JP2023016656A - Method of recycling copper and phosphorous resource in copper pyrophosphate plating waste water - Google Patents
Method of recycling copper and phosphorous resource in copper pyrophosphate plating waste water Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
Abstract
Description
本発明は、産業廃水処理およびリサイクルの技術分野に関し、具体的にピロリン酸銅めっ
き廃水中の銅およびリン資源をリサイクルする方法に関する。
The present invention relates to the technical field of industrial wastewater treatment and recycling, and specifically to a method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater.
電気めっきは、電気化学的原理を使用して、材料の導電性、耐摩耗性、耐食性、およびそ
の他の物理的および化学的特性を改善するために、金属または合金の層を金属または非金
属材料の表面にめっきするプロセスである。加工製造の一環として、電気めっきは中国の
国内産業の不可欠な部分になっている。
銅メッキは、その優れた可塑性、接着性、および研磨の容易さから、装飾保護メッキの最
下層として広く使用されている。ピロリン酸銅めっきは、ピロリン酸銅を主塩として使用
し、さらに錯化剤やその他の補助錯化剤、光沢剤などの成分を使用し、ｐＨ、電流密度、
空気攪拌、温度などのプロセス条件を制御することで、結晶性の微細で明るいコーティン
グを実現するプロセスの一つである。めっき液はシアン化物を含まないため、安定してお
り、電流効率が高く、研磨性能も良好で、換気装置や吸引装置を追加する必要がないため
、工業的な大量生産に使用されている。
ピロリン酸銅めっきの幅広い用途もまた、ピロリン酸銅めっき廃水の処分の問題を引き起
こしている。ピロリン酸銅めっき廃水には、大量の重金属銅に加えて、大量のピロリン酸
も含まれている。水域に過剰に排出された銅は、水生動植物にストレスを与える可能性が
あり、重金属銅はまた、生物学的鎖の濃縮を通じて人体に侵入し、人体に害を及ぼす可能
性がある。廃水中のリンは効果的な処理をせずに水域に排出されると、水域の富栄養化を
引き起こしやすくなる。
同時に、銅とリンも貴重で希少な資源である。国際市場での銅とクロムの価格は３万元/
トンを超えて、リン資源も中国で希少な資源のひとつであり、中国国土資源省は、２０１
０年以降の国家経済発展のニーズを満たすことができない重要な鉱物の１つとしてリン鉱
石資源を登録する。近年、多くの学者が、国内の下水処理施設で発生する汚泥からますま
す貴重なリン資源を抽出する方法を研究している。ピロリン酸銅廃液中の銅とリンを恣意
的にリサイクル・排出しないと、必然的にそのような希少で貴重な資源の浪費になってい
る。
Electroplating uses electrochemical principles to deposit layers of metals or alloys on metallic or non-metallic materials in order to improve the material's electrical conductivity, wear resistance, corrosion resistance, and other physical and chemical properties. It is a process of plating on the surface of As part of processing manufacturing, electroplating has become an integral part of China's domestic industry.
Copper plating is widely used as the bottom layer of decorative protective plating due to its excellent plasticity, adhesion, and ease of polishing. Copper pyrophosphate plating uses copper pyrophosphate as the main salt, and further uses components such as complexing agents, other auxiliary complexing agents, and brighteners to control pH, current density,
By controlling process conditions such as air agitation and temperature, it is one of the processes that realize fine, bright, crystalline coatings. Because the plating solution does not contain cyanide, it is stable, has high current efficiency, has good polishing performance, and does not require additional ventilation or suction devices, so it is used for industrial mass production.
Widespread use of copper pyrophosphate plating also poses problems of disposal of copper pyrophosphate plating wastewater. Copper pyrophosphate plating wastewater contains a large amount of pyrophosphate in addition to a large amount of heavy metal copper. Excess copper discharged into water bodies can stress aquatic animals and plants, and heavy metal copper can also enter and harm the human body through the concentration of biological chains. Phosphorus in wastewater is likely to cause eutrophication of water bodies if discharged into water bodies without effective treatment.
At the same time, copper and phosphorus are also precious and scarce resources. The price of copper and chromium in the international market is 30,000 yuan/
Beyond tons, phosphorus resources are also one of the scarce resources in China.
Register phosphate rock resources as one of the important minerals that cannot meet the needs of national economic development after 0 years. In recent years, many scholars have been researching methods to extract increasingly valuable phosphorus resources from the sludge generated by domestic sewage treatment plants. Failure to arbitrarily recycle and discharge the copper and phosphorus in the copper pyrophosphate waste liquid inevitably leads to the waste of such scarce and valuable resources.
本発明の目的は、ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法を
提供することである。
It is an object of the present invention to provide a method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater.
本発明の技術的解決策は、以下のピロリン酸銅めっき廃水中の銅およびリン資源をリサイ
クルする方法を提供し、それは、
Ｓ１：ピロリン酸銅めっき廃水を前処理して廃液中の粒子状不純物を除去するステップと
、
Ｓ２：前処理されたピロリン酸銅めっき廃水を電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜を通過してリン含有濃縮液プ
ールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮するステ
ップと、
Ｓ３：銅含有濃縮液を再処理して銅含有濃縮液から金属銅を回収するステップと、を含む
。
The technical solution of the present invention provides the following method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater, which includes:
S1: A step of pretreating copper pyrophosphate plating wastewater to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater;
S2-1: The pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are removed under the action of an electric field force through the total anion exchange membrane to obtain a phosphorus-containing concentrate. pooling to separate and concentrate phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater;
S3: Reprocessing the copper-containing concentrate to recover metallic copper from the copper-containing concentrate.
本発明の一側面として、Ｓ１の前処理は、具体的に、セキュリティフィルターシステムを
使用して、ピロリン酸銅めっき廃水を処理して廃液中の粒子状不純物を除去することを含
み、セキュリティフィルターシステムを直接使用することで、工業化されたプラントの準
備とプロセスサポート施設の確立がより容易になる。
In one aspect of the present invention, the pretreatment of S1 specifically includes treating copper pyrophosphate plating wastewater to remove particulate impurities in the wastewater using a security filter system, The direct use makes it easier to prepare industrialized plants and establish process support facilities.
