WO2024113798A1 - Membrane treatment technology for copper-containing wastewater generated in pcb production process - Google Patents

Membrane treatment technology for copper-containing wastewater generated in pcb production process Download PDF

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Publication number
WO2024113798A1
WO2024113798A1 PCT/CN2023/102630 CN2023102630W WO2024113798A1 WO 2024113798 A1 WO2024113798 A1 WO 2024113798A1 CN 2023102630 W CN2023102630 W CN 2023102630W WO 2024113798 A1 WO2024113798 A1 WO 2024113798A1
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copper
membrane
production process
nanofiltration
wastewater generated
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PCT/CN2023/102630
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French (fr)
Chinese (zh)
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刘久清
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湖南维胜科技电路板有限公司
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Publication of WO2024113798A1 publication Critical patent/WO2024113798A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D29/00—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor
    • B01D29/11—Filters with filtering elements stationary during filtration, e.g. pressure or suction filters, not covered by groups B01D24/00 - B01D27/00; Filtering elements therefor with bag, cage, hose, tube, sleeve or like filtering elements
    • B01D29/13—Supported filter elements
    • B01D29/23—Supported filter elements arranged for outward flow filtration
    • B01D29/27—Filter bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • 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
    • 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
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/10—Cellulose; Modified cellulose
    • 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
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03B—INSTALLATIONS OR METHODS FOR OBTAINING, COLLECTING, OR DISTRIBUTING WATER
    • E03B1/00—Methods or layout of installations for water supply
    • E03B1/04—Methods or layout of installations for water supply for domestic or like local supply
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for treating wastewater generated in the production process of printed circuit boards, in particular to a method for treating copper-containing heavy metal wastewater generated in the production process of printed circuit boards (PCBs).
  • PCBs printed circuit boards
  • This type of wastewater is generally collected in one place and treated centrally, so it is collectively referred to as comprehensive wastewater.
  • heavy metals After a large amount of heavy metals enter the human body, they will interact with physiological polymer substances and make them inactive, and may also accumulate in the human body to cause chronic poisoning; when heavy metal wastewater is used for irrigation, it will cause soil salinization and affect the growth of crops. Therefore, from the perspective of human health, agricultural development and environmental protection, heavy metal wastewater must be treated. On the one hand, the valuable metals can be recovered, and more importantly, the damage to the environment can be reduced.
  • the patent with publication number CN101974695A discloses a method for treating copper-containing wastewater.
  • the method mainly adjusts the acidity of the wastewater and then replaces and reduces the copper therein with iron under the condition of adding appropriate additives.
  • the copper concentration of the treated copper-containing wastewater is about 30g/L. Under the condition of assisting certain additives, a high recovery rate can be obtained.
  • this method requires external iron for replacement, and generally cannot produce high-grade copper, and impurities are inevitably present on its surface.
  • the neutralization method is to add reagents to the wastewater to remove the heavy metal ions in the wastewater by forming hydroxides or carbonates with low solubility. Soda lime and other reagents are cheap and can remove heavy metals other than mercury. The operation is simple. However, the neutralization method will generate a large amount of heavy metal slag, which is easy to cause secondary pollution, and sometimes the treated water cannot meet the discharge standards.
  • the invention patent with the announcement number CN1403385 provides a double-circulation recovery method for cyanide and heavy metal electroplating, which includes the following steps: exchange by the recovery device, treatment with the regeneration agent, destruction of cyanide ions, and recovery of heavy metals.
  • the recovery device uses an ion exchange column to absorb cyanide in the wastewater. Heavy metal ions are adsorbed and desorbed, and the desorbed liquid is electrolyzed to recover the heavy metals at the cathode.
  • the ion exchange resin is difficult to regenerate in this process and needs to be replaced frequently, which affects production efficiency.
  • the first problem that the new technology should solve should be how to thoroughly treat heavy metal wastewater and prevent secondary pollution.
  • the treatment cost, water quality and resource recovery should also be considered.
  • Membrane technology is a discipline that has developed very rapidly in recent years. It has the advantages of simple process, good effluent quality and low treatment cost, and has been applied in many fields. Among them, the retention rate of nanofiltration membrane for high-valent metal ions is more than 95%, and the reverse osmosis membrane can retain all solutes and only allow water to pass through.
  • the heavy metal wastewater generated in the production process of printed circuit boards contains a variety of metal ions.
  • the neutralization method is prone to secondary pollution, the replacement method consumes pure metals and the product purity is difficult to control, and the cost of the ion exchange method is relatively high compared to membrane technology. Therefore, the membrane technology treatment scheme adopted by the present invention has obvious advantages in both treatment effect and treatment cost.
  • the purpose of the present invention is to provide an energy-saving and environmentally friendly membrane treatment process for copper-containing heavy metal wastewater generated in the PCB production process in view of the shortcomings of the existing process for treating copper-containing heavy metal wastewater generated in the PCB production process.
