阅读说明：本技术 一种废碱性蚀刻液的环保处理方法及其装置 (Environment-friendly treatment method and device for waste alkaline etching solution ) 是由 王水平 于 2020-07-21 设计创作，主要内容包括：本发明公开了一种废碱性蚀刻液的环保处理方法及其装置,所述方法包括下述步骤：将废碱性蚀刻液收集在带搅拌及加热装置的废液收集罐中,检测罐体内的氯离子含量,向废液收集罐中加入氯离子摩尔量1～1.05倍的氢氧化钠,边搅拌边缓慢升温至40～100℃,析出氧化铜,加热保温至溶液无色透明,液体pH为7～9时,停止加热,将物料放出至氧化铜过滤机过滤、洗涤,烘干,即得氧化铜产品；本发明方法及装置,碱用量只有原来的40%,且获得的氧化铜产品纯度可达到98%以上,符合国家标准,且可副收硫酸铵产品,废水质量优于排放标准；本发明方法及装置同时达到了节能、环保、资源最大利用及经济效益最高的目的,适合广泛推广使用。(The invention discloses an environment-friendly treatment method and device for waste alkaline etching solution, wherein the method comprises the following steps: collecting the waste alkaline etching solution in a waste liquid collecting tank with a stirring and heating device, detecting the content of chloride ions in the tank body, adding sodium hydroxide with the mole amount of 1-1.05 times of that of the chloride ions into the waste liquid collecting tank, slowly heating to 40-100 ℃ while stirring, precipitating copper oxide, heating and insulating until the solution is colorless and transparent, stopping heating when the pH value of the liquid is 7-9, discharging the material to a copper oxide filter, filtering, washing and drying to obtain a copper oxide product; according to the method and the device, the alkali consumption is only 40% of the original consumption, the purity of the obtained copper oxide product can reach more than 98%, the copper oxide product meets the national standard, the ammonium sulfate product can be secondarily recovered, and the quality of the wastewater is superior to the discharge standard; the method and the device simultaneously achieve the purposes of energy conservation, environmental protection, maximum utilization of resources and highest economic benefit, and are suitable for wide popularization and application.)

1. An environment-friendly treatment method of waste alkaline etching solution is characterized by comprising the following steps: collecting the waste alkaline etching solution in a waste liquid collecting tank with a stirring and heating device, detecting the content of chloride ions in the tank body, adding sodium hydroxide with the mole weight of 1-1.05 times of that of the chloride ions into the waste liquid collecting tank, slowly heating to 40-100 ℃ while stirring, precipitating copper oxide, heating and insulating until the solution is colorless and transparent, stopping heating when the pH of the liquid is 7-9, discharging the material in the waste liquid collecting tank, conveying the discharged material to a copper oxide filter for filtering and washing, and drying by a copper oxide dryer to obtain a copper oxide product; and adding the next batch of waste alkaline etching solution into the waste liquid collecting tank for next batch treatment.

2. The method for environmentally friendly treating waste alkaline etching solution as claimed in claim 1, wherein: the top of waste liquid collection tank still is equipped with supply air duct 6, carries the ammonia and the carbon dioxide gas that produce of reaction in the waste liquid collection tank to sulphuric acid ammonia absorption tower through draught fan and supply air duct, sulphuric acid ammonia absorption tower's top is equipped with sulphuric acid spray set for absorb ammonia and generate ammonium sulfate, when liquid pH reaches 5 ~ 6 in the sulphuric acid ammonia absorption tower, emits liquid and sends into vacuum concentration jar and concentrate, the material after the concentration is sent into the ammonium sulfate crystallizer and is crystallized, the material after the crystallization sends into centrifuge together with crystallization mother liquor, the ammonium sulfate product is retrieved in the centrifugation, crystallization mother liquor after the centrifugation returns vacuum concentration jar raw materials entry for ammonium sulfate is retrieved in the cyclic concentration.

