WO2018040223A1 - Simple and convenient method for improving efficiency of closed nickel-zinc electrolytic-plating rinse-water online recycling membrane system - Google Patents

Simple and convenient method for improving efficiency of closed nickel-zinc electrolytic-plating rinse-water online recycling membrane system Download PDF

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WO2018040223A1
WO2018040223A1 PCT/CN2016/101463 CN2016101463W WO2018040223A1 WO 2018040223 A1 WO2018040223 A1 WO 2018040223A1 CN 2016101463 W CN2016101463 W CN 2016101463W WO 2018040223 A1 WO2018040223 A1 WO 2018040223A1
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nickel
closure system
membrane
zinc electroplating
rinsing wastewater
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PCT/CN2016/101463
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French (fr)
Chinese (zh)
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靳强
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上海交通大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • 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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/08—Thin film evaporation
    • 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
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • 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
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/14—Maintenance of water treatment installations

Definitions

  • the invention relates to the field of environmental protection, in particular to a simple method for improving the efficiency of an online resource-removing membrane closure system for nickel-zinc electroplating and rinsing wastewater.
  • Electroplating is an important process in the manufacturing industry, and the composition of wastewater is complex.
  • the annual average discharge of electroplating wastewater in China is as high as 4 billion tons, of which rinsing wastewater accounts for 80%, about 3.2 billion tons.
  • Nickel-plated zinc is a main type of plating in China, and the corresponding nickel-zinc plating rinsing wastewater is also a large-scale electroplating rinsing wastewater.
  • organic compounds such as additives and brighteners.
  • the most commonly used methods for nickel-zinc electroplating and rinsing wastewater treatment are chemical precipitation method, ion exchange method and membrane separation method.
  • the chemical precipitation method is aimed at achieving discharge standards, the sludge volume is large, the treatment cost is high, and the heavy metal nickel zinc is not It is regarded as a kind of resource reuse, which makes the economic benefits basically negative.
  • the ion exchange method can only achieve the reuse of heavy metal nickel-zinc ions, while other substances such as various additives cannot be reused, and the waste water contains various additives other than nickel-zinc ions, which must be further removed before being discharged or recycled. After the ion exchange resin is saturated and adsorbed, it is necessary to regenerate the agent to generate secondary pollution.
  • the patent application No. 201610331251.7 discloses a method for online recycling of plating parts rinsing wastewater, which is characterized in that the rinsing wastewater of the plating part is subjected to multi-stage countercurrent cleaning, filtration, reverse osmosis treatment, nanofiltration treatment and evaporation concentration. Or directly reuse, recover the metal ions and additives in the rinsing wastewater of the plating part, return it as the plating solution liquid in the plating tank, recover the water in the rinsing wastewater of the plating part, and use it as the rinsing water of the plating part to realize the online resource utilization. .
  • the invention adopts a novel combination mode of the reverse osmosis membrane module in the front and the nanofiltration membrane module, and can effectively reuse the heavy metal ions and various additives and water in the rinsing wastewater of the plating part to realize the plating part.
  • the online recycling of rinsing wastewater greatly reduces operating energy consumption and economic costs.
  • the membrane method is not only a treatment method, but also a resource method to realize the recycling of pollutants.
  • the membrane method also has a disadvantage in that the membrane is easily contaminated by the composition of the plating solution, so that the flux is decreased and the energy consumption is increased.
  • chemical cleaning is the primary method of controlling membrane fouling.
  • the membrane flux in the apparatus increased from 0.5MPa before cleaning 13.9L / m 2 ⁇ h to 28.3L / m 2 ⁇ h, flux returns to the initial 89.4%.
  • the chemical cleaning method has the following drawbacks: it needs to be washed and washed; it needs to add cleaning agent every time; after the cleaning, the waste liquid produces secondary pollution.
  • the object of the present invention is to provide a simple method for improving the efficiency of an on-line resource-based membrane closure system for nickel-zinc electroplating rinsing wastewater in order to overcome the drawbacks of the prior art described above.
  • the object of the present invention can be achieved by the following technical solution: a simple method for improving the efficiency of the on-line resource-based membrane closure system for nickel-zinc electroplating and rinsing wastewater, characterized in that the method is on-line resource utilization of the nickel-zinc electroplating rinsing wastewater.
  • a phosphinopolycarboxylate and a polysuccinic acid sodium binary composite reagent with a mass ratio of 1:10 to 10:1 are added to inhibit nickel sulfate, zinc chloride and boric acid in the nickel zinc plating solution.
  • the complex physicochemical polymerization process of five components, sodium lauryl sulfate and AB-type polyamide brightener especially breaks the core role of boric acid, prevents the formation of inorganic-organic composite pollution, maintains high membrane flux for a long time, and improves
  • the performance of the nickel-zinc electroplating rinsing wastewater on-line resource-based membrane closure system reduces economic operation costs.
  • the phosphinopolycarboxylate and the poly(epoxysuccinate) binary complex reagent are added in an amount such that the total concentration on the rich side of the membrane in the system is from 1.0 to 100 ppm.
  • the nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closure system comprises a plating tank, and a cleaning tank, a regulating tank, a low-pressure pump, a security filter, a high-pressure pump, a reverse osmosis membrane device, and a nanofiltration membrane sequentially connected through a pipeline.
  • the device and the falling film evaporator, the falling film evaporator also has a concentrated liquid outlet and a condensed water outlet, wherein the concentrated liquid outlet is also connected to the plating tank, and the condensed water outlet is also connected to the cleaning tank to form a membrane closed system.
  • the cleaning tank is provided with at least one stage.
  • the clear water side of the reverse osmosis membrane device is connected to the cleaning tank, and the concentrated water side is connected to the nanofiltration membrane device.
  • the addition amount of the phosphine-based polycarboxylate and the poly(epoxysuccinate) binary composite reagent in the system is such that the composite reagent is
  • the total concentration of the reverse osmosis membrane device on the concentrated water side is 1.0 to 100 ppm.
  • the fresh water side of the nanofiltration membrane device is connected to the water inlet side of the reverse osmosis device, and the concentrated water side is connected to the falling film evaporator.
