阅读说明：本技术 酸性蚀刻废液回收碱式碳酸铜的反应装置及其使用方法 (Reaction device for recovering basic copper carbonate from acidic etching waste liquid and use method thereof ) 是由 欧胜 舒良 白坤生 谢彬 李赳 于 2020-07-06 设计创作，主要内容包括：本公开公开了酸性蚀刻废液回收碱式碳酸铜的反应装置,包括进料箱、碱液箱、反应釜、离心机、树脂柱、第一泵和第二泵,反应釜包括釜体、上封头、搅拌装置、第一喷头、第二喷头和第三喷头,上封头连接在釜体的顶部上,第一喷头、第二喷头、第三喷头和搅拌装置均安装在上封头上,第二喷头和第三喷头对称分布在第一喷头的两侧,所述进料箱通过第一泵与第一喷头相连通,所述碱液箱通过第二泵分别与第二喷头和第三喷头相连通,反应釜与离心机相连通,离心机与树脂柱相连通。本发明通过设置第一喷头、第二喷头和第三喷头同时喷洒,实现中和液与第二碱液在喷洒过程中充分接触混合,改善了生成的碱式碳酸铜晶体的晶型,减少了晶体中的杂质。(The utility model discloses a reaction unit of acid etching waste liquid recovery basic copper carbonate, including feeding case, lye tank, reation kettle, centrifuge, resin column, first pump and second pump, reation kettle includes the cauldron body, upper cover, agitating unit, first shower nozzle, second shower nozzle and third shower nozzle, and the upper cover is connected on the top of the cauldron body, and first shower nozzle, second shower nozzle, third shower nozzle and agitating unit all install on the upper cover, and second shower nozzle and third shower nozzle symmetric distribution are in the both sides of first shower nozzle, the feeding case is linked together with first shower nozzle through first pump, lye tank is linked together with second shower nozzle and third shower nozzle respectively through the second pump, and reation kettle is linked together with centrifuge, and centrifuge is linked together with the resin column. According to the invention, the first nozzle, the second nozzle and the third nozzle are arranged for spraying simultaneously, so that the neutralization solution and the second alkali solution are fully contacted and mixed in the spraying process, the crystal form of the generated basic copper carbonate crystal is improved, and impurities in the crystal are reduced.)

1. Acid etching waste liquid retrieves reaction unit of basic copper carbonate, wherein, including feeding case, lye tank, reation kettle, centrifuge, resin column, first pump and second pump, reation kettle includes the cauldron body, upper cover, agitating unit, first shower nozzle, second shower nozzle and third shower nozzle, the upper cover is connected on the top of the cauldron body, first shower nozzle, second shower nozzle, third shower nozzle and agitating unit all install on the upper cover, second shower nozzle and third shower nozzle symmetric distribution are in the both sides of first shower nozzle, the feeding case is linked together through first pump and first shower nozzle, lye tank is linked together with second shower nozzle and third shower nozzle respectively through the second pump, reation kettle is linked together with centrifuge, centrifuge is linked together with the resin column.

2. The reaction device for recovering basic copper carbonate from acidic etching waste liquid according to claim 1, wherein the kettle body comprises an inner kettle body and an outer kettle body, the upper end enclosure and the inner kettle body enclose a reaction cavity, the outer kettle body is sleeved outside the inner kettle body, and a heating cavity is enclosed between the outer kettle body and the inner kettle body.

3. The reaction device for recovering basic copper carbonate from acidic etching waste liquid according to claim 2, wherein the reaction kettle further comprises a thermometer, a heating rod and an air nozzle, the thermometer is mounted on the upper sealing head and extends into the reaction cavity, the heating rod is mounted on the outer kettle body and extends into the heating cavity, the air nozzle is provided with an air nozzle, the air nozzle is fixedly mounted on the inner wall of the inner kettle body, the air nozzles are uniformly distributed on the air nozzle, and the air nozzle has an air injection direction downward.

4. The reaction device for recovering basic copper carbonate from acidic etching waste liquid according to claim 1, wherein the stirring device comprises a motor, a frame, a stirring shaft, a first stirring paddle and a second stirring paddle, the motor is mounted on the frame, the frame is mounted on the upper end closure, the stirring shaft is connected with the motor, the stirring shaft extends into the reaction cavity, and the first stirring paddle and the second stirring paddle are both mounted on the stirring shaft.