本発明の一側面として、Ｓ１の前処理は、具体的に、ピロリン酸銅めっき廃水をグリッド
で粗ろ過処理した後、ゼオライトフィルターで二次ろ過して廃液中の粒子状不純物を除去
することであり、処理コストは比較的低くなる。
As one aspect of the present invention, the pretreatment of S1 is specifically performed by coarsely filtering copper pyrophosphate plating wastewater with a grid and then secondary filtering with a zeolite filter to remove particulate impurities in the wastewater. Yes, and processing costs are relatively low.
本発明の一側面として、Ｓ１の前処理は、具体的に、水とともに空気を噴出するエジェク
ターを使用してピロリン酸銅めっき廃水中に空気を混合し、エアフロート法により廃液中
の粒子状不純物を除去し、使用する設備がシンプルで、エアフロート原理により粒子状不
純物を効率的に除去することができる。
As one aspect of the present invention, the pretreatment of S1 specifically involves mixing air into copper pyrophosphate plating wastewater using an ejector that ejects air together with water, and removing particulate impurities in the wastewater by an air float method. The equipment used is simple, and the air float principle can effectively remove particulate impurities.
本発明の一側面として、Ｓ２-２の全陽イオン交換膜は修飾陽イオン交換膜である。 In one aspect of the invention, all cation exchange membranes of S2-2 are modified cation exchange membranes.
本発明の一側面として、前記修飾陽イオン交換膜の調製方法は、
１）１:３～１３:１１～１５の質量比で、ガラス繊維、炭素繊維、アラミド繊維を多軸布
機で調製して多軸生地を得るステップと、
２）ポリ塩化ビニルとスチレン-ブタジエン-スチレントリブロック共重合体、修飾ナノ酸
化チタンを３５～５５:３～７:０．２～１．３の質量比でブレンドした後、１８０～２２
０℃の条件下で多軸生地に塗布するステップと、
３）自然冷却後、脱イオン水で２０～２５分間超音波洗浄し、次に５０～６０℃の条件下
で４～８時間真空乾燥して、マトリックス膜を得るステップと、
４）マトリックス膜を１～２時間スルホン化し、次に濃度７５～８５ｗｔ％の濃硫酸、濃
度２５～４０ｗｔ％の希硫酸に順次２時間浸漬し、そして濃度３～１５ｗｔ％の塩化ナト
リウム溶液に１５～２０時間浸漬して修飾陽イオン交換膜を得るステップと、を含む。
In one aspect of the invention, the method for preparing the modified cation exchange membrane comprises:
1) preparing glass fiber, carbon fiber, aramid fiber in a mass ratio of 1:3-13:11-15 with a multiaxial cloth machine to obtain a multiaxial fabric;
2) Polyvinyl chloride, styrene-butadiene-styrene triblock copolymer, and modified nanotitanium oxide are blended at a weight ratio of 35-55:3-7:0.2-1.3, and then 180-22.
applying to a multiaxial fabric under conditions of 0° C.;
3) After natural cooling, ultrasonically clean with deionized water for 20 to 25 minutes, then vacuum dry at 50 to 60° C. for 4 to 8 hours to obtain a matrix membrane;
4) The matrix membrane is sulfonated for 1-2 hours, then immersed in concentrated sulfuric acid with a concentration of 75-85 wt%, dilute sulfuric acid with a concentration of 25-40 wt% for 2 hours, and then immersed in a sodium chloride solution with a concentration of 3-15 wt% for 15 hours. Soaking for ~20 hours to obtain a modified cation exchange membrane.
本発明の一側面として、前記修飾陽イオン交換膜の調製方法包括：
１）１:３～１３:１１～１５の質量比でガラス繊維、炭素繊維、アラミド繊維を多軸布機
で調製して多軸生地を得るステップと、
２）塩化ベンジルトリエチルアンモニウムとリンタングステン酸を３～５:２．３～３の
質量比で混合して、転移活性剤を得るステップと、
３）ポリビニルアルコール樹脂を８０～９０℃の条件下で脱イオン水に溶解し、９５℃に
加熱した後、ポリビニルアルコール樹脂との質量比２～７:２２～３５でオルトケイ酸エ
チルを加え、磁力で２～３時間攪拌し、次にオルトケイ酸エチルとの質量比０．５～１．
３:１で転移活性剤を加え、磁力で１～２時間攪拌して、ゾルマトリックスを得るステッ
プと、
４）多軸生地を８０～９０℃の条件下でゾルマトリックスに１５～２０時間浸漬した後、
濃度３～１５ｗｔ％の塩化ナトリウム溶液に１５～２０時間浸漬して、修飾陽イオン交換
膜を得るステップと、を含む。
本発明の一側面として、Ｓ３の再処理は、具体的に、サイクロン電解装置を使用して銅含
有濃縮液を処理し、廃液中の有機複合体をアノードで酸化し、銅イオンがカソードに還元
され金属銅として堆積し、サイクロン電解処理した後、銅含有濃縮液中の銅を１０ｇ/Ｌ
から０．５ｇ/Ｌ以下に減らし、残りの濃縮液を電気透析陽イオン一方向膜に戻して濃縮
し、その中の金属銅をさらに回収する。
In one aspect of the invention, a method for preparing the modified cation exchange membrane includes:
1) preparing glass fiber, carbon fiber, and aramid fiber in a mass ratio of 1:3-13:11-15 with a multiaxial cloth machine to obtain a multiaxial fabric;
2) mixing benzyltriethylammonium chloride and phosphotungstic acid in a weight ratio of 3-5:2.3-3 to obtain a transfer activator;
3) Polyvinyl alcohol resin is dissolved in deionized water under conditions of 80 to 90° C., heated to 95° C., ethyl orthosilicate is added at a mass ratio of 2 to 7:22 to 35 with respect to polyvinyl alcohol resin, and magnetic force is applied. for 2 to 3 hours, and then mixed with ethyl orthosilicate in a mass ratio of 0.5 to 1.5.
adding a transfer activator at 3:1 and magnetically stirring for 1-2 hours to obtain a sol matrix;
4) After immersing the multiaxial fabric in a sol matrix for 15 to 20 hours at 80 to 90 ° C.,
immersing in a sodium chloride solution with a concentration of 3-15 wt% for 15-20 hours to obtain a modified cation exchange membrane.