  • the phosphinopolycarboxylate and sodium polysuccinate binary complexing agent can be added at any point in the nickel-zinc electroplating rinsing wastewater online resource-recovering system closure system.
  • the phosphinopolycarboxylate and sodium polysuccinate binary complex reagents are in a crystalline form or in a solution state.
  • the present invention has the following advantages:
  • Additive phosphine sodium polycarboxylate and sodium polysuccinate sodium complex reagent can inhibit nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel zinc plating solution 5
  • the chemical cleaning method requires parking cleaning when the membrane flux drops more.
  • the plating solution is cyclically closed.
  • the inert inhibitor phosphinopolycarboxylate and the poly(epoxysuccinate) binary composite reagent are added to the plating solution for closed cycle. Therefore, no parking is required, and it can be carried out continuously;
  • FIG. 1 is a schematic diagram of a nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closure system.
  • the nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closure system comprises a plating tank 1 and a cleaning tank, a regulating tank 5, a low-pressure pump 6, a security filter 7, and a high-pressure pump 8, which are sequentially connected by a pipeline.
  • the reverse osmosis membrane device 9, the nanofiltration membrane device 10 and the falling film evaporator 11, the falling film evaporator 11 is further provided with a concentrated liquid outlet and a condensed water outlet, wherein the concentrated liquid outlet is also connected to the plating tank 1 and condensed
  • the water outlet is also connected to the cleaning tank, and the cleaning tank is provided with three stages, as shown in the figure: the first-stage cleaning tank 2, the second-stage cleaning tank 3 and the third-stage cleaning tank 4 are connected in parallel.
  • the fresh water side of the reverse osmosis membrane device 9 is connected to the washing tank, the cleaned water filtered by the reverse osmosis membrane device 9 is recovered, and the nanofiltration membrane device 10 is connected to the concentrated water side, and further filtered, and the phosphine-based polycarboxylate and the polymer are collected in the system.
  • the amount of the sodium epoxysuccinate binary composite reagent added is such that the total concentration on the concentrated water side of the reverse osmosis membrane device 9 is 1.0 to 100 ppm.
  • the fresh water side of the nanofiltration membrane device 10 is connected to the water inlet side of the reverse osmosis membrane device 9, and the clean water is recovered, and the concentrated water side is connected to the falling film evaporator 11.
  • the entire system forms a membrane closure system.
  • the plating part is electroplated in the plating tank 1 according to the plating direction a, the electroplating wastewater is initially concentrated by the three-stage countercurrent rinsing in the cleaning tank, and is collected in the regulating tank 5, and under the action of the low pressure pump 3, the solid particles larger than 5 ⁇ m are removed by the security filter 4. To protect the safe operation of the subsequent membrane filter.
  • the rinsing wastewater of the plating part After being pressurized by the high pressure pump 8 to 1.0 MPa, the rinsing wastewater of the plating part enters the pre-reverse osmosis membrane module 6, and the effluent water of the reverse osmosis water side can completely meet the requirements of the rinsing quality of the plating part, and the supplementary cleaning after the recovery and the tertiary cleaning tank
  • the water b is mixed; the plating rinsing wastewater is concentrated to obtain the reverse osmosis concentrated water side effluent d, and is sent to the post-nanofiltration membrane module 10 for further concentration.
  • the water filter e on the fresh water side of the nanofiltration membrane module cannot meet the requirements of the rinsing quality of the plating part, and is further purified as the influent water entering the pre-reverse osmosis membrane module 9.
  • the concentrated water side effluent f of the nanofiltration membrane module is further concentrated in the falling film evaporator 11, the obtained concentrated liquid g enters the plating tank 1 and the condensed water h is reused as rinsing water.
  • a phosphine-based polycarboxylate and a polysuccinic acid sodium succinate composite reagent crystal are added at a mass ratio of 1:10, and the film is added in the system.
  • the total concentration of the concentrated side is 1.0 ppm, which is particularly effective in suppressing the complex physicochemical polymerization process of nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB-type polyamide brightener in nickel-zinc plating bath.
  • Boron The core role of acid prevents the formation of inorganic-organic composite pollution, maintains high membrane flux for a long time, improves the performance of the nickel-zinc electroplating wastewater on-line resource-based membrane closure system, and reduces economic operation costs.
  • Additive phosphine sodium polycarboxylate and sodium polysuccinate sodium complex reagent can inhibit nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel zinc plating solution 5
  • the operation time of maintaining more than 80% of the membrane flux is extended by 3 times, which greatly improves the performance of the nickel-zinc electroplating and rinsing wastewater on-line resource-based membrane closure system, and reduces the economic operation cost.
  • the inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent used in the invention are inert, no electrode reaction occurs during system operation, and the whole process is basically no consumption, so there is no need to Add cleaning agent at a time. Compared with the chemical cleaning method, the economic operation cost is saved by 40%;
  • the invention combines the inert inhibitor phosphinopolycarboxylate and polysuccinic acid sodium succinate composite reagent into the plating solution for closed cycle, and can be continuously performed without stopping the chemical compared with the chemical cleaning method;
  • the inert inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent are recycled, and no waste liquid is generated in the whole process, and no secondary pollution is formed. Compared with the chemical cleaning method, the processing cost of the cleaning waste liquid is saved, which accounts for about 30% of the operating cost.
  • the plating solution is added with a phosphinopolycarboxylate and a polysuccinic acid sodium binary composite reagent solution at a mass ratio of 5:5, and the film is added in the system after the addition.
  • the total concentration of the concentrated side is 50.0 ppm, which is particularly effective in suppressing the complex physicochemical polymerization process of nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB-type polyamide brightener in nickel-zinc plating bath.
  • boric acid prevents the formation of inorganic-organic composite pollution, maintains high membrane flux for a long time, improves the performance of the nickel-zinc electroplating wastewater online resource-based membrane closure system, and reduces economic operation costs.
  • Additive phosphine sodium polycarboxylate and sodium polysuccinate sodium complex reagent can inhibit nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel zinc plating solution 5
  • the operating time to maintain more than 80% of the membrane flux is extended by 6 times.
  • the performance of the on-line resource-based membrane closure system for nickel-zinc electroplating and rinsing wastewater is greatly improved, and the economic operation cost is reduced.