  • the present invention provides a membrane treatment process for copper-containing wastewater generated in a PCB production process, comprising the following steps:
  • Copper-containing filtrate treated by multi-media filter + mechanical filter The copper-containing wastewater is first treated by a multi-media filter, and the obtained multi-media filter filtrate is then treated by a mechanical filter equipped with a filter bag to obtain a copper-containing filtrate treated by the multi-media filter + mechanical filter;
  • Pre-concentration and dialyzate containing copper by multi-stage nanofiltration membrane the copper-containing filtrate treated by the multi-media filter + mechanical filter is passed through the multi-stage nanofiltration membrane, and the copper-containing filtrate is pre-concentrated by the nanofiltration process to obtain the multi-stage nanofiltration membrane copper-containing pre-concentrate and dialyzate;
  • Multi-stage reverse osmosis membrane concentration The copper-containing pre-concentrated liquid from the multi-stage nanofiltration membrane is passed through a multi-stage reverse osmosis membrane to achieve deep concentration and recover copper ions in the copper-containing PCB waste liquid.
  • the reverse osmosis copper-containing concentrated liquid is used in the PCB production line to achieve copper electroplating recycling.
  • the copper-containing dialysate from the reverse osmosis membrane can be mixed with the copper-containing dialysate from the multi-stage nanofiltration membrane and then passed through a first-stage nanofiltration to obtain the nanofiltration permeate, which is then returned to production as flushing water.
  • the multi-media filter added in step 1) includes activated carbon + sand filtration for filtration, and the pore size range of the activated carbon is 0.1-10 microns.
  • the mechanical filter adopts a security filter containing a filter bag
  • the filter bag material used is one of polypropylene, polyethylene, and polytetrafluoroethylene.
  • the operating conditions of the multi-stage nanofiltration in step 2) are: the number of nanofiltration stages is 1-3, the nanofiltration operating temperature is 10-40° C., and the pressure is 0.5-2.0 MPa.
  • the operating conditions of the multi-stage reverse osmosis in step 3) are: the reverse osmosis operation stage is 1-3, the reverse osmosis operation temperature is 10-40° C., and the pressure is 1.0-4.0 MPa.
  • the membrane component material of the nanofiltration membrane in step 2) is an organic polymer, wherein the membrane material is one of cellulose derivatives, polysulfones, and polyamides, and the membrane support material is one of polyesters and polyolefins.
  • the membrane component material of the reverse osmosis membrane in step 3) is an organic polymer, wherein the membrane material is one of cellulose derivatives, polysulfones, and polyamides, and the membrane support material is one of polyesters and polyolefins.
  • the membrane assembly of the nanofiltration membrane in step 2) is in the form of a tubular type, a flat plate type, or a rolled type.
  • the membrane assembly of the reverse osmosis membrane in step 3) is in the form of a tubular type, a flat plate type, or a rolled type.
  • the present invention combines efficient membrane separation technology with traditional low-cost physical and chemical methods to form a new process for treating copper-containing heavy metal wastewater generated in the PCB production process by using a mechanical filter + security filter pretreatment + nanofiltration + reverse osmosis two-stage membrane process instead of the traditional neutralization precipitation method, thereby preventing the transfer of pollution.
  • the new process has the advantages of high treatment efficiency, environmental protection, energy saving and low cost. Under the influence of the national energy conservation and emission reduction policy, the development prospects of this process are very optimistic.
  • FIG. 1 is a flow chart of the process of the present invention.
  • the copper-containing wastewater generated during the PCB production process passes through a mechanical filter + security filter pretreatment system, and the filtrate (300 liters) enters a roll-type 2-stage nanofiltration system with a membrane pore size greater than 1nm.
  • the operating temperature of the nanofiltration system is controlled to be 30°C and the pressure is 1.25MPa; the concentrated liquid (30 liters) is then passed through a roll-type 2-stage reverse osmosis system with a pore size of 0.2nm at a temperature of 40°C and a pressure of 2.0MPa, and finally a concentrated liquid (5 liters) is obtained, in which the copper ion concentration reaches 3g/L, which can enter the electroplating process; the nanofiltration permeate (270 liters) is obtained, which is similar to the composition of the comprehensive wastewater, so it can be mixed with the comprehensive wastewater to enter the nanofiltration system, and the nanofiltration permeate can be returned to the production system as flushing water.
