exchange resin is filled; the top of the shell 12 of section B of the exchange column is threadedly connected to the connector 3 and a second gasket 7 is provided; a perforated partition, i.e., the first filter partition 8, is built into the connector 3, and the shell 11 of section A of the exchange column is connected to the connector 3 and a first gasket 6 is provided; after filling with adsorption resin, a detachable part 10 is installed on the top of the shell 11 of section A of the exchange column.

[0068] In the specific implementation process, the method for determining heavy metals in battery wastewater includes the following steps:

[0069] Step 1: Weigh out a quantitative amount of adsorption resin, m1g, to be filled into section A 1 of the exchange column; weigh out a quantitative amount of gel-type ion exchange resin, m2g, to be filled into section B 2 of the exchange column; use the macroporous adsorption resin to adsorb insoluble heavy metals in the battery wastewater, and use the gel-type ion exchange resin to selectively exchange soluble heavy metals in the battery wastewater, so as to achieve complete transfer of non-ionic heavy metals and ionic heavy metals.

[0070] The second step is to install a device for transferring and enriching heavy metals in battery wastewater.

[0071] Step 3: Measure a quantitative amount of battery wastewater, VL, adjust the pH to 2-4 using nitric acid, and pass it sequentially through section A1 and section B2 of the flow exchange column at a flow rate of 1-3 mL / min. The effluent from section B2 is returned to section A1 of the flow exchange column, and the cycle is repeated multiple times.

[0072] Step 4: Separate section A1 and section B2 of the exchange column, remove the adsorption resin and gel ion exchange resin packed in section A1 and section B2 to obtain the adsorption resin and gel ion exchange resin to be tested. Mix them thoroughly to obtain a mixed resin and remove moisture.

[0073] Step 5: Weigh an appropriate amount of the mixed resin from Step 4, m3g, add boric acid edging and bottom padding, and use a tableting machine to obtain a mixed resin tablet for testing;

[0074] Step 6: Select one or more standard solutions of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic, and prepare a series of mixed standard solutions with concentrations of 0 mg / L, 0.10 mg / L, 0.50 mg / L, 1.00 mg / L, 2.00 mg / L, 5.00 mg / L, and 10.00 mg / L. Repeat steps one through five above to prepare a series of standard pellets. Following the operating procedures of the X-ray fluorescence spectrometer, adjust the working parameters, analyze the standard pellets, and plot a standard working curve with fluorescence intensity as the ordinate and the content of each heavy metal element as the abscissa. Using X-ray fluorescence spectroscopy, simultaneous qualitative and quantitative analysis of multiple heavy metal elements can be achieved.

[0075] Step 7: Under the same conditions and parameters as in Step 6, measure the fluorescence intensity of the mixed resin tablet from Step 5 using an X-ray fluorescence spectrometer. Calculate the content of each heavy metal in the mixed resin tablet based on the standard working curve. i The content of each heavy metal in the battery wastewater, Q, was calculated using formula (1). i .

[0076] Furthermore, in the first step, a macroporous adsorption resin is selected for the adsorption type. For the gel-type ion exchange resin, a mixed gel-type ion exchange resin containing methyl mercaptan functional groups (reacting with mercury, platinum, and palladium), iminodiacetic acid functional groups (reacting with nickel, cobalt, and lead), and type I quaternary ammonium functional groups (reacting with arsenic) is selected. Both the adsorption type resin and the gel-type ion exchange resin need to be used in excess relative to the battery wastewater.

[0077] Optionally, the mass ratio of the resin containing methyl mercaptan functional groups, the resin containing iminodiacetic acid functional groups, and the resin containing type I quaternary ammonium functional groups in the gel-type ion exchange resin is not greater than 1:1:1. The dosage ratio of adsorption resin to battery wastewater is not less than 30 g:1 L, and the dosage ratio of gel-type ion exchange resin to battery wastewater is not less than 90 g:1 L, to ensure that the resin is in excess and sufficient to adsorb and exchange heavy metals in the wastewater.