5. The reaction device for recovering basic copper carbonate from acidic etching waste liquid according to claim 4, wherein the first stirring paddle and the second stirring paddle are both fixedly connected with a stirring shaft, the first stirring paddle is positioned outside the second stirring paddle, the width ratio of the first stirring paddle to the second stirring paddle is 4:1, the first stirring paddle is a screw-type blade, and the second stirring paddle is a ribbon-type blade.

6. The reaction device for recovering basic copper carbonate from acidic etching waste liquid according to claim 1, wherein a discharge port is formed in the bottom of the inner kettle body and is communicated with the reaction chamber, a pH meter port is formed in the side surface of the inner kettle body and is communicated with the reaction chamber, and a water hole is formed in the outer kettle body and is communicated with the heating chamber.

7. The reaction device for recovering basic copper carbonate from acidic waste etching solution according to claim 1, wherein the resin column comprises a column body and resin, the column body is provided with a liquid inlet, a liquid outlet and a cavity, and the resin is filled in the cavity.

8. Method of use of a reaction device according to any of claims 1-7, wherein the following steps are included:

the preparation of basic copper carbonate comprises the following steps:

step a, adding a first alkali liquor into the acidic etching waste liquid to obtain a neutralized liquid, wherein the concentration of hydrogen ions in the neutralized liquid is 0.01-0.5 mol/L; adding a base solution into the reaction cavity, injecting a heat-conducting medium into the heating cavity, and heating by using a heating rod to ensure that the temperature in the reaction cavity reaches the reaction temperature, wherein the base solution is a mixture of basic copper carbonate crystals and water, and the mass fraction of the basic copper carbonate crystals in the base solution is 5-30%;

step b, simultaneously starting a first pump and a second pump, spraying a second alkali liquor and a neutralization solution into the reaction cavity through a first spray head, a second spray head and a third spray head respectively, wherein the flow rate of the second spray head is the same as that of the third spray head, the spraying radius of the second spray head is the same as that of the third spray head, the ratio of the spraying radius of the second spray head to that of the third spray head to that of the first spray head is 1-1.3: 1, and the ratio of the flow rate of the second spray head to that of the third spray head to that of the first spray head is 0.5-0.7: 1;

step c, starting a motor, rotating a stirring shaft, and stirring the neutralization solution, the second alkali solution and the bottom solution by using a first stirring paddle and a second stirring paddle;

d, after the addition of the neutralization solution and the second alkali solution is finished, obtaining a mixed solution, turning off the motor, the first pump and the second pump, stopping stirring, adjusting the pH value of the mixed solution to 6.0-9.0, and reacting within a certain reaction time, wherein the base solution accounts for 15-30% of the volume of the mixed solution;

step e, obtaining a basic copper carbonate suspension after the reaction is finished, wherein the basic copper carbonate suspension comprises a first part of products and a second part of products, the volume ratio of the first part of products to the second part of products is 3-4: 1, the first part of products flow out of the discharge hole, and the discharge hole is closed; the second part of products are used as bottom liquid of the next reaction and are left in the reaction cavity, and the gas injection pipe injects gas to flush the basic cupric carbonate crystals adhered on the inner wall of the inner kettle body to the bottom of the inner kettle body;

f, continuously and circularly repeating the steps b to e to continuously carry out the reaction, and recovering the acidic etching waste liquid;

the separation of basic copper carbonate comprises the following steps:

the first part of products enter the centrifugal machine, centrifugal separation and filtration are carried out to obtain basic copper carbonate solid and filtrate, and the basic copper carbonate solid is washed and dried to obtain a finished product;

the purification comprises the following steps:

the filtrate enters the liquid inlet and is adsorbed and purified by the resin in the cavity to obtain clear liquid, the clear liquid is discharged through the liquid outlet, the skeleton of the resin is styrene-divinylbenzene copolymer, the functional group of the resin is iminodiacetic acid group, and the ratio of styrene: the molar ratio of the iminodiacetic acid groups is 1: 1.

9. the use method of claim 8, wherein the reaction temperature in step a is 65-85 degrees, the heat transfer medium is heat transfer oil or water vapor, and the reaction time in step d is 1 hour.

10. The use method of claim 8, wherein the first alkali solution is NaOH, KOH or K₂CO₃、KHCO₃Or NaHCO₃One or more of the above-mentioned secondary alkali liquor is K₂CO₃、KHCO₃Or NaHCO₃The molar ratio of the neutralization solution to the second alkali solution is 1: 1.01-1.40.