  • the inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent used in the invention are inert, no electrode reaction occurs during system operation, and the whole process is basically no consumption, so there is no need to Add cleaning agent at a time. Compared with the chemical cleaning method, the economic operation cost is saved by 50%;
  • the invention combines the inert inhibitor phosphinopolycarboxylate and polysuccinic acid sodium succinate composite reagent into the plating solution for closed cycle, and can be continuously performed without stopping the chemical compared with the chemical cleaning method;
  • the inert inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent are recycled, and no waste liquid is generated in the whole process, and no secondary pollution is formed. Compared with the chemical cleaning method, the processing cost of the cleaning waste liquid is saved, which accounts for about 30% of the operating cost.
  • a phosphine-based polycarboxylate sodium and a poly(epoxysuccinate) binary composite reagent solution are added at a mass ratio of 10:1, and the film is added in the system after the addition.
  • the total concentration of the concentrated side is 100.0ppm, which is particularly effective in suppressing the complex physicochemical polymerization process of five components of nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel-zinc plating bath.
  • the core role of boric acid prevents the formation of inorganic-organic composite pollution, maintains high membrane flux for a long time, improves the performance of the nickel-zinc electroplating wastewater online resource-based membrane closure system, and reduces economic operation costs.
  • Additive phosphine sodium polycarboxylate and sodium polysuccinate sodium complex reagent can inhibit nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel zinc plating solution 5
  • the operation time of maintaining the membrane flux of more than 80% is extended by 12 times, which greatly improves the performance of the on-line resource-based membrane closure system of the nickel-zinc electroplating and rinsing wastewater, and reduces the economic operation cost.
  • the inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent used in the invention are inert, no electrode reaction occurs during system operation, and the whole process is basically no consumption, so there is no need to Add cleaning agent at a time. Compared with the chemical cleaning method, the economic operation cost is saved by 60%;
  • the invention combines the inert inhibitor phosphinopolycarboxylate and polysuccinic acid sodium succinate composite reagent into the plating solution for closed cycle, and can be continuously performed without stopping the chemical compared with the chemical cleaning method;
  • the inert inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent are recycled, and no waste liquid is generated in the whole process, and no secondary pollution is formed. Compared with the chemical cleaning method, the processing cost of the cleaning waste liquid is saved, which accounts for about 30% of the operating cost.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

Provided is a simple and convenient method for improving efficiency of closed nickel-zinc electrolytic-plating rinse-water online recycling membrane system; said method is: adding a phosphine sodium polycarboxylate and sodium polyepoxysuccinate binary compound reagent having a mass ratio of 1:10 to 10:1 to a closed nickel-zinc electrolytic-plating rinse-water online recycling membrane system, the added amount being an amount that causes the total concentration of the membrane-rich side in the system to 1.0 to 100 ppm.

Description

提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法A Simple Method for Improving the Efficiency of Closed System of Nickel-Zinc Electroplating and Rinsing Wastewater by Online Reactive Membrane Method 技术领域Technical field
本发明涉及环境保护领域，具体地说，涉及的是一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法。The invention relates to the field of environmental protection, in particular to a simple method for improving the efficiency of an online resource-removing membrane closure system for nickel-zinc electroplating and rinsing wastewater.
背景技术Background technique
电镀是制造行业的重要工艺环节，排放废水成分复杂。我国电镀废水年均排放量高达40亿吨，其中漂洗废水占80％，约32亿吨。镀镍锌在我国是一种主要的镀种，相应的镍锌电镀漂洗废水也是排放量较大的电镀漂洗废水。除了含有镍锌离子的重金属类污染物，还含有相当数量的添加剂、光亮剂等有机化合物，这些化学物质进入环境，必然会对人类健康以及环境造成及其严重的危害。Electroplating is an important process in the manufacturing industry, and the composition of wastewater is complex. The annual average discharge of electroplating wastewater in China is as high as 4 billion tons, of which rinsing wastewater accounts for 80%, about 3.2 billion tons. Nickel-plated zinc is a main type of plating in China, and the corresponding nickel-zinc plating rinsing wastewater is also a large-scale electroplating rinsing wastewater. In addition to heavy metal pollutants containing nickel and zinc ions, they also contain a considerable amount of organic compounds such as additives and brighteners. These chemicals enter the environment and are bound to cause serious harm to human health and the environment.
目前镍锌电镀漂洗废水处理最常用的方法有化学沉淀法、离子交换法和膜分离法，但化学沉淀法是以达标排放为目的，污泥量大，处理成本高，且未将重金属镍锌视为一种资源回用，致使经济效益基本为负。离子交换法只能实现重金属镍锌离子的回用，而其它物质如各类添加剂则无法回用，且废水中含有除镍锌离子外的各类添加剂而必需进一步去除之后才能排放或回收，此外，离子交换树脂吸附饱和后还需药剂再生，产生二次污染。专利申请号为201610331251.7的发明专利公开了一种镀件漂洗废水在线资源化的方法，该方法是将镀件漂洗废水依次经过多级逆流清洗、过滤、反渗透处理、纳滤处理以及蒸发提浓或直接回用，回收镀件漂洗废水中的金属离子和添加剂，作为镀件液返回镀件槽中，回收镀件漂洗废水中的水，作为镀件漂洗水而回用，实现在线资源化利用。与现有技术相比，该发明采用反渗透膜组件在前、纳滤膜组件在后的新型组合方式，能够有效回用镀件漂洗废水中的重金属离子及各类添加剂和水，实现镀件漂洗废水的在线资源化，且大大降低了运行能耗和经济成本。At present, the most commonly used methods for nickel-zinc electroplating and rinsing wastewater treatment are chemical precipitation method, ion exchange method and membrane separation method. However, the chemical precipitation method is aimed at achieving discharge standards, the sludge volume is large, the treatment cost is high, and the heavy metal nickel zinc is not It is regarded as a kind of resource reuse, which makes the economic benefits basically negative. The ion exchange method can only achieve the reuse of heavy metal nickel-zinc ions, while other substances such as various additives cannot be reused, and the waste water contains various additives other than nickel-zinc ions, which must be further removed before being discharged or recycled. After the ion exchange resin is saturated and adsorbed, it is necessary to regenerate the agent to generate secondary pollution. The patent application No. 201610331251.7 discloses a method for online recycling of plating parts rinsing wastewater, which is characterized in that the rinsing wastewater of the plating part is subjected to multi-stage countercurrent cleaning, filtration, reverse osmosis treatment, nanofiltration treatment and evaporation concentration. Or directly reuse, recover the metal ions and additives in the rinsing wastewater of the plating part, return it as the plating solution liquid in the plating tank, recover the water in the rinsing wastewater of the plating part, and use it as the rinsing water of the plating part to realize the online resource utilization. . Compared with the prior art, the invention adopts a novel combination mode of the reverse osmosis membrane module in the front and the nanofiltration membrane module, and can effectively reuse the heavy metal ions and various additives and water in the rinsing wastewater of the plating part to realize the plating part. The online recycling of rinsing wastewater greatly reduces operating energy consumption and economic costs.
