Chemical plating waste liquid treatment process and device and application

Abstract

The invention relates to the technical field of wastewater treatment, in particular to a chemical plating waste liquid treatment process and device and application. The treatment method comprises the following steps: sequentially introducing to-be-treated chemical plating waste liquid into the protection filter and the precision filter for filtering treatment, then introducing into the activity reduction storage tank to reduce the activity of the chemical plating waste liquid, sequentially introducing into the ultra-precision filter, the pH regulating tank, the ion exchange resin and the activated carbon adsorption device for treatment, and collecting a discharged product to obtain the chemical plating waste liquid. According to the wastewater treatment process, heavy metal ions and a complexing agent are effectively separated from a waste liquid system on the premise that an overall chemical plating system is not damaged through a multi-step membrane separation technical method, and the recycling effect is achieved while impurities are removed.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and in particular to a chemical plating waste liquid treatment process, a device and an application thereof. Background Art

[0002] With the rapid development of industry, chemical plating, as a surface treatment process that can effectively enhance the surface properties of substrate materials, has been applied in more and more fields. With the development of manufacturing industry and the popularization of chemical plating, a large amount of chemical plating waste liquid is generated. The chemical plating solution contains a large amount of heavy metal ions (such as copper ions, iron ions, nickel ions, and cobalt ions) combined with chelating agents. Direct discharge will cause environmental pollution and waste of resources. Therefore, the treatment of chemical plating waste liquid containing heavy metal ions is the key to industrial wastewater treatment.

[0003] The commonly used treatment method at present is to completely separate heavy metal ions from water so that the wastewater meets the discharge standard. Chemical reagents (such as ferrous sulfate) are mainly used to break the metal complex, and then an alkaline solution is added to precipitate the metal ions. The metal ions are separated from the wastewater by adding flocculants for flocculation, filtration and other processes, and the wastewater meets the discharge standard through a complex process flow. However, such a treatment method has a complex process flow, a high processing cost, and a limited degree of recovery for heavy metals, which is prone to waste of resources. At the same time, the prior art is difficult to achieve resource recycling when treating chemical plating waste liquid, resulting in a large waste of resources.

[0004] Chinese patent CN 110451688 A discloses a method for treating PCB chemical copper plating wastewater. The method removes copper from chemical copper wastewater by the steps of Fenton oxidation precipitation after complex breaking precipitation, so that the copper content in the wastewater is stable and meets the water discharge requirements. However, the invention destroys the chemical copper plating solution system and cannot effectively recover the complexing agent. The copper ion contains more impurities after precipitation, which is a great waste of resources. Chinese patent CN 112479458A discloses a method for treating chemical copper plating wastewater in PCB. The method adds a certain proportion of drugs to treat the chemical copper plating solution by multiple treatment methods such as complex breaking, flocculation, and concentrated crystallization, so as to achieve the technical requirements of recovering copper and complexing agent at the same time. However, the invention also destroys the chemical copper plating solution system and cannot be reused; and the invention is only applicable to the complexing agent EDTA system, which has great limitations.

[0005] In this context, providing a process method for simply and efficiently treating chemical plating waste liquid and realizing resource recycling has become a technical problem to be solved urgently in this field. Summary of the invention

[0006] The purpose of the present invention is to provide a chemical plating waste liquid treatment process to solve the problems of complicated process flow and high treatment cost of existing waste liquid treatment process. On the one hand, the present invention can accurately make heavy metals close to zero emission through membrane separation technology, acid-base neutralization, organic pollutant degradation and other methods, and various emission indicators can reach national emission standards. On the other hand, the treatment process method can be applied to a variety of complexing agent systems, so that heavy metal ions and complexing agents can be recycled at the same time without destroying the overall chemical plating system.

[0007] The first aspect of the present invention provides a chemical plating waste liquid treatment process, the treatment steps comprising: passing the chemical plating waste liquid to be treated into a protective filter and a precision filter in sequence for filtering treatment, then passing it into a deactivation storage tank to reduce the activity of the chemical plating waste liquid, then passing it into an ultra-precision filter, a pH adjustment tank, an ion exchange resin, and an activated carbon adsorption device in sequence for treatment, and collecting and discharging the product.

[0008] 1) Protect filter treatment:

[0009] The wastewater to be treated is filtered through a protective filter for the first step of treatment. The impurities and turbidity in the chemical plating waste liquid can be intercepted and adsorbed by the microporous filter membrane of the protective filter.