Technical Field

The disclosure relates to the field of waste liquid treatment design, in particular to a reaction device for recovering basic copper carbonate from acidic etching waste liquid and a using method thereof.

Background

The copper printed circuit board can be etched by an etching process according to a pre-designed circuit diagram, and the residual copper after etching is the finished product of the same circuit board. In the etching process, the concentration of copper ions in the etching solution is continuously increased, the corrosion efficiency of the etching solution is also continuously reduced, and when the concentration of the copper ions in the etching solution is saturated, the etching solution can not be used for preparing a copper printed circuit board any more and is discharged as waste liquid. The waste etching solution of acidic copper printed circuit boards has been recorded in the national hazardous waste records (hazardous waste numbering is HW22), and if a large amount of metal copper ions are put into the waste etching solution and are discharged randomly without being treated, not only is the waste of resources caused, but also the cost of subsequent sewage treatment is increased. The patent number 201711453601.8 is as follows: patent literature of a method for recycling acidic etching solution discloses a method for recovering copper by electrolysis using acidic etching waste solution as a raw material, but the method generates a large amount of chlorine gas, has potential safety hazards, has limited copper removal effect, still has a large amount of copper ions in the electrolyzed solution, and cannot be directly discharged.

Disclosure of Invention

According to one aspect of the disclosure, a reaction device for recovering basic copper carbonate from acidic etching waste liquid comprises a feeding box, an alkaline liquid box, a reaction kettle, a centrifugal machine, a resin column, a first pump and a second pump, wherein the reaction kettle comprises a kettle body, an upper sealing head, a stirring device, a first spray head, a second spray head and a third spray head, the upper sealing head is connected to the top of the kettle body, the first spray head, the second spray head, the third spray head and the stirring device are all mounted on the upper sealing head, the second spray head and the third spray head are symmetrically distributed on two sides of the first spray head, the feeding box is communicated with the first spray head through the first pump, the alkaline liquid box is respectively communicated with the second spray head and the third spray head through the second pump, the reaction kettle is communicated with the centrifugal machine, and the centrifugal machine is communicated with the resin column.

The beneficial effect of this disclosure: according to the invention, the first spray head, the second spray head and the third spray head are arranged on the upper end enclosure of the reaction kettle for spraying simultaneously, so that the neutralization solution and the second alkali solution are fully contacted and mixed in the spraying process, the crystal form of the generated basic copper carbonate crystal is improved, impurities in the generated basic copper carbonate crystal are reduced, and meanwhile, the basic copper carbonate is centrifuged by the centrifuge to prepare the basic copper carbonate finished product; and adsorbing and purifying the trace copper ions in the filtrate by using a resin column to ensure that the content of the copper ions in the clear liquid is lower than 0.01ppm and reaches the discharge standard.

In some embodiments, the kettle body comprises an inner kettle body and an outer kettle body, the upper end enclosure and the inner kettle body enclose a reaction cavity, the outer kettle body is sleeved outside the inner kettle body, and a heating cavity is enclosed between the outer kettle body and the inner kettle body. The inner kettle body is used for containing neutralization solution, second alkali liquor and bottom liquor for reaction, and the reaction cavity is used for the neutralization solution, the second alkali liquor and the bottom liquor for reaction, so that the stirring device is convenient to stir. The heating cavity is used for containing heat-conducting media, so that the heating rod can heat the heat-conducting media conveniently, the temperature in the reaction cavity can be promoted and kept conveniently, and the reaction is facilitated.

In some embodiments, reation kettle still includes thermometer, heating rod and air blast, and the thermometer is installed on last closing head to stretch into the reaction chamber, and the heating rod is installed on outer cauldron body, and stretches into the heating intracavity, and the air blast is equipped with the air nozzle, and the inner wall of cauldron body including the air blast fixed mounting, air nozzle evenly distributed are on the air blast, and the jet-propelled direction of air nozzle is downward. The thermometer is used to monitor the reaction temperature in the reaction chamber. The heating rod heats the heat-conducting medium in the heating cavity, and the temperature in the reaction cavity is increased and maintained. The air nozzles of the air nozzles can blow the basic copper carbonate crystals adhered to the inner wall of the inner kettle body to the bottom of the inner kettle body by air flow.