[0078] Furthermore, the fourth step involves removing moisture, including both external free water and internal equilibrium water. This is done by transferring the resin (adsorption-type and gel-type ion exchange resins) from the exchange column to a filter tube, centrifuging it at 1800–2200 rpm for 5 minutes, then transferring it to an evaporating dish and drying it at 100–105°C for 3 hours. Centrifugation and drying remove external free water and internal equilibrium water from the resin, preventing problems such as loose, easily flaking, and contamination of the instrument chamber caused by damp raw materials.

[0079] Furthermore, the operating conditions for mercury, platinum, palladium, nickel, cobalt, lead, and arsenic in step six shall include at least the following: a spectroscopic crystal LiF200, a detector SC, and a pulse height PHA of 60%-140%.

[0080] The above-mentioned determination method provided in this application can accurately determine the total content of non-ionic and ionic heavy metals in battery wastewater. The method has good reproducibility and is easy to implement and promote.

[0081] Example 1

[0082] Step 1: Using an electronic balance, weigh 30.5034g of D101 styrene-type macroporous adsorption resin to fill section A1 of the exchange column; weigh 30.2189g of methyl mercaptan ion exchange resin (which reacts with mercury, platinum, and palladium), 31.5579g of iminodiacetic acid ion exchange resin (which reacts with nickel, cobalt, and lead), and 31.7088g of type I quaternary ammonium ion exchange resin (which reacts with arsenic), mix them thoroughly, and fill section B2 of the exchange column.

[0083] Step 2: Install the second filter septum 9 at the bottom of the shell 12 of section B of the exchange column and fill it with gel-type ion exchange resin; rotate, tighten and connect the shell 12 of section B of the exchange column and the connector 3 in the direction of the thread; install the first filter septum 8 in the connector 3, rotate, tighten and connect the shell 11 of section A of the exchange column and the connector 3 in the direction of the thread; fill with adsorption resin, rotate, tighten and connect the detachable part 10 on the upper part of the shell 11 of section A of the exchange column in the direction of the thread, and complete the installation of the heavy metal transfer and enrichment device in battery wastewater.

[0084] Step 3: Measure 1.0L of wastewater using a glass graduated cylinder. Adjust the pH of the wastewater to 2-4 using 1mol / L nitric acid (3.5 is optional) to ensure efficient adsorption and exchange. Flow the wastewater through section A of the exchange column 1 at a flow rate of 1-3mL / min (2mL / min is optional) to adsorb insoluble heavy metals in the battery wastewater. Then, flow the wastewater through section B of the exchange column 2 at a flow rate of 1-3mL / min (2mL / min is optional). This section exhibits specific selectivity for mercury, platinum, palladium, nickel, cobalt, lead, and arsenic, especially in acidic environments, where it has a strong binding effect on ionic states. The effluent from section B of the exchange column is refluxed back to section A of the exchange column, and this cycle is repeated three times to extend the reaction time and increase the enrichment level.

[0085] Step 4: Separate section A1 and section B2 of the exchange column, remove the adsorption resin and gel ion exchange resin filled in section A1 and section B2 to obtain the adsorption resin and gel ion exchange resin to be tested. Mix them evenly to obtain a mixed resin, transfer it to a centrifuge adapter filter tube, place it in a centrifuge, set the centrifugation speed to 1800-2200 r / min (selected at 1800 r / min), and the rotation time to 5 min to remove free moisture carried on the outside of the resin particles; transfer the centrifuged resin particles to a glass evaporating dish, set the oven temperature to 100-105℃ (selected at 100℃), and the drying time to 3 h.

[0086] Step 5: Weigh 3g of the mixed resin from Step 4 using an electronic balance, add boric acid edging and bottom padding, and compress the mixture into a tablet using a tablet press to obtain a mixed resin tablet for testing.

