CN212770968U - Alkaline etching solution in-situ electrolysis copper extraction recycling device - Google Patents
Alkaline etching solution in-situ electrolysis copper extraction recycling device Download PDFInfo
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Abstract
The utility model provides an alkaline etching solution in-situ electrolysis copper extraction recycling device, which has outstanding etching stability, etching speed, fineness and high copper ion concentration of 180-; the method has the advantages that a simple controllable etching solution in-situ electrolysis recycling mode is realized, the smooth and bright high-purity copper plate is obtained, no electrolysis tail solution needs deep environment-friendly treatment, no blending cylinder needs manual intervention for blending regeneration solution, and the copper plate can directly return to an etching machine for etching circuit board production.
Description
Technical Field
The utility model belongs to circuit board alkaline etching field especially involves a copper regeneration device is carried in electrolysis of alkaline etching solution normal position.
Background
The circuit alkaline etching manufacturing process of the circuit board adopts alkaline etching sub-liquid rich in ammonium chloride and ammonia ions to etch copper foil on a copper-clad plate (copper ammonia complexation reaction) to form a circuit, and simultaneously generates copper-containing alkaline etching waste liquid rich in copper chloride, ammonium chloride and ammonia ions and having complex components. The conventional alkaline etching process uses alkaline etching solution composed of 250-280g/L ammonium chloride, 100-120g/L ammonia and 600-650g/L water to etch the copper-clad plate to form alkaline etching waste solution containing 140-160g/L copper ions, 250-280g/L ammonium chloride, 100-120g/L ammonia and 440-460g/L water.
The copper in the copper-containing alkaline etching waste liquid can be removed by chemical or physical reaction methods such as an acid neutralization precipitation method, a displacement reduction method, distillation and the like, so that the components of the etching liquid are damaged, and the tail liquid after copper removal needs further environmental-friendly physical or chemical treatment and cannot be recycled, thereby causing great environmental-friendly disposal cost and resource waste. Such as Kunshan Zhixianglong electronics, Inc. CN201920750262.8, Huizhou Daizian environmental protection technologies, Inc. CN201811002592.5, Lu Ming; plum dawn clear; liu Yu CN201710665696.3, Kun shan Uning Ding environmental protection science and technology Limited CN201110385711.1, CN201010269561.3, Jiang De Xin, CN201010505221.6, Chong Qing Han Yu regeneration resources Limited CN201721178953.2, Shenzhen Wanshan hong environmental protection practice Limited CN200720121065.7, Guangdong Bo county Xiang fine chemistry Limited CN201710321291.8 and other patents mention the method of obtaining copper-containing compounds by neutralizing alkaline etching liquid with acid and alkali, such as obtaining copper hydroxide, cuprous chloride and the like. In CN201210023824.1, the patent of Fujian university Fuqing school CN200910112525.3, Jieshan environmental protection science and technology development Co., Ltd, of Jiiche, Kunshan city mentions a process for obtaining copper powder from alkaline etching waste liquid by using a chemical reduction or displacement method. CN201310528684.8, a method for resourceful treatment and cyclic utilization of PCB circuit board etching waste liquid, which adopts evaporation to obtain copper hydroxide, ammonia water and ammonium chloride.
The copper-containing alkaline etching waste liquid can realize copper extraction and etching liquid recycling by a method of extracting copper ions from the etching liquid, reversely extracting the copper ions from the sulfuric acid solution and electrolyzing the copper sulfate solution to obtain an electrolytic copper plate, and the alkaline waste etching liquid is used for etching production after being prepared and regenerated by an extracting agent to extract the copper ions. Such as French Jinyuitong electronics (Tungyuan) Limited CN201920437891.5, CN201210171978.5, Guangzhou De ya New environmental science and technology Limited CN201920059660.5, CN201910034200.1, Foshan TuoLu environmental protection science and technology Limited CN201820828872.0, Shenzhen Qixintian Zhengzhen environmental protection science and technology Limited CN201820344909.2, CN201220013823.4, CN201910448747.6, Shenzhen Jichi science and technology Limited CN201721481325.1, CN201620842159.2, Foshan Xinnayuan environmental protection science and technology Limited CN201720545796.8, CN201710346673.6 Guangzhou environmental protection engineering Limited CN201720536382.9, Dongguan Zhongke China electromechanical installation engineering Limited CN201720333372.5, Jiangsu Jingzhen environmental protection science and technology Limited CN201620094212.5, CN642016642016407. X, Huizhou Zhen environmental protection science ancient CN201520832187.1, Jiangsu Jishiyan environmental protection science and technology corporation CN201520197326.8, Shenzheng Xinyu environmental protection technology corporation CN201420421044.7, Dongguangyitong environmental protection technology Limited CN201220088036.6, Shenzhou environmental protection technology CN201120387384.9, Shenzhou Shenyu environmental protection technology Limited CN 5928, CN 598, Shenzhou environmental protection technology Ji CN 598, Shenzhou environmental protection technology Jijujuju CN 5926, in the patent of Hefei municipal Utility department precision die Co., Ltd CN201710437644.0, Ganxiangzhou polycyclic science Co., Ltd CN201210439048.3, Tufangxiang CN200810198673.7 and the like, it is mentioned that an extractant is adopted to capture copper ions from an etching solution, then the copper ions are released in a sulfuric acid solution, and finally, the copper plate is obtained by electrolytic decoppering of the copper sulfate solution. The process adopts an extracting agent as a medium to capture copper ions, a large amount of water washing media are needed in the process of capturing and releasing the copper ions to prevent cross contamination of etching solution and sulfuric acid electrolyte, so that the ammonia nitrogen waste liquid is formed and rinsed in large quantity side by side, the process is complex, the full recycling can not be realized, and the ammonia nitrogen waste liquid generated by rinsing needs to be subjected to environment-friendly advanced treatment.
