CN119219244A - A chemical plating waste liquid treatment process, device and application - Google Patents
A chemical plating waste liquid treatment process, device and application Download PDFInfo
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- CN119219244A CN119219244A CN202411436997.5A CN202411436997A CN119219244A CN 119219244 A CN119219244 A CN 119219244A CN 202411436997 A CN202411436997 A CN 202411436997A CN 119219244 A CN119219244 A CN 119219244A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
- B01D71/16—Cellulose acetate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
- B01D71/381—Polyvinylalcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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Abstract
The invention relates to the technical field of wastewater treatment, in particular to a process, a device and application of an electroless plating waste liquid treatment. The treatment steps comprise sequentially introducing the electroless plating waste liquid to be treated into a protective filter, filtering the electroless plating waste liquid by a precise filter, introducing the electroless plating waste liquid into a deactivation storage tank to reduce the activity of the electroless plating waste liquid, sequentially introducing the electroless plating waste liquid into an ultra-precise filter, a pH adjusting tank, an ion exchange resin and an active carbon adsorption device for treatment, and collecting the discharged product. The core of the wastewater treatment process is that heavy metal ions and complexing agents are effectively separated from a waste liquid system by a multi-step membrane separation technology method on the premise of not damaging the whole electroless plating system, and the effect of recycling is achieved while impurities are removed.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a process, a device and application of an electroless plating waste liquid treatment.
Background
With the rapid development of industry, electroless plating is becoming a surface treatment process capable of effectively enhancing the surface properties of a substrate material, and its application field is becoming wider and wider. With the development of manufacturing industry and the popularization of electroless plating, a large amount of waste liquid from chemical plating 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 a complexing agent, and the direct discharge can cause environmental pollution and resource waste, so that the treatment of the chemical plating waste liquid containing the heavy metal ions is the key of industrial waste water treatment.
The current common treatment mode is to completely separate heavy metal ions from water, so that the wastewater reaches the discharge standard. The metal complex is broken by chemical reagent (such as ferrous sulfate), then alkaline solution is added to precipitate metal ions, and the metal ions are separated from the waste water by processes of flocculating and filtering by adding flocculating agent, and the waste water reaches the discharge standard by complex process flow. However, such a treatment method has complicated process flow, high treatment cost, and limited recovery degree of heavy metals, and is easy to cause resource waste. Meanwhile, in the prior art, when the electroless plating waste liquid is treated, recycling of resources is difficult to achieve, and great waste of the resources is caused.
Chinese patent CN 110451688A discloses a method for treating copper-plating wastewater of PCB, which removes copper in the wastewater of chemical copper by the steps of Fenton oxidation precipitation treatment after broken-vein precipitation, so that the copper content in the wastewater stably reaches the requirement of yielding water. However, the invention damages the electroless copper plating solution system, can not effectively recycle the complexing agent, contains more impurities after copper ions are precipitated, and has larger waste on resources. Chinese patent CN 112479458A discloses a method for treating electroless copper plating waste liquid in PCB, which adds a certain proportion of medicines to treat electroless copper plating liquid in a plurality of treatment modes such as breaking collaterals, flocculating, concentrating and crystallizing, etc., thereby achieving the technical requirement of recovering copper and complexing agent simultaneously, but the invention also destroys an electroless copper plating liquid system and can not realize recycling, and the invention is only applicable to EDTA system as complexing agent and has larger limitation.
Under the background, the technical method for simply and efficiently treating the electroless plating waste liquid and realizing the recycling of resources is provided, and is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide an electroless plating waste liquid treatment process, which aims to solve the problems of complex flow and high treatment cost of the existing waste liquid treatment process. On one hand, the invention can ensure that heavy metals are close to zero emission by membrane separation technology, acid-base neutralization, organic pollutant degradation and other modes, and each emission index can reach the national emission standard. On the other hand, the treatment process method is applicable to various complexing agent systems, and the heavy metal ions and the complexing agent can be recycled simultaneously on the premise of not damaging the whole electroless plating system.