[0010] Preferably, the protection filter is provided with a first filter membrane, and the pore size of the first filter membrane is 1-100 μm; more preferably, it is 1-20 μm.

[0011] Preferably, the filter material of the first filter membrane is at least one of cotton core, polypropylene, polytetrafluoroethylene, cellulose acetate, ceramic, activated carbon, polyethersulfone, mixed fiber resin, polyamide, and polyvinylidene fluoride.

[0012] 2) Precision filter treatment:

[0013] The chemical plating waste liquid discharged from the protective filter membrane is subjected to a second layer of filtration treatment. The chemical plating solution is protected by the treatment of the precision filter membrane. Without destroying the complexing agent and metal ion structure in the solution, the complexing system still maintains the macromolecular structure of the substance while further filtering out tiny impurities to obtain the secondary filtered filtrate.

[0014] Preferably, the precision filter is provided with a second filter membrane, and the pore size of the second filter membrane is 1-500nm; more preferably, it is 1-50nm.

[0015] Preferably, the filter material of the second filter membrane is at least one of polypropylene, polytetrafluoroethylene, cellulose acetate, ceramics, and activated carbon.

[0016] 3) Deactivation of storage tank treatment:

[0017] The filtrate treated by the protective filter and the precision filter is passed into the deactivation storage tank, and the deactivation storage tank is connected to an air pump to reduce the activity of the chemical plating solution.

[0018] Preferably, the deactivation storage tank has a built-in cooling device.

[0019] Preferably, the capacity of the deactivation storage tank is 50-500L.

[0020] Preferably, the body material of the deactivation storage tank is at least one of PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), PTFE (polytetrafluoroethylene), FRP (fiber reinforced composite material, also known as fiberglass), acrylic material, and glass.

[0021] 4) Ultra-precision filter treatment:

[0022] The chemical plating waste liquid that has been deactivated enters the third-layer filtration system, and the third filter membrane is set as a nanofiltration membrane to effectively separate the chemical plating system. In this filtration process, the macromolecular structure of the chelating agent and the heavy metal chelating system is intercepted, and the inorganic salts and other small molecular structure substances in the chemical plating solution are discharged. The intercepted macromolecules of the chelating system return to the original plating solution tank for repeated use. This process greatly reduces the discharge of waste liquid. No chemical additives are added to the separation system. The entire filtration process uses physical methods to separate the chelating agent and heavy metal ions from the waste liquid system, achieving the technical effect of emission reduction, reuse and pollution reduction.

[0023] Preferably, the ultra-precision filter is provided with a third filter membrane, and the pore size of the third filter membrane is 0.1-50nm; more preferably, it is 0.2-5nm.

[0024] Preferably, the filter material of the third filter membrane is at least one of a composite nanofiltration membrane or a reverse osmosis membrane.

[0025] The composite nanofiltration membrane can be listed as cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone, polyvinyl alcohol, polyamide, aluminum oxide, titanium oxide, zirconium oxide and other nanofiltration membranes and their composite nanofiltration membranes, polyester composite nanofiltration membranes, polyethersulfone / polyamide composite nanofiltration membranes, polysulfone / polyamide composite nanofiltration membranes, polyimide / polyamide composite nanofiltration membranes, polyetheretherketone / polyamide composite nanofiltration membranes, nanomaterial modified composite nanofiltration membranes, porous support layer / separation layer composite nanofiltration membranes and modified composite nanofiltration membranes.

[0026] Examples of the reverse osmosis membrane include cellulose acetate and its derivatives reverse osmosis membranes, polyamide and its derivatives reverse osmosis membranes, polyethersulfone and its derivatives reverse osmosis membranes, polyhydrazide and its derivatives reverse osmosis membranes, and composite reverse osmosis membranes.

[0027] 5) pH adjustment tank treatment:

[0028] The chemical plating waste liquid from which the complexing agent and heavy metal ions are separated continues to enter the pH adjustment tank, at which time an appropriate amount of pH adjuster is added to adjust the pH of the chemical plating waste liquid to 7-8.

[0029] Preferably, the pH adjuster is at least one of an aqueous solution of sulfuric acid, hydrochloric acid, boric acid, citric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium bicarbonate.

[0030] Preferably, the capacity of the pH adjustment tank is 50-500L.

[0031] Preferably, the body material of the pH adjustment tank is at least one of PVC, PP, PE, PTFE, FRP, acrylic material, and glass.