The Changsha green iridium environmental protection science and technology limited CN200410047003.7 also provides a membrane separation and electrodeposition copper removal recycling method. The Jiaxing school Baoji Qing CN201210162539.8 also provides a method for preparing cuprous chloride in a cathode area by an electrochemical method. The environmental protection science and technology limited corporation CN201810324639.3 of Changshelijie mentioned a method of combining membrane separation technology and precipitation reduction technology to realize the recycling of etching solution.
The copper-containing alkaline etching waste liquid can also be used for realizing the copper removal of the etching liquid by directly electrolyzing the alkaline etching liquid to obtain a copper plate, and the regenerated and blended alkaline etching sub-liquid is adjusted and then returned to the production line for recycling. For example, CN201920853624.6, CN201920322054.8, CN201910294649.1, CN201821277082.4, Nanjing hua shengyu environmental science and technology Limited, CN201820381299.3, Guangdong Sanyun environmental science and technology Limited, CN201710213366.0, CN201710213366.0, Shenzhen Zhengyu environmental science and technology Limited, CN201720649755.3, Shenjing hua Shenzhou environmental science and technology Limited, CN201720061243.5, Fengshun jian electronics CN2, CN201711257417.6, Shencheng CN201620848666.7, Chenghua environmental protection and technology Limited 201620854966.6, CN201610646086.4, CN 201304304210522, CN201220369 421.2, CN 58, CN 72, CN201220423587.3, CN 8672, CN201220423587.3, Shenyun Shenyu environmental protection science and technology No. CN 8672, Shenyun Shenyu environmental protection technology limited, CN201220423587.3, Shenyu CN201220423587.3, CN201910285485.6, CN201910040826.3, CN201810743885.2, CN201810979855.1, the limited of the environmental protection science and technology of Shunhun industry, Anhui oasis, and the like, which are patents, mention the method, the concentration of copper ions in the etching solution is unstable in the direct electrolysis process of the alkaline etching solution, and the concentration of the copper ions is reduced from 150g/L to 0-30g/L along with the continuous deposition of the copper ions at the cathode, so that the cathode copper plate obtained by electrolyzing and extracting copper has large copper nodules, which easily causes the short circuit of the cathode and the anode; the electrolytic cathode copper plate is brittle and has insufficient toughness. The whole copper electrolysis process can only work intermittently, but can not work continuously. The electrolyzed etching regeneration liquid has unstable components and high quality risk of recycling of the etching regeneration liquid, needs to be manually prepared by a preparation cylinder and then returned to a production line for continuous use, and easily causes the problems of poor etching circuit, unqualified circuit precision and the like in the process of etching production of circuit boards. The electrolysis copper extraction equipment has high power consumption and large heat release, and also needs auxiliary facilities such as a circulating cylinder, a cooling system, an ammonia waste gas collecting system, a blending cylinder and the like to be matched, so that the equipment has large floor area, the system is complex, the system has large safety operation difficulty and the like.
In order to overcome the problems of low stability and low etching quality of the regeneration and recycling of the etching solution and improve the service life of the etching regeneration solution, Shenzhen Jieshi scientific and technological Limited CN200910238823.7 provides a regeneration solution of an alkaline copper etching solution and a method for improving the etching speed of the regeneration solution, wherein an organic thio compound containing a first accelerating agent containing NH 2-CS-NH-groups and a second accelerating agent are additionally added in the preparation process of the regeneration solution of the alkaline copper etching solution, and the second accelerating agent is at least one substance selected from a compound of chlorite ions and a compound of perborate ions. Shenzhen, Qixintian Zhengzhen environmental protection science and technology Limited CN201910225092.6 mentions an additive of an alkaline etching regeneration liquid and the alkaline etching regeneration liquid in parts by mass, wherein the additive of the alkaline etching regeneration liquid contains: 0.1-2.2 parts of accelerator; 0.2-2.8 parts of inhibitor; 0.3-1.8 parts of catalyst; 0.1 to 1.0 portion of stabilizer. The accelerator is at least one of bithiourea, thiosemicarbazide, thiourea and phenylthiourea; the inhibitor is at least one of ammonium sulfate, sodium sulfite, sodium silicate and ammonium bicarbonate; at least one of potassium thiocyanate, ammonium thiocyanate, potassium thiosulfate and ammonium thiosulfate. The stabilizer is at least one selected from ethylenediamine, triethanolamine and ethanolamine. An alkaline etching solution and a recycling method thereof are disclosed in CN201810324639.3, Changshelijie environmental protection science and technology Limited company, wherein the alkaline etching solution comprises copper chloride, organic amine, an oxidant, an additive and deionized water; each liter of alkaline etching solution contains 10-150g of copper chloride, 10200 g of organic amine, 1-100g of oxidant, 1-100g of additive and the balance of deionized water. The organic amine is one or more selected from ethylamine, ethanolamine, o-phenylenediamine, ethylenediamine and triethylene tetramine; the oxidant is selected from one or more of oxygen, chlorate, hydrogen peroxide and permanganate; the additive is selected from one or more of disulfate, carbonate, bicarbonate, ammonia water, thiocyanate and sodium thiosulfate, and the cyclic utilization of the etching solution is realized by adopting a method combining a membrane separation technology and a precipitation reduction technology.