与化学沉淀法和离子交换法相比，膜法不仅是治理方法，而且是一种资源化方法，实现污染物的回收利用。但是膜法也存在一个缺点，即膜易受到电镀 液成分的污染，从而通量下降，能耗增加。对于反渗透和纳滤膜，化学清洗是控制膜污染的主要方法。《南京师大学报(自然科学版)》第33卷第2期“应用于电镀废水处理的反渗透膜的化学清洗”一文，对应用于电镀废水处理的反渗透装置进行了化学清洗的研究，首先采用1％盐酸酸洗去除重金属污染，再采用1％NaOH和0.025％十二烷基苯磺酸钠(SDS)混合清洗液进行碱洗去除膜面的有机污染物，最后采用浓度为50mg/L的非氧化性杀菌剂2,2-双溴代-3-次氮基-丙酰胺(DBNPA)清洗生物污染。清洗后，该装置在0.5MPa下的膜通量由清洗前的13.9L/m2·h提高到28.3L/m2·h，膜通量恢复到初期的89.4％。显然，化学清洗法存在着如下弊端：需要停车清洗；每次均需添加清洗剂；清洗后废液产生二次污染。Compared with the chemical precipitation method and the ion exchange method, the membrane method is not only a treatment method, but also a resource method to realize the recycling of pollutants. However, the membrane method also has a disadvantage in that the membrane is easily contaminated by the composition of the plating solution, so that the flux is decreased and the energy consumption is increased. For reverse osmosis and nanofiltration membranes, chemical cleaning is the primary method of controlling membrane fouling. "Journal of Nanjing Normal University (Natural Science Edition)", Vol. 33, No. 2, "Chemical Cleaning of Reverse Osmosis Membrane for Electroplating Wastewater Treatment", corresponding to the chemical cleaning of reverse osmosis devices for electroplating wastewater treatment, Firstly, 1% hydrochloric acid pickling was used to remove heavy metal pollution, and then 1% NaOH and 0.025% sodium dodecylbenzene sulfonate (SDS) mixed cleaning solution were used for alkali washing to remove organic pollutants on the membrane surface. Finally, the concentration was 50 mg/ L's non-oxidizing biocide 2,2-dibromo-3-nitrilo-propionamide (DBNPA) cleans biological contamination. After washing, the membrane flux in the apparatus increased from 0.5MPa before cleaning 13.9L / m 2 · h to 28.3L / m 2 · h, flux returns to the initial 89.4%. Obviously, the chemical cleaning method has the following drawbacks: it needs to be washed and washed; it needs to add cleaning agent every time; after the cleaning, the waste liquid produces secondary pollution.
发明内容Summary of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法。SUMMARY OF THE INVENTION The object of the present invention is to provide a simple method for improving the efficiency of an on-line resource-based membrane closure system for nickel-zinc electroplating rinsing wastewater in order to overcome the drawbacks of the prior art described above.
本发明的目的可以通过以下技术方案来实现：一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法，其特征在于，该方法是在所述镍锌电镀漂洗废水在线资源化膜法闭合系统中加入质量比为1:10～10:1的膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂，通过抑制镍锌电镀液中硫酸镍、氯化锌、硼酸、十二烷基硫酸钠和AB型聚酰胺光亮剂5种成分的复杂的物化聚合过程，尤其破除硼酸的核心作用，阻止无机有机的复合污染形成，长时间维持较高的膜通量，改善镍锌电镀漂洗废水在线资源化膜法闭合系统的性能，降低经济运行成本。膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂的加入量为使其在系统中膜浓侧的总浓度为1.0～100ppm。The object of the present invention can be achieved by the following technical solution: a simple method for improving the efficiency of the on-line resource-based membrane closure system for nickel-zinc electroplating and rinsing wastewater, characterized in that the method is on-line resource utilization of the nickel-zinc electroplating rinsing wastewater. In the membrane closure system, a phosphinopolycarboxylate and a polysuccinic acid sodium binary composite reagent with a mass ratio of 1:10 to 10:1 are added to inhibit nickel sulfate, zinc chloride and boric acid in the nickel zinc plating solution. The complex physicochemical polymerization process of five components, sodium lauryl sulfate and AB-type polyamide brightener, especially breaks the core role of boric acid, prevents the formation of inorganic-organic composite pollution, maintains high membrane flux for a long time, and improves The performance of the nickel-zinc electroplating rinsing wastewater on-line resource-based membrane closure system reduces economic operation costs. The phosphinopolycarboxylate and the poly(epoxysuccinate) binary complex reagent are added in an amount such that the total concentration on the rich side of the membrane in the system is from 1.0 to 100 ppm.
所述的镍锌电镀漂洗废水在线资源化膜法闭合系统包括镀件槽，以及通过管线依次连接的清洗槽、调节池、低压泵、保安过滤器、高压泵、反渗透膜装置、纳滤膜装置和降膜式蒸发器，降膜式蒸发器上还设有浓缩液出口和冷凝水出口，其中，浓缩液出口还连接镀件槽，冷凝水出口还连接清洗槽，形成膜法闭合系统。The nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closure system comprises a plating tank, and a cleaning tank, a regulating tank, a low-pressure pump, a security filter, a high-pressure pump, a reverse osmosis membrane device, and a nanofiltration membrane sequentially connected through a pipeline. The device and the falling film evaporator, the falling film evaporator also has a concentrated liquid outlet and a condensed water outlet, wherein the concentrated liquid outlet is also connected to the plating tank, and the condensed water outlet is also connected to the cleaning tank to form a membrane closed system.