As an aspect of the present invention, the reprocessing of S3 specifically uses a cyclone electrolyzer to process a copper-containing concentrate, anodicly oxidizing the organic complexes in the effluent, and reducing the copper ions to the cathode. It was deposited as metallic copper, and after cyclone electrolysis, 10 g/L of copper in the copper-containing concentrate was
is reduced to less than 0.5 g/L, and the remaining concentrate is returned to the electrodialysis cationic unidirectional membrane for concentration and further recovery of metallic copper therein.
従来技術と比べると、本発明は以下の有益な効果を有する。本発明は、ピロリン酸銅めっ
き廃水中の銅およびリン資源のリサイクルおよび利用の困難さを考慮して、比較的単純な
プロセスを使用することにより、銅およびリンの高効率の分離および濃縮を実現し、銅の
効果的な回収を実現し、廃水中のリン資源、および廃液の環境への汚染を低減する。
Compared with the prior art, the present invention has the following beneficial effects. Considering the difficulty of recycling and utilization of copper and phosphorus resources in copper pyrophosphate plating wastewater, the present invention achieves highly efficient separation and enrichment of copper and phosphorus by using a relatively simple process. and realize effective recovery of copper, reduce phosphorus resource in waste water and pollution of waste liquid to environment.
実施例１：ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法は、
Ｓ１：セキュリティフィルターシステムを使用してピロリン酸銅めっき廃水を処理し、廃
液中の粒子状不純物を除去するステップと、
Ｓ２：前処理されたピロリン酸銅めっき廃水を３０分間電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で全陰イオン交換膜に通過させてリン含有濃縮液プ
ールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮するステ
ップと、
Ｓ３：銅含有濃縮液を再処理して銅含有濃縮液から金属銅を回収し、再処理は具体的に硫
化法を使用して金属銅を回収するステップと、を含む。
Example 1: A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater comprises:
S1: treating copper pyrophosphate plating wastewater using a security filter system to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater for 30 minutes;
S2-1: The pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and the pyrophosphate ions in the wastewater are passed through the total anion exchange membrane under the action of an electric field force to form a phosphorus-containing concentrate pool. to separate and concentrate the phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater;
S3: Reprocessing the copper-containing concentrate to recover metallic copper from the copper-containing concentrate, wherein the reprocessing specifically uses a sulfidation method to recover metallic copper.
実施例２：ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法は、
Ｓ１：ピロリン酸銅めっき廃水を、グリッドで粗ろ過処理した後、ゼオライトフィルター
で二次ろ過して廃液中の粒子状不純物を除去するステップと、
Ｓ２：前処理されたピロリン酸銅めっき廃水を３０分間電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜に通過させてリン含有濃縮液
プールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮するステ
ップと、
Ｓ３：銅含有濃縮液を再処理して銅含有濃縮液から金属銅を回収し、再処理は具体的に硫
化法を使用して金属銅を回収するステップと、を含む。
Example 2: A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater comprises:
S1: A step of subjecting copper pyrophosphate plating wastewater to rough filtration treatment with a grid, followed by secondary filtration with a zeolite filter to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater for 30 minutes;
S2-1: Pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are passed through the total anion exchange membrane under the action of an electric field force to obtain a phosphorus-containing concentrate. pooling to separate and concentrate phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater;
S3: Reprocessing the copper-containing concentrate to recover metallic copper from the copper-containing concentrate, wherein the reprocessing specifically uses a sulfidation method to recover metallic copper.
実施例３：ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法は、
Ｓ１：ピロリン酸銅めっき廃水を、グリッドで粗ろ過処理した後、ゼオライトフィルター
で二次ろ過して廃液中の粒子状不純物を除去するステップと、
Ｓ２：前処理されたピロリン酸銅めっき廃水を３０分間電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜に通過させてリン含有濃縮液
プールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮するステ
ップと、
Ｓ３：サイクロン電解装置を使用して銅含有濃縮液を処理し、廃液中の有機複合体がアノ
ードに酸化され、銅イオンがカソードに還元され金属銅として堆積するステップと、
Ｓ４：２０分間サイクロン電解処理するステップと、を含む。
Example 3: A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater is
S1: A step of subjecting copper pyrophosphate plating wastewater to rough filtration treatment with a grid, followed by secondary filtration with a zeolite filter to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater for 30 minutes;
S2-1: Pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are passed through the total anion exchange membrane under the action of an electric field force to obtain a phosphorus-containing concentrate. pooling to separate and concentrate phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater;
S3: Using a cyclone electrolyzer to treat a copper-containing concentrate, the organic complexes in the effluent being oxidized to the anode and the copper ions being reduced to the cathode and deposited as metallic copper;
S4: Cyclone electrolytic treatment for 20 minutes.