SUMMERY OF THE UTILITY MODEL
The utility model discloses an aim at provide an alkaline etching solution normal position electrolysis copper extraction regeneration device to provide at least the advantage that will explain later.
The utility model also aims to provide an alkaline etching solution in-situ electrolysis copper extraction recycling device, which has excellent etching stability, etching speed, fineness and high copper ion concentration of 180-; the method has the advantages that a simple controllable etching solution in-situ electrolysis recycling mode is realized, the smooth and bright high-purity copper plate is obtained, no electrolysis tail solution needs deep environment-friendly treatment, no blending cylinder needs manual intervention for blending regeneration solution, and the copper plate can directly return to an etching machine for etching circuit board production.
The technical scheme of the utility model as follows:
the utility model provides an alkaline etching solution normal position electrolysis is carried copper and is recycled device, it includes:
the etching machine adopts alkaline etching solution to etch the copper-clad plate to form the circuit board, wherein the alkaline etching solution comprises the following components in parts by weight: 100-150 parts of ammonium bicarbonate, 10-20 parts of ammonium nitrate, 10-20 parts of ammonium phosphate, 10-20 parts of ammonium oxalate, 50-100 parts of ammonium chloride, 100-120 parts of ammonia, 180-200 parts of copper ions, 400-500 parts of water and 1-10 parts of allylthiourea, wherein the etching machine is provided with an alkaline etching solution inlet and a waste liquid tank for storing the etched alkaline etching waste liquid;
the electrolytic bath is provided with an alkaline etching waste liquid inlet and an alkaline etching electrolyte outlet, a circulating pump is arranged between the alkaline etching waste liquid inlet and the waste liquid bath, and the alkaline etching electrolyte outlet is communicated with the alkaline etching liquid inlet;
a copper ion concentration sensor which is disposed in the alkaline etching waste liquid tank and detects a copper ion concentration value of the current alkaline etching waste liquid;
the electrolytic rectifier is inserted into the electrolytic bath to electrolyze the alkaline etching waste liquid to obtain a copper plate and alkaline etching electrolyte, and is electrically connected with the copper ion concentration sensor, and the electrolytic rectifier adjusts the electrolytic current according to the copper ion concentration value of the current alkaline etching waste liquid so that the copper extraction electrolysis speed is the same as the copper-clad plate etching speed;
a pH sensor for detecting the pH value of the current alkaline etching solution;
the ammonia gas supply valve is electrically connected with the pH sensor and is opened when the pH value is lower than a set value so as to introduce ammonia gas into the alkaline etching solution;
an ampere-hour sensor disposed on the electrolytic rectifier;
and the allyl thiourea replenishment metering pump is communicated with the alkaline etching waste liquid tank, and is electrically connected with the ampere hour sensor and is started at regular time.
The utility model provides an alkaline etching solution normal position electrolysis is carried copper and is recycled device, it includes:
the etching machine adopts alkaline etching solution to etch the copper-clad plate to form the circuit board, wherein the alkaline etching solution comprises the following components in parts by weight: 100-150 parts of ammonium bicarbonate, 10-20 parts of ammonium nitrate, 10-20 parts of ammonium phosphate, 10-20 parts of ammonium oxalate, 50-100 parts of ammonium chloride, 100-120 parts of ammonia, 180-200 parts of copper ions, 400-500 parts of water and 1-10 parts of allylthiourea, wherein the etching machine is provided with an alkaline etching solution inlet and a waste liquid tank for storing the etched alkaline etching waste liquid;
the alkaline etching waste liquid barrel is provided with a first alkaline etching waste liquid inlet and an alkaline etching waste liquid outlet, and the alkaline etching waste liquid inlet is communicated with the waste liquid tank through an alkaline etching waste liquid pump;
the alkaline etching regeneration liquid barrel is provided with a second alkaline etching waste liquid inlet, an alkaline etching electrolyte inlet, a first alkaline etching regeneration liquid outlet and a second alkaline etching regeneration liquid outlet, the second alkaline etching waste liquid inlet is communicated with the alkaline etching waste liquid outlet through an alkaline etching waste liquid replenishing pump, and the second alkaline etching regeneration liquid outlet is communicated with the alkaline etching liquid inlet through an alkaline etching regeneration liquid replenishing pump;
the electrolytic bath is provided with an alkaline etching regeneration liquid inlet and an alkaline etching electrolyte outlet, the alkaline etching regeneration liquid inlet is communicated with the first alkaline etching regeneration liquid outlet through a circulating pump, and the alkaline etching electrolyte outlet is communicated with the alkaline etching electrolyte inlet;
an electrolytic rectifier inserted into the electrolytic bath and inserted into the electrolytic bath to electrolyze the alkaline etching waste liquid to obtain a copper plate and an alkaline etching electrolyte;
the first pH sensor is used for detecting the pH value of the current alkaline etching solution;