所述的清洗槽设有至少一级。 The cleaning tank is provided with at least one stage.
所述的反渗透膜装置的清水侧连接清洗槽，浓水侧连接纳滤膜装置，系统中膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂的添加量为使复合试剂在反渗透膜装置的浓水侧的总浓度为1.0～100ppm。The clear water side of the reverse osmosis membrane device is connected to the cleaning tank, and the concentrated water side is connected to the nanofiltration membrane device. The addition amount of the phosphine-based polycarboxylate and the poly(epoxysuccinate) binary composite reagent in the system is such that the composite reagent is The total concentration of the reverse osmosis membrane device on the concentrated water side is 1.0 to 100 ppm.
所述的纳滤膜装置的清水侧连接反渗透装置的进水侧，浓水侧连接降膜式蒸发器。The fresh water side of the nanofiltration membrane device is connected to the water inlet side of the reverse osmosis device, and the concentrated water side is connected to the falling film evaporator.
所述的膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂可以在所述的镍锌电镀漂洗废水在线资源化膜法闭合系统中任一处加入。The phosphinopolycarboxylate and sodium polysuccinate binary complexing agent can be added at any point in the nickel-zinc electroplating rinsing wastewater online resource-recovering system closure system.
所述的膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂是晶体形态或者是溶液状态。The phosphinopolycarboxylate and sodium polysuccinate binary complex reagents are in a crystalline form or in a solution state.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
1.添加剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂能够抑制镍锌电镀液中硫酸镍、氯化锌、硼酸、十二烷基硫酸钠和AB型聚酰胺光亮剂5种成分的复杂的物化聚合过程，尤其破除硼酸的核心作用，有效地阻止无机有机的复合污染形成，从而长时间维持较高的膜通量，大大改善镍锌电镀漂洗废水在线资源化膜法闭合系统的性能，降低经济运行成本。1. Additive phosphine sodium polycarboxylate and sodium polysuccinate sodium complex reagent can inhibit nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel zinc plating solution 5 The complex physicochemical polymerization process of the components, especially breaking the core role of boric acid, effectively prevents the formation of inorganic-organic composite pollution, thereby maintaining a high membrane flux for a long time, greatly improving the on-line resource-based membrane closure of nickel-zinc electroplating rinsing wastewater. System performance, reducing economic operating costs.
2.化学清洗法每次清洗均需加入清洗剂。本发明所使用的抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂具有惰性，在系统运行过程中不发生电极反应，整个过程基本无消耗，因此也不需每次添加清洗剂，节约了经济成本；2. Chemical cleaning method requires cleaning agent for each cleaning. The inhibitor phosphinopolycarboxylate and sodium polysuccinate binary composite reagent used in the invention are inert, no electrode reaction occurs during system operation, and the whole process is basically no consumption, so there is no need to add each time. Cleaning agent saves economic costs;
3.化学清洗法在膜通量下降较多时需停车清洗。在镍锌电镀漂洗废水在线资源化膜法系统中镀液是循环闭合的，本发明将惰性抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂加入镀液进行闭合循环，因此不需停车，可连续进行；3. The chemical cleaning method requires parking cleaning when the membrane flux drops more. In the nickel-zinc electroplating rinsing wastewater online resource-removing membrane system, the plating solution is cyclically closed. In the present invention, the inert inhibitor phosphinopolycarboxylate and the poly(epoxysuccinate) binary composite reagent are added to the plating solution for closed cycle. Therefore, no parking is required, and it can be carried out continuously;
4.化学清洗法必然产生废液，且需要处理才能排放。本发明中惰性抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂是循环的，整个过程不产生额外废液，不形成二次污染。4. Chemical cleaning method will inevitably produce waste liquid, and it needs to be treated to discharge. In the present invention, the inert inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent are recycled, and no waste liquid is generated in the whole process, and no secondary pollution is formed.
附图说明DRAWINGS
图1为镍锌电镀漂洗废水在线资源化膜法闭合系统的示意图。 1 is a schematic diagram of a nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closure system.
具体实施方式detailed description
下面结合附图和具体实施例对本发明进行详细说明。The invention will be described in detail below with reference to the drawings and specific embodiments.
如图1所示，镍锌电镀漂洗废水在线资源化膜法闭合系统包括镀件槽1，以及通过管线依次连接的清洗槽、调节池5、低压泵6、保安过滤器7、高压泵8、反渗透膜装置9、纳滤膜装置10和降膜式蒸发器11，降膜式蒸发器11上还设有浓缩液出口和冷凝水出口，其中，浓缩液出口还连接镀件槽1，冷凝水出口还连接清洗槽，清洗槽设有三级，如图所述：并联的一级清洗槽2、二级清洗槽3和三级清洗槽4。As shown in FIG. 1 , the nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closure system comprises a plating tank 1 and a cleaning tank, a regulating tank 5, a low-pressure pump 6, a security filter 7, and a high-pressure pump 8, which are sequentially connected by a pipeline. The reverse osmosis membrane device 9, the nanofiltration membrane device 10 and the falling film evaporator 11, the falling film evaporator 11 is further provided with a concentrated liquid outlet and a condensed water outlet, wherein the concentrated liquid outlet is also connected to the plating tank 1 and condensed The water outlet is also connected to the cleaning tank, and the cleaning tank is provided with three stages, as shown in the figure: the first-stage cleaning tank 2, the second-stage cleaning tank 3 and the third-stage cleaning tank 4 are connected in parallel.
所述的反渗透膜装置9的清水侧连接清洗槽，回收反渗透膜装置9过滤后的清水，浓水侧连接纳滤膜装置10，进一步进行过滤，系统中膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂的添加量为使其在反渗透膜装置9的浓水侧总浓度为1.0～100ppm。The fresh water side of the reverse osmosis membrane device 9 is connected to the washing tank, the cleaned water filtered by the reverse osmosis membrane device 9 is recovered, and the nanofiltration membrane device 10 is connected to the concentrated water side, and further filtered, and the phosphine-based polycarboxylate and the polymer are collected in the system. The amount of the sodium epoxysuccinate binary composite reagent added is such that the total concentration on the concentrated water side of the reverse osmosis membrane device 9 is 1.0 to 100 ppm.