[0087] Step 6: Select certified standard solutions of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic at a concentration of 100.00 mg / L. Using a pipette, transfer 0 mL, 1 mL, 2 mL, 5 mL, and 10 mL to 100 mL volumetric flasks, respectively, and dilute to volume to obtain standard solutions of 0 mg / L, 1.00 mg / L, 2.00 mg / L, 5.00 mg / L, and 10.00 mg / L. Using a pipette, transfer 1 mL and 5 mL to 1000 mL volumetric flasks, respectively, and dilute to volume to obtain standard solutions of 0.10 mg / L and 0.50 mg / L. Using a pipette, transfer 1.00 mL of each standard solution to a 100 mL volumetric flask, and dilute to volume to obtain eight mixed standard solutions with concentrations of 0 mg / L, 0.10 mg / L, 0.50 mg / L, 1.00 mg / L, 2.00 mg / L, 5.00 mg / L, and 10.00 mg / L.

[0088] Repeat steps one through five to prepare eight standard pellets. Following the operating procedure of an X-ray fluorescence spectrometer, set the spectrophotometer to LiF200, detector SC, and pulse height PHA 60%–140%. Analyze the eight standard pellets and plot a standard working curve with fluorescence intensity as the ordinate and the content of each heavy metal element as the abscissa.

[0089] Step 7: Following the operation method of the X-ray fluorescence spectrometer, set the spectrophotometer to LiF200, detector SC, and pulse height PHA 60%-140%, and measure the fluorescence intensity of the mixed resin tablet from Step 5. According to the standard working curve, the contents of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic in the mixed resin tablet are 21.38ppm, 3.90ppm, 0.16ppm, 91.63ppm, 30.98ppm, 52.12ppm, and 10.00ppm, respectively. Combined with formula (1), the contents of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic in the battery wastewater are calculated to be 2.63mg / L for mercury, 0.48mg / L for platinum, 0.02mg / L for palladium, 11.27mg / L for nickel, 3.81mg / L for cobalt, 6.41mg / L for lead, and 1.23mg / L for arsenic.

[0090] Example 2

[0091] Step 1: Using an electronic balance, weigh 40.0679g of DA-201 styrene-type macroporous adsorption resin to fill section A1 of the exchange column; weigh 30.2374g of methyl mercaptan ion exchange resin (which reacts with mercury, platinum, and palladium), 40.2188g of iminodiacetic acid ion exchange resin (which reacts with nickel, cobalt, and lead), and 30.4752g of type I quaternary ammonium ion exchange resin (which reacts with arsenic), mix them thoroughly, and fill section B2 of the exchange column.

[0092] Step 2: Install the second filter septum 9 at the bottom of the shell 12 of section B of the exchange column and fill it with gel-type ion exchange resin; rotate, tighten and connect the shell 12 of section B of the exchange column and the connector 3 in the direction of the thread; install the first filter septum 8 in the connector 3, rotate, tighten and connect the shell 11 of section A of the exchange column and the connector 3 in the direction of the thread; fill with adsorption resin, rotate, tighten and connect the detachable part 10 on the upper part of the shell 11 of section A of the exchange column in the direction of the thread, and complete the installation of the heavy metal transfer and enrichment device in battery wastewater.

[0093] Step 3: Measure 1.2L of wastewater using a glass graduated cylinder. Adjust the pH of the wastewater to 3.5 using 1mol / L nitric acid to ensure efficient adsorption and exchange. Flow the wastewater through section A of the exchange column 1 at a flow rate of 1–3 mL / min (2 mL / min is optional) to adsorb insoluble heavy metals from the battery wastewater. Then, flow the wastewater through section B of the exchange column 2 at a flow rate of 1–3 mL / min (2 mL / min is optional). This section exhibits specific selectivity for mercury, platinum, palladium, nickel, cobalt, lead, and arsenic, especially in acidic environments, where it has a strong binding effect on ionic states. The effluent from section B of the exchange column is refluxed back to section A of the exchange column, and this cycle is repeated three times to extend the reaction time and increase the enrichment level.