In some embodiments, the stirring device includes a motor, a frame, a stirring shaft, a first stirring paddle and a second stirring paddle, the motor is mounted on the frame, the frame is mounted on the upper end cap, the stirring shaft is connected with the motor, the stirring shaft extends into the reaction chamber, and both the first stirring paddle and the second stirring paddle are mounted on the stirring shaft. The motor drives the stirring shaft, the first stirring paddle and the second stirring paddle to rotate, and the neutralization solution, the second alkali solution and the bottom solution in the reaction cavity are stirred, so that the neutralization solution, the second alkali solution and the bottom solution are uniformly mixed, and the reaction efficiency is improved.

In some embodiments, the first stirring paddle and the second stirring paddle are both fixedly connected with the stirring shaft, the first stirring paddle is positioned outside the second stirring paddle, the width ratio of the first stirring paddle to the second stirring paddle is 4:1, the first stirring paddle is a screw-type blade, and the second stirring paddle is a ribbon-type blade. When the first stirring paddle and the second stirring paddle are used for stirring, the screw type paddle at the outer side and the helical ribbon type paddle at the inner side can form inner and outer bidirectional runoff, so that substances in the reaction cavity are stirred more uniformly, a neutralization solution and a second alkali solution in the reaction cavity are in full contact and react, the crystal form optimization of basic copper carbonate generated by the reaction is facilitated, and the reaction efficiency can be improved.

In some embodiments, the bottom of the inner kettle body is provided with a discharge hole communicated with the reaction cavity, the side surface of the inner kettle body is provided with a pH meter port communicated with the reaction cavity, and the outer kettle body is provided with a water hole communicated with the heating cavity. The discharge port is used for discharging a first part of products generated by the reaction, and the pH meter port is used for monitoring the pH value in the reaction cavity by using a pH agent in the reaction process. The water hole is used for injecting heat conducting media such as heat conducting oil or water vapor and the like into the heating cavity.

In some embodiments, the resin column comprises a column body and resin, the column body is provided with a liquid inlet, a liquid outlet and a cavity, and the resin is filled in the cavity. The resin in the resin column adsorbs and purifies the residual trace copper ions in the filtrate, and the specific copper ion adsorption resin can ensure that the content of the copper ions in the clear liquid discharged from the liquid outlet is lower than 0.01 ppm.

The use method of the reaction device for recovering basic copper carbonate from the acidic etching waste liquid comprises the following steps:

the preparation of basic copper carbonate comprises the following steps:

step a, adding a first alkali liquor into the acidic etching waste liquor to obtain a neutralization solution, wherein the concentration of hydrogen ions in the neutralization solution is 0.01-0.5 mol/L; adding a base solution into the reaction cavity, injecting a heat-conducting medium into the heating cavity, and heating by using a heating rod to ensure that the temperature in the reaction cavity reaches the reaction temperature, wherein the base solution is a mixture of basic copper carbonate crystals and water, and the mass fraction of the basic copper carbonate crystals in the base solution is 5-30%; the concentration of hydrogen ions in the neutralization solution is 0.01-0.5mol/L, which is convenient for the rapid generation of the subsequent basic copper carbonate, and the basic copper carbonate crystals existing in the base solution play a role of seed crystals and are used for culturing newly generated basic copper carbonate crystals. The mass fraction of the basic copper carbonate crystals in the base solution is less than 5%, which cannot act as seed crystals and is not favorable for culturing new crystals. If the mass fraction of the basic copper carbonate crystals in the base solution exceeds 30%, the basic copper carbonate crystals do not play a significant beneficial role in culturing the seed crystals, and the cost is wasted.

Step b, simultaneously starting a first pump and a second pump, and spraying a second alkali solution and a neutralization solution into the reaction cavity through a first spray head, a second spray head and a third spray head respectively, wherein the flow rate of the second spray head is the same as that of the third spray head, the spraying radius is the same, the ratio of the spraying radius of the second spray head to that of the third spray head to that of the first spray head is 1-1.3: 1, and the ratio of the flow rate of the second spray head to that of the third spray head to that of the first spray head is 0.5-0.7: 1; the second spray head and the third spray head are symmetrically distributed on two sides of the first spray head, the first spray head sprays neutralization liquid, and the second spray head and the third spray head respectively spray second alkali liquor, so that the neutralization liquid and the second alkali liquor can be fully contacted and mixed in the spraying process, the crystal form of the generated basic copper carbonate crystal is favorably optimized and improved, impurities in the generated basic copper carbonate crystal are reduced, and the reaction efficiency is improved.

Step c, starting a motor, rotating a stirring shaft, and stirring the neutralization solution, the second alkali solution and the bottom solution by using a first stirring paddle and a second stirring paddle; the first stirring paddle and the second stirring paddle are driven by the motor to stir, so that the neutralization solution, the second alkali solution and the bottom solution in the reaction cavity are uniformly mixed.