実施例４：ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法は、
Ｓ１：水とともに空気を噴出するエジェクターを使用して、ピロリン酸銅めっき廃水に空
気を混合してエアフロート法により廃液中の粒子状不純物を除去するステップと、
Ｓ２：前処理されたピロリン酸銅めっき廃水を２５分間電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜に通過させてリン含有濃縮液
プールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮するステ
ップと、
Ｓ３：サイクロン電解装置を使用して銅含有濃縮液を処理し、廃液中の有機複合体がアノ
ードに酸化され、銅イオンがカソードに還元され金属銅として堆積するステップと、
Ｓ４：２０分間サイクロン電解処理し、残りの濃縮液を電気透析陽イオン一方向膜に戻し
てステップＳ２-２で濃縮した後、その中の金属銅を回収するステップと、を含む。
Example 4: A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater is
S1: A step of removing particulate impurities in the wastewater by an air float method by mixing air into copper pyrophosphate plating wastewater using an ejector that ejects air together with water;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater for 25 minutes;
S2-1: Pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are passed through the total anion exchange membrane under the action of an electric field force to obtain a phosphorus-containing concentrate. pooling to separate and concentrate phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater;
S3: Using a cyclone electrolyzer to treat a copper-containing concentrate, the organic complexes in the effluent being oxidized to the anode and the copper ions being reduced to the cathode and deposited as metallic copper;
S4: Cyclone electrolysis for 20 minutes, returning the remaining concentrate to the electrodialysis cationic unidirectional membrane for concentration in step S2-2, and then recovering metallic copper therein.
実施例５：ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法は、
Ｓ１：セキュリティフィルターシステムを使用し、ピロリン酸銅めっき廃水を処理して廃
液中の粒子状不純物を除去するステップと、
Ｓ２：前処理されたピロリン酸銅めっき廃水を２５分間電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜に通過させてリン含有濃縮液
プールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮するステ
ップと、
Ｓ３：サイクロン電解装置を使用して銅含有濃縮液を処理し、廃液中の有機複合体がアノ
ードに酸化され、銅イオンがカソードに還元され金属銅として堆積するステップと、
Ｓ４：３０分間サイクロン電解処理し、残りの濃縮液を電気透析陽イオン一方向膜に戻し
てステップＳ２-２で濃縮した後、その中の金属銅を回収するステップと、を含む。
Example 5: A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater comprises:
S1: Using a security filter system to treat copper pyrophosphate plating wastewater to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater for 25 minutes;
S2-1: Pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are passed through the total anion exchange membrane under the action of an electric field force to obtain a phosphorus-containing concentrate. pooling to separate and concentrate phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater;
S3: Using a cyclone electrolyzer to treat a copper-containing concentrate, the organic complexes in the effluent being oxidized to the anode and the copper ions being reduced to the cathode and deposited as metallic copper;
S4: Cyclone electrolysis for 30 minutes, returning the remaining concentrate to the electrodialysis cation unidirectional membrane for concentration in step S2-2, and then recovering metallic copper therein.
実施例６：ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法は、
Ｓ１：セキュリティフィルターシステムを使用して、ピロリン酸銅めっき廃水を処理して
廃液中の粒子状不純物を除去するステップと、
Ｓ２：前処理されたピロリン酸銅めっき廃水を３０分間電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜に通過させリン含有濃縮液プ
ールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮し、全陽
イオン交換膜は修飾陽イオン交換膜であるステップと、を含む。
Example 6: A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater comprises:
S1: Using a security filter system to treat copper pyrophosphate plating wastewater to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater for 30 minutes;
S2-1: Pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are passed through the total anion exchange membrane under the action of an electric field force to form a phosphorus-containing concentrate pool. to separate and concentrate the phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater, wherein all the cation exchange membranes are modified cation exchange membranes.
修飾陽イオン交換膜の調製方法は、
１）１:３:１１の質量比でガラス繊維、炭素繊維、アラミド繊維を多軸布機で調製して多
軸生地を得るステップと、
２）ポリ塩化ビニルとスチレン-ブタジエン-スチレントリブロック共重合体、修飾ナノ酸
化チタンを３５:３:０．２の質量比でブレンドした後、１８０℃の条件下で多軸生地に塗
布するステップと、
３）自然冷却後、脱イオン水で２０分間超音波洗浄し、次に５０℃の条件下で４時間真空
乾燥して、マトリックス膜を得るステップと、
４）マトリックス膜を１時間スルホン化し次に濃度７５ｗｔ％の濃硫酸、濃度２５ｗｔ％
の希硫酸に順次２時間浸漬し、そして濃度３ｗｔ％の塩化ナトリウム溶液に１５時間浸漬
浸漬して修飾陽イオン交換膜を得るステップと、
Ｓ３：サイクロン電解装置を使用して銅含有濃縮液を処理し、廃液中の有機複合体がアノ
ードに酸化され、銅イオンがカソードに還元され金属銅として堆積するステップと、
Ｓ４：２０分間サイクロン電解処理し、残りの濃縮液を電気透析陽イオン一方向膜に戻し
てステップＳ２-２の濃縮した後、その中の金属銅をさらに回収するステップと、を含む
。
A method for preparing a modified cation exchange membrane comprises:
1) preparing glass fiber, carbon fiber and aramid fiber in a mass ratio of 1:3:11 with a multiaxial cloth machine to obtain a multiaxial fabric;
2) A step of blending polyvinyl chloride, styrene-butadiene-styrene triblock copolymer, and modified nano-titanium oxide at a weight ratio of 35:3:0.2, and then applying the mixture to a multiaxial fabric at 180°C. and,
3) After natural cooling, ultrasonically clean with deionized water for 20 minutes, then vacuum dry at 50° C. for 4 hours to obtain a matrix membrane;
4) The matrix membrane was sulfonated for 1 hour, then concentrated sulfuric acid at a concentration of 75 wt%, a concentration of 25 wt%.
of dilute sulfuric acid for 2 hours, and then immersed in a sodium chloride solution with a concentration of 3 wt% for 15 hours to obtain a modified cation exchange membrane;
S3: Using a cyclone electrolyzer to treat a copper-containing concentrate, the organic complexes in the effluent being oxidized to the anode and the copper ions being reduced to the cathode and deposited as metallic copper;
S4: Cyclone electrolysis for 20 minutes, returning the remaining concentrate to the electrodialysis cation unidirectional membrane to further recover metallic copper therein after the concentration of step S2-2.
実施例７：ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法は、
Ｓ１：セキュリティフィルターシステムを使用して、ピロリン酸銅めっき廃水を処理して
廃液中の粒子状不純物を除去するステップと、
Ｓ２：前処理されたピロリン酸銅めっき廃水を２５分間電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜に通過させリン含有濃縮液プ
ールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮し、全陽
イオン交換膜は修飾陽イオン交換膜であるステップと、を含む。
修飾陽イオン交換膜の調製方法は、
１）１:７．３:１１．５の質量比でガラス繊維、炭素繊維、アラミド繊維を多軸布機で調
製して多軸生地を得るステップと、
２）ポリ塩化ビニルとスチレン-ブタジエン-スチレントリブロック共重合体、修飾ナノ酸
化チタンを４５:５:１．１の質量比でブレンドした後、１９５℃の条件下で多軸生地に塗
布するステップと、
３）自然冷却後、脱イオン水で２３分間超音波洗浄し、次に５５℃の条件下で６時間真空
乾燥して、マトリックス膜を得るステップと、
４）マトリックス膜を２時間スルホン化し、次に濃度８０ｗｔ％の濃硫酸、濃度３０ｗｔ
％の希硫酸に順次２時間浸漬して、そして濃度１０ｗｔ％の塩化ナトリウム溶液に１８時
間浸漬した後、修飾陽イオン交換膜を得るステップと、
Ｓ３：サイクロン電解装置を使用して銅含有濃縮液を処理し、廃液中の有機複合体がアノ
ードに酸化され、銅イオンがカソードに還元され金属銅として堆積するステップと、
Ｓ４：２０分間サイクロン電解処理し、残りの濃縮液を電気透析陽イオン一方向膜に戻し
てステップＳ２-２の濃縮した後、その中の金属銅をさらに回収するステップとを含む。
Example 7: A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater comprises:
S1: Using a security filter system to treat copper pyrophosphate plating wastewater to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater for 25 minutes;
S2-1: Pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are passed through the total anion exchange membrane under the action of an electric field force to form a phosphorus-containing concentrate pool. to separate and concentrate the phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater, wherein all the cation exchange membranes are modified cation exchange membranes.
A method for preparing a modified cation exchange membrane comprises:
1) preparing glass fiber, carbon fiber and aramid fiber in a mass ratio of 1:7.3:11.5 on a multiaxial cloth machine to obtain a multiaxial fabric;
2) A step of blending polyvinyl chloride, styrene-butadiene-styrene triblock copolymer, and modified nano-titanium oxide at a weight ratio of 45:5:1.1, and then applying the mixture to a multiaxial fabric at 195°C. and,
3) After natural cooling, ultrasonically clean with deionized water for 23 minutes, then vacuum dry at 55° C. for 6 hours to obtain a matrix membrane;
4) sulfonate the matrix membrane for 2 hours, then concentrated sulfuric acid with a concentration of 80 wt%, concentration of 30 wt.
% dilute sulfuric acid for 2 hours and then immersed in a sodium chloride solution with a concentration of 10 wt% for 18 hours to obtain a modified cation exchange membrane;
S3: Using a cyclone electrolyzer to treat a copper-containing concentrate, the organic complexes in the effluent being oxidized to the anode and the copper ions being reduced to the cathode and deposited as metallic copper;
S4: Cyclone electrolysis for 20 minutes, returning the remaining concentrate to the electrodialysis cation unidirectional membrane to further recover metallic copper therein after the concentration of step S2-2.
実施例８：ピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルする方法は、
Ｓ１：セキュリティフィルターシステムを使用して、ピロリン酸銅めっき廃水を処理して
廃液中の粒子状不純物を除去するステップと、
Ｓ２：前処理されたピロリン酸銅めっき廃水を２０分間電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜に通過させリン含有濃縮液プ
ールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮し、全陽
イオン交換膜は修飾陽イオン交換膜であるステップと、を含む。
Example 8: A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater comprises:
S1: Using a security filter system to treat copper pyrophosphate plating wastewater to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater for 20 minutes;
S2-1: Pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are passed through the total anion exchange membrane under the action of an electric field force to form a phosphorus-containing concentrate pool. to separate and concentrate the phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater, wherein all the cation exchange membranes are modified cation exchange membranes.
修飾陽イオン交換膜の調製方法は、
１）１:１３:１５の質量比でガラス繊維、炭素繊維、アラミド繊維を多軸布機で調製して
多軸生地を得るステップと、
２）ポリ塩化ビニルとスチレン-ブタジエン-スチレントリブロック共重合体、修飾ナノ酸
化チタンを５５:７:１．３の質量比でブレンドした後、２２０℃の条件下で多軸生地に塗
布するステップと、
３）自然冷却後、脱イオン水で２５分間超音波洗浄し、次に６０℃の条件下で８時間真空
乾燥して、マトリックス膜を得るステップと、
４）マトリックス膜を２時間スルホン化し、濃度８５ｗｔ％の濃硫酸、濃度４０ｗｔ％の
希硫酸に順次２時間浸漬し、そして濃度１５ｗｔ％の塩化ナトリウム溶液に２０時間浸漬
して、修飾陽イオン交換膜を得るステップと、
Ｓ３：サイクロン電解装置を使用して銅含有濃縮液を処理し、廃液中の有機複合体がアノ
ードに酸化され、銅イオンがカソードに還元され金属銅として堆積するステップと、
Ｓ４：２０分間サイクロン電解処理し、残りの濃縮液を電気透析陽イオン一方向膜に戻し
てステップＳ２-２の濃縮した後、その中の金属銅をさらに回収するステップとを含む。
A method for preparing a modified cation exchange membrane comprises:
1) preparing glass fiber, carbon fiber and aramid fiber in a mass ratio of 1:13:15 on a multiaxial cloth machine to obtain a multiaxial fabric;
2) A step of blending polyvinyl chloride, styrene-butadiene-styrene triblock copolymer, and modified nano-titanium oxide at a weight ratio of 55:7:1.3, and then applying the mixture to a multiaxial fabric at 220°C. and,
3) After natural cooling, ultrasonically clean with deionized water for 25 minutes, then vacuum dry at 60° C. for 8 hours to obtain a matrix membrane;
4) The matrix membrane was sulfonated for 2 hours, immersed in concentrated sulfuric acid with a concentration of 85 wt%, dilute sulfuric acid with a concentration of 40 wt% for 2 hours, and then immersed in a sodium chloride solution with a concentration of 15 wt% for 20 hours to obtain a modified cation exchange membrane. a step of obtaining
S3: Using a cyclone electrolyzer to treat a copper-containing concentrate, the organic complexes in the effluent being oxidized to the anode and the copper ions being reduced to the cathode and deposited as metallic copper;
S4: Cyclone electrolysis for 20 minutes, returning the remaining concentrate to the electrodialysis cation unidirectional membrane to further recover metallic copper therein after the concentration of step S2-2.
実施例９：実施例７と異なり、本実施例の修飾陽イオン交換膜の調製方法は、
１）１:３:１１の質量比でガラス繊維、炭素繊維、アラミド繊維を多軸布機で調製して多
軸生地を得るステップと、
２）塩化ベンジルトリエチルアンモニウムとリンタングステン酸を３:２．３の質量比で
混合して、転移活性剤を得るステップと、
３）ポリビニルアルコール樹脂を８０℃の条件下で脱イオン水に溶解し、次に９５℃に加
熱した後ポリビニルアルコール樹脂との質量比１:１１のオルトケイ酸エチルを加え、２
時間磁力攪拌し、そしてオルトケイ酸エチルとの質量比０．５:１の転移活性剤を加え、
１時間磁力攪拌して、ゾルマトリックスを得るステップと、
２）多軸生地を８０℃の条件下でゾルマトリックスに１５時間浸漬し、次に濃度３ｗｔ％
の塩化ナトリウム溶液に１５時間浸漬して、修飾陽イオン交換膜を得るステップとを含む
。
Example 9: Unlike Example 7, the method for preparing the modified cation exchange membrane of this example comprises:
1) preparing glass fiber, carbon fiber and aramid fiber in a mass ratio of 1:3:11 with a multiaxial cloth machine to obtain a multiaxial fabric;
2) mixing benzyltriethylammonium chloride and phosphotungstic acid in a weight ratio of 3:2.3 to obtain a transfer activator;
3) Dissolve polyvinyl alcohol resin in deionized water at 80°C, then heat to 95°C, add ethyl orthosilicate in a mass ratio of 1:11 to polyvinyl alcohol resin,
magnetically stirred for an hour, and added a transfer activator in a mass ratio of 0.5:1 to ethyl orthosilicate;
Magnetic stirring for 1 hour to obtain a sol matrix;
2) The multiaxial fabric is immersed in the sol matrix for 15 hours under the condition of 80 ° C, then the concentration is 3 wt%
sodium chloride solution for 15 hours to obtain a modified cation exchange membrane.
実施例１０：実施例７と異なり、本実施例の修飾陽イオン交換膜の調製方法は、
１）１:７:１２の質量比でガラス繊維、炭素繊維、アラミド繊維を多軸布機で調製して多
軸生地を得るステップと、
２）塩化ベンジルトリエチルアンモニウムとリンタングステン酸を４:２．８の質量比で
混合して、転移活性剤を得るステップと、
３）ポリビニルアルコール樹脂を８５℃の条件下で脱イオン水に溶解し、次に９５℃に加
熱してポリビニルアルコール樹脂との質量比１:６のオルトケイ酸エチルを加え、３時間
磁力攪拌し、そしてオルトケイ酸エチルとの質量比１:１の転移活性剤を加え、１．５時
間磁力攪拌して、ゾルマトリックスを得るステップと、
４）多軸生地を８５℃の条件下でゾルマトリックスに１８時間浸漬し、次に濃度８ｗｔ％
の塩化ナトリウム溶液に１８時間浸漬して、修飾陽イオン交換膜を得るステップとを含む
。
Example 10: Unlike Example 7, the method for preparing the modified cation exchange membrane of this example comprises:
1) preparing glass fiber, carbon fiber and aramid fiber in a mass ratio of 1:7:12 on a multiaxial cloth machine to obtain a multiaxial fabric;
2) mixing benzyltriethylammonium chloride and phosphotungstic acid in a mass ratio of 4:2.8 to obtain a transfer activator;
3) Dissolve polyvinyl alcohol resin in deionized water at 85°C, then heat to 95°C, add ethyl orthosilicate in a mass ratio of 1:6 to polyvinyl alcohol resin, magnetically stir for 3 hours, a step of adding a transfer activator with a mass ratio of 1:1 to ethyl orthosilicate and magnetically stirring for 1.5 hours to obtain a sol matrix;
4) The multiaxial fabric is immersed in the sol matrix for 18 hours under the condition of 85 ° C., then the concentration is 8 wt%
sodium chloride solution for 18 hours to obtain a modified cation exchange membrane.
実施例１１：実施例７と異なり、本実施例の修飾陽イオン交換膜の調製方法は、
１）１:１３:１５の質量比でガラス繊維、炭素繊維、アラミド繊維を多軸布機で調製して
多軸生地を得るステップと、
２）塩化ベンジルトリエチルアンモニウムとリンタングステン酸を５:３の質量比で混合
して、転移活性剤を得るステップと、
３）ポリビニルアルコール樹脂を９０℃の条件下で脱イオン水に溶解し、次に９５℃に加
熱してポリビニルアルコール樹脂との質量比１:５のオルトケイ酸エチルを加え、３時間
磁力攪拌し、そしてオルトケイ酸エチルとの質量比１．３:１の転移活性剤を加え、２時
間磁力攪拌して、ゾルマトリックスを得るステップと、
４）多軸生地を８０～９０℃の条件下でゾルマトリックスに２０時間浸漬し、次に濃度１
５ｗｔ％の塩化ナトリウム溶液に２０時間浸漬して、修飾陽イオン交換膜を得るステップ
とを含む。
Example 11: Unlike Example 7, the method for preparing the modified cation exchange membrane of this example comprises:
1) preparing glass fiber, carbon fiber and aramid fiber in a mass ratio of 1:13:15 on a multiaxial cloth machine to obtain a multiaxial fabric;
2) mixing benzyltriethylammonium chloride and phosphotungstic acid in a weight ratio of 5:3 to obtain a transfer activator;
3) Dissolve polyvinyl alcohol resin in deionized water at 90°C, then heat to 95°C, add ethyl orthosilicate in a mass ratio of 1:5 to polyvinyl alcohol resin, magnetically stir for 3 hours, a step of adding a transfer activator with a mass ratio of 1.3:1 to ethyl orthosilicate and magnetically stirring for 2 hours to obtain a sol matrix;
4) The multiaxial fabric is immersed in the sol matrix for 20 hours under the conditions of 80-90 ° C., and then the concentration is 1
and immersing in a 5 wt% sodium chloride solution for 20 hours to obtain a modified cation exchange membrane.