[0032] 6) Ion exchange resin treatment:

[0033] The chemical plating waste liquid, after the pH is adjusted in the pH adjusting tank, enters the ion exchange resin device. The ion exchange resin filtration device in this step can adsorb the metal ions and complexes that are not completely recycled in the ultra-precision filter, so that the heavy metal ions and complexes are completely separated from the filtrate. After being treated by the ion exchange resin device, most of the impurities in the filtrate can be removed.

[0034] Preferably, the ion exchange resin is selected from strongly acidic cation exchange resins, weakly acidic cation exchange resins, chelating resins, redox resins, novel metal ion exchange resins (copper, palladium, nickel and mixed metals thereof) and composite ion exchange resins thereof.

[0035] Further preferably, the strong acid cation exchange resin is a macroporous strong acid ion exchange resin.

[0036] 7) Activated carbon adsorption device treatment:

[0037] The filtrate after filtration by the ion exchange resin system enters the activated carbon adsorption device in the next step. This filtration system can completely separate the organic impurities in the filtrate to obtain pure filtrate.

[0038] Preferably, the activated carbon adsorption device is provided with an activated carbon adsorption membrane, and the material of the activated carbon adsorption membrane is an activated carbon material, such as one or more of pure activated carbon, modified activated carbon, activated carbon fiber, and modified activated carbon fiber.

[0039] Preferably, the pore size of the activated carbon adsorption membrane is 1-100 nm; more preferably, it is 10-50 nm.

[0040] The core of the wastewater treatment process of the present invention is to effectively separate heavy metal ions and complexing agents without destroying the overall chemical plating system through a multi-step membrane separation technology method, and to achieve a technical method for recycling while removing impurities. The core content of the present invention is to use a filter membrane (including but not limited to a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a composite nanofiltration membrane, and a reverse osmosis membrane) to filter the chemical plating solution, intercept complexes and heavy metals and other macromolecular substances for reuse, and all treatment methods using this principle process are the technical content of the present invention. Further, the wastewater treatment process of the present invention uses membrane separation technology, acid-base neutralization, and activated carbon adsorption treatment to cooperate, and a simple treatment process can achieve zero discharge of heavy metal ions, complexes, and other pollutants; first, the chemical plating solution is filtered through a filter membrane of a specific particle size, and complexes and heavy metals and other macromolecular substances are separated for reuse, and the waste liquid after throttling uses acid-base neutralization, ion exchange, activated carbon adsorption, etc. to remove small molecule contamination impurities. The present invention completely relies on physical means, and can efficiently and thoroughly purify chemical plating waste liquid without the need for external chemical reagents. It has significant technical progress in both filtering effect and practicality. The impurity components of the chemical plating waste liquid treated by the process of the present invention can meet the national emission standards and can be promoted for use.

[0041] Preferably, the chemical plating waste liquid comes from the waste liquid generated by chemical copper plating, chemical nickel plating, chemical gold plating, chemical tin plating, chemical cobalt plating, chemical silver plating, chemical palladium plating, chemical iron plating, chemical zinc plating, chemical plating platinum plating, chemical lead plating, chemical aluminum plating, chemical scandium plating, chemical titanium plating, chemical rhodium plating and various metal alloys.

[0042] Preferably, the chemical plating waste liquid can also be derived from the waste liquid generated by chemical copper plating, which includes a horizontal copper deposition system and a gantry copper deposition system.

[0043] The heavy metal ions that can be separated by the present invention include but are not limited to copper ions, nickel ions, tin ions, gold ions, palladium ions, mercury ions, palladium ions, iron ions, silver ions, cobalt ions, scandium ions, titanium ions, rhodium ions, etc., and one or more of the coordination compounds / complexes containing the above heavy metal ions can be separated.

[0044] Preferably, the heavy metal ions are mainly used to reduce the emission of copper ions, and copper ions include monovalent copper, divalent copper and copper-containing complexes thereof.

[0045] The complexing agent that can be separated by the present invention includes, but is not limited to, a compound containing at least one of an amine group, a carboxyl group, a thiol group, and a hydroxyl group.