  • the concentrated liquid (6 liters) is obtained, in which the copper ion concentration is about 4g/L, which can enter the electroplating process;
  • the nanofiltration permeate (240 liters) is obtained, which is similar to the comprehensive wastewater composition, so it can be mixed with the comprehensive wastewater to enter the nanofiltration system, and the nanofiltration permeate can be returned to the production system as flushing water.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Disclosed in the present invention is a membrane treatment technology for copper-containing wastewater generated in a printed circuit board (PCB) production process, comprising: copper-containing wastewater generated in a PCB production process first passing through a multi-medium filter and a mechanical filter to remove large-particle suspended substances; then implementing preconcentration by means of a multi-stage nanofiltration system; and finally, performing deep concentration by means of a multi-stage reverse osmosis system to recover heavy metal ions in the wastewater, wherein a concentrated solution can be used for electrolysis, a dialysate and comprehensive wastewater pass through a multi-stage nanofiltration membrane together, and the dialysate can reach a discharge standard. The technology has the advantages of low resource consumption, less environmental pollution, and good economic benefit and the like.

Description

一种PCB生产过程中产生的含铜废水的膜法处理工艺A membrane treatment process for copper-containing wastewater generated during PCB production
本申请要求于2022年11月29日提交中国专利局的中国专利申请的优先权，中国专利申请的申请号为202211507404.0，发明名称为“一种PCB生产过程中产生的含铜废水的膜法处理工艺”，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on November 29, 2022. The application number of the Chinese patent application is 202211507404.0, and the name of the invention is "A membrane treatment process for copper-containing wastewater generated in the PCB production process", all of which are incorporated by reference in this application.
技术领域Technical Field
本发明是关于一种对印刷电路板生产过程中产生的废水进行处理的方法，尤其是对印刷电路板(PCB)生产过程中产生的含铜的重金属废水的处理方法。The present invention relates to a method for treating wastewater generated in the production process of printed circuit boards, in particular to a method for treating copper-containing heavy metal wastewater generated in the production process of printed circuit boards (PCBs).
背景技术Background technique
随着我国现代化程度的提高，对电子产品的需求越来越大，而大多高新的电子元件多依托在印刷电路板上，因此每天都会有大量的印刷电路板出产，不可避免的会产生大量的重金属废水。PCB生产过程中会多次涉及电镀铜工序，而镀板又很容易被氧化，进行下一步处理之前需要采用盐酸及双氧水对其进行酸洗除去氧化层，于是会产生大量的酸洗废水，此类废水中主要的重金属离子含量较高。综合废水则是指在印制线路板制作过程中的除油、显影等前后处理工序中产生的含多种金属的废水，此类废水一般汇合一处，集中处理，因此统称为综合废水。大量重金属进入人体后会与生理高分子物质相互作用而使其失去活性，也可能积累在人体造成慢性中毒；重金属废水用于灌溉时，会使土壤盐渍化，影响农作物生长。因此，从人身健康、农业发展以及环境保护角度考虑，重金属废水必需经过处理， 一方面可以回收其中的有价金属，更重要的是减小对环境的损害。With the improvement of my country's modernization, the demand for electronic products is increasing, and most high-tech electronic components rely on printed circuit boards. Therefore, a large number of printed circuit boards are produced every day, and a large amount of heavy metal wastewater will inevitably be generated. The PCB production process involves copper electroplating processes many times, and the plated board is easily oxidized. Before the next step of treatment, it is necessary to use hydrochloric acid and hydrogen peroxide to pickle it to remove the oxide layer, so a large amount of pickling wastewater will be generated. The main heavy metal ion content in this type of wastewater is relatively high. Comprehensive wastewater refers to wastewater containing multiple metals generated in the pre- and post-processing processes such as degreasing and development in the production process of printed circuit boards. This type of wastewater is generally collected in one place and treated centrally, so it is collectively referred to as comprehensive wastewater. After a large amount of heavy metals enter the human body, they will interact with physiological polymer substances and make them inactive, and may also accumulate in the human body to cause chronic poisoning; when heavy metal wastewater is used for irrigation, it will cause soil salinization and affect the growth of crops. Therefore, from the perspective of human health, agricultural development and environmental protection, heavy metal wastewater must be treated. On the one hand, the valuable metals can be recovered, and more importantly, the damage to the environment can be reduced.
目前，对重金属废水的处理研究已成为冶金、环保专家共同关注的热点。目前针对重金属废水的处理技术主要有化学法、离子交换法、生物法等。但是这些方法都是将重金属污染转移到沉淀或更容易处理的形式。At present, the treatment of heavy metal wastewater has become a hot topic of concern for metallurgical and environmental experts. At present, the main treatment technologies for heavy metal wastewater include chemical method, ion exchange method, biological method, etc. However, these methods transfer heavy metal pollution to precipitation or a form that is easier to handle.