所述的纳滤膜装置10的清水侧连接反渗透膜装置9的进水侧，回收清水，浓水侧连接降膜式蒸发器11。The fresh water side of the nanofiltration membrane device 10 is connected to the water inlet side of the reverse osmosis membrane device 9, and the clean water is recovered, and the concentrated water side is connected to the falling film evaporator 11.
整个系统形成膜法闭合系统。The entire system forms a membrane closure system.
镀件按镀件走向a于电镀槽1中进行电镀，电镀废水经清洗槽三级逆流漂洗初步浓缩，汇集于调节池5，在低压泵3作用下，经保安过滤器4去除大于5μm固体颗粒物，保护后续膜滤器的安全运行。经高压泵8增压至1.0Mpa，镀件漂洗废水进入前置反渗透膜组件6，反渗透清水侧出水c能够完全达到镀件漂洗水质的要求，回收后与三级清洗槽中的补充清洗水b混合；镀件漂洗废水提浓得到反渗透浓水侧出水d，并输送至后置纳滤膜组件10中进一步提浓。纳滤膜组件清水侧出水e，不能达到镀件漂洗水质的要求，作为进水进入前置反渗透膜组件9进一步净化。纳滤膜组件浓水侧出水f在降膜式蒸发器11中进一步提浓后，所得浓缩液g进入镀件槽1，冷凝水h作为漂洗水回用。The plating part is electroplated in the plating tank 1 according to the plating direction a, the electroplating wastewater is initially concentrated by the three-stage countercurrent rinsing in the cleaning tank, and is collected in the regulating tank 5, and under the action of the low pressure pump 3, the solid particles larger than 5 μm are removed by the security filter 4. To protect the safe operation of the subsequent membrane filter. After being pressurized by the high pressure pump 8 to 1.0 MPa, the rinsing wastewater of the plating part enters the pre-reverse osmosis membrane module 6, and the effluent water of the reverse osmosis water side can completely meet the requirements of the rinsing quality of the plating part, and the supplementary cleaning after the recovery and the tertiary cleaning tank The water b is mixed; the plating rinsing wastewater is concentrated to obtain the reverse osmosis concentrated water side effluent d, and is sent to the post-nanofiltration membrane module 10 for further concentration. The water filter e on the fresh water side of the nanofiltration membrane module cannot meet the requirements of the rinsing quality of the plating part, and is further purified as the influent water entering the pre-reverse osmosis membrane module 9. After the concentrated water side effluent f of the nanofiltration membrane module is further concentrated in the falling film evaporator 11, the obtained concentrated liquid g enters the plating tank 1 and the condensed water h is reused as rinsing water.
实施例1Example 1
在镍锌电镀漂洗废水在线资源化膜法闭合系统中调节池处加入膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂晶体，质量比为1:10，添加后在系统中膜浓侧的总浓度为1.0ppm，通过抑制镍锌电镀液中硫酸镍、氯化锌、硼酸、十二烷基硫酸钠和AB型聚酰胺光亮剂5种成分的复杂的物化聚合过程，尤其破除硼 酸的核心作用，阻止无机有机的复合污染形成，长时间维持较高的膜通量，改善镍锌电镀漂洗废水在线资源化膜法闭合系统的性能，降低经济运行成本。In the nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closed system, a phosphine-based polycarboxylate and a polysuccinic acid sodium succinate composite reagent crystal are added at a mass ratio of 1:10, and the film is added in the system. The total concentration of the concentrated side is 1.0 ppm, which is particularly effective in suppressing the complex physicochemical polymerization process of nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB-type polyamide brightener in nickel-zinc plating bath. Boron The core role of acid prevents the formation of inorganic-organic composite pollution, maintains high membrane flux for a long time, improves the performance of the nickel-zinc electroplating wastewater on-line resource-based membrane closure system, and reduces economic operation costs.
本实施例实施效果：The implementation effect of this embodiment:
1.添加剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂能够抑制镍锌电镀液中硫酸镍、氯化锌、硼酸、十二烷基硫酸钠和AB型聚酰胺光亮剂5种成分的复杂的物化聚合过程，尤其破除硼酸的核心作用，有效地阻止无机有机的复合污染形成。与化学清洗法相比，维持80％以上膜通量的运行时间延长3倍，大大改善镍锌电镀漂洗废水在线资源化膜法闭合系统的性能，降低经济运行成本。1. Additive phosphine sodium polycarboxylate and sodium polysuccinate sodium complex reagent can inhibit nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel zinc plating solution 5 The complex physicochemical polymerization process of the components, especially breaking the core role of boric acid, effectively prevents the formation of inorganic and organic composite pollution. Compared with the chemical cleaning method, the operation time of maintaining more than 80% of the membrane flux is extended by 3 times, which greatly improves the performance of the nickel-zinc electroplating and rinsing wastewater on-line resource-based membrane closure system, and reduces the economic operation cost.
2.本发明所使用的抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂具有惰性，在系统运行过程中不发生电极反应，整个过程基本无消耗，因此也不需每次添加清洗剂。与化学清洗法相比，节约了经济运行成本40％；2. The inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent used in the invention are inert, no electrode reaction occurs during system operation, and the whole process is basically no consumption, so there is no need to Add cleaning agent at a time. Compared with the chemical cleaning method, the economic operation cost is saved by 40%;
3.本发明将惰性抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂加入镀液进行闭合循环，与化学清洗法相比，不需停车，可连续进行；3. The invention combines the inert inhibitor phosphinopolycarboxylate and polysuccinic acid sodium succinate composite reagent into the plating solution for closed cycle, and can be continuously performed without stopping the chemical compared with the chemical cleaning method;
4.本发明中惰性抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂是循环的，整个过程不产生额外废液，不形成二次污染。与化学清洗法相比，节约了清洗废液的处理费用，约占运行费用的30％。4. In the present invention, the inert inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent are recycled, and no waste liquid is generated in the whole process, and no secondary pollution is formed. Compared with the chemical cleaning method, the processing cost of the cleaning waste liquid is saved, which accounts for about 30% of the operating cost.