the first ammonia gas replenishing valve is electrically connected with the first pH sensor and is opened when the pH value of the current alkaline etching solution is lower than a first set value;
a second pH sensor which is disposed in the alkaline etching regeneration liquid barrel and detects a pH value of the current alkaline etching regeneration liquid;
the second ammonia gas replenishing valve is electrically connected with the second pH sensor and is opened when the pH value of the current alkaline etching regeneration liquid is lower than a second set value;
the first copper ion concentration sensor is arranged in the alkaline etching waste liquid groove and is used for detecting the copper ion concentration value of the current alkaline etching waste liquid, the first copper ion concentration sensor is electrically connected with an alkaline etching regeneration liquid replenishing pump, and the alkaline etching regeneration liquid replenishing pump is started when the copper ion concentration value of the current alkaline etching waste liquid is lower than a first set concentration value;
the second copper ion concentration sensor is arranged in the alkaline etching regeneration liquid barrel and is used for detecting the copper ion concentration value of the current alkaline etching regeneration liquid, the second copper ion concentration sensor is electrically connected with an alkaline etching waste liquid replenishing pump, and the alkaline etching waste liquid replenishing pump is started when the copper ion concentration value of the current alkaline etching regeneration liquid is lower than a second set concentration value;
an ampere-hour sensor disposed on the electrolytic rectifier;
and the allyl thiourea replenishment metering pump is communicated with the alkaline etching waste liquid tank, and is electrically connected with the ampere hour sensor and is started at regular time.
The utility model discloses following beneficial effect has:
in-situ online circulating electrolysis copper extraction or offline electrolysis copper extraction can be carried out, the copper ion concentration is kept to be detected online through a copper ion concentration sensor, the electrolytic current of a rectifier is adjusted, the copper ion concentration of the etching solution is stable, ammonia gas is automatically supplemented through online pH detection, the ammonia concentration is kept stable, the current and the operation time of the electrolysis rectifier are detected through an ampere hour sensor, and allylthiourea is automatically supplemented through a metering pump;
the volatilized waste gas of the electrolytic cell is directly connected with a waste gas absorption pipeline of the etching machine, and a waste gas absorption device is not required to be additionally arranged;
obtaining a bright and compact electrolytic copper plate and a stable regenerated and recycled etching solution.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic diagram of a fine etching process using the alkaline etchant of the present invention;
FIG. 2 is a schematic structural diagram of an embodiment of the device for in-situ electrolysis of alkaline etchant to extract copper for recycling;
fig. 3 is a schematic structural diagram of an embodiment of the device for in-situ electrolysis and copper extraction and recycling of alkaline etching solution provided by the present invention.
Detailed Description
The present invention is further described in detail below with reference to the drawings so that those skilled in the art can implement the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The utility model provides an alkaline etching solution, it includes the following components by weight:
100-150 parts of ammonium bicarbonate, 10-20 parts of ammonium nitrate, 10-20 parts of ammonium phosphate, 10-20 parts of ammonium oxalate, 50-100 parts of ammonium chloride, 100-120 parts of ammonia, 180-200 parts of copper ions, 400-500 parts of water and 1-10 parts of allylthiourea.
The utility model discloses a 100-plus 150g/L ammonium bicarbonate, 10-20g/L ammonium nitrate, 10-20g/L ammonium phosphate, 10-20g/L ammonium oxalate, 50-100g/L ammonium chloride multicomponent composite salt, make the etching solution possess good buffering stability, wettability and permeability on the copper face, realize good etching rate, can maintain copper etching rate and be about 60-80um/min, traditional alkaline etching liquid medicine can only reach 40-60 um/min's etching rate. The composite ammonium salt type etching solution has the advantages of nonvolatility, no reduction of component concentration and no need of subsequent adjustment and addition.
The allyl thiourea is a weak corrosion inhibitor and can form a weak copper-allyl thiourea complex layer on the copper surface. As shown in fig. 1, the copper-allylthiourea complex layer on the copper surface 1 can be destroyed by the etching solution during the spray etching process without affecting the further etching of the bottom copper. After the copper-allylthiourea complex layer is washed and etched away, the allylthiourea is re-dissolved in the etching solution, and the components are kept inconvenient. With the further progress of etching, the allylthiourea and the copper of the side 2 of the circuit form a copper-allylthiourea complex layer, and because the scouring force of the etching liquid medicine sprayed and etched on the side 2 is small and is not damaged, a side corrosion prevention layer is formed, the etching production of fine circuits is realized, the highest capability can reach the precision etching production of the line width and the line distance of 25um, and the traditional alkaline etching liquid medicine can only reach the line width and the line distance etching precision of 75-100 um.