[0094] Step 4: Separate section A1 and section B2 of the exchange column, remove the adsorption resin and gel ion exchange resin filled in section A1 and section B2 to obtain the adsorption resin and gel ion exchange resin to be tested. Mix them evenly to obtain a mixed resin, transfer it to a centrifuge adapter filter tube, place it in a centrifuge, set the centrifugation speed to 1800-2200 r / min (2000 r / min is optional) and the rotation time to 5 min to remove free moisture carried on the outside of the resin particles; transfer the centrifuged resin particles to a glass evaporating dish, set the oven temperature to 100-105℃ (100℃ is optional) and the drying time to 3 h.

[0095] Step 5: Weigh 4.3965g of the mixed resin from Step 4 using an electronic balance, add boric acid edging and bottom padding, and compress the mixture into a tablet using a tablet press to obtain a mixed resin tablet for testing.

[0096] Step 6: Select certified standard solutions of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic at a concentration of 100.00 mg / L. Using a pipette, transfer 0 mL, 1 mL, 2 mL, 5 mL, and 10 mL to 100 mL volumetric flasks, respectively, and dilute to volume to obtain standard solutions of 0 mg / L, 1.00 mg / L, 2.00 mg / L, 5.00 mg / L, and 10.00 mg / L. Using a pipette, transfer 1 mL and 5 mL to 1000 mL volumetric flasks, respectively, and dilute to volume to obtain standard solutions of 0.10 mg / L and 0.50 mg / L. Using a pipette, transfer 1.00 mL of each standard solution to a 100 mL volumetric flask, and dilute to volume to obtain eight mixed standard solutions with concentrations of 0 mg / L, 0.10 mg / L, 0.50 mg / L, 1.00 mg / L, 2.00 mg / L, 5.00 mg / L, and 10.00 mg / L.

[0097] Repeat steps one through five to prepare eight standard pellets. Following the operating procedure of an X-ray fluorescence spectrometer, set the spectrophotometer to LiF200, detector SC, and pulse height PHA 60%–140%. Analyze the eight standard pellets and plot a standard working curve with fluorescence intensity as the ordinate and the content of each heavy metal element as the abscissa.

[0098] Step 7: Following the operation method of the X-ray fluorescence spectrometer, set the spectrophotometer to LiF200, detector SC, and pulse height PHA 60%-140%, and measure the fluorescence intensity of the mixed resin tablet from Step 5. According to the standard working curve, the contents of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic in the mixed resin tablet are 22.21ppm, 3.91ppm, 0.17ppm, 95.92ppm, 32.43ppm, 54.55ppm, and 10.30ppm, respectively. Combined with formula (1), the contents of mercury, platinum, palladium, nickel, cobalt, lead, and arsenic in the battery wastewater are calculated to be 2.61mg / L for mercury, 0.46mg / L for platinum, 0.02mg / L for palladium, 11.27mg / L for nickel, 3.81mg / L for cobalt, 6.41mg / L for lead, and 1.21mg / L for arsenic.

[0099] Comparing the test results of Example 1 and Example 2, it can be seen that the detection method provided in this application has high reliability and strong repeatability.

[0100] The foregoing has shown and described the basic principles, main features, and advantages of this application. It will be apparent to those skilled in the art that this application is not limited to the details of the exemplary embodiments described above, and that this application can be implemented in other specific forms without departing from the spirit or basic characteristics of this application. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of this application is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within this application. No reference numerals in the claims should be construed as limiting the scope of the claims.

[0101] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can be appropriately combined to form other embodiments that can be understood by those skilled in the art. The above content is only for illustrating the technical concept of this application and should not be used to limit the scope of protection of this application. Any modifications made to the technical solutions based on the technical concept proposed in this application fall within the scope of protection of the claims of this application.

Claims

1. A device for the transfer and enrichment of heavy metals in battery wastewater, characterized by, The exchange column A section (1) is connected with the exchange column B section (2) through the connecting piece (3) below, the exchange column A section (1) and the exchange column B section (2) can be detached; the outlet of the exchange column B section (2) is connected with the inlet of the storage tank (5), the outlet of the storage tank (5) is connected with the inlet of the exchange column A section (1), and the connecting pipeline between the outlet of the storage tank (5) and the inlet of the exchange column A section (1) is provided with the pump (4); The inside of the exchange column A section (1) is filled with adsorption resin, and the inside of the exchange column B section (2) is filled with gel type ion exchange resin.