3. The method for environmentally friendly treating waste alkaline etching solution as claimed in claim 1, wherein: the main component of the waste alkaline etching solution is Cu (NH)₃）₄Cl₂And Cu (NH)₃）₄CO₃。

4. The apparatus for use in the method of environmentally friendly disposal of spent alkaline etching solution according to claim 1 or 2, having a spent solution collecting tank, characterized in that: the waste liquid collecting tank is provided with a stirring and heating device, the top of the waste liquid collecting tank is provided with a waste alkaline etching liquid inlet and an alkaline liquid feeding port, the bottom of the waste liquid collecting tank is provided with a discharge port, the discharge port is connected with a copper oxide filter through a pipeline, and a copper oxide collecting tank is arranged below the copper oxide filter; the top of the waste liquid collecting tank is also provided with an air supply pipeline, and the waste liquid collecting tank is sequentially connected with an ammonia absorbing tower of sulfuric acid, a vacuum concentration tank, an ammonium sulfate crystallization tank and a centrifuge in series; the ammonia gas and the carbon dioxide gas that the waste liquid collecting tank produced are sucked through the draught fan on the supply air duct, send into sulphuric acid and inhale in the ammonia tower, sulphuric acid inhales the ammonia tower top and is equipped with sulphuric acid spray set, after spraying the formation ammonium sulfate through sulphuric acid, send into the vacuum concentration jar and concentrate, the ammonium sulfate crystallizer is sent into to the ammonium sulfate mother liquor that concentrates in the crystallization, the ammonium sulfate crystal after the crystallization is sent into centrifuge together with the crystallization mother liquor and is retrieved the ammonium sulfate, the ammonium sulfate crystallization mother liquor after the centrifugation sends into vacuum concentration jar raw materials entrance through the centrifuge drain pipe, get into vacuum concentration jar circulation concentration and retrieve the ammonium sulfate, pump and valve are equipped with as required on above-mentioned.

5. The apparatus according to claim 4, wherein the apparatus comprises: and a copper oxide dryer is also arranged behind the copper oxide filter and used for drying the copper oxide.

Technical Field

The invention relates to the technical field of environment-friendly treatment of waste alkaline etching solution, in particular to an environment-friendly treatment method and device of waste alkaline etching solution.

Background

The main component of the waste alkaline etching solution is Cu (NH)₃）₄Cl₂And Cu (NH)₃）₄CO₃. Existing method for treating alkaline etching solutionThe method comprises the following steps: adding sulfuric acid for acidification, precipitating basic copper chloride, removing trace copper from mother liquor, adding alkali, heating, evaporating, recovering ammonia water, and discharging the brine from which ammonia nitrogen is removed; the basic copper chloride is acidified by sulfuric acid to prepare copper sulfate, and after the copper sulfate is crystallized, the mother liquor continuously reacts with the alkaline etching solution, so that the circulation is realized. The main chemical reaction equation of the process principle is as follows:

4Cu（NH₃）₄Cl₂+ 5H₂SO₄= CuCl₂·3Cu（OH）₂↓+ 5（NH₄）₂SO₄+ 6NH₄Cl；

2Cu（NH₃）₄CO₃+ 5H₂SO₄= Cu₂（OH）₂SO₄↓+ 4（NH₄）₂SO₄+ 2CO₂↑；

CuCl₂·3Cu（OH）₂+ 3H₂SO₄=3CuSO₄+ 2CuCl₂+ 6H₂O；

（NH₄）₂SO₄+ NH₄Cl +3NaOH = Na₂SO₄+ NaCl+ 3NH₃↑+ 3H₂O；

2NH₃+ H₂SO₄= （NH₄）₂SO₄。

although the copper sulfate product can be obtained in the treatment process, the content of chlorine seriously exceeds the standard, the copper sulfate can only be sold as a crude product or an agricultural product, and the relative value is low, more importantly, the waste liquid containing ammonium sulfate and ammonium chloride is difficult to process into a standard product, only the alkali is added and ammonia is evaporated for discharge, the treatment cost is extremely high, the waste of resources is also caused, and the economic cost is extremely low. Therefore, a new method and a new device for treating waste alkaline etching solution with low cost and environmental protection are developed to solve the above problems, which become a problem to be solved in the industry.

Disclosure of Invention

The invention aims to provide an environment-friendly treatment method and device for waste alkaline etching solution, aiming at the problems that the existing method for treating alkaline etching solution can only produce low-value copper sulfate products, ammonium sulfate and ammonium chloride contained in mother solution after copper sulfate recovery are difficult to process into standard products, only alkali can be added for ammonia distillation and emission, the treatment cost is extremely high and resource waste is caused. The method has low treatment cost, the content of the obtained product copper oxide can reach more than 98 percent, and the discharged wastewater is superior to the discharge standard specified by environmental protection, thereby having extremely high economic benefit and environmental protection benefit.

The invention relates to an environment-friendly treatment method of waste alkaline etching solution, which comprises the following steps: collecting the waste alkaline etching solution in a waste liquid collecting tank with a stirring and heating device, detecting the content of chloride ions in the tank body, adding sodium hydroxide with the mole weight of 1-1.05 times of that of the chloride ions into the waste liquid collecting tank, slowly heating to 40-100 ℃ while stirring, precipitating copper oxide, heating and insulating until the solution is colorless and transparent, stopping heating when the pH of the liquid is 7-9, discharging the material in the waste liquid collecting tank, conveying the discharged material to a copper oxide filter for filtering and washing, and drying by a copper oxide dryer to obtain a copper oxide product; and adding the next batch of waste alkaline etching solution into the waste liquid collecting tank for next batch treatment.

The top of waste liquid collection tank still is equipped with supply air duct 6, carries the ammonia and the carbon dioxide gas that produce of reaction in the waste liquid collection tank to sulphuric acid ammonia absorption tower through draught fan and supply air duct, sulphuric acid ammonia absorption tower's top is equipped with sulphuric acid spray set for absorb ammonia and generate ammonium sulfate, when liquid pH reaches 5 ~ 6 in the sulphuric acid ammonia absorption tower, emits liquid and sends into vacuum concentration jar and concentrate, the material after the concentration is sent into the ammonium sulfate crystallizer and is crystallized, the material after the crystallization sends into centrifuge together with crystallization mother liquor, the ammonium sulfate product is retrieved in the centrifugation, crystallization mother liquor after the centrifugation returns vacuum concentration jar raw materials entry for ammonium sulfate is retrieved in the cyclic concentration.

The main component of the waste alkaline etching solution is Cu (NH)₃）₄Cl₂And Cu (NH)₃）₄CO₃。

The device used in the environment-friendly treatment method of the waste alkaline etching solution comprises a waste solution collecting tank, wherein the waste solution collecting tank is provided with a stirring and heating device, the top of the waste solution collecting tank is provided with a waste alkaline etching solution inlet and an alkali solution feeding port, the bottom of the waste solution collecting tank is provided with a discharge port, the discharge port is connected with a copper oxide filter through a pipeline, and a copper oxide collecting tank is arranged below the copper oxide filter; the top of the waste liquid collecting tank is also provided with an air supply pipeline, and the waste liquid collecting tank is sequentially connected with an ammonia absorbing tower of sulfuric acid, a vacuum concentration tank, an ammonium sulfate crystallization tank and a centrifuge in series; the ammonia gas and the carbon dioxide gas that the waste liquid collecting tank produced are sucked through the draught fan on the supply air duct, send into sulphuric acid and inhale in the ammonia tower, sulphuric acid inhales the ammonia tower top and is equipped with sulphuric acid spray set, after spraying the formation ammonium sulfate through sulphuric acid, send into the vacuum concentration jar and concentrate, the ammonium sulfate crystallizer is sent into to the ammonium sulfate mother liquor that concentrates in, the ammonium sulfate crystal after the crystallization is sent into centrifuge together with the crystallization mother liquor and is retrieved the ammonium sulfate, the ammonium sulfate crystallization mother liquor after the centrifugation sends into vacuum concentration jar raw materials entrance through the centrifuge drain pipe, get into vacuum concentration jar circulation concentration and retrieve the ammonium sulfate, all be equipped with pump and valve as required on above-mentioned each pipeline.

And a copper oxide dryer is also arranged behind the copper oxide filter and used for drying the copper oxide.

The process principle of the invention is as follows: the main component of the waste alkaline etching solution is Cu (NH) through research₃）₄Cl₂And Cu (NH)₃）₄CO₃Using Cu (NH)₃）₄Cl₂Can react with sodium hydroxide under heating condition to generate copper oxide, Cu (NH)₃）₄CO₃The characteristic that decomposition reaction can also occur to generate copper oxide under the heating condition is that slightly excessive sodium hydroxide is added into waste alkaline etching solution, copper oxide precipitate is generated under the heating condition, ammonia gas generated by heating is introduced into an ammonia sulfate absorption tower through an induced draft fan and an air supply pipeline to generate ammonium sulfate for recovery, and the related main chemical reaction equation is as follows:

Cu（NH₃）₄Cl₂+ 2NaOH

CuO↓+ 2NaCl + 4NH₃↑；

Cu（NH₃）₄CO₃ CuO↓+4NH₃+CO₂↑；

2NH₃+ H₂SO₄= （NH₄）₂SO₄。

in the scheme of the invention, the determination of chemical components in the waste alkaline etching solution is particularly important, which is the premise of the method, but the sulfuric acid consumption is huge and the alkali consumption is not less by adopting a sulfuric acid adding treatment mode in the prior art method, but the obtained product has serious over-standard chlorine content, copper sulfate can only be sold as a crude product or an agricultural product, the relative value is lower, more importantly, the waste liquid containing ammonium sulfate and ammonium chloride is difficult to be processed into a standard product, only the alkali is added to evaporate ammonia and is discharged, the treatment cost is extremely high, the waste of resources is also caused, and the economic cost is extremely low. The basic reason for the above treatment method is that the prior art is not clear enough to study the chemical composition of the waste alkaline etching solution, so that they cannot obtain a simple and rapid treatment process as in the present invention.

The device is a set of waste alkaline etching solution treatment device specially designed and researched for better implementing the method, and by adopting the device, the waste alkaline etching solution can be simply and conveniently utilized to obtain a high-purity copper oxide product, and an ammonium sulfate product is secondarily recovered, so that the purposes of environment-friendly treatment of the waste alkaline etching solution and maximum utilization of resources are achieved.

The method and the device for treating the waste alkaline etching solution have the advantages of simplicity, low cost and high recovery rate of high-value products, wherein the recovery rate of copper reaches 100 percent, the recovery rate of ammonia reaches more than 99 percent, and all indexes of the discharged wastewater are superior to the discharge standard (COD is detected by Hubei Zhongshi detection technology Limited company)_OH·KI: 40.8mg/L, ammonia nitrogen: 0.668mg/L, total copper: 0.48 mg/L).

According to the method and the device, the alkali consumption is only 40% of the original consumption, the purity of the obtained copper oxide product can reach more than 98%, the copper oxide product meets the national standard, the ammonium sulfate product can be secondarily recovered, and the quality of the wastewater is superior to the discharge standard; the method and the device simultaneously achieve the purposes of energy conservation, environmental protection, maximum utilization of resources and highest economic benefit, greatly reduce the environmental protection pressure of enterprises, improve the overall economic benefit of the enterprises, and are suitable for wide popularization and use.

Drawings

FIG. 1 is a 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-a waste liquid collecting tank, 2-a waste alkaline etching liquid inlet, 3-an alkaline liquid charging port, 4-a discharging port, 5-a copper oxide filter, 6-an air supply pipeline, 7-a sulfuric acid ammonia absorption tower, 8-a vacuum concentration tank, 9-an ammonium sulfate crystallizing tank, 10-a centrifuge, 11-a pump and 12-a valve.

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.