実験例：
一、実験廃水：ある工場のめっき部品浸出水からピロリン酸銅めっき廃水を入手し、廃水
が薄青色であり、そのうちに、Ｃｕ２+質量濃度が４７．５１ｍｇ/Ｌで、Ｐ２Ｏ７
４-質
量濃度が４３７．３５ｍｇ/Ｌで、ＴＰ質量濃度が６４．７２ｍｇ/Ｌで、ｐＨ＝８．７で
ある。
二、実施例１～１１に記載の方法を使用して回収実験を行い、１組の対照実験を用意し、
対照実験は、具体的に電解法を使用して銅を回収し、試験終了後、合計時間、銅の回収率
、リンの回収率を記録し、上澄み液Ｃｕ２+、ＴＰ質量濃度を測定し、そのうちに、銅の
回収率＝（粉末回収質量×銅含有量）÷持ち込まれた銅量であり、銅含有量はＸＲＤ分光
法により測定され、持ち込まれた銅量＝Ｃｕ２+質量濃度×ピロリン酸銅めっき廃水量で
あり、具体的に表１に示される。
表１：試験データ記録テーブル
Experimental example:
1. Experimental wastewater: Obtained copper pyrophosphate plating wastewater from the leachate of plated parts in a factory. - Mass concentration is 437.35 mg/L, TP mass concentration is 64.72 mg/L, pH=8.7.
2. Perform recovery experiments using the methods described in Examples 1-11 and provide a set of control experiments;
In the control experiment, the electrolytic method was specifically used to recover copper, and after the end of the test, the total time, copper recovery rate, phosphorus recovery rate were recorded, and the supernatant Cu 2+ and TP mass concentrations were measured. , In the meantime, the recovery rate of copper = (mass of powder recovered × copper content) ÷ the amount of copper brought in, the copper content was measured by XRD spectroscopy, the amount of copper brought in = Cu 2+ mass concentration × It is the amount of copper pyrophosphate plating wastewater, which is specifically shown in Table 1.
Table 1: Test data recording table
三、結論：実施例１～１１の方法はすべて良好な回収効果を達成し、Ｃｕ２+、Ｐ２Ｏ７
４-回収率がともに９９．５％より高かった。
3. Conclusion: The methods of Examples 1-11 all achieved good recovery effect, Cu 2+ , P 2 O 7
4 --both recoveries were greater than 99.5%.
Claims (6)
、
Ｓ２：前処理されたピロリン酸銅めっき廃水を電気透析処理するステップと、
Ｓ２-１：前処理されたピロリン酸銅めっき廃水を全陰イオン交換膜に通過させ、廃液中
のピロリン酸イオンを電界力の作用下で、全陰イオン交換膜を通過してリン含有濃縮液プ
ールに入れ、ピロリン酸銅めっき廃水中のリンを分離および濃縮するステップと、
Ｓ２-２：電気透析全陰イオン一方向膜を通過したピロリン酸銅めっき廃水を全陽イオン
交換膜に通過させ、廃液中の銅イオンを電界力の作用下で、全陽イオン交換膜を通過させ
て銅含有濃縮液プールに入れ、ピロリン酸銅めっき廃水中の銅を分離および濃縮するステ
ップと、
Ｓ３：銅含有濃縮液を再処理して銅含有濃縮液から金属銅を回収するステップと、
を含む、ことを特徴とするピロリン酸銅めっき廃水中の銅およびリン資源をリサイクルす
る方法。 S1: A step of pretreating copper pyrophosphate plating wastewater to remove particulate impurities in the wastewater;
S2: A step of electrodialyzing the pretreated copper pyrophosphate plating wastewater;
S2-1: The pretreated copper pyrophosphate plating wastewater is passed through a total anion exchange membrane, and pyrophosphate ions in the wastewater are removed under the action of an electric field force through the total anion exchange membrane to obtain a phosphorus-containing concentrate. pooling to separate and concentrate phosphorus in the copper pyrophosphate plating wastewater;
S2-2: Pyrophosphate copper plating wastewater that has passed through electrodialysis all-anion unidirectional membrane is passed through all-cation exchange membrane, and copper ions in the wastewater are passed through all-cation exchange membrane under the action of electric field force. into a copper-containing concentrate pool to separate and concentrate the copper in the copper pyrophosphate plating wastewater;
S3: reprocessing the copper-containing concentrate to recover metallic copper from the copper-containing concentrate;
A method for recycling copper and phosphorus resources in copper pyrophosphate plating wastewater, comprising:
を処理して廃液中の粒子状不純物を除去することを含む、
ことを特徴とする請求項１に記載の方法。 The S1 pretreatment includes treating the copper pyrophosphate plating wastewater to remove particulate impurities in the wastewater using a security filter system.