2. The apparatus for the transfer and enrichment of heavy metals from battery wastewater according to claim 1, characterized in that, The exchange column A section (1) comprises a detachable piece (10) and an exchange column A section shell (11); the detachable piece (10) is movably connected with the top of the exchange column A section shell (11).

3. The apparatus for the removal and concentration of heavy metals from battery wastewater of claim 1, wherein, The top of the connecting piece (3) is provided with the first gasket (6), the first filter partition (8) is built-in in the top of the connecting piece (3), and the bottom of the connecting piece (3) is provided with the second gasket (7).

4. The apparatus for the removal and concentration of heavy metals from battery wastewater of claim 1, wherein, The exchange column B section (2) comprises an exchange column B section shell (12) and a second filter partition (9); the second filter partition (9) is arranged in the inside of the exchange column B section shell (12).

5. The apparatus for the removal and concentration of heavy metals from battery wastewater of claim 1, wherein, The adsorption resin is macroporous adsorption resin, and the gel type ion exchange resin is one or more of resin containing methyl mercaptan functional groups, imino diacetic acid group functional groups and type I quaternary amine functional groups.

6. A method for determining heavy metals in battery wastewater, characterized by, The method comprises the following steps: S1: adsorption resin is filled in the exchange column A section (1), and gel type ion exchange resin is filled in the exchange column B section (2); S2: battery wastewater is taken and the pH value is adjusted by using acid liquid, then the battery wastewater is transferred through the exchange column A section (1) and the exchange column B section (2) in turn at a set flow rate, and the enrichment is carried out for multiple times to obtain the adsorption resin to be tested and the gel type ion exchange resin to be tested; S3: after the adsorption resin to be tested and the gel type ion exchange resin to be tested are mixed, the water is removed, the tablet sample is prepared by pressing, and the mixed resin tablet is obtained; S4: the metal mixed standard solution corresponding to each heavy metal in the battery wastewater is selected, S1 to S3 are repeated, the standard tablet is prepared, the standard tablet is analyzed, a standard working curve is drawn according to the X-ray fluorescence spectrometer operation method; S5: under the same conditions of analyzing the standard tablet in S4, the fluorescence intensity of the mixed resin tablet is measured, and the content of each heavy metal in the battery wastewater is calculated in combination with the standard working curve.

7. The method according to claim 6, wherein In S1, the adsorption resin and the gel type ion exchange resin are used in excess relative to the battery wastewater; Not less than 30g of adsorption resin is used per 1L of battery wastewater, and not less than 90g of gel type ion exchange resin is used per 1L of battery wastewater.

8. The method according to claim 6, wherein In S2, the pH value ranges from 2 to 4, the set flow rate is 1 to 3 mL / min, and the number of cycles is not less than two times. In S3, the process of removing water is as follows: Rotation centrifugation is carried out at a rotation speed of 1800 to 2200 r / min for 5 min, and then drying is carried out at a temperature of 100 to 105 DEG C for 3 h.

9. The method according to claim 6, wherein In the S4, the metal corresponding to each heavy metal in the battery wastewater is one or more of mercury, platinum, palladium, nickel, cobalt, lead and arsenic; the concentration of the mixed standard solution is 0 mg / L-10.00 mg / L; the ordinate of the standard working curve is the fluorescence intensity, and the abscissa of the standard working curve is the content of each heavy metal element.

10. The method according to claim 6, wherein In the S5, the formula used for calculating the content of each heavy metal in the battery wastewater is as follows: wherein Q i is the content of each heavy metal i in the battery wastewater, in mg / L; q i is the content of each heavy metal i in the mixed resin tablet determined by the X-ray fluorescence spectrometer, in ppm; m1 is the mass of the adsorption resin, in g; m2 is the mass of the gel type ion exchange resin, in g; m3 is the mass of the mixed resin for tabletting, in g; and V is the volume of the battery wastewater, in L.

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