As shown in fig. 2, the utility model provides a copper regeneration device is carried in electrolysis of alkaline etching solution normal position, it includes:
the etching machine 1 is used for etching the copper-clad plate by adopting alkaline etching solution to form a circuit board, wherein the alkaline etching solution comprises the following components in parts by weight: 100-150 parts of ammonium bicarbonate, 10-20 parts of ammonium nitrate, 10-20 parts of ammonium phosphate, 10-20 parts of ammonium oxalate, 50-100 parts of ammonium chloride, 100-120 parts of ammonia, 180-200 parts of copper ions, 400-500 parts of water and 1-10 parts of allylthiourea, wherein the etching machine is provided with an alkaline etching solution inlet and a waste liquid tank for storing the etched alkaline etching waste liquid;
the electrolytic bath 2 is provided with an alkaline etching waste liquid inlet and an alkaline etching electrolyte outlet, a circulating pump 7 is arranged between the alkaline etching waste liquid inlet and the waste liquid bath, and the alkaline etching electrolyte outlet is communicated with the alkaline etching liquid inlet;
a copper ion concentration sensor 3 which is provided in the alkaline etching waste liquid tank and detects a copper ion concentration value of the current alkaline etching waste liquid;
the electrolytic rectifier 4 is inserted into the electrolytic bath 2 to electrolyze the alkaline etching waste liquid to obtain a copper plate and alkaline etching electrolyte, the electrolytic rectifier 4 is electrically connected with the copper ion concentration sensor 3, and the electrolytic rectifier 4 adjusts the electrolytic current according to the copper ion concentration value of the current alkaline etching waste liquid so that the copper extraction electrolysis speed is the same as the copper-clad plate etching speed;
a pH sensor 5 for detecting the pH value of the current alkaline etching solution;
an ammonia gas supply valve 6 which is electrically connected with the pH sensor 5 and is opened when the pH value is lower than a set value so as to introduce ammonia gas into the alkaline etching solution;
an ampere-hour sensor provided on the electrolytic rectifier 4;
and the allyl thiourea replenishment metering pump is communicated with the alkaline etching waste liquid tank, and is electrically connected with the ampere hour sensor and is started at regular time.
The allyl thiourea is a cyanide-free copper plating additive and brightener, forms a complex layer with an electrolytic copper surface in the etching solution in-situ electrolysis copper extraction process, has the functions of uniform copper surface current distribution and potential difference improvement, enables the copper plate surface obtained by electrolysis to be bright, smooth and high in density, has no copper nodules, effectively prevents negative and positive short circuits, reduces the electrode polarization side effect, improves the electrolysis efficiency, and is low in heat release. The purity of the copper plate obtained by electrolysis reaches more than 99 percent. And (3) automatically supplementing the allylthiourea according to the detected electrolytic current and the operating time of the ampere hour sensor, wherein the supplemented allylthiourea is absorbed to the surface of the copper plate along with the electrolytic process, and the supplementing amount is 0.1-1g/100 A.h.
A small amount of ammonia gas volatilizes in the processes of the alkaline etching process and the electrolytic recycling process, and the ammonia gas is automatically supplemented through online pH agent detection, so that the ammonia concentration of the multi-component composite salt etching solution is ensured. If the pH value is set to 8.6, when the pH value is lower than the set value, an ammonia gas replenishing solenoid valve is opened. The time for supplementing and supplementing ammonia gas once can be set to be 0-300 seconds, the time for waiting once after supplementing and supplementing ammonia gas can be set to be 0-300 seconds, and the cycle number of supplementing and waiting can be set to be 0-1000 times. Through the logic circulation addition control, stable pH can be obtained, the fluctuation range is less than 0.01, the traditional fluctuation control mode of low start and high stop of pH control is avoided, and etching liquid medicine with stable components is obtained.
The copper ion concentration in the alkaline etching process and the electrolytic recycling process is increased along with the etching, and is reduced along with the electrolysis. And (3) carrying out on-line in-situ electrolysis copper extraction and circular etching, automatically adjusting the magnitude of electrolysis current by detecting the concentration of copper ions, wherein the concentration of the copper ions is 180g/L, and the electrolysis current is 500-800A, continuously electrolyzing, keeping the speed of copper extraction electrolysis the same as that of copper-clad plate etching, and keeping the speed of copper extraction and copper corrosion at 7 kg/h.
The method for carrying out the on-line in-situ electrolysis of the alkaline etching solution and the copper extraction recycling by adopting the device provided by the utility model comprises the following steps:
etching the copper-clad plate by adopting alkaline etching solution to form a circuit board and simultaneously obtaining alkaline etching waste liquid, wherein the alkaline etching solution comprises the following components in parts by weight: 100-150 parts of ammonium bicarbonate, 10-20 parts of ammonium nitrate, 10-20 parts of ammonium phosphate, 10-20 parts of ammonium oxalate, 50-100 parts of ammonium chloride, 100-120 parts of ammonia, 180-200 parts of copper ions, 400-500 parts of water and 1-10 parts of allylthiourea;
the alkaline etching waste liquid reaches the electrolytic bath through the circulating pump to be electrolyzed to obtain alkaline etching electrolyte and a copper plate, the alkaline etching electrolyte returns to the etching machine to be mixed with the alkaline etching liquid and then etches the copper-clad plate, the circulation is completed, the concentration of the alkaline etching liquid in the electrolytic copper extracting machine and the alkaline etching liquid in the etching machine is consistent, and the circulation is uniform;
detecting the concentration value of copper ions in the current alkaline etching waste liquid, and adjusting the electrolytic current by an electrolytic rectifier according to the concentration value so that the copper extraction electrolytic speed is the same as the copper-clad plate etching speed;
detecting the pH value of the current alkaline etching solution, and opening an ammonia gas supply valve when the pH value is lower than a set value;
opening an allylthiourea supply metering pump at regular time to supplement allylthiourea into the alkaline etching waste liquid, wherein the supplement amount is 0.1-1g/100 A.h;
the compact bright copper-nodule-free 99% high-purity copper plate is obtained through the processes, and the copper plate is lifted every 3 to 7 days.