公开号为CN101974695A的专利公开了一种处理含铜废水的方法，该法主要通过调节废水的酸度后，在加入适当的添加剂的情况下，用铁置换还原其中的铜，其处理的含铜废水铜浓度在30g/L左右，在辅助一定的添加剂的条件下能够得到很高的回收率。但此法需要外加铁进行置换，且一般不能制备高品位的铜，其表面难免会有杂质存在。The patent with publication number CN101974695A discloses a method for treating copper-containing wastewater. The method mainly adjusts the acidity of the wastewater and then replaces and reduces the copper therein with iron under the condition of adding appropriate additives. The copper concentration of the treated copper-containing wastewater is about 30g/L. Under the condition of assisting certain additives, a high recovery rate can be obtained. However, this method requires external iron for replacement, and generally cannot produce high-grade copper, and impurities are inevitably present on its surface.
中和法即向废液中投加药剂，使废水中的重金属离子形成溶解度较小的氢氧化物或碳酸盐沉淀而得以除去。碱石灰等药剂价格低廉，可以除去除汞以外的重金属，操作简便。但是中和法会生成大量的重金属渣，容易造成二次污染，而且有时候处理后的水并不能达到排放标准。The neutralization method is to add reagents to the wastewater to remove the heavy metal ions in the wastewater by forming hydroxides or carbonates with low solubility. Soda lime and other reagents are cheap and can remove heavy metals other than mercury. The operation is simple. However, the neutralization method will generate a large amount of heavy metal slag, which is easy to cause secondary pollution, and sometimes the treated water cannot meet the discharge standards.
公开号为CN101003396A发明专利公开了一种印刷线路板微蚀含铜废水的处理系统，其包含铜分离系统，电解系统，废水前处理系统和废水后处理系统。其铜分离系统包含一台萃取分离机和一台反萃取分离机，电解系统采用隔膜电解，其前后废水处理系统包含隔油槽、升降吸油器等。该法能有效处理微蚀含铜废水，但其电解流程中对含铜废水的除油处理效果直接影响电解效果，不易于控制。The invention patent with publication number CN101003396A discloses a treatment system for copper-containing wastewater from micro-etching of printed circuit boards, which includes a copper separation system, an electrolysis system, a wastewater pre-treatment system and a wastewater post-treatment system. The copper separation system includes an extraction separator and a stripping separator, the electrolysis system adopts diaphragm electrolysis, and the front and rear wastewater treatment systems include an oil separator, a lifting oil absorber, etc. This method can effectively treat copper-containing wastewater from micro-etching, but the degreasing effect of copper-containing wastewater in the electrolysis process directly affects the electrolysis effect and is not easy to control.
公告号为CN1403385的发明专利提供了一种氰系及含有重金属电镀的双循环回收方法，他包括以下步骤：回收装置进行交换、再生剂处理、破坏氰离子、回收重金属。其回收装置采用离子交换柱，吸附废水中的氰化 物重金属离子，吸附饱和和解吸，解吸液再经电解工序，即可在阴极回收得到重金属。但该工艺中离子交换树脂再生困难，需经常更换，影响生产效率。The invention patent with the announcement number CN1403385 provides a double-circulation recovery method for cyanide and heavy metal electroplating, which includes the following steps: exchange by the recovery device, treatment with the regeneration agent, destruction of cyanide ions, and recovery of heavy metals. The recovery device uses an ion exchange column to absorb cyanide in the wastewater. Heavy metal ions are adsorbed and desorbed, and the desorbed liquid is electrolyzed to recover the heavy metals at the cathode. However, the ion exchange resin is difficult to regenerate in this process and needs to be replaced frequently, which affects production efficiency.
由于重金属废水传统处理工艺，尤其中和沉淀法产生的大量重金属渣已经引发多起重金属污染事件，开发新的重金属废水处理方法迫在眉睫。新的技术首先要解决的问题应该是如何彻底处理重金属废水，杜绝二次污染。同时也要考虑处理成本及产水质量以及资源回收等。膜技术是近年来发展十分迅速的一门学科，其具有工艺简单、出水水质好、处理成本低等优点，已在很多领域得到应用。其中纳滤膜对高价金属离子的截留率95％以上，反渗透膜能截留所有溶质，仅让水透过。印刷电路板生产过程产生的重金属废水含有多种金属离子，中和法容易形成二次污染，置换法消耗纯金属且产品纯度不易控制，离子交换法的成本相对膜技术较高，因此本发明所采用的膜技术处理方案无论在处理效果还是处理成本上都具有明显的优势。Since the traditional treatment process of heavy metal wastewater, especially the large amount of heavy metal slag produced by the neutralization precipitation method, has caused many heavy metal pollution incidents, it is urgent to develop a new method for treating heavy metal wastewater. The first problem that the new technology should solve should be how to thoroughly treat heavy metal wastewater and prevent secondary pollution. At the same time, the treatment cost, water quality and resource recovery should also be considered. Membrane technology is a discipline that has developed very rapidly in recent years. It has the advantages of simple process, good effluent quality and low treatment cost, and has been applied in many fields. Among them, the retention rate of nanofiltration membrane for high-valent metal ions is more than 95%, and the reverse osmosis membrane can retain all solutes and only allow water to pass through. The heavy metal wastewater generated in the production process of printed circuit boards contains a variety of metal ions. The neutralization method is prone to secondary pollution, the replacement method consumes pure metals and the product purity is difficult to control, and the cost of the ion exchange method is relatively high compared to membrane technology. Therefore, the membrane technology treatment scheme adopted by the present invention has obvious advantages in both treatment effect and treatment cost.