2. The method of claim 1, wherein:
ことを特徴とする請求項１に記載の方法。 All cation exchange membranes of S2-2 are modified cation exchange membranes,
2. The method of claim 1, wherein:
１）１:３～１３:１１～１５の質量比で、ガラス繊維、炭素繊維、アラミド繊維を多軸布
機で調製して多軸生地を得るステップと、
２）ポリ塩化ビニルとスチレン-ブタジエン-スチレントリブロック共重合体、修飾ナノ酸
化チタンを３５～５５:３～７:０．２～１．３の質量比でブレンドした後、１８０～２２
０℃の条件下で多軸生地に塗布するステップと、
３）自然冷却後、脱イオン水で２０～２５分間超音波洗浄し、次に５０～６０℃の条件下
で４～８時間真空乾燥して、マトリックス膜を得るステップと、
４）マトリックス膜を１～２時間スルホン化し、次に濃度７５～８５ｗｔ％の濃硫酸、濃
度２５～４０ｗｔ％の希硫酸に順次２時間浸漬し、そして濃度３～１５ｗｔ％の塩化ナト
リウム溶液に１５～２０時間浸漬して修飾陽イオン交換膜を得るステップと、
を含むことを特徴とする請求項３に記載の方法。 The method for preparing the modified cation exchange membrane comprises:
1) preparing glass fiber, carbon fiber, aramid fiber in a mass ratio of 1:3-13:11-15 with a multiaxial cloth machine to obtain a multiaxial fabric;
2) Polyvinyl chloride, styrene-butadiene-styrene triblock copolymer, and modified nanotitanium oxide are blended at a weight ratio of 35-55:3-7:0.2-1.3, and then 180-22.
applying to a multiaxial fabric under conditions of 0° C.;
3) After natural cooling, ultrasonically clean with deionized water for 20 to 25 minutes, then vacuum dry at 50 to 60° C. for 4 to 8 hours to obtain a matrix membrane;
4) The matrix membrane is sulfonated for 1-2 hours, then immersed in concentrated sulfuric acid with a concentration of 75-85 wt%, dilute sulfuric acid with a concentration of 25-40 wt% for 2 hours, and then immersed in a sodium chloride solution with a concentration of 3-15 wt% for 15 hours. soaking for ~20 hours to obtain a modified cation exchange membrane;
4. The method of claim 3, comprising:
１）１:３～１３:１１～１５の質量比でガラス繊維、炭素繊維、アラミド繊維を多軸布機
で調製して多軸生地を得るステップと、
２）塩化ベンジルトリエチルアンモニウムとリンタングステン酸を３～５:２．３～３の
質量比で混合して、転移活性剤を得るステップと、
３）ポリビニルアルコール樹脂を８０～９０℃の条件下で脱イオン水に溶解し、９５℃に
加熱した後、ポリビニルアルコール樹脂との質量比２～７:２２～３５でオルトケイ酸エ
チルを加え、磁力で２～３時間攪拌し、次にオルトケイ酸エチルとの質量比０．５～１．
３:１で転移活性剤を加え、磁力で１～２時間攪拌して、ゾルマトリックスを得るステッ
プと、
４）多軸生地を８０～９０℃の条件下でゾルマトリックスに１５～２０時間浸漬した後、
濃度３～１５ｗｔ％の塩化ナトリウム溶液に１５～２０時間浸漬して、修飾陽イオン交換
膜を得るステップと、
を含むことを特徴とする請求項３に記載の方法。 The method for preparing the modified cation exchange membrane comprises:
1) preparing glass fiber, carbon fiber, and aramid fiber in a mass ratio of 1:3-13:11-15 with a multiaxial cloth machine to obtain a multiaxial fabric;
2) mixing benzyltriethylammonium chloride and phosphotungstic acid in a weight ratio of 3-5:2.3-3 to obtain a transfer activator;
3) Polyvinyl alcohol resin is dissolved in deionized water under conditions of 80 to 90° C., heated to 95° C., ethyl orthosilicate is added at a mass ratio of 2 to 7:22 to 35 with respect to polyvinyl alcohol resin, and magnetic force is applied. for 2 to 3 hours, and then mixed with ethyl orthosilicate in a mass ratio of 0.5 to 1.5.
adding a transfer activator at 3:1 and magnetically stirring for 1-2 hours to obtain a sol matrix;
4) After immersing the multiaxial fabric in a sol matrix for 15 to 20 hours at 80 to 90 ° C.,
immersing in a sodium chloride solution with a concentration of 3-15 wt% for 15-20 hours to obtain a modified cation exchange membrane;
4. The method of claim 3, comprising:
合体をアノードで酸化し、銅イオンがカソードに還元され金属銅として堆積し、サイクロ
ン電解処理した後、銅含有濃縮液中の銅を１０ｇ/Ｌから０．５ｇ/Ｌ以下に減らし、残り
の濃縮液を電気透析陽イオン一方向膜に戻して濃縮し、その中の金属銅をさらに回収する
、
ことを特徴とする請求項１に記載の方法。 Reprocessing of S3 used a cyclone electrolyzer to treat the copper-containing concentrate, oxidizing organic complexes in the effluent at the anode, copper ions being reduced at the cathode and deposited as metallic copper, and subjected to cyclone electrolysis. After that, the copper in the copper-containing concentrate is reduced from 10 g/L to 0.5 g/L or less, and the remaining concentrate is returned to the electrodialysis cationic unidirectional membrane for concentration, and the metallic copper therein is further recovered. ,
2. The method of claim 1, wherein:
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| US7790016B2 (en) * | 2005-04-05 | 2010-09-07 | King Fahd University Of Petroleum And Minerals | Integrated electrolytic-electrodialytic apparatus and process for recovering metals from metal ion-containing waste streams |
| TWI362367B (en) * | 2009-02-20 | 2012-04-21 | Kismart Corp | Electrodialysis method for purifying of silicate-containing potassium hydroxide etching solution |
| DK3041795T3 (en) * | 2013-09-06 | 2020-03-23 | Univ Denmark Tech Dtu | Electrodialytic separation of heavy metals from heavy metal-containing particulate matter |
| CN104108812B (en) * | 2014-07-03 | 2017-01-11 | 苏州联科纳米净化科技有限公司 | Treating method for copper pyrophosphate electroplating wastewater |
| CN106044965B (en) * | 2016-08-12 | 2023-01-10 | 宁波市海智材料产业创新研究院 | Device and method for recovering heavy metals in electroplating wastewater |
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