The invention provides an electroless plating waste liquid treatment process, which comprises the steps of sequentially introducing electroless plating waste liquid to be treated into a protective filter, filtering by a precision filter, then introducing into a deactivation storage tank to reduce the activity of the electroless plating waste liquid, sequentially introducing into an ultra-precision filter, a pH adjusting tank, an ion exchange resin and an active carbon adsorption device for treatment, and collecting a discharged product.
1) Protection filter treatment:
the waste water to be treated is subjected to the first-step filtering treatment through the protective filter, and impurities and turbid matters in the electroless plating waste liquid can be intercepted and adsorbed through the interception of the microporous filter membrane of the protective filter.
Preferably, the protective filter is provided with a first filter membrane having a pore size of 1-100 μm, more preferably 1-20 μm.
Preferably, the filtering material of the first filtering membrane is at least one of cotton core, polypropylene, polytetrafluoroethylene, cellulose acetate, ceramic, activated carbon, polyethersulfone, mixed fiber resin, polyamide and polyvinylidene fluoride.
2) Precision filter treatment:
the chemical plating waste liquid discharged from the protective filtering membrane is subjected to a second layer of filtering treatment, the chemical plating solution is protected by the treatment of the precise filtering membrane, and the complexing agent and the metal ion structure in the solution are not damaged, so that the complexing system still keeps macromolecular structure substances, and tiny impurities are filtered out, thereby obtaining secondary filtered filtrate.
Preferably, the precise filter is provided with a second filter membrane, the pore size of the second filter membrane is 1-500nm, and more preferably 1-50nm.
Preferably, the filtering material of the second filtering membrane is at least one of polypropylene, polytetrafluoroethylene, cellulose acetate, ceramic and activated carbon.
3) And (3) treatment of a deactivation storage tank:
The filtrate after being treated by the protective filter and the precise filter is introduced into a deactivation storage tank which is communicated with an inflating pump for reducing the activity of the chemical plating solution.
Preferably, a cooling device is arranged in the activity-reducing storage tank.
Preferably, the capacity of the deactivation storage tank is 50-500L.
Preferably, the tank body of the deactivation storage tank is made of at least one of PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), PTFE (polytetrafluoroethylene), FRP (fiber reinforced composite material, also referred to as glass fiber reinforced plastic), acrylic material and glass.
4) Ultra-precise filter treatment:
The chemical plating waste liquid after deactivation treatment enters a third layer of filtering system, a third filtering film is arranged as a nanofiltration film, the chemical plating system is effectively separated, the macromolecular structure of the complexing agent and the heavy metal complexing system is intercepted in the filtering process, inorganic salt and other micromolecular structure substances in the chemical plating liquid are discharged, the intercepted complexing system macromolecules return to the original plating liquid tank for recycling, the discharge amount of the waste liquid is greatly reduced, no chemical additive is added in the separating system, and the complexing agent and the heavy metal ions can be separated from the waste liquid system by adopting a physical method in the whole filtering process, so that the technical effects of emission reduction, recycling and pollution reduction are achieved.
Preferably, the ultra-precise filter is provided with a third filtering membrane, and the pore diameter of the third filtering membrane is 0.1-50nm, and more preferably 0.2-5nm.
Preferably, the filtering material of the third filtering membrane is at least one of a composite nanofiltration membrane or a reverse osmosis membrane.
The composite nanofiltration membrane can be exemplified by cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone, polyvinyl alcohol, polyamide, alumina, titanium oxide, zirconium oxide and other nanofiltration membranes and composite nanofiltration membranes thereof, polyester composite nanofiltration membranes, polyethersulfone/polyamide composite nanofiltration membranes, polysulfone/polyamide composite nanofiltration membranes, polyimide/polyamide composite nanofiltration membranes, polyether ether ketone/polyamide composite nanofiltration membranes, nanomaterial modified composite nanofiltration membranes, porous support layer/separation layer composite nanofiltration membranes and modified composite nanofiltration membranes thereof.
Examples of the reverse osmosis membrane include cellulose acetate and its derivative reverse osmosis membrane, polyamide and its derivative reverse osmosis membrane, polyether sulfone and its derivative reverse osmosis membrane, polyhydrazide and its derivative reverse osmosis membrane, and composite reverse osmosis membrane.