发明内容Summary of the invention
本发明的目的在于针对现有处理PCB生产过程中产生的含铜重金属废水的工艺存在的不足，提供一种节能环保的PCB生产过程中产生的含铜的重金属废水的膜处理工艺。The purpose of the present invention is to provide an energy-saving and environmentally friendly membrane treatment process for copper-containing heavy metal wastewater generated in the PCB production process in view of the shortcomings of the existing process for treating copper-containing heavy metal wastewater generated in the PCB production process.
为了实现本发明的目的，本发明提供了一种PCB生产过程中产生的含铜废水的膜法处理工艺，包括如下步骤：In order to achieve the purpose of the present invention, the present invention provides a membrane treatment process for copper-containing wastewater generated in a PCB production process, comprising the following steps:
1)多介质过滤器+机械过滤器处理的含铜滤液：将PCB生产过程中产生 的含铜废水首先经过多介质过滤器处理，得到的多介质过滤器滤液再经过装有滤袋的机械过滤器处理，得到多介质过滤器+机械过滤器处理的含铜滤液；1) Copper-containing filtrate treated by multi-media filter + mechanical filter: The copper-containing wastewater is first treated by a multi-media filter, and the obtained multi-media filter filtrate is then treated by a mechanical filter equipped with a filter bag to obtain a copper-containing filtrate treated by the multi-media filter + mechanical filter;
2)多级纳滤膜含铜的预浓缩和透析液：将多介质过滤器+机械过滤器处理的含铜滤液通过多级纳滤膜，通过纳滤过程实现含铜滤液的预浓缩，得到多级纳滤膜含铜的预浓缩液和透析液；2) Pre-concentration and dialyzate containing copper by multi-stage nanofiltration membrane: the copper-containing filtrate treated by the multi-media filter + mechanical filter is passed through the multi-stage nanofiltration membrane, and the copper-containing filtrate is pre-concentrated by the nanofiltration process to obtain the multi-stage nanofiltration membrane copper-containing pre-concentrate and dialyzate;
3)多级反渗透膜浓缩：将多级纳滤膜含铜的预浓缩液通过多级反渗透膜，实现深度浓缩，回收含铜PCB废液中的铜离子，反渗透含铜浓缩液用于PCB生产线实现铜的电镀回收利用，反渗透膜的含铜透析液可与多级纳滤膜的含铜透析液一起混合后再通过一级纳滤，得到纳滤透过液回用于生产作为冲洗水。3) Multi-stage reverse osmosis membrane concentration: The copper-containing pre-concentrated liquid from the multi-stage nanofiltration membrane is passed through a multi-stage reverse osmosis membrane to achieve deep concentration and recover copper ions in the copper-containing PCB waste liquid. The reverse osmosis copper-containing concentrated liquid is used in the PCB production line to achieve copper electroplating recycling. The copper-containing dialysate from the reverse osmosis membrane can be mixed with the copper-containing dialysate from the multi-stage nanofiltration membrane and then passed through a first-stage nanofiltration to obtain the nanofiltration permeate, which is then returned to production as flushing water.
进一步地，步骤1)中加入的多介质过滤器包括活性炭+砂滤进行过滤，活性炭孔径范围为0.1-10微米。Furthermore, the multi-media filter added in step 1) includes activated carbon + sand filtration for filtration, and the pore size range of the activated carbon is 0.1-10 microns.
进一步地，步骤1)中机械过滤器采用含有滤袋的保安过滤器，所用滤袋材质为聚丙烯、聚乙烯、聚四氟乙烯类中的一种。Furthermore, in step 1), the mechanical filter adopts a security filter containing a filter bag, and the filter bag material used is one of polypropylene, polyethylene, and polytetrafluoroethylene.
进一步地，步骤2)中所述的多级纳滤的操作条件为：纳滤级数为1-3级，纳滤操作温度为10-40℃，压力为0.5-2.0MPa。Furthermore, the operating conditions of the multi-stage nanofiltration in step 2) are: the number of nanofiltration stages is 1-3, the nanofiltration operating temperature is 10-40° C., and the pressure is 0.5-2.0 MPa.