实施例2Example 2
在镍锌电镀漂洗废水在线资源化膜法闭合系统中电镀槽处加入膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂溶液，质量比为5:5，添加后在系统中膜浓侧的总浓度为50.0ppm，通过抑制镍锌电镀液中硫酸镍、氯化锌、硼酸、十二烷基硫酸钠和AB型聚酰胺光亮剂5种成分的复杂的物化聚合过程，尤其破除硼酸的核心作用，阻止无机有机的复合污染形成，长时间维持较高的膜通量，改善镍锌电镀漂洗废水在线资源化膜法闭合系统的性能，降低经济运行成本。In the nickel-zinc electroplating rinsing wastewater online resource-removing membrane method, the plating solution is added with a phosphinopolycarboxylate and a polysuccinic acid sodium binary composite reagent solution at a mass ratio of 5:5, and the film is added in the system after the addition. The total concentration of the concentrated side is 50.0 ppm, which is particularly effective in suppressing the complex physicochemical polymerization process of nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB-type polyamide brightener in nickel-zinc plating bath. The core role of boric acid prevents the formation of inorganic-organic composite pollution, maintains high membrane flux for a long time, improves the performance of the nickel-zinc electroplating wastewater online resource-based membrane closure system, and reduces economic operation costs.
本实施例实施效果：The implementation effect of this embodiment:
1.添加剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂能够抑制镍锌电镀液中硫酸镍、氯化锌、硼酸、十二烷基硫酸钠和AB型聚酰胺光亮剂5种成分的复杂的物化聚合过程，尤其破除硼酸的核心作用，有效地阻止无机有机的复合污染形成。与化学清洗法相比，维持80％以上膜通量的运行时间延长6倍， 大大改善镍锌电镀漂洗废水在线资源化膜法闭合系统的性能，降低经济运行成本。1. Additive phosphine sodium polycarboxylate and sodium polysuccinate sodium complex reagent can inhibit nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel zinc plating solution 5 The complex physicochemical polymerization process of the components, especially breaking the core role of boric acid, effectively prevents the formation of inorganic and organic composite pollution. Compared with chemical cleaning, the operating time to maintain more than 80% of the membrane flux is extended by 6 times. The performance of the on-line resource-based membrane closure system for nickel-zinc electroplating and rinsing wastewater is greatly improved, and the economic operation cost is reduced.
2.本发明所使用的抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂具有惰性，在系统运行过程中不发生电极反应，整个过程基本无消耗，因此也不需每次添加清洗剂。与化学清洗法相比，节约了经济运行成本50％；2. The inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent used in the invention are inert, no electrode reaction occurs during system operation, and the whole process is basically no consumption, so there is no need to Add cleaning agent at a time. Compared with the chemical cleaning method, the economic operation cost is saved by 50%;
3.本发明将惰性抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂加入镀液进行闭合循环，与化学清洗法相比，不需停车，可连续进行；3. The invention combines the inert inhibitor phosphinopolycarboxylate and polysuccinic acid sodium succinate composite reagent into the plating solution for closed cycle, and can be continuously performed without stopping the chemical compared with the chemical cleaning method;
4.本发明中惰性抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂是循环的，整个过程不产生额外废液，不形成二次污染。与化学清洗法相比，节约了清洗废液的处理费用，约占运行费用的30％。4. In the present invention, the inert inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent are recycled, and no waste liquid is generated in the whole process, and no secondary pollution is formed. Compared with the chemical cleaning method, the processing cost of the cleaning waste liquid is saved, which accounts for about 30% of the operating cost.
实施例3Example 3
在镍锌电镀漂洗废水在线资源化膜法闭合系统中调节池处加入膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂溶液，质量比为10:1，添加后在系统中膜浓侧的总浓度为100.0ppm，通过抑制镍锌电镀液中硫酸镍、氯化锌、硼酸、十二烷基硫酸钠和AB型聚酰胺光亮剂5种成分的复杂的物化聚合过程，尤其破除硼酸的核心作用，阻止无机有机的复合污染形成，长时间维持较高的膜通量，改善镍锌电镀漂洗废水在线资源化膜法闭合系统的性能，降低经济运行成本。In the nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closed system, a phosphine-based polycarboxylate sodium and a poly(epoxysuccinate) binary composite reagent solution are added at a mass ratio of 10:1, and the film is added in the system after the addition. The total concentration of the concentrated side is 100.0ppm, which is particularly effective in suppressing the complex physicochemical polymerization process of five components of nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel-zinc plating bath. The core role of boric acid prevents the formation of inorganic-organic composite pollution, maintains high membrane flux for a long time, improves the performance of the nickel-zinc electroplating wastewater online resource-based membrane closure system, and reduces economic operation costs.
本实施例实施效果：The implementation effect of this embodiment:
1.添加剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂能够抑制镍锌电镀液中硫酸镍、氯化锌、硼酸、十二烷基硫酸钠和AB型聚酰胺光亮剂5种成分的复杂的物化聚合过程，尤其破除硼酸的核心作用，有效地阻止无机有机的复合污染形成。与化学清洗法相比，维持80％以上膜通量的运行时间延长12倍，大大改善镍锌电镀漂洗废水在线资源化膜法闭合系统的性能，降低经济运行成本。1. Additive phosphine sodium polycarboxylate and sodium polysuccinate sodium complex reagent can inhibit nickel sulfate, zinc chloride, boric acid, sodium lauryl sulfate and AB type polyamide brightener in nickel zinc plating solution 5 The complex physicochemical polymerization process of the components, especially breaking the core role of boric acid, effectively prevents the formation of inorganic and organic composite pollution. Compared with the chemical cleaning method, the operation time of maintaining the membrane flux of more than 80% is extended by 12 times, which greatly improves the performance of the on-line resource-based membrane closure system of the nickel-zinc electroplating and rinsing wastewater, and reduces the economic operation cost.