D, after the addition of the neutralization solution and the second alkaline solution is finished, obtaining a mixed solution, turning off the motor, the first pump and the second pump, stopping stirring, adjusting the pH value of the mixed solution to 6.0-9.0, and reacting within a certain reaction time, wherein the base solution accounts for 15-30% of the volume of the mixed solution; the base solution plays a role of seed crystals in the mixed solution, and the base solution accounts for less than 15% of the volume of the mixed solution, so that the culture of the basic copper carbonate crystals generated in the reaction is influenced. The volume proportion of the base solution in the mixed solution is higher than 30%, so that the cost is increased and the waste is caused.

Step e, after the reaction is finished, obtaining basic copper carbonate suspension, wherein the basic copper carbonate suspension comprises a first part of products and a second part of products, the volume ratio of the first part of products to the second part of products is 3-4: 1, the first part of products flow out of a discharge hole, and the discharge hole is closed; the second part of products are used as the bottom liquid of the next reaction and are left in the reaction cavity, and the gas injection pipe injects gas to flush the basic cupric carbonate crystals adhered on the inner wall of the inner kettle body to the bottom of the inner kettle body; the second part of products are used as the bottom liquid of the next reaction and are left in the reaction area, so that basic copper carbonate crystals do not need to be additionally added into the reaction kettle, and the cost is reduced.

F, continuously and circularly repeating the steps b to e to continuously carry out the reaction, and recovering the acidic etching waste liquid; the finished basic copper carbonate crystal does not need to be used for preparing the base solution, so that the circular continuity of production operation is realized, the operation steps and the operation time are saved, and the production efficiency is improved.

The separation of basic copper carbonate comprises the following steps:

the first part of products enter a centrifuge for centrifugal separation and filtration to obtain basic copper carbonate solid and filtrate, and the basic copper carbonate solid is washed and dried to obtain a finished product;

the purification comprises the following steps:

the filtrate enters the liquid inlet and is absorbed and purified by the resin in the cavity to obtain clear liquid, the clear liquid is discharged from the liquid outlet, the skeleton of the resin is styrene-divinylbenzene copolymer, the functional group of the resin is iminodiacetic group, and the ratio of styrene: the molar ratio of the iminodiacetic acid groups is 1: 1. and (3) the filtrate after centrifugation still contains trace copper ions, and the resin is used for adsorbing and purifying the trace copper ions in the filtrate to ensure that the content of the copper ions in the clear liquid is lower than 0.01ppm and the clear liquid reaches the discharge standard.

In some embodiments, the reaction temperature of step a is 65-85 ℃, the heat-conducting medium is heat-conducting oil or water vapor, and the reaction time in step d is 1 hour. The reaction temperature is 65-85 ℃, which is beneficial to the rapid and efficient reaction. And heating the reaction cavity by using heat conduction oil or water vapor as a heat conduction medium to enable substances in the reaction cavity to reach the reaction temperature. The reaction time is 1 hour, and the neutralization solution and the second alkali solution are sprayed simultaneously for feeding, so that the reaction time can be shortened by 20 percent, and the reaction efficiency is greatly improved.

In some embodiments, the first alkali solution is NaOH, KOH, K₂CO₃、KHCO₃Or NaHCO₃One or more of them, and the second alkali solution is K₂CO₃、KHCO₃Or NaHCO₃The molar ratio of the neutralizing solution to the second alkali solution is 1: 1.01-1.40. If the molar ratio of the neutralization solution to the second alkali solution is less than 1.01, the conversion of copper ions is insufficient, and if the molar ratio of the neutralization solution to the second alkali solution is more than 1.40, the waste and the cost are unnecessarily increased.

Drawings

Fig. 1 is a schematic structural diagram of a reaction apparatus for recovering basic copper carbonate from acidic waste etching solution according to an embodiment of the present disclosure.

FIG. 2 is a schematic structural view of the reaction vessel in FIG. 1.

Fig. 3 is a top view of the header of fig. 2.

Fig. 4 is a flowchart of a method for using a reaction apparatus for recovering basic copper carbonate from an acidic etching waste liquid according to an embodiment of the present disclosure.

Fig. 5 is a flow chart of a method for using a reaction device for recovering basic copper carbonate from acidic waste etching solution according to another embodiment of the disclosure.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings.