阅读说明：本技术 一种无害化处理回收碱式氯化铜的方法及装置 (method and device for harmlessly treating and recycling basic copper chloride ) 是由 李伟 万黎明 宁瑞 乐安胜 刘臻伟 任鹏博 马登峰 于 2019-10-16 设计创作，主要内容包括：本发明公开了一种无害化处理回收碱式氯化铜的方法及装置,包括：(1)将回收碱式氯化铜加酸溶解；(2)将料液转移至一级反应釜中,通入硫化氢气体与料液中金属离子反应生成沉淀；(3)将一级反应釜中的物料放出压滤,滤渣作为铜精矿处理回收其中有价金属元素,滤液放入二级反应釜中,通入热空气,将料液中的氟、氯元素转化为氟化氢、氯化氢气体；(4)将二级反应釜产生的氟化氢、氯化氢气体导入一级吸收塔,水喷淋吸收氟化氢、氯化氢气体,没吸收的尾气导入二级吸收塔,碱液喷淋吸收尾气；本发明方法解决了传统火式冶金和湿法冶金处理回收碱式氯化铜的不足,提出了绿色环保处理回收碱式氯化铜的新工艺,最大化的回收了其中的有价金属元素。(The invention discloses a method and a device for harmlessly treating and recycling basic copper chloride, which comprises the following steps: (1) adding acid to the recovered basic copper chloride for dissolving; (2) transferring the feed liquid into a first-stage reaction kettle, and introducing hydrogen sulfide gas to react with metal ions in the feed liquid to generate precipitate; (3) discharging the materials in the first-stage reaction kettle, performing filter pressing, treating filter residues as copper concentrate to recover valuable metal elements, putting the filtrate into a second-stage reaction kettle, introducing hot air, and converting fluorine and chlorine elements in the feed liquid into hydrogen fluoride and hydrogen chloride gas; (4) introducing hydrogen fluoride and hydrogen chloride gas generated by the secondary reaction kettle into a primary absorption tower, spraying water to absorb the hydrogen fluoride and hydrogen chloride gas, introducing unabsorbed tail gas into a secondary absorption tower, and spraying alkali liquor to absorb the tail gas; the method provided by the invention overcomes the defects of the conventional pyrometallurgical and hydrometallurgical treatment and recovery of the basic copper chloride, provides a new environment-friendly treatment and recovery process of the basic copper chloride, and maximally recovers valuable metal elements therein.)

1. A method for harmlessly treating and recovering basic copper chloride is characterized by comprising the following steps:

(1) Adding the recovered basic copper chloride into a dissolving kettle with a stirring device, slowly adding a sulfuric acid solution with the mass fraction of 20-80%, stirring while adding until the pH of the feed liquid is stabilized to 7-8, and detecting the copper ion content C (Cu) in the feed liquid²⁺)；

(2) transferring the feed liquid to a first-stage reaction kettle to enable the feed liquid to fill 2/3-3/4 of the volume of the first-stage reaction kettle, sealing the top of the first-stage reaction kettle, slowly introducing hydrogen sulfide gas into the first-stage reaction kettle from the bottom of the kettle, and controlling the flow velocity of the hydrogen sulfide gas to be 0.5-1 m³Min, wherein the introduction amount of hydrogen sulfide = the molar amount of copper ions x (0.50-0.85) x 22.4L/mol, and the sealing state is kept for 10-20 min after the introduction of the hydrogen sulfide is finished;

(3) Discharging the materials from the bottom of the primary reaction kettle, performing filter pressing, washing a filter cake, and then concentrating the filter cake to be treated as copper concentrate, and sequentially extracting valuable metals such as copper, gold, silver and the like; adding the filtrate into a secondary reaction kettle, introducing hot air of 180-200 ℃ into a secondary sealing tank from the kettle bottom, reacting with fluorine and chlorine ions in the feed liquid to generate hydrogen fluoride and hydrogen chloride gas, and inputting the hydrogen fluoride and the hydrogen chloride gas into a primary absorption tower after converging at the top of the secondary reaction kettle; a hydrogen chloride gas detection device is arranged at the top of the secondary reaction kettle; when the hydrogen chloride gas cannot be detected by the hydrogen chloride detection device at the top of the secondary reaction kettle to overflow, returning to the step (1) to dissolve and recover the basic copper chloride;

(4) Hydrogen fluoride, the hydrogen chloride gas that come out from second grade reation kettle top get into first order absorption tower bottom, and first order absorption tower top shower water contacts with hydrogen fluoride, hydrogen chloride gas adverse current, generates hydrofluoric acid, hydrochloric acid and retrieves, and during tail gas lets in the second grade absorption tower, the second grade absorption tower is equipped with alkali lye, and alkali lye circulates in the second grade absorption tower and sprays, absorbs remaining tail gas, and when alkali lye concentration was not enough to absorb tail gas, emit and retrieve salt, supply new alkali lye.

2. The method for harmlessly processing and recovering copper oxychloride as claimed in claim 1, wherein: the recovered basic copper chloride is obtained by recovering waste circuit boards, printed waste circuit boards and waste etching liquid of the printed circuit boards.

3. the method for harmlessly processing and recovering copper oxychloride as claimed in claim 1, wherein: and (4) the alkali liquor in the secondary absorption tower in the step (4) is sodium hydroxide, potassium hydroxide or sodium carbonate solution, when the mass fraction of the salt solution generated by the reaction reaches 10-20%, the recovered salt is discharged, and new alkali liquor is supplemented and continuously used for tail gas recovery.

4. The apparatus for use in a method for the innocent treatment of copper oxychloride for recovery of claim 1, wherein: the device comprises a dissolving kettle, a first-stage reaction kettle, a filter press, a second-stage reaction kettle, a first-stage absorption tower and a second-stage absorption tower which are connected in series in sequence; the dissolving kettle is provided with a stirring device, the top of the dissolving kettle is provided with a basic copper chloride feeding port and a sulfuric acid solution feeding hole, a dissolving kettle discharging pipe is connected with a first-stage reaction kettle feeding pipe, the bottom of the first-stage reaction kettle is provided with a hydrogen sulfide conveying pipeline, the discharging pipe of the first-stage reaction kettle is connected with a filter press feeding hole, a filter press slag hole is provided with a filter cake collecting device, a filter press discharging pipe is connected with a second-stage reaction kettle feeding pipe, the bottom of the second-stage reaction kettle is provided with a hot air conveying pipeline which is led into the second-stage reaction kettle, the top of the second-stage reaction kettle is provided with an air duct which guides gas generated by the second-stage reaction kettle to the bottom of the first-stage absorption tower, the top of the first-stage absorption tower is provided with a water spraying device which is contacted, the device is characterized in that alkali liquor is filled in the secondary absorption tower, a spraying device is arranged at the top of the secondary absorption tower, an alkali liquor circulating pump is arranged on one side of the bottom of the secondary absorption tower, the alkali liquor in the secondary absorption tower is circularly conveyed to the top of the secondary absorption tower to be sprayed, and valves are arranged on connecting pipelines of the devices according to needs.

5. The apparatus for use in a method of harmlessly processing and recovering copper oxychloride as claimed in claim 4, wherein: the top of the dissolving kettle is also provided with a sulfuric acid solution circulating feed hole, the bottom of the second-stage reaction kettle is provided with a liquid outlet pipe, and the liquid outlet pipe is connected with the sulfuric acid solution circulating feed hole at the top of the dissolving kettle.

6. The apparatus for use in a method of harmlessly processing and recovering copper oxychloride as claimed in claim 4, wherein: and a hydrogen chloride gas detection device is arranged at the top of the secondary reaction kettle.

7. The apparatus for use in a method of harmlessly processing and recovering copper oxychloride as claimed in claim 4, wherein: and gas distributors are arranged at the bottoms of the first-stage reactivity reactor and the second-stage reaction kettle, and a hydrogen sulfide conveying pipeline and a hot air conveying pipeline are respectively connected with the gas distributors of the first-stage reaction kettle and the second-stage reaction kettle.

Technical Field

The invention relates to the technical field of waste circuit board recovery, in particular to a method and a device for recovering basic copper chloride through harmless treatment.

background

with the rapid development of the electronic information industry since the 20 th century, the amount of generated electronic garbage is increased at a rate of 10-15% per year. China is the largest electronic product consuming country, and the discarded electronic products are not less than 700 million tons every year due to updating, wherein the waste circuit boards are important components of electronic garbage and the most valuable components of the electronic garbage. The waste circuit board is different from household garbage, and generally contains about 30% of glass fiber reinforced resin, about 30% of inert oxide and about 40% of valuable metals, wherein the valuable metals mainly comprise about 20% of copper, about 8% of iron, about 2% of nickel, about 4% of tin, about 2% of zinc and the like, approximately account for 39% of the waste circuit board, and the valuable metals comprise gold, silver, palladium and the like; the waste printed circuit board is also treated together with the waste printed circuit board. The enrichment amount of noble metals and common metals in the waste circuit boards is far higher than that of common raw ores, so that the waste circuit boards have higher recovery value, but the recovery difficulty is high due to complex components. Therefore, how to clean and efficiently comprehensively recover and treat valuable metals in waste circuit boards is an important issue of long-term research in the industry.

the existing method for recovering valuable metals in waste circuit boards comprises the following steps: mechanical physical methods, pyrometallurgical methods, hydrometallurgical methods, pyrogenic methods, etc., each have their advantages and disadvantages. The method which is applied more generally comprises the following steps: firstly, physically crushing the waste circuit board, then sequentially soaking the waste circuit board by hydrochloric acid and neutralizing by alkali liquor to obtain a recovered copper chloride hydroxide precipitate crude product, and further recovering valuable metals in the recovered copper chloride hydroxide precipitate crude product. In addition, the etching waste liquid of the printed circuit board is usually the basic copper chloride crude product which is obtained by recycling firstly, and then is further recycled. The basic copper chloride obtained by recovering the waste circuit board or the circuit board etching waste liquid has complex components, not only contains various metal elements in the waste circuit board, but also contains residual fluorine and chlorine elements after the glass fiber reinforced resin is decomposed. Therefore, crude basic copper chloride prepared by recycling waste circuit boards is not easy to treat, and by adopting pyrometallurgy, fluorine and chlorine in the copper chloride can generate HF and HCl gases, so that equipment is seriously corroded, and the copper chloride has great environmental pollution; the method adopts hydrometallurgy, various impurities are required to be removed firstly to obtain solution with simpler components, and then valuable metals are recovered by an electrolytic method, and the problems that the types of reagents required are various, the flow is complicated, only small-batch production can be realized, and large-scale production cannot be realized are solved. In addition, when the method is adopted to treat and recover the basic copper chloride crude product, the recovery and utilization of valuable elements are not maximized. Therefore, the development of a new process method which can recycle the crude basic copper chloride product and recover valuable elements in the crude basic copper chloride product in an environment-friendly and simple way becomes an urgent problem to be solved in the industry.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the method and the device for harmlessly treating and recycling the basic copper chloride are provided for solving the problems that the basic copper chloride crude product obtained by recycling the waste circuit boards, the waste printed circuit boards and the etching waste liquid of the printed circuit boards at present has certain problems when valuable metals are further recycled by adopting the conventional pyrometallurgical or hydrometallurgical mode. The method has simple process flow, high recovery rate of valuable elements and environmental protection.

the invention relates to a method for harmlessly treating and recycling basic copper chloride, which comprises the following steps:

(1) Adding the recovered basic copper chloride into a dissolving kettle with a stirring device, slowly adding a sulfuric acid solution with the mass fraction of 20-80%, stirring while adding until the pH of the feed liquid is stabilized to 7-8, and detecting the copper ion content C (Cu) in the feed liquid²⁺)；

(2) Transferring the feed liquid to a first-stage reaction kettle to enable the feed liquid to fill 2/3-3/4 of the volume of the first-stage reaction kettle, sealing the top of the first-stage reaction kettle, slowly introducing hydrogen sulfide gas into the first-stage reaction kettle from the bottom of the kettle, and controlling the flow velocity of the hydrogen sulfide gas to be 0.5-1 m³Min, hydrogen sulfide introduction amount = copper ion molar amount × (0.50-0.85) × 22.4L/mol, and after the hydrogen sulfide introduction is finished,Keeping the sealing state for 10-20 min;

(3) Discharging the materials from the bottom of the primary reaction kettle, performing filter pressing, washing a filter cake, and then concentrating the filter cake to be treated as copper concentrate, and sequentially extracting valuable metals such as copper, gold, silver and the like; adding the filtrate into a secondary reaction kettle, introducing hot air of 180-200 ℃ into a secondary sealing tank from the kettle bottom, reacting with fluorine and chlorine ions in the feed liquid to generate hydrogen fluoride and hydrogen chloride gas, and inputting the hydrogen fluoride and the hydrogen chloride gas into a primary absorption tower after converging at the top of the secondary reaction kettle; a hydrogen chloride gas detection device is arranged at the top of the secondary reaction kettle; when the hydrogen chloride gas cannot be detected by the hydrogen chloride detection device at the top of the secondary reaction kettle to overflow, returning to the step (1) to dissolve and recover the basic copper chloride;

(4) hydrogen fluoride, the hydrogen chloride gas that come out from second grade reation kettle top get into first order absorption tower bottom, and first order absorption tower top shower water contacts with hydrogen fluoride, hydrogen chloride gas adverse current, generates hydrofluoric acid, hydrochloric acid and retrieves, and during tail gas lets in the second grade absorption tower, the second grade absorption tower is equipped with alkali lye, and alkali lye circulates in the second grade absorption tower and sprays, absorbs remaining tail gas, and when alkali lye concentration was not enough to absorb tail gas, emit and retrieve salt, supply new alkali lye.

The recovered basic copper chloride is obtained by recovering waste circuit boards, printed waste circuit boards and waste etching liquid of the printed circuit boards.

And (4) the alkali liquor in the secondary absorption tower in the step (4) is sodium hydroxide, potassium hydroxide or sodium carbonate solution, when the mass fraction of the salt solution generated by the reaction reaches 10-20%, the recovered salt is discharged, and new alkali liquor is supplemented and continuously used for tail gas recovery.

The device used in the method for harmlessly treating and recovering the copper chloride hydroxide comprises a dissolving kettle, a first-stage reaction kettle, a filter press, a second-stage reaction kettle, a first-stage absorption tower and a second-stage absorption tower which are sequentially connected in series; the dissolving kettle is provided with a stirring device, the top of the dissolving kettle is provided with a basic copper chloride feeding port and a sulfuric acid solution feeding hole, a dissolving kettle discharging pipe is connected with a first-stage reaction kettle feeding pipe, the bottom of the first-stage reaction kettle is provided with a hydrogen sulfide conveying pipeline, the discharging pipe of the first-stage reaction kettle is connected with a filter press feeding hole, a filter press slag hole is provided with a filter cake collecting device, a filter press discharging pipe is connected with a second-stage reaction kettle feeding pipe, the bottom of the second-stage reaction kettle is provided with a hot air conveying pipeline which is led into the second-stage reaction kettle, the top of the second-stage reaction kettle is provided with an air duct which guides gas generated by the second-stage reaction kettle to the bottom of the first-stage absorption tower, the top of the first-stage absorption tower is provided with a water spraying device which is contacted, the device is characterized in that alkali liquor is filled in the secondary absorption tower, a spraying device is arranged at the top of the secondary absorption tower, an alkali liquor circulating pump is arranged on one side of the bottom of the secondary absorption tower, the alkali liquor in the secondary absorption tower is circularly conveyed to the top of the secondary absorption tower to be sprayed, and valves are arranged on connecting pipelines of the devices according to needs.

The top of the dissolving kettle is also provided with a sulfuric acid solution circulating feed hole, the bottom of the second-stage reaction kettle is provided with a liquid outlet pipe, and the liquid outlet pipe is connected with the sulfuric acid solution circulating feed hole at the top of the dissolving kettle.

And a hydrogen chloride gas detection device is arranged at the top of the secondary reaction kettle.

and gas distributors are arranged at the bottoms of the first-stage reactivity reactor and the second-stage reaction kettle, and a hydrogen sulfide conveying pipeline and a hot air conveying pipeline are respectively connected with the gas distributors of the first-stage reaction kettle and the second-stage reaction kettle.

The process principle of the invention is as follows: firstly, adding acid into the recovered basic copper chloride for dissolving to ensure that Cu is dissolved₄(OH)₆Cl₂Decomposition to Cu under acidic conditions²⁺、Cl^-Entering solution, the inclusion part of the basic copper chloride enters the solution, and the part which is not dissolved in sulfuric acid enters precipitation, wherein the main chemical reactions involved are as follows:

Cu₄(OH)₆Cl₂+H₂SO₄→CuCl₂+ CuSO₄ +H₂O；

Ni₄(OH)₆Cl₂+H₂SO₄→NiCl₂+ NiSO₄ +H₂O；

Zn₄(OH)₆Cl₂+H₂SO₄→ZnCl₂+ ZnSO₄ +H₂O；

Cu（OH）₂+H₂SO₄→CuSO₄ +H₂O；

Ni（OH）₂+H₂SO₄→NiSO₄ +H₂O；

Fe₂(OH)₃+H₂SO₄→Fe₂（SO₄）₃ +H₂O；

Zn (OH)₂+H₂SO₄→ZnSO₄ +2H₂O；

……

Then the dissolved feed liquid is put into a first-stage reaction kettle, hydrogen sulfide gas is slowly introduced into the first-stage reaction kettle (the introduction amount is slightly less than the required amount so as to avoid excessive overflow of the hydrogen sulfide gas), the hydrogen sulfide gas reacts with copper ions, silver ions and the like in the solution to generate copper sulfide, silver sulfide and the like, and the related main chemical reactions are as follows:

Cu²⁺+H₂S→CuS↓+2H⁺；

Ni²⁺+H₂S→NiS↓+2H⁺；

2Fe³⁺+3H₂S→Fe₂S₃↓+6H⁺；

Zn³⁺+H₂S→ZnS↓+2H⁺；

2Ag²⁺+H₂S→Ag₂S↓+2H⁺；

……

after the introduction of the hydrogen sulfide is finished, sealing is kept for 10-20 minutes to ensure that the hydrogen sulfide is fully absorbed and reacted by the solution, then the feed liquid is discharged and filter-pressed, a filter cake is collected, the filter cake contains more than 35 percent of copper (0.02 percent of gold and 0.3 percent of silver) and is treated as copper concentrate, and valuable metal elements such as copper, gold, silver and the like in the filter cake are sequentially recovered; the main chemical reactions involved are as follows (main chemical reaction formula for recovering valuable metals from copper concentrate):

CuS+O₂→Cu +SO₂↑；

NiS+O₂→Ni+SO₂↑；

Zn+ O₂→Zn+SO₂↑；

Fe₂S₃+O₂→Fe+SO₂↑；

Ag S+O₂→Ag +SO₂↑；

……

Putting the filtrate generated by the filter press into a secondary reaction kettle, introducing hot air with the temperature of 180-200 ℃ into the bottom of the secondary reaction kettle, reacting with fluorine and chlorine ions in the filtrate to generate hydrogen fluoride and hydrogen chloride gas, collecting the hydrogen fluoride and the hydrogen chloride gas at the top of the secondary reaction kettle, arranging a hydrogen chloride detection device at the top of the secondary reaction kettle, and completely removing the fluorine and chlorine ions in the filtrate when the hydrogen chloride gas cannot overflow, wherein the filtrate can be returned to the step (1) for dissolving the basic copper chloride;

hydrogen fluoride and hydrogen chloride gas generated in the secondary reaction kettle are introduced into the primary absorption tower and are in countercurrent contact with water to generate hydrofluoric acid and hydrochloric acid, and tail gas enters the secondary absorption tower and is circularly sprayed and absorbed by alkali liquor;

After the treatment, valuable metal elements in the basic copper chloride are dissolved, precipitated again and filtered, enter a filter cake and are recovered as copper concentrate, and valuable metal elements such as copper, gold, silver and the like in the copper concentrate are extracted; and the non-precipitated valuable metal elements enter the secondary reaction kettle along with the filtrate to remove harmful elements such as fluorine, chlorine and the like in the filtrate, and then circularly enter the dissolving kettle to dissolve and recover the basic copper chloride, so that the valuable metal elements are not wasted, the removed fluorine and chlorine elements are converted into hydrogen fluoride and hydrogen chloride gas and then absorbed by the primary and secondary absorption towers, and harmful tail gas is prevented from being discharged to the atmosphere.

Compared with the prior art, the process method of the invention has the following advantages:

(1) The whole process adopts wet processing, so that the problems that in the traditional pyrometallurgical processing process, gases such as hydrogen fluoride, hydrogen chloride, sulfur dioxide and the like corrode equipment, seriously pollute the environment and do not meet the environmental protection requirement are avoided;

(2) The whole process adopts wet processing, the adopted medicament is simple, the process flow is simple, the processing capacity is large, and the problems that the traditional wet metallurgy needs various medicaments, the equipment investment is large, and the mass production cannot be realized are solved;

(3) The whole process from dissolving liquid to filtering liquid is recycled, the problem that valuable metals are wasted along with the filtering liquid is avoided, acid liquid and salt liquid generated by recycling harmful gas can be recycled, and the dual purposes of resource utilization maximization and environment protection optimization are achieved;

(4) The method is environment-friendly, greatly reduces the environmental protection treatment cost of enterprises, improves the economic benefit of the enterprises, and is worth of great popularization and application.

according to the method, the purpose of treating and recovering valuable metal elements in the basic copper chloride by a whole wet method is achieved by carefully researching the components of the recovered basic copper chloride and redesigning a process route, the problems that the traditional pyrometallurgical method does not meet the environmental protection requirement, the process flow of the hydrometallurgical method is complex, and the large-batch treatment cannot be carried out are solved, the novel green and environment-friendly process for treating and recovering the basic copper chloride is provided, the valuable metal elements in the basic copper chloride are recovered to the maximum degree, the economic benefit is high, and the method is suitable for wide popularization and use.

Drawings

FIG. 1 is a schematic process flow diagram of the present invention;

Fig. 2 is a schematic view of the connection of the apparatus of the present invention.

in the figure, 1-dissolution kettle, 2-first-stage reaction kettle, 3-filter press, 4-second-stage reaction kettle, 5-first-stage absorption tower, 6-second-stage absorption tower, 7-basic copper chloride feed opening, 8-sulfuric acid solution feed hole, 9-hydrogen sulfide pipeline conveying pipe, 10-filter cake collecting device, 11-hot air conveying pipe, 12-water spraying device, 13-alkali liquor spraying device, 14-alkali liquor circulating pump, 15-valve, 16-sulfuric acid solution circulating feed hole and 17-hydrogen chloride gas detecting device.

Detailed Description

the process of the present invention is further illustrated by the following specific examples, which are intended to be purely exemplary and are not intended to limit the invention in any way.