As shown in fig. 3, the utility model also provides an alkaline etching solution normal position electrolysis copper extraction recycling device, it includes:
the etching machine 8 is used for etching the copper-clad plate by adopting alkaline etching solution to form a circuit board, and the alkaline etching solution comprises the following components in parts by weight: 100-150 parts of ammonium bicarbonate, 10-20 parts of ammonium nitrate, 10-20 parts of ammonium phosphate, 10-20 parts of ammonium oxalate, 50-100 parts of ammonium chloride, 100-120 parts of ammonia, 180-200 parts of copper ions, 400-500 parts of water and 1-10 parts of allylthiourea, wherein the etching machine 8 is provided with an alkaline etching solution inlet and a waste liquid tank for storing the etched alkaline etching waste liquid;
an alkaline etching waste liquid barrel 9 having a first alkaline etching waste liquid inlet and an alkaline etching waste liquid outlet, the alkaline etching waste liquid inlet being in communication with the waste liquid tank via an alkaline etching waste liquid pump 10;
an alkaline etching regeneration liquid barrel 11, which has a second alkaline etching waste liquid inlet, an alkaline etching electrolyte inlet, a first alkaline etching regeneration liquid outlet and a second alkaline etching regeneration liquid outlet, wherein the second alkaline etching waste liquid inlet is communicated with the alkaline etching waste liquid outlet through an alkaline etching waste liquid replenishing pump 12, and the second alkaline etching regeneration liquid outlet is communicated with the alkaline etching liquid inlet through an alkaline etching regeneration liquid replenishing pump 13;
an electrolytic bath 14 having an alkaline etching regeneration liquid inlet communicating with the first alkaline etching regeneration liquid outlet through a circulation pump 15 and an alkaline etching electrolyte outlet communicating with the alkaline etching electrolyte inlet;
an electrolytic rectifier 16 inserted into the electrolytic bath 14 and inserted into the electrolytic bath 14 to electrolyze the alkaline etching waste liquid to obtain a copper plate and an alkaline etching electrolyte;
a first pH sensor 17 that detects a pH value of the current alkaline etching solution;
a first ammonia gas supply valve 18 electrically connected to the first pH sensor 17 and opened when the pH of the current alkaline etching solution is lower than a first set value;
a second pH sensor 19 which is provided in the alkaline etching regeneration liquid tank 11 and detects a pH value of the current alkaline etching regeneration liquid;
a second ammonia gas supply valve 20 electrically connected to the second pH sensor 19 and opened when the pH value of the current alkaline etching regeneration liquid is lower than a second set value;
a first copper ion concentration sensor 21 disposed in the alkaline etching waste liquid tank and detecting a copper ion concentration value of the current alkaline etching waste liquid, wherein the first copper ion concentration sensor 21 is electrically connected to an alkaline etching regeneration liquid replenishing pump 13, and the alkaline etching regeneration liquid replenishing pump 13 is turned on when the copper ion concentration value of the current alkaline etching waste liquid is lower than a first set concentration value;
a second copper ion concentration sensor 22, which is disposed in the alkaline etching regeneration liquid barrel 11 and detects the copper ion concentration value of the current alkaline etching regeneration liquid, wherein the second copper ion concentration sensor 22 is electrically connected with an alkaline etching waste liquid replenishing pump 12, and the alkaline etching waste liquid replenishing pump 12 is turned on when the copper ion concentration value of the current alkaline etching regeneration liquid is lower than a second set concentration value;
an ampere-hour sensor disposed on the electrolytic rectifier;
and the allyl thiourea replenishment metering pump is communicated with the alkaline etching waste liquid tank, and is electrically connected with the ampere hour sensor and is started at regular time.
During off-line in-situ electrolysis, the electrolysis current of a fixed rectifier is continuously electrolyzed at 300A, the concentration of copper ions is controlled at 50g/L, and etching solution with high copper content is automatically added by detecting the concentration of the copper ions to keep the copper extraction speed at 3.5 kg/h. The etching regeneration liquid with low copper ion concentration of 50g/L is continuously obtained for the online supplement of the alkaline etching production line. The etching production line detects the concentration of copper ions, such as 180g/L, through a copper ion concentration sensor, and when the concentration of the copper ions is higher than a set value, an etching regeneration liquid replenishing pump with low copper ion concentration is automatically started. The time for replenishing the etching regeneration liquid with low copper ion concentration can be set to be 0-300 seconds, the time for waiting for one time after replenishing the etching regeneration liquid with low copper ion concentration can be set to be 0-300 seconds, and the cycle number of replenishing and waiting can be set to be 0-1000 times. Through the logic circulation addition control, the stable etching concentration of the copper ion concentration can be obtained, the fluctuation range is less than 5g/L, the traditional fluctuation control mode of controlling high start and low stop is avoided, and the etching liquid medicine with stable components is obtained.
The method for carrying out in-situ electrolysis copper extraction recycling of alkaline etching solution by adopting the device provided by the utility model comprises the following steps:
etching the copper-clad plate by adopting alkaline etching solution to form a circuit board and simultaneously obtaining alkaline etching waste liquid, wherein the alkaline etching solution comprises the following components in parts by weight: 100-150 parts of ammonium bicarbonate, 10-20 parts of ammonium nitrate, 10-20 parts of ammonium phosphate, 10-20 parts of ammonium oxalate, 50-100 parts of ammonium chloride, 100-120 parts of ammonia, 180-200 parts of copper ions, 400-500 parts of water and 1-10 parts of allylthiourea;
the method comprises the following steps that alkaline etching waste liquid reaches an alkaline etching waste liquid barrel through an alkaline etching waste liquid pump, then reaches an alkaline etching regeneration liquid barrel through an alkaline etching waste liquid replenishing pump, reaches an electrolytic bath through a circulating pump, is electrolyzed to obtain alkaline etching electrolyte and a copper plate, the alkaline etching electrolyte returns to the alkaline etching regeneration liquid barrel, and is mixed with the alkaline etching liquid through the alkaline etching regeneration liquid replenishing pump to etch the copper-clad plate, so that circulation is completed;
detecting the pH value of the current alkaline etching solution, and opening a first ammonia gas supply valve when the pH value is lower than a first set value;
detecting the pH value of the current alkaline etching regeneration liquid, and opening a second ammonia gas supply valve when the pH value is lower than a second set value;
detecting a copper ion concentration value of the current alkaline etching waste liquid, and starting an alkaline etching regeneration liquid replenishing pump when the copper ion concentration value of the current alkaline etching waste liquid is lower than a first set concentration value;
detecting the copper ion concentration value of the current alkaline etching regeneration liquid, and starting an alkaline etching waste liquid replenishing pump when the copper ion concentration value of the current alkaline etching regeneration liquid is lower than a second set concentration value;
and (3) opening the allyl thiourea supply metering pump at regular time to supply allyl thiourea into the alkaline etching waste liquid, wherein the supply amount is 0.1-1g/100 A.h.
The specific implementation case one:
alkaline etching copper extraction and recycling in a certain circuit board factory in Jiangsu adopt an on-line in-situ electrolysis circulating copper extraction scheme. Through determination, 120g/L ammonium bicarbonate, 10g/L ammonium nitrate, 10g/L ammonium phosphate, 10g/L ammonium oxalate, 100g/L ammonium chloride, 100g/L ammonia, 180g/L copper ions, 5g/L allylthiourea and 465g/L water, the etching speed is 5 m/min, the copper etching amount is 5kg/h, and the circuit board line precision is 50 um. The in-situ electrolysis copper extraction equipment is directly connected with the etching line, the etching solution in the etching machine and the electrolysis copper extraction equipment is uniformly mixed through a circulating pump, the current of an electrolysis rectifier is 600A (the working range of the rectifier is 0-1000A), the copper extraction speed is 5kg/h, and the change of copper ions is monitored in real time to adjust the current of the rectifier. After 5 days and 24 hours of etching production and electrolytic cycle regeneration, 580kg of electrolytic copper plate with the purity of 99.1 percent is obtained in total. And (3) detecting the pH value in the etching machine to be 8.6 on line, automatically opening an ammonia gas supply valve when the pH value is lower than a set value, and opening and waiting for logical addition to obtain a stable etching speed. And (3) automatically supplementing the allylthiourea according to the detected electrolytic current and the operating time of the ampere hour sensor, wherein the supplemented allylthiourea is absorbed to the surface of the copper plate along with the electrolytic process, and the supplementing amount is 0.1-1g/100 A.h.
The specific implementation case two:
alkaline etching copper extraction and cyclic regeneration utilization are carried out in a certain circuit board factory in Zhejiang, and an off-line in-situ electrolysis regeneration circulation scheme is adopted. According to the determination, 125g/L ammonium bicarbonate, 15g/L ammonium nitrate, 15g/L ammonium phosphate, 15g/L ammonium oxalate, 110g/L ammonium chloride, 100g/L ammonia, 200g/L copper ions, 5g/L allylthiourea and 415g/L water are contained in the alkaline etching waste liquid, the etching speed is 4.8 m/min, the copper etching amount is 5kg/h, and the circuit board line precision is 75 um. The in-situ electrolysis copper extraction equipment is circularly connected with the etching regeneration liquid barrel, the etching machine and the etching liquid in the etching regeneration liquid barrel are uniformly mixed through a circulating pump, the concentration of copper ions is controlled to be 50g/L, the current of an electrolysis rectifier is 350A (the working range of the rectifier is 0-1000A), the copper extraction speed is 3.5kg/h, and the concentration of the copper ions in the regeneration liquid barrel is monitored in real time to automatically supplement alkaline etching waste liquid. After 10 days and 24 hours of etching production and electrolytic cycle regeneration, 840kg of electrolytic copper plate with the purity of 99.3 percent is obtained in total. And (3) detecting the pH value of the regeneration liquid to be 8.6 in real time, automatically opening an ammonia gas supply valve when the pH value is lower than a set value, and opening a waiting logic to add so as to obtain stable etching liquid concentration. Detecting the copper ion concentration of 200g/L in the etching machine in real time on line, and when the copper ion concentration is higher than a set value, automatically replenishing regeneration liquid by starting a waiting logic to obtain stable copper ion concentration; and (3) detecting the pH value in the etching machine to be 8.6 in real time, and automatically opening an ammonia gas supply valve to obtain stable alkalinity of the etching solution when the pH value is lower than a set value.