[0046] Examples of complexing agents include citric acid, pyrophosphate, EDTA (ethylenediaminetetraacetic acid), lactic acid, tartaric acid and its salts, sodium salicylate, sodium salt of ethylenediaminetetraacetic acid, nitriloacetic acid and its alkali metal salts, gluconic acid, gluconate, triethanolamine, modified ethylenediaminetetraacetic acid, S,S-ethylenediaminedisuccinic acid, glycine, malic acid, malonic acid, succinic acid, succinic acid, glycolic acid, aminoacetic acid, HEDP (hydroxyethylidene diphosphonic acid), ATMP (aminotri (methylene phosphonic acid)), etc.

[0047] The waste liquid treatment process provided by the present invention can be applied to chemical plating wastewater treatment processes in different fields, so as to achieve zero discharge of heavy metal ions and their pollutants, reduce pollution and reduce resource waste, which is of great significance to the development of industrial environmental protection.

[0048] The second aspect of the present invention provides a chemical plating waste liquid treatment device, whose structure includes a protection filter, a precision filter, a deactivation storage tank, an ultra-precision filter, a pH adjustment tank, an ion exchange resin, and an activated carbon adsorption device connected in sequence.

[0049] Preferably, the chemical plating waste liquid treatment device further comprises a high-pressure pump, which is arranged between 1) the deactivation storage tank and the ultra-precision filter; and 2) the pH adjustment tank and the ion exchange resin.

[0050] Preferably, the chemical plating waste liquid treatment device further comprises a lifting pump, and when the treatment device treats the waste liquid, the waste liquid to be treated is transported to the protective filter through the lifting pump.

[0051] The various components of the processing device are tightly connected through pipelines.

[0052] The material of the pipe is not particularly limited as long as it can achieve the transmission purpose, for example, PVC, PP, PE, PTFE, FRP, PVDF (polyvinylidene fluoride), etc. can be used.

[0053] The third aspect of the present invention provides the application of the processing process or processing device as described above, which is specifically applied to the fields of electronics and electrical industry, automobile industry, aerospace industry, medical equipment, powder metallurgy, machinery manufacturing, etc.

[0054] Beneficial effects:

[0055] The present invention provides a chemical plating waste liquid treatment process and application, which has the following advantages:

[0056] (1) The core of the wastewater treatment process of the present invention is to effectively separate heavy metal ions and complexing agents from the waste liquid system through a multi-step membrane separation technology method without destroying the overall chemical plating system, thereby achieving the effect of recycling while removing impurities.

[0057] (2) The present invention first filters the chemical plating solution through a filter membrane with a specific particle size to separate complexes and macromolecular substances such as heavy metals for reuse. The waste liquid after throttling is then subjected to acid-base neutralization, ion exchange, activated carbon adsorption, etc. to remove small molecular contaminants, which can effectively remove heavy metal ions and complexing agents in various chemical plating waste liquids.

[0058] (3) The present invention completely relies on physical means and can efficiently and thoroughly purify chemical plating waste liquid without the need for external chemical reagents; there are significant technical advances in both filtering effect and practicality, and it has extremely high practicality.

[0059] (4) The present invention achieves the effect of recycling heavy metal ions and complexing agents at the same time without destroying the overall chemical plating system, thus avoiding waste of resources.

[0060] (5) The waste liquid treatment process provided by the present invention can be applied to chemical plating wastewater treatment processes in different fields, making heavy metal ions and their pollutants close to zero emission, reducing pollution while reducing resource waste, which is of great significance to the development of industrial environmental protection.

[0061] (6) The treatment and reuse process of the present invention can be applied to various chemical plating waste liquids on the market, achieving excellent purification effects and having strong technical universality. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 . Schematic diagram of the processing equipment of Example 1 DETAILED DESCRIPTION

[0063] Note: The meanings of the units involved in the present invention are explained as follows: min: minute; ms: millisecond; um: micrometer; ppm: part per million; ppb: part per billion; ℃: degree Celsius; g / L: gram per liter; A: ampere; dm: decimeter; DI: deionized; wt%: weight percentage; M: molar concentration moL / LN: mass concentration g / L. And, unless otherwise specified, the reagents, equipment and materials described in the embodiments can be obtained through commercial channels.

[0064] Example

[0065] The first aspect of this embodiment provides a chemical plating waste liquid treatment process, and the treatment steps include: passing the chemical plating waste liquid to be treated into a protective filter and a precision filter in sequence for filtering treatment, and then passing it into a deactivation storage tank to reduce the activity of the chemical plating waste liquid, and then passing it into an ultra-precision filter, a pH adjustment tank, an ion exchange resin, and an activated carbon adsorption device in sequence for treatment, and collecting and discharging the product.

[0066] The protective filter is provided with a first filter membrane, specifically a PP cotton core filter membrane with a pore size of 5 μm; it comes from Qinzhiyuan Environmental Protection Technology Co., Ltd.

[0067] The precision filter is provided with a second filter membrane, specifically a ceramic filter membrane with a pore size of 5 nm; the model is Delemil DED100.

[0068] The deactivation storage tank is connected to an air pump to reduce the activity of the chemical plating solution.

[0069] The deactivation storage tank is provided with a built-in cooling device.

[0070] The pump has a power of 35W and an exhaust volume of 65L / min.

[0071] The cooling device is set at 24-26°C

[0072] The capacity of the deactivation storage tank is 100L.

[0073] The body material of the activation storage tank is PVC.

[0074] The ultra-precision filter is provided with a third filter membrane, specifically a polyimide / polyamide composite nanofiltration membrane with a pore size of 0.5 nm; the filter membrane is DuPont FilmTec TM Nanofiltration membrane products are provided by DuPont China Group Co., Ltd.

[0075] During the treatment in the pH adjustment tank, the chemical plating waste liquid from which the complexing agent and heavy metal ions are separated continues to enter the pH adjustment tank, at which time a pH adjuster is added to adjust the pH of the chemical plating waste liquid to 7.5±0.5.

[0076] The pH adjuster is a sulfuric acid aqueous solution.

[0077] The capacity of the pH adjustment tank is 100L.

[0078] The body material of the pH regulating tank is PVC.

[0079] The ion exchange resin is selected from the strongly acidic cation exchange resin 107MB (provided by Zhejiang Zhengguang Industrial Co., Ltd.).

[0080] The activated carbon adsorption device is provided with an activated carbon adsorption membrane, the material of the activated carbon adsorption membrane is granular activated carbon, and the pore size of the activated carbon adsorption membrane is 30nm; it is provided by Shenzhen Moliquan Co., Ltd.

[0081] The chemical plating waste liquid comes from the waste liquid generated by chemical copper plating.

[0082] The second aspect of this embodiment provides a chemical plating waste liquid treatment device, whose structure includes a lifting pump, a protection filter, a precision filter, a deactivation storage tank, a high-pressure pump, an ultra-precision filter, a pH adjustment tank, a high-pressure pump, an ion exchange resin, and an activated carbon adsorption device connected in sequence.

[0083] The various components of the processing device are tightly connected through pipelines; the pipeline material is PVC.

[0084] The lifting pump is an IHF fluoroplastic chemical lifting pump, model IHF80-65-160A, power 1.5KW; provided by Shanghai Maike Pump Manufacturing Co., Ltd.

[0085] The high-pressure pump is a multi-stage centrifugal high-pressure pump with a power of 1.5KW and a model of BL2-15S, which is provided by New Territory Pump Industry Group Co., Ltd.

[0086] The third aspect of this embodiment provides the application of the treatment process or treatment device as described above, which is specifically applied to the electronic and electrical industry for the collection and treatment of wastewater in PCB (printed circuit board) systems.

[0087] Performance Testing Methods

[0088] The chemical plating waste liquid treatment process described in Example 1 was used to treat chemical plating waste liquids 1 to 10.

[0089] Specific:

[0090] Chemical plating waste liquid 1 was provided by Guangdong Shuocheng Technology Co., Ltd., model SCC-A08LP, the component formula is shown in Table 1, and the measurement results are shown in Table 2.

[0091] Chemical plating waste liquid 2 was provided by Guangdong Shuocheng Technology Co., Ltd., model SCC-A08SP, the component formula is shown in Table 3, and the measurement results are shown in Table 4.

[0092] Chemical plating waste liquid 3 was provided by Atotech Co., Ltd., model U Plus, the component formula is shown in Table 5, and the test results are shown in Table 6.

[0093] Chemical plating waste liquid 4 was provided by Rohm and Haas Electronic Materials CPM Holdings, model Circuposit 880, the component formula is shown in Table 7, and the measurement results are shown in Table 8.

[0094] Chemical plating waste liquid 5 was provided by Guangdong Tiancheng Technology Co., Ltd., model SkyCopp 365SP, the component formula is shown in Table 9, and the measurement results are shown in Table 10.

[0095] Chemical plating waste liquid 6 was provided by Guangdong Tiancheng Technology Co., Ltd., model SkyCopp 3651, the component formula is shown in Table 11, and the measurement results are shown in Table 12.

[0096] Chemical plating waste liquid 7 was provided by Guangdong Tiancheng Technology Co., Ltd., model SkyCopp 3652, the component formula is shown in Table 13, and the measurement results are shown in Table 14.

[0097] Chemical plating waste liquid 8 was provided by Yancheng Baikal Electronic Materials Co., Ltd., model LM1000 series, the component formula is shown in Table 15, and the measurement results are shown in Table 16.

[0098] Chemical plating waste liquid 9 was provided by Shenzhen Zhengtianwei Technology Co., Ltd., model FEC-3088 series, the component formula is shown in Table 17, and the measurement results are shown in Table 18.

[0099] Chemical plating waste liquid 10 was provided by Shenzhen Fulite Technology Co., Ltd., model HDP-380 series, the component formula is shown in Table 19, and the measurement results are shown in Table 20.

[0100] The analysis methods for each indicator are as follows.

[0101] 1. Analyze the chemical components of the treated product; the analysis and calculation methods are as follows:

[0102] (1) Copper ion analysis method (additives)

[0103] a) Use a pipette to draw 25.0 mL of the sample to be tested into a 300 mL conical flask.

[0104] b) Add 25 ml of distilled water and 20 mL of 20 wt% H2SO4 aqueous solution and shake evenly.

[0105] c) Add 20mL (50g / L KI + 200g / L KSCN) solution and shake evenly.

[0106] d) Add 2-3 drops of 1wt% starch solution

[0107] e) Titrate with 0.1N Na2S2O3 solution until the blue color disappears

[0108] calculate:

[0109] Copper ion (g / L) = 0.1N Na2S2O3 dosage (mL) × 0.254

[0110] Other additives can be calculated in a similar way, that is, additive (mL / L) = 0.1N Na2S2O3 dosage (mL) × 5.08

[0111] (2) Analysis method of complexing agent (basic agent)

[0112] A. Potassium Sodium Tartrate System

[0113] a) Use a pipette to draw 2.0 mL of the sample to be tested into a 250 mL conical flask.

[0114] b) Add 50ml of distilled water and 5mL of 20% H2SO4 aqueous solution and shake evenly.

[0115] c) Heat and keep boiling for 10 minutes

[0116] d) Add 100 mL of distilled water and 5 g of MnSO4·H2O

[0117] e) Heat until completely dissolved, add 20mL of 0.1N KMnO4 standard solution with a pipette, heat and keep boiling for 10 minutes, then cool to room temperature (25℃)

[0118] f) Add 2g KI and 2mL 1wt% starch solution

[0119] g) Titrate with 0.1N Na2S2O3 solution until the blue color disappears and record the volume as V (mL)

[0120] calculate:

[0121]

[0122] Other basic agents can be calculated in a similar way, i.e.

[0123] Basic agent mL / L = [0.1N KMnO4 volume (mL) - 0.1N Na2S2O3 dosage (mL)] × 6.3B. EDTA system

[0124] a) Pipette 10.0 ml of the sample to be tested into a 250 ml volumetric flask and add 75 ml of distilled water

[0125] b) Add 20 ml of pH 10.0 buffer and 12 drops of 0.1 wt% PAN indicator (the main component is 1-(2-pyridyl azo)-2-naphthol)

[0126] c) With 0.016M Cu 2+ The standard solution is titrated to violet as the endpoint, and the volume is recorded as V (mL)

[0127] Calculation: Complexed EDTA g / L = 6.55 × copper ion concentration g / L

[0128]

[0129] Total EDTA*(g / L)=complexed EDTA+free EDTA

[0130] Note: Quantitative calculation is performed based on EDTA·4Na·2H2O.

[0131] (3) Analysis method of sodium hydroxide and formaldehyde (reducing agent)

[0132] a) Pipette 5.0 mL of the sample to be tested into a 250 mL beaker

[0133] b) Add 100 mL of distilled water

[0134] c) Titrate to pH 10.2 with 0.10N HCL standard solution using a pH meter (pH 10.0 buffer meter). d) Record the volume V1 used to determine the NaOH concentration.