进一步地，步骤3)中所述的多级反渗透的操作条件为：反渗透操作级数为1-3级，反渗透操作温度为10-40℃，压力为1.0-4.0MPa。Furthermore, the operating conditions of the multi-stage reverse osmosis in step 3) are: the reverse osmosis operation stage is 1-3, the reverse osmosis operation temperature is 10-40° C., and the pressure is 1.0-4.0 MPa.
进一步地，步骤2)中所述纳滤膜的膜组件材料为有机高分子，其中膜材料为纤维素衍生物类、聚砜类、聚酰胺类中的一种，膜支撑材料为聚酯类、聚烯烃类中的一种。 Furthermore, the membrane component material of the nanofiltration membrane in step 2) is an organic polymer, wherein the membrane material is one of cellulose derivatives, polysulfones, and polyamides, and the membrane support material is one of polyesters and polyolefins.
进一步地，步骤3)中所述反渗透膜的膜组件材料为有机高分子，其中膜材料为纤维素衍生物类、聚砜类、聚酰胺类中的一种，膜支撑材料为聚酯类、聚烯烃类中的一种。Furthermore, the membrane component material of the reverse osmosis membrane in step 3) is an organic polymer, wherein the membrane material is one of cellulose derivatives, polysulfones, and polyamides, and the membrane support material is one of polyesters and polyolefins.
进一步地，步骤2)中所述纳滤膜的膜组件形式为管式、平板式、卷式中的一种。Furthermore, the membrane assembly of the nanofiltration membrane in step 2) is in the form of a tubular type, a flat plate type, or a rolled type.
进一步地，步骤3)中所述反渗透膜的膜组件形式为管式、平板式、卷式中的一种。Furthermore, the membrane assembly of the reverse osmosis membrane in step 3) is in the form of a tubular type, a flat plate type, or a rolled type.
本发明将高效的膜分离技术与传统的低成本物化方法结合，形成对PCB生产过程中产生的含铜重金属废水拟采用机械过滤器+保安过滤器预处理+纳滤+反渗透两级膜过程代替传统中和沉淀法对PCB生产过程中产生的含铜重金属废水进行处理的新工艺，防止了污染的转移，新工艺具备处理效率高、环保节能和低成本等优点。在国家节能减排政策的影响下，此工艺的发展前景非常乐观。The present invention combines efficient membrane separation technology with traditional low-cost physical and chemical methods to form a new process for treating copper-containing heavy metal wastewater generated in the PCB production process by using a mechanical filter + security filter pretreatment + nanofiltration + reverse osmosis two-stage membrane process instead of the traditional neutralization precipitation method, thereby preventing the transfer of pollution. The new process has the advantages of high treatment efficiency, environmental protection, energy saving and low cost. Under the influence of the national energy conservation and emission reduction policy, the development prospects of this process are very optimistic.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.
图1为本发明所述工艺的流程图。FIG. 1 is a flow chart of the process of the present invention.
具体实施方式Detailed ways
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白 了解，下面结合具体实施例进一步阐述本发明，而不会限制本发明。In order to make the technical means, creative features, objectives and effects of the present invention easy to understand It is understood that the present invention is further described below in conjunction with specific embodiments, but the present invention is not limited thereto.
实施例1Example 1
PCB生产过程中产生的含铜废水通过机械过滤器+保安过滤器预处理系统，滤液(300升)进入膜孔径大于1nm的卷式2级纳滤系统，控制纳滤系统的操作温度为30℃，压力为1.25MPa；浓缩液(30升)再在温度为40℃，压力为2.0MPa的条件下经过孔径为0.2nm的卷式2级反渗透系统，最终得到浓缩液(5升)，其中铜离子浓度达到3g/L，可以进入电镀工序；得到纳滤渗透液(270升)，与综合废水成分类似，故可与综合废水混合进入纳滤系统，纳滤渗透液可返回生产系统作为冲洗水。The copper-containing wastewater generated during the PCB production process passes through a mechanical filter + security filter pretreatment system, and the filtrate (300 liters) enters a roll-type 2-stage nanofiltration system with a membrane pore size greater than 1nm. The operating temperature of the nanofiltration system is controlled to be 30°C and the pressure is 1.25MPa; the concentrated liquid (30 liters) is then passed through a roll-type 2-stage reverse osmosis system with a pore size of 0.2nm at a temperature of 40°C and a pressure of 2.0MPa, and finally a concentrated liquid (5 liters) is obtained, in which the copper ion concentration reaches 3g/L, which can enter the electroplating process; the nanofiltration permeate (270 liters) is obtained, which is similar to the composition of the comprehensive wastewater, so it can be mixed with the comprehensive wastewater to enter the nanofiltration system, and the nanofiltration permeate can be returned to the production system as flushing water.