2.本发明所使用的抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂具有惰性，在系统运行过程中不发生电极反应，整个过程基本无消耗，因此也不需每次添加清洗剂。与化学清洗法相比，节约了经济运行成本60％；2. The inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent used in the invention are inert, no electrode reaction occurs during system operation, and the whole process is basically no consumption, so there is no need to Add cleaning agent at a time. Compared with the chemical cleaning method, the economic operation cost is saved by 60%;
3.本发明将惰性抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂加入镀液进行闭合循环，与化学清洗法相比，不需停车，可连续进行； 3. The invention combines the inert inhibitor phosphinopolycarboxylate and polysuccinic acid sodium succinate composite reagent into the plating solution for closed cycle, and can be continuously performed without stopping the chemical compared with the chemical cleaning method;
4.本发明中惰性抑制剂膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂是循环的，整个过程不产生额外废液，不形成二次污染。与化学清洗法相比，节约了清洗废液的处理费用，约占运行费用的30％。 4. In the present invention, the inert inhibitor phosphinopolycarboxylate and sodium polysuccinate binary complex reagent are recycled, and no waste liquid is generated in the whole process, and no secondary pollution is formed. Compared with the chemical cleaning method, the processing cost of the cleaning waste liquid is saved, which accounts for about 30% of the operating cost.

Claims (7)

  1. 一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法，其特征在于，该方法是在所述镍锌电镀漂洗废水在线资源化膜法闭合系统中加入质量比为1:10～10:1的膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂，加入量为使其在系统中膜浓侧的总浓度为1.0～100ppm。A simple method for improving the efficiency of the on-line resource-based membrane closure system for nickel-zinc electroplating and rinsing wastewater, characterized in that the method is to add a mass ratio of 1:10 in the nickel-zinc electroplating rinsing wastewater online resource-removing membrane closure system. ～10:1 phosphinopolycarboxylate and sodium polysuccinate binary complex reagent are added in an amount such that the total concentration of the membrane on the concentrated side of the system is 1.0 to 100 ppm.
  2. 根据权利要求1所述的一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法，其特征在于，所述的镍锌电镀漂洗废水在线资源化膜法闭合系统包括镀件槽(1)，以及通过管线依次连接的清洗槽、调节池(5)、低压泵(6)、保安过滤器(7)、高压泵(8)、反渗透膜装置(9)、纳滤膜装置(10)和降膜式蒸发器(11)，降膜式蒸发器(11)上还设有浓缩液出口和冷凝水出口，其中，浓缩液出口还连接镀件槽(1)，冷凝水出口还连接清洗槽，形成膜法闭合系统。The invention relates to a simple method for improving the efficiency of a nickel-zinc electroplating rinsing wastewater online resource-removing membrane closure system according to claim 1, wherein the nickel-zinc electroplating rinsing wastewater online resource-removing membrane method closure system comprises a plating tank (1), and the cleaning tank, the regulating tank (5), the low pressure pump (6), the security filter (7), the high pressure pump (8), the reverse osmosis membrane device (9), and the nanofiltration membrane device which are sequentially connected through the pipeline (10) and falling film evaporator (11), the falling film evaporator (11) is further provided with a concentrated liquid outlet and a condensed water outlet, wherein the concentrated liquid outlet is also connected to the plating tank (1), the condensed water outlet A cleaning tank is also connected to form a membrane closure system.
  3. 根据权利要求2所述的一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法，其特征在于，所述的清洗槽设有至少一级。A simple method for improving the efficiency of a nickel-zinc electroplating rinsing wastewater online resource-removing membrane closure system according to claim 2, wherein the cleaning tank is provided with at least one stage.
  4. 根据权利要求2所述的一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法，其特征在于，所述的反渗透膜装置(9)的清水侧连接清洗槽，浓水侧连接纳滤膜装置(10)，系统中膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂的添加量为使其在反渗透膜装置(9)的浓水侧浓度为1.0～100ppm。A simple method for improving the efficiency of a nickel-zinc electroplating rinsing wastewater online resource-removing membrane closure system according to claim 2, wherein the fresh water side of the reverse osmosis membrane device (9) is connected to a cleaning tank, concentrated water The side is connected to the nanofiltration membrane device (10), and the phosphine-based sodium polycarboxylate and the sodium polysuccinate-synthesis binary complex reagent are added in such a manner that the concentration on the concentrated water side of the reverse osmosis membrane device (9) is 1.0. ~100ppm.
  5. 根据权利要求2所述的一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法，其特征在于，所述的纳滤膜装置(10)的清水侧连接反渗透膜装置(9)的进水侧，浓水侧连接降膜式蒸发器(11)。A simple method for improving the efficiency of an on-line resource-removing membrane closure system for nickel-zinc electroplating and rinsing wastewater according to claim 2, wherein the water-filtering side of the nanofiltration membrane device (10) is connected to a reverse osmosis membrane device ( 9) On the inlet side, the concentrated water side is connected to the falling film evaporator (11).
  6. 根据权利要求1所述的一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法，其特征在于，所述的膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂可以在所述的镍锌电镀漂洗废水在线资源化膜法闭合系统中任一处加入。 A simple method for improving the efficiency of an on-line resource-removing membrane closure system for nickel-zinc electroplating and rinsing wastewater according to claim 1, characterized in that the phosphinopolycarboxylate and polysuccinic acid sodium succinate complex The reagent can be added at any point in the nickel-zinc electroplating rinsing wastewater online resource-removal membrane closure system.
  7. 根据权利要求1所述的一种提高镍锌电镀漂洗废水在线资源化膜法闭合系统效率的简便方法，其特征在于，所述的膦基聚羧酸钠和聚环氧琥珀酸钠二元复合试剂是晶体形态或者是溶液状态。 A simple method for improving the efficiency of an on-line resource-removing membrane closure system for nickel-zinc electroplating and rinsing wastewater according to claim 1, characterized in that the phosphinopolycarboxylate and polysuccinic acid sodium succinate complex The reagent is in the form of a crystal or a solution.
PCT/CN2016/101463 2016-08-31 2016-10-08 Simple and convenient method for improving efficiency of closed nickel-zinc electrolytic-plating rinse-water online recycling membrane system WO2018040223A1 (en)

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