[0135] e) Titrate with 0.10N HCL standard solution to pH 10.0

[0136] f) Add 25 mL of 1M sodium sulfite solution

[0137] g) Titrate with 0.10N HCl standard solution to pH 10.0, record the volume V2 used in this step, and use it to calculate the formaldehyde concentration / reducing agent content

[0138] calculate:

[0139]

[0140] Other basic agents can be calculated in a similar way, i.e. reducing agent mL / L = V2 (mL) × 2.00 (4) Nickel content analysis method

[0141] The analysis was performed using an atomic spectrophotometer. The specific operation process was as follows: power on - online - select nickel lamp - correct / select nickel element gas flow and wavelength (flow rate is 1700, wavelength is 232.0) - peak search - preheat for 20 minutes - turn on acetylene gas, ignite - energy adjustment - test

[0142] 2. Calculate the throttling rate:

[0143]

[0144] 3. National indicators testing:

[0145] According to the national emission standard GB21900-2008, ICP-MS was used to detect the designated elements, specifically using the American Agilent 7700 / 7800 (MS) for determination; a pH meter was used to detect the pH of the solution, specifically using the Raman pH meter pHS-3G for determination.

[0146] Note: All reagents used in the above analysis can be purchased on the market. Unless otherwise specified, the solvent of the solution is water.

[0147] Performance Test Results

[0148] 1. The component contents and throttling rate results of chemical plating waste liquid 1, chemical plating waste liquid 2 and chemical plating waste liquid 3 before and after treatment are shown in Tables 1-20 respectively.

[0149] Table 1

[0150]

[0151] Table 2

[0152] Main components Discharge of waste liquid after treatment Throttling rate Potassium Sodium Tartrate 1.32g / L 96.22％ Copper sulfate pentahydrate 0.42g / L 95.80％ formaldehyde 3.12g / L 22.00％ Sodium hydroxide 7.46g / L 25.40％

[0153] Table 3

[0154]

[0155] Table 4

[0156]

[0157]

[0158] Table 5

[0159]

[0160] Table 6

[0161] Main components Discharge of waste liquid after treatment Throttling rate Basic dose P 2.50mL / L 97.05％ Copper sulfate pentahydrate 0.12g / L 98.80％ Sodium hydroxide 8.24g / L 17.6％ formaldehyde 3.43g / L 23.77％

[0162] Table 7

[0163]

[0164] Table 8

[0165] Main components Discharge of waste liquid after treatment Throttling rate EDTA·4Na·2H2O 0.75g / L 97.87％ Copper ions 0.10g / L 95.45％ formaldehyde 1.88g / L 24.80％ Sodium hydroxide 10.34g / L 20.46％

[0166] Table 9

[0167]

[0168]

[0169] Table 10

[0170] Main components Discharge of waste liquid after treatment Throttling rate Potassium Sodium Tartrate 2.88g / L 91.77％ Copper sulfate pentahydrate 0.15g / L 98.50％ Nickel Ion 0.037g / L 91.19％ formaldehyde 3.87g / L 14.00％ Sodium hydroxide 8.67g / L 13.30％

[0171] Table 11

[0172]

[0173]

[0174] Table 12

[0175] Main components Discharge of waste liquid after treatment Throttling rate Potassium Sodium Tartrate 2.08g / L 94.80％ Copper sulfate pentahydrate 0.21g / L 97.90％ formaldehyde 3.76g / L 16.40％ Sodium hydroxide 8.56g / L 14.40％

[0176] Table 13

[0177]

[0178] Table 14

[0179] Main components Discharge of waste liquid after treatment Throttling rate Potassium Sodium Tartrate 1.53g / L 96.17％ Copper sulfate pentahydrate 0.82g / L 91.80％ Nickel Ion 0.085g / L 91.50％ formaldehyde 3.88g / L 13.77％ Sodium hydroxide 8.26g / L 17.40％

[0180] Table 15

[0181]

[0182] Table 16

[0183]

[0184]

[0185] Table 17

[0186]

[0187] Table 18

[0188] Main components Discharge of waste liquid after treatment Throttling rate FEC-3088M-Basic agent 3.47mL / L 95.91％ Copper ions 0.15g / L 93.18％ NaOH 7.85g / L 21.50％ formaldehyde 6.08g / L 18.93％

[0189] Table 19

[0190]

[0191] Table 20

[0192] Main components Discharge of waste liquid after treatment Throttling rate FEC-3088M-Basic agent 6.43mL / L 93.57％ Copper ions 0.18g / L 91.81％ NaOH 7.81g / L 21.90％ formaldehyde 5.96g / L 14.80％

[0193] 2. The test results of various indicators in the waste liquid discharged after the whole waste liquid treatment process are shown in Table 21 below.

[0194] Table 21

[0195]

[0196]

[0197] Continued

[0198]

[0199]

[0200] It can be seen from the results of Tables 1-21 that the chemical plating waste liquid treatment process / device provided in the embodiment of the present invention can significantly improve the purification effect of chemical plating waste liquid; after being treated by the chemical plating waste liquid treatment process / equipment, the content of chelating agent and heavy metal (such as copper ion) in the waste liquid is greatly reduced, and can be recycled and reused, which greatly reduces the waste of resources. The treatment process of the present invention is relatively simple, and all indicators of the chemical plating waste liquid after treatment can meet the national emission standards, which is safe and environmentally friendly. At the same time, the treatment and reuse process of the present invention can be applied to various chemical plating waste liquids on the market, achieving excellent purification effects, and the technology has strong universality.

[0201] Although the specific implementation modes of the present invention are described above, those skilled in the art should understand that the specific implementation modes described are only illustrative and are not intended to limit the scope of the present invention. Equivalent modifications and changes made by those skilled in the art in accordance with the spirit of the present invention should be included in the scope of protection of the claims of the present invention.

Claims

1. A process for treating chemical plating waste liquid, characterized in that: The treatment steps include: passing the chemical plating waste liquid to be treated into a protective filter and a precision filter in sequence for filtering treatment, then passing it into a deactivation storage tank to reduce the activity of the chemical plating waste liquid, then passing it into an ultra-precision filter, a pH adjustment tank, an ion exchange resin, and an activated carbon adsorption device in sequence for treatment, and collecting and discharging the product to obtain.

2. The chemical plating waste liquid treatment process according to claim 1, characterized in that: The protection filter is provided with a first filter membrane; The filtering material of the first filtering membrane is at least one of cotton core, polypropylene, polytetrafluoroethylene, cellulose acetate, ceramics, activated carbon, polyethersulfone, mixed fiber resin, polyamide, and polyvinylidene fluoride; the pore size of the first filtering membrane is 1-100 μm.

3. The process for treating chemical plating waste liquid according to claim 1, characterized in that: The precision filter is provided with a second filter membrane; The filtering material of the second filtering membrane is at least one of polypropylene, polytetrafluoroethylene, cellulose acetate, ceramics, and activated carbon; the pore size of the second filtering membrane is 1-500nm.

4. The process for treating chemical plating waste liquid according to claim 1, characterized in that: The ultra-precision filter is provided with a third filter membrane; The filtering material of the third filtering membrane is a composite nanofiltration membrane or a reverse osmosis membrane, and the pore size of the third filtering membrane is 0.1-50nm.

5. The process for treating chemical plating waste liquid according to claim 1, characterized in that: The pH of the chemical plating waste liquid is adjusted to 7-8 after entering the pH adjustment tank.

6. The process for treating chemical plating waste liquid according to claim 1, characterized in that: The ion exchange resin is selected from a composite of one or more of a strongly acidic cation exchange resin, a weakly acidic cation exchange resin, a chelating resin, a redox resin, and a metal ion exchange resin.

7. The process for treating chemical plating waste liquid according to claim 1, characterized in that: The activated carbon adsorption device is provided with an activated carbon adsorption membrane, and the pore size of the activated carbon adsorption membrane is 1-100nm.

8. The process for treating chemical plating waste liquid according to any one of claims 1 to 7, characterized in that: The chemical plating waste liquid comes from the waste liquid generated by chemical copper plating, chemical nickel plating, chemical gold plating, chemical tin plating, chemical cobalt plating, chemical silver plating, chemical palladium plating, chemical iron plating, chemical zinc plating, chemical plating platinum plating, chemical lead plating, chemical aluminum plating, chemical scandium plating, chemical titanium plating, chemical rhodium plating and various metal alloys.

9. A chemical plating waste liquid treatment device, characterized in that: The structure includes a protection filter, a precision filter, an activation storage tank, an ultra-precision filter, a pH adjustment tank, an ion exchange resin, and an activated carbon adsorption device which are connected in sequence.

10. Use of the treatment process according to claim 1 or the treatment device according to claim 9, characterized in that: It is used in the fields of electronic and electrical industry, automotive industry, aerospace industry, medical equipment, powder metallurgy, and machinery manufacturing.

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