5) And (3) pH adjustment tank treatment:
The chemical plating waste liquid from which the complexing agent and the heavy metal ions are separated continuously enters a pH adjusting tank, and a proper amount of pH regulator is added to adjust the pH of the chemical plating waste liquid to 7-8.
Preferably, the pH adjuster is at least one of sulfuric acid, hydrochloric acid, boric acid, citric acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and aqueous solution of sodium bicarbonate.
Preferably, the capacity of the pH adjusting tank is 50-500L.
Preferably, the tank body of the pH adjusting tank is made of at least one of PVC, PP, PE, PTFE, FRP, acrylic acid material and glass.
6) Ion exchange resin treatment:
The chemical plating waste liquid with the pH adjusted by the pH adjusting tank enters an ion exchange resin device, and the ion exchange resin filtering device of the step can absorb metal ions and complexes which are not completely recycled by the ultra-precise filter, so that the heavy metal ions and the complexes are completely separated from the filtrate, and most impurities in the filtrate are removed after the treatment by the ion exchange resin device.
Preferably, the ion exchange resin is selected from the group consisting of strong acid cation exchange resins, weak acid cation exchange resins, chelating resins, redox resins, novel metal ion exchange resins (copper, palladium, nickel and mixed metals thereof), and complex ion exchange resins thereof.
Further preferably, the strongly acidic cation exchange resin is a macroporous strongly acidic ion exchange resin.
7) And (3) treating by an activated carbon adsorption device:
The filtrate filtered by the ion exchange resin system is next step into an active carbon adsorption device, and the filter system can completely separate organic impurities in the filtrate to obtain pure filtrate.
Preferably, the activated carbon adsorption device is provided with an activated carbon adsorption film, and the material of the activated carbon adsorption film 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.
Preferably, the aperture of the activated carbon adsorption film is 1-100nm, and more preferably 10-50nm.
The core of the wastewater treatment process is that heavy metal ions and complexing agents are effectively separated by a multi-step membrane separation technical method on the premise of not damaging the whole electroless plating system, and the technical method for recycling is achieved while impurities are removed. The core content of the invention is that a filtering membrane (including but not limited to a micro-filtration membrane, an ultrafiltration membrane, a nanofiltration membrane, a composite nanofiltration membrane and a reverse osmosis membrane) is used for filtering the chemical plating solution, and macromolecular substances such as complex and heavy metal are retained for recycling. Furthermore, the wastewater treatment process disclosed by the invention is matched with a membrane separation technology, acid-base neutralization and activated carbon adsorption treatment, the effect of zero emission of heavy metal ions, complexes and other pollutants can be achieved by using a simple treatment process, the chemical plating solution is filtered through a filter membrane with specific particle size, and macromolecular substances such as the complexes, heavy metals and the like are separated for recycling, and small molecular pollution impurities are removed from throttled waste liquid by using acid-base neutralization, ion exchange, activated carbon adsorption and the like. The invention can purify the chemical plating waste liquid efficiently and thoroughly without adding chemical reagent by means of physical means, and has remarkable technical progress in both filtration effect and practical dimension. The impurity components of the electroless plating waste liquid treated by the process can reach national discharge standards, and can be popularized and used.
Preferably, the electroless plating waste liquid is derived from waste liquid generated by electroless copper plating, electroless nickel plating, electroless gold plating, electroless tin plating, electroless cobalt plating, electroless silver plating, electroless palladium plating, electroless iron plating, electroless zinc plating, electroless platinum plating, electroless lead plating, electroless aluminum plating, electroless scandium plating, electroless titanium plating, electroless rhodium plating and various metal alloys.
Preferably, the electroless plating waste solution can also be derived from waste solution generated by electroless copper plating, and comprises a horizontal copper deposition system and a gantry copper deposition system
Heavy metal ions that can be separated according to 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., while being capable of separating one or more of the complexes/complexes containing the above heavy metal ions.
Preferably, the heavy metal ions are mainly used for reducing the emission of copper ions, and the copper ions comprise monovalent copper, divalent copper and copper-containing complexes thereof.