实施例2Example 2
PCB生产过程中产生的含铜废水通过机械过滤器+保安过滤器预处理系统，滤液(300升)进入膜孔径大于1nm的平板3级纳滤系统，控制纳滤系统的操作温度为35℃，压力为2.0MPa；浓缩液(60升)再在温度为40℃，压力为2.0MPa的条件下经过孔径为0.2nm的平板3级反渗透系统。最终得到浓缩液(6升)，其中铜离子浓度约4g/L，可以进入电镀工序；得到纳滤渗透液(240升)，与综合废水成分类似，故可与综合废水混合进入纳滤系统，纳滤渗透液可返回生产系统作为冲洗水。The copper-containing wastewater generated during the PCB production process passes through the mechanical filter + security filter pretreatment system, and the filtrate (300 liters) enters the flat plate 3-stage nanofiltration system with a membrane pore size greater than 1nm. The operating temperature of the nanofiltration system is controlled to be 35℃ and the pressure is 2.0MPa; the concentrated liquid (60 liters) is then passed through the flat plate 3-stage reverse osmosis system with a pore size of 0.2nm under the conditions of temperature of 40℃ and pressure of 2.0MPa. Finally, the concentrated liquid (6 liters) is obtained, in which the copper ion concentration is about 4g/L, which can enter the electroplating process; the nanofiltration permeate (240 liters) is obtained, which is similar to the comprehensive wastewater composition, so it can be mixed with the comprehensive wastewater to enter the nanofiltration system, and the nanofiltration permeate can be returned to the production system as flushing water.
实施例3Example 3
PCB生产过程中产生的含铜废水通过机械过滤器+保安过滤器预处理系统，滤液(300升)升进入膜孔径大于1nm的卷式纳滤系统，控制纳滤系统的温度为20℃，操作压力为1.25MPa。最终得到270升渗透液和30升浓缩液，浓缩液可进入一般酸洗废水的反渗透处理工序，透过液能达到国家 排放标准，可直接排放。The copper-containing wastewater generated during the PCB production process passes through the mechanical filter + security filter pretreatment system, and the filtrate (300 liters) enters the roll nanofiltration system with a membrane pore size greater than 1nm. The temperature of the nanofiltration system is controlled at 20℃ and the operating pressure is 1.25MPa. Finally, 270 liters of permeate and 30 liters of concentrate are obtained. The concentrate can enter the reverse osmosis treatment process of general pickling wastewater, and the permeate can reach the national Emission standards, can be discharged directly.
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。 The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims (9)

  1. 一种PCB生产过程中产生的含铜废水的膜法处理工艺，其特征在于，包括如下步骤：A membrane treatment process for copper-containing wastewater generated in a PCB production process, characterized in that it comprises the following steps:
    1)多介质过滤器+机械过滤器处理的含铜滤液：将PCB生产过程中产生的含铜废水首先经过多介质过滤器处理，得到的多介质过滤器滤液再经过装有滤袋的机械过滤器处理，得到多介质过滤器+机械过滤器处理的含铜滤液；1) Copper-containing filtrate treated by multi-media filter + mechanical filter: The copper-containing wastewater generated in the PCB production process is first treated by a multi-media filter, and the obtained multi-media filter filtrate is then treated by a mechanical filter equipped with a filter bag to obtain a copper-containing filtrate treated by a multi-media filter + mechanical filter;
    2)多级纳滤膜含铜的预浓缩和透析液：将多介质过滤器+机械过滤器处理的含铜滤液通过多级纳滤膜，通过纳滤过程实现含铜滤液的预浓缩，得到多级纳滤膜含铜的预浓缩液和透析液；2) Pre-concentration and dialyzate containing copper by multi-stage nanofiltration membrane: the copper-containing filtrate treated by the multi-media filter + mechanical filter is passed through the multi-stage nanofiltration membrane, and the copper-containing filtrate is pre-concentrated by the nanofiltration process to obtain the multi-stage nanofiltration membrane copper-containing pre-concentrate and dialyzate;
    3)多级反渗透膜浓缩：将多级纳滤膜含铜的预浓缩液通过多级反渗透膜，实现深度浓缩，回收含铜PCB废液中的铜离子，反渗透含铜浓缩液用于PCB生产线实现铜的电镀回收利用，反渗透膜的含铜透析液可与多级纳滤膜的含铜透析液一起混合后再通过一级纳滤膜，得到纳滤膜透过液回用于生产作为冲洗水。3) Multi-stage reverse osmosis membrane concentration: The copper-containing pre-concentrated liquid from the multi-stage nanofiltration membrane is passed through a multi-stage reverse osmosis membrane to achieve deep concentration and recover copper ions in the copper-containing PCB waste liquid. The reverse osmosis copper-containing concentrated liquid is used in the PCB production line to achieve copper electroplating recycling. The copper-containing dialysate from the reverse osmosis membrane can be mixed with the copper-containing dialysate from the multi-stage nanofiltration membrane and then passed through a primary nanofiltration membrane to obtain the nanofiltration membrane permeate, which is then used back in production as flushing water.
  2. 根据权利要求1所述的一种PCB生产过程中产生的含铜废水的膜法处理工艺，其特征在于，步骤1)中加入的多介质过滤器包括活性炭+砂滤进行过滤，活性炭孔径范围为0.1-10微米。The membrane treatment process for copper-containing wastewater generated in a PCB production process according to claim 1 is characterized in that the multi-media filter added in step 1) comprises activated carbon + sand filtration for filtration, and the pore size range of the activated carbon is 0.1-10 microns.
  3. 根据权利要求1所述的一种PCB生产过程中产生的含铜废水的膜法处理工艺，其特征在于，步骤1)机械过滤器采用含有滤袋的保安过滤器，所用滤袋材质为聚丙烯、聚乙烯、聚四氟乙烯类中的一种。The membrane treatment process for copper-containing wastewater generated in a PCB production process according to claim 1 is characterized in that the mechanical filter in step 1) adopts a security filter containing a filter bag, and the filter bag material used is one of polypropylene, polyethylene, and polytetrafluoroethylene.
  4. 根据权利要求1所述的一种PCB生产过程中产生的含铜废水的膜法 处理工艺，其特征在于，步骤2)的多级纳滤的操作条件为：纳滤级数为1-3级，纳滤操作温度为10-40℃，压力为0.5-2.0MPa。The membrane method for treating copper-containing wastewater generated in a PCB production process according to claim 1 The treatment process is characterized in that the operating conditions of the multi-stage nanofiltration in step 2) are: the nanofiltration stage is 1-3, the nanofiltration operating temperature is 10-40°C, and the pressure is 0.5-2.0MPa.
  5. 根据权利要求1所述的一种PCB生产过程中产生的含铜废水的膜法处理工艺，其特征在于，步骤3)中的多级反渗透的操作条件为：反渗透操作级数为1-3级，反渗透操作温度为10-40℃，压力为1.0-4.0MPa。The membrane treatment process for copper-containing wastewater generated in a PCB production process according to claim 1 is characterized in that the operating conditions of the multi-stage reverse osmosis in step 3) are: the reverse osmosis operation level is 1-3 levels, the reverse osmosis operation temperature is 10-40° C., and the pressure is 1.0-4.0 MPa.
  6. 根据权利要求1所述的一种PCB生产过程中产生的含铜废水的膜法处理工艺，其特征在于，步骤2)中所述纳滤膜的膜组件材料为有机高分子，其中膜面材料为纤维素衍生物类、聚砜类、聚酰胺类中的一种，膜面支撑材料为聚酯类、聚烯烃类中的一种。According to claim 1, the membrane treatment process for copper-containing wastewater generated in the PCB production process is characterized in that the membrane component material of the nanofiltration membrane in step 2) is an organic polymer, wherein the membrane surface material is one of cellulose derivatives, polysulfones, and polyamides, and the membrane surface support material is one of polyesters and polyolefins.
  7. 根据权利要求1所述的一种PCB生产过程中产生的含铜废水的膜法处理工艺，其特征在于，步骤3)中所述反渗透膜的膜组件材料为有机高分子，其中膜面材料为纤维素衍生物类、聚砜类、聚酰胺类中的一种，膜面支撑材料为聚酯类、聚烯烃类中的一种。According to claim 1, the membrane treatment process for copper-containing wastewater generated in a PCB production process is characterized in that the membrane component material of the reverse osmosis membrane in step 3) is an organic polymer, wherein the membrane surface material is one of cellulose derivatives, polysulfones, and polyamides, and the membrane surface support material is one of polyesters and polyolefins.
  8. 根据权利要求1所述的一种PCB生产过程中产生的含铜废水的膜法处理工艺，其特征在于，步骤2)中所述纳滤膜的膜组件形式为管式、平板式、卷式中的一种。According to the membrane treatment process for copper-containing wastewater generated in a PCB production process as described in claim 1, it is characterized in that the membrane component of the nanofiltration membrane in step 2) is in the form of a tubular type, a flat plate type, or a roll type.
  9. 根据权利要求1所述的一种PCB生产过程中产生的含铜废水的膜法处理工艺，其特征在于，步骤3)中所述反渗透膜的膜组件形式为管式、平板式、卷式中的一种。。 The membrane treatment process for copper-containing wastewater generated in a PCB production process according to claim 1 is characterized in that the membrane assembly of the reverse osmosis membrane in step 3) is in the form of a tubular type, a flat plate type, or a roll type.
PCT/CN2023/102630 2022-11-29 2023-06-27 Membrane treatment technology for copper-containing wastewater generated in pcb production process WO2024113798A1 (en)

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CN115745298A (en) * 2022-11-29 2023-03-07 中南大学 Membrane method treatment process for tin-containing wastewater generated in PCB production process

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