While the embodiments of the invention have been described above, it is not intended to be limited to the details shown, or described, but rather to cover all modifications, which would come within the scope of the appended claims, and all changes which come within the meaning and range of equivalency of the art are therefore intended to be embraced therein.
Claims (2)
1. Alkaline etching solution normal position electrolysis copper extraction regeneration utilizes device, its characterized in that includes:
the etching machine is used for etching the copper-clad plate by adopting alkaline etching liquid to form a circuit board and is provided with an alkaline etching liquid inlet and a waste liquid tank for storing the etched alkaline etching waste liquid;
the electrolytic bath is provided with an alkaline etching waste liquid inlet and an alkaline etching electrolyte outlet, a circulating pump is arranged between the alkaline etching waste liquid inlet and the waste liquid bath, and the alkaline etching electrolyte outlet is communicated with the alkaline etching liquid inlet;
a copper ion concentration sensor which is disposed in the alkaline etching waste liquid tank and detects a copper ion concentration value of the current alkaline etching waste liquid;
the electrolytic rectifier is inserted into the electrolytic bath to electrolyze the alkaline etching waste liquid to obtain a copper plate and alkaline etching electrolyte, and is electrically connected with the copper ion concentration sensor, and the electrolytic rectifier adjusts the electrolytic current according to the copper ion concentration value of the current alkaline etching waste liquid so that the copper extraction electrolysis speed is the same as the copper-clad plate etching speed;
a pH sensor for detecting the pH value of the current alkaline etching solution;
an ammonia gas supply valve electrically connected with the pH sensor;
an ampere-hour sensor disposed on the electrolytic rectifier;
and the allyl thiourea replenishment metering pump is communicated with the alkaline etching waste liquid tank, and is electrically connected with the ampere hour sensor and is started at regular time.
2. Alkaline etching solution normal position electrolysis copper extraction regeneration utilizes device, its characterized in that includes:
the etching machine is used for etching the copper-clad plate by adopting alkaline etching liquid to form a circuit board and is provided with an alkaline etching liquid inlet and a waste liquid tank for storing the etched alkaline etching waste liquid;
the alkaline etching waste liquid barrel is provided with a first alkaline etching waste liquid inlet and an alkaline etching waste liquid outlet, and the alkaline etching waste liquid inlet is communicated with the waste liquid tank through an alkaline etching waste liquid pump;
the alkaline etching regeneration liquid barrel is provided with a second alkaline etching waste liquid inlet, an alkaline etching electrolyte inlet, a first alkaline etching regeneration liquid outlet and a second alkaline etching regeneration liquid outlet, the second alkaline etching waste liquid inlet is communicated with the alkaline etching waste liquid outlet through an alkaline etching waste liquid replenishing pump, and the second alkaline etching regeneration liquid outlet is communicated with the alkaline etching liquid inlet through an alkaline etching regeneration liquid replenishing pump;
the electrolytic bath is provided with an alkaline etching regeneration liquid inlet and an alkaline etching electrolyte outlet, the alkaline etching regeneration liquid inlet is communicated with the first alkaline etching regeneration liquid outlet through a circulating pump, and the alkaline etching electrolyte outlet is communicated with the alkaline etching electrolyte inlet;
an electrolytic rectifier inserted into the electrolytic bath and inserted into the electrolytic bath to electrolyze the alkaline etching waste liquid to obtain a copper plate and an alkaline etching electrolyte;
the first pH sensor is used for detecting the pH value of the current alkaline etching solution;
a first ammonia gas supply valve electrically connected to the first pH sensor;
a second pH sensor which is disposed in the alkaline etching regeneration liquid barrel and detects a pH value of the current alkaline etching regeneration liquid;
a second ammonia make-up valve in electrical communication with the second pH sensor;
a first copper ion concentration sensor which is arranged in the alkaline etching waste liquid groove and detects the copper ion concentration value of the current alkaline etching waste liquid, wherein the first copper ion concentration sensor is electrically connected with an alkaline etching regeneration liquid replenishing pump;
the second copper ion concentration sensor is arranged in the alkaline etching regeneration liquid barrel and is used for detecting the copper ion concentration value of the current alkaline etching regeneration liquid, and the second copper ion concentration sensor is electrically connected with the alkaline etching waste liquid replenishing pump;
an ampere-hour sensor disposed on the electrolytic rectifier;
and the allyl thiourea replenishment metering pump is communicated with the alkaline etching waste liquid tank, and is electrically connected with the ampere hour sensor and is started at regular time.
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| CN113652694A (en) * | 2021-06-24 | 2021-11-16 | 广东桐鸣环保科技有限公司 | Copper plating layer stripping liquid and stripping method |
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