Complexing agents that can be isolated according to the present invention include, but are not limited to, compounds containing at least one of amine groups, carboxyl groups, sulfhydryl groups, and hydroxyl groups.
Examples of the complexing agent include citric acid, pyrophosphates, EDTA (ethylenediamine tetraacetic acid), lactic acid, tartaric acid and salts thereof, sodium salicylate, ethylenediamine tetraacetic acid sodium salt, nitriloacetic acid and alkali metal salts thereof, gluconic acid, gluconate, triethanolamine, modified ethylenediamine tetraacetic acid, S-ethylenediamine disuccinic acid, glycine, malic acid, malonic acid, succinic acid, glycolic acid, glycine, HEDP (hydroxyethylidene diphosphonic acid), ATMP (aminotrimethylene phosphonic acid) and the like.
The waste liquid treatment process provided by the invention can be applied to chemical plating waste water treatment processes in different fields, so that the zero emission of heavy metal ions and pollutants thereof is achieved, the pollution is reduced, the resource waste is reduced, and the method has important significance for the development of industrial environmental protection.
The invention provides an electroless plating waste liquid treatment device which structurally comprises a protection filter, a precision filter, a deactivation storage tank, an ultra-precision filter, a pH adjusting tank, ion exchange resin and an activated carbon adsorption device which are sequentially connected.
Preferably, the electroless plating waste liquid treatment device further comprises a high-pressure pump arranged between 1) the deactivation storage tank and the ultra-precise filter, and 2) the pH adjusting tank and the ion exchange resin.
Preferably, the electroless plating waste liquid treatment device further comprises a lift pump, and when the treatment device is used for treating waste liquid, the waste liquid to be treated is conveyed into the protection filter through the lift pump.
The components of the treatment device are tightly connected through pipelines.
The material of the pipe is not particularly limited, and may be any material that can achieve the purpose of transportation, and for example PVC, PP, PE, PTFE, FRP, PVDF (polyvinylidene fluoride) or the like may be used.
A third aspect of the invention provides the use of a treatment process or treatment device as described above, in particular in the fields of electronics and electrical industry, automotive industry, aerospace industry, medical equipment, powder metallurgy, mechanical manufacturing and the like.
The beneficial effects are that:
the invention provides a treatment process and application of electroless plating waste liquid, and the treatment process has the following advantages:
(1) The core of the wastewater treatment process is that heavy metal ions and complexing agents are effectively separated from a waste liquid system by a multi-step membrane separation technology method on the premise of not damaging the whole electroless plating system, and the effect of recycling is achieved while impurities are removed.
(2) The invention filters the electroless plating solution through the filter membrane with specific particle size, separates the complex and the macromolecular substances such as heavy metal for recycling, and removes the small molecular pollution impurities by acid-base neutralization, ion exchange, active carbon adsorption and the like of the throttled waste liquid, thereby effectively removing heavy metal ions and complexing agents in various electroless plating waste liquids.
(3) The invention can purify the chemical plating waste liquid efficiently and thoroughly by means of physical means without adding chemical reagent, has obvious technical progress in both filtering effect and practical dimension, and has extremely high practicability.
(4) The invention can simultaneously recycle heavy metal ions and complexing agents on the premise of not damaging the whole electroless plating system, thereby avoiding resource waste.
(5) The waste liquid treatment process provided by the invention can be applied to chemical plating waste water treatment processes in different fields, so that the heavy metal ions and pollutants thereof are close to zero emission, the pollution is reduced, and the resource waste is reduced, thereby having great significance for the development of industrial environmental protection.
(6) The treatment recycling process can be applied to various electroless plating waste solutions on the market, and has excellent purification effect and strong technical universality.
Drawings
FIG. 1A schematic view of a treatment apparatus of example 1
Detailed Description
Note that the units referred to in this invention are interpreted as min, ms, um, microns, ppm, ppb, billion, C, g/L, A, amp, dm, DI, deionized, wt%, M, mols/L N, g/L. And, unless otherwise specified, reagents, equipment and materials described in the examples are all available through commercial sources.
Examples
The first aspect of the embodiment provides an electroless plating waste liquid treatment process, which comprises the steps of sequentially introducing electroless plating waste liquid to be treated into a protection filter, filtering by a precision filter, then introducing into a deactivation storage tank to reduce the activity of the electroless plating waste liquid, sequentially introducing into an ultra-precision filter, a pH adjusting tank, an ion exchange resin and an active carbon adsorption device for treatment, and collecting a discharged product.
The protection filter is provided with a first filtering membrane, in particular a PP cotton core filtering membrane, the aperture of which is 5 mu m, and is sourced from Qin source environmental protection technology Co.
The precise filter is provided with a second filtering membrane, in particular a ceramic filtering membrane, the aperture of which is 5nm, and the model of which is Delamel (Delemil) DED100.
The activity-reducing storage tank is communicated with an inflating pump for reducing the activity of the chemical plating solution.
And a cooling device is arranged in the activity-reducing storage tank.
The pumping power of the pumping pump is 35W, and the exhaust capacity is 65L/min
The temperature reduction device is set to be 24-26 DEG C
The capacity of the deactivation storage tank is 100L.
The tank body of the active reduction storage tank is made of PVC.
The ultra-precise filter is provided with a third filter membrane, specifically a polyimide/polyamide composite nanofiltration membrane, the aperture of which is 0.5nm, and the filter membrane is a DuPont FilmTec TM nanofiltration membrane product provided by DuPont China group Co.
When the pH adjusting tank is used for treatment, the chemical plating waste liquid from which the complexing agent and the heavy metal ions are separated continuously enters the pH adjusting tank, and the pH regulator is added to adjust the pH of the chemical plating waste liquid to 7.5+/-0.5.
The pH regulator is sulfuric acid water solution.
The capacity of the pH adjusting tank was 100L.
The cell body material of pH adjustment tank is PVC.
The ion exchange resin was selected from the group consisting of strongly acidic cation exchange resins 107MB (available from Zhejiang light control industries Co., ltd.).
The active carbon adsorption device is provided with an active carbon adsorption film, the active carbon adsorption film is made of granular active carbon, the aperture of the active carbon adsorption film is 30nm, and the active carbon adsorption film is provided by Shenzhen film Liquan Limited company.
The electroless plating waste liquid is derived from waste liquid generated by electroless copper plating.
The second aspect of the embodiment provides an electroless plating waste liquid treatment device, which structurally comprises a lifting pump, a protection filter, a precision filter, a deactivation storage tank, a high-pressure pump, an ultra-precision filter, a pH adjusting tank, a high-pressure pump, ion exchange resin and an activated carbon adsorption device which are sequentially connected.
All parts of the treatment device are tightly connected through pipelines, and the pipelines are made of PVC.
The lifting pump is an IHF fluoroplastic chemical lifting pump, the model of which is IHF80-65-160A, and the power of which is 1.5KW, and is provided by Shanghai Michael pump industry manufacturing company.
The high-pressure pump is a multistage centrifugal high-pressure pump, the power is 1.5KW, the model is BL2-15S, and the high-pressure pump is provided by New-world pump industry group Co.
A third aspect of the present embodiment provides the use of a treatment process or treatment device as described above, in particular in the field of electronics and electrical industry, for the collection and treatment of waste water of PCB (printed circuit board) systems.
Performance test method
The electroless plating waste solutions 1 to 10 were treated by the electroless plating waste solution treatment process described in example 1.
Specific:
Electroless plating waste liquid 1 is provided by Guangdong scientific and technical Co., ltd., model SCC-A08LP, the composition formula is shown in Table 1, and the measurement result is shown in Table 2.
Electroless plating waste liquid 2 was supplied by Guangdong Co., ltd., model SCC-A08SP, the composition formula was shown in Table 3, and the measurement results were shown in Table 4.
Electroless plating waste liquid 3 is supplied by Amite Co., ltdU Plus, composition formula shown in Table 5, and measurement results shown in Table 6.
Electroless plating waste liquid 4 is provided by CPM control company of Rogowski electronic material, model Circuposit 880,880, the composition formula is shown in Table 7, and the measurement result is shown in Table 8.
Electroless plating waste liquid 5 is provided by Guangdong Chengsu Co., ltd., model SkyCopp SP, the composition formula is shown in Table 9, and the measurement result is shown in Table 10.
Electroless plating waste liquid 6 is provided by Guangdong Chengsu Co., ltd., model SkyCopp 3651,3651, the composition formula is shown in Table 11, and the measurement result is shown in Table 12.
Electroless plating waste liquid 7 is provided by Guangdong Chengsu Co., ltd., model SkyCopp 3652,3652, the composition formula is shown in Table 13, and the measurement result is shown in Table 14.
Electroless plating waste liquid 8 is provided by Begale electronic materials Co., ltd., salt city, model LM1000 series, the composition formula is shown in Table 15, and the measurement result is shown in Table 16.
Electroless plating waste liquid 9 is provided by Shenzhen Zhengtianwei technology Co., ltd., model FEC-3088 series, the composition formula is shown in Table 17, and the measurement result is shown in Table 18.
Electroless plating waste liquid 10 is provided by Shenzhen Fulite technology Co., ltd, model HDP-380 series, the composition formula is shown in Table 19, and the measurement result is shown in Table 20.
The method for analyzing each index is as follows.
1. The chemical composition analysis is carried out on the treated product, and the analysis and calculation method is as follows:
(1) Copper ion analysis method (additive)
A) Pipette 25.0mL of sample to be measured into a 300mL conical flask
B) Adding 25ml distilled water, 20ml 20wt% H 2SO4 water solution, and shaking uniformly
C) Adding 20mL (50 g/L KI+200g/L KSCN) solution, and swinging uniformly
D) Adding 2-3 drops of 1wt% starch solution
E) Titration with 0.1N Na 2S2O3 titration solution until blue disappeared
And (3) calculating:
Copper ion (g/L) =0.1N Na 2S2O3 usage (mL) ×0.254
Other additives can be calculated by reference to a similar method, i.e. additive (mL/L) =0.1N Na 2S2O3 usage (mL) ×5.08
(2) Complexing agent analysis method (basic agent)
A. potassium sodium tartrate system
A) Pipette 2.0mL of sample to be measured into a 250mL conical flask
B) Adding 50ml distilled water, 5ml 20% H 2SO4 aqueous solution, and swinging uniformly
C) Heating and keeping boiling for 10 min
D) 100mL of distilled water and 5g of MnSO 4·H2 O are added
E) Heating to dissolve completely, adding 20mL 0.1N KMnO 4 standard solution with a pipette, heating to boil for 10min, and cooling to room temperature (25deg.C)
F) 2g KI and 2mL of 1wt% starch solution were added
G) Titration of the solution with 0.1N Na 2S2O3 until blue disappeared, recording volume V (mL)
And (3) calculating:
Other basic agents can be calculated by reference to similar methods, i.e
Basic agent mL/l= [0.1n KMnO4 volume (mL) -0.1n na2s2o3 usage (mL) ]x6.3b.edta system
A) Pipette 10.0ml of the sample to be measured into a 250ml volumetric flask and add 75ml of distilled water
B) 20ml of pH10.0 buffer and 12 drops of 0.1wt% PAN indicator (1- (2-pyridylazo) -2-naphthol as the main component) were added
C) Titration with 0.016M Cu 2+ standard solution to violet as end point, recording volume V (mL)
Calculation of complexing EDTAg/L=6.55×copper ion concentration g/L
Total EDTA =complex edta+free EDTA (g/L)
Note that the quantitative calculation was performed on EDTA.4Na.2H2H 2 O.
(3) Sodium hydroxide and Formaldehyde analysis method (reducing agent)
A) Pipette 5.0mL of sample to be measured into a 250mL beaker
B) 100mL of distilled water was added
C) Titration with a 0.10N HCL standard solution to pH 10.2, the procedure being carried out with a pH meter (pH 10.0 buffer meter), d) recording the volume V1 used to determine the NaOH concentration
E) Titrating with 0.10N HCL standard solution to pH value of 10.0
F) 25mL of 1M sodium sulfite solution was added
G) Titration with 0.10N HCl standard solution to pH 10.0 was performed, the volume V2 used in this step was recorded, and the formaldehyde concentration/reductant content was calculated
And (3) calculating:
Other base agents can be calculated by reference to a similar method, i.e., reducing agent mL/l=v2 (mL) ×2.00 (4) nickel content analysis method
The analysis is carried out by adopting an atomic spectrophotometer, and the specific operation processes comprise starting-on-line-selecting a nickel lamp-correcting/selecting nickel element gas flow and wavelength (the flow is 1700, the wavelength is 232.0), peak searching-preheating for 20 min-opening acetylene gas, igniting-energy adjusting-testing
2. Calculating a throttle rate:
3. Detecting various indexes of the country:
According to national emission standard GB21900-2008, the specified elements are detected using ICP-MS, in particular using U.S. Agilent 7700/7800 (MS), the solution pH is detected using a pH meter, in particular using Lei Ci pH meter pHS-3G.
Note that the reagents used in the above analysis are commercially available. And unless otherwise specified, the solvent of the solution is water.
Results of Performance test
1. The composition contents before and after the treatment of the electroless plating waste liquid 1, the electroless plating waste liquid 2 and the electroless plating waste liquid 3 and the throttle rate results are shown in tables 1 to 20, respectively.
TABLE 1
TABLE 2
| Main component | After treatment discharge of waste liquid | Throttle 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% |
TABLE 3 Table 3
TABLE 4 Table 4
TABLE 5
TABLE 6
| Main component | After treatment discharge of waste liquid | Throttle rate |
| Basic agent 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% |
TABLE 7
TABLE 8
| Main component | After treatment discharge of waste liquid | Throttle 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% |
TABLE 9
Table 10
| Main component | After treatment discharge of waste liquid | Throttle rate |
| Potassium sodium tartrate | 2.88g/L | 91.77% |
| Copper sulfate pentahydrate | 0.15g/L | 98.50% |
| Nickel ions | 0.037g/L | 91.19% |
| Formaldehyde | 3.87g/L | 14.00% |
| Sodium hydroxide | 8.67g/L | 13.30% |
TABLE 11
Table 12
| Main component | After treatment discharge of waste liquid | Throttle 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% |
TABLE 13
TABLE 14
| Main component | After treatment discharge of waste liquid | Throttle rate |
| Potassium sodium tartrate | 1.53g/L | 96.17% |
| Copper sulfate pentahydrate | 0.82g/L | 91.80% |
| Nickel ions | 0.085g/L | 91.50% |
| Formaldehyde | 3.88g/L | 13.77% |
| Sodium hydroxide | 8.26g/L | 17.40% |
TABLE 15
Table 16
TABLE 17
TABLE 18
| Main component | After treatment discharge of waste liquid | Throttle rate |
| FEC-3088M base 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% |
TABLE 19
Table 20
| Main component | After treatment discharge of waste liquid | Throttle rate |
| FEC-3088M base 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% |
2. The results of the detection of each index in the discharged waste liquid after the whole waste liquid treatment and the whole process are shown in the following table 21.
Table 21
Continuous watch
From the results shown in tables 1 to 21, the electroless plating waste liquid treatment process/device provided by the embodiment of the invention can remarkably improve the purification effect of electroless plating waste liquid, greatly reduce the contents of complexing agent and heavy metal (such as copper ions) in the waste liquid after being treated by the electroless plating waste liquid treatment process/device, and can be recycled, thereby greatly reducing the waste of resources. The treatment process is simple, and all indexes of the treated electroless plating waste liquid can reach national emission standards, so that the method is safe and environment-friendly. Meanwhile, the treatment recycling process can be applied to various electroless plating waste solutions on the market, and has excellent purification effect and strong technical universality.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that the specific embodiments described are illustrative only and not intended to limit the scope of the invention, and that equivalent modifications and variations of the invention in light of the spirit of the invention will be covered by the claims of the present invention.
Claims (10)
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