阅读说明：本技术 一种含氨废水中氯化亚铜的回收方法 (Method for recovering cuprous chloride in ammonia-containing wastewater ) 是由 张曙光 周耀明 于 2020-12-23 设计创作，主要内容包括：本发明公开了一种含氨废水中氯化亚铜的回收方法,包括下列步骤：1)往反应烧瓶里加入含氨废水,搅拌条件下用碱调节PH=6-7,结束后,往反应烧瓶里加入少量还原剂,进行搅拌并溶解,在30～50℃继续搅拌2～5小时；2)冷却至10～20℃,固体析出来,过滤,滤液套用,固体用稀盐酸洗2～3次,水洗,干燥,得到白色至浅绿色固体氯化亚铜。本申请用一种新方法回收处理含氨废水中的氯化亚铜,不涉及有机溶剂等其他复杂物料,处理方法简单方便,回收率高,可有效降低废水中重金属含量,利用PH与溶解度的差异合理、高效回收氯化亚铜,且成本低。(The invention discloses a method for recovering cuprous chloride in ammonia-containing wastewater, which comprises the following steps: 1) adding ammonia-containing wastewater into a reaction flask, adjusting the pH =6-7 with alkali under the stirring condition, adding a small amount of reducing agent into the reaction flask after the completion of stirring, stirring and dissolving, and continuously stirring for 2-5 hours at the temperature of 30-50 ℃; 2) and cooling to 10-20 ℃, precipitating solids, filtering, mechanically using filtrate, washing the solids with dilute hydrochloric acid for 2-3 times, washing with water, and drying to obtain white to light green solid cuprous chloride. This application does not relate to other complicated materials such as organic solvent with cuprous chloride in new method recovery processing ammonia wastewater, and the processing method is simple and convenient, and the rate of recovery is high, can effectively reduce heavy metal content in the waste water, utilizes PH and difference of solubility reasonable, the high-efficient cuprous chloride of retrieving, and with low costs.)

1. A method for recovering cuprous chloride in ammonia-containing wastewater is characterized by comprising the following steps:

1) adding ammonia-containing wastewater into a reaction flask, adjusting the pH =6-7 with alkali under the stirring condition, adding a reducing agent into the reaction flask after the completion of the adjustment, stirring and dissolving, and stirring for 2-5 hours at the temperature of 30-50 ℃;

2) and cooling to 10-20 ℃, precipitating solids, filtering, mechanically using filtrate, washing the solids with dilute hydrochloric acid for 2-3 times, washing with water, and drying to obtain white to light green solid cuprous chloride.

2. The method for recovering cuprous chloride in ammonia-containing wastewater according to claim 1, characterized by comprising the following steps: the alkali is potassium hydroxide or sodium hydroxide solution.

3. The method for recovering cuprous chloride in ammonia-containing wastewater according to claim 1, characterized by comprising the following steps: the reducing agent is a water-soluble reducing agent.

4. The method for recovering cuprous chloride in ammonia-containing wastewater according to claim 3, characterized by comprising the following steps: the reducing agent is: the ratio of the ammonia-containing wastewater is 0.1-5: 100.

5. The method for recovering cuprous chloride in ammonia-containing wastewater according to claim 1, characterized by comprising the following steps: the concentration of the dilute hydrochloric acid for washing is 1-20%.

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a method for recovering cuprous chloride in ammonia-containing wastewater.

Background

Copper (I) chloride (copper (I) chloride) is also known as cupric chloride, as white cubic crystal or white powder, is poorly soluble in water, is soluble in concentrated hydrochloric acid and aqueous ammonia to form a complex, and is insoluble in ethanol. Used as catalyst, bactericide, mordant and decolorant batch; the metallurgical industry; the method is used for determining carbon monoxide and acetylene in gas analysis. Cuprous chloride has a wide range of uses due to its unique physicochemical properties.

In the production process of the propyzamide, a large amount of ammonia-containing wastewater containing 1-2 g/L copper is generated, and the existing treatment methods are few and have various problems.

The recycling method of cuprous chloride wastewater disclosed in CN111620495A has been disclosed to add alkali to the miscellaneous salt wastewater to adjust PH to 3-10, and cuprous chloride will precipitate in this PH range, but for the ammonia-containing wastewater in this patent, precipitation is limited in the PH =3-6 and 7-10 ranges due to the complexation of cuprous chloride with ammonia or concentrated hydrochloric acid. And the method also relates to layering and membrane treatment, the process is complicated and complex, and the realization in the production process is very difficult.

The article, "research on cuprous chloride wastewater treatment by extraction and ion exchange method", respectively starts from the coordination bond theory of the complex and the solution thermodynamics, calculates and researches the particle structure and properties of the cuprous chloride wastewater solution, and adopts ion exchange and extraction methods to perform experimental research on the cuprous chloride wastewater. But the method is complicated and has certain difficulty in application to industrial production.

The research on the process for preparing cuprous chloride from the copper-containing waste liquid and the research on the mutual condensation treatment of the cuprous chloride production wastewater and the coking wastewater are not strong in pertinence, and the utilization value of the target wastewater is not high.

Disclosure of Invention

In order to solve the problems, the method does not adopt other complex materials such as organic solvents and the like, is simple and convenient in treatment method, reasonably and efficiently recovers cuprous chloride by utilizing the difference between PH and solubility, and is low in cost.

The invention provides a method for recovering cuprous chloride in ammonia-containing wastewater, which comprises the following steps:

1) adding ammonia-containing wastewater into a reaction flask, adjusting the pH =6-7 with alkali under the stirring condition, adding a small amount of reducing agent into the reaction flask after the completion of stirring, stirring and dissolving, and continuously stirring for 2-5 hours at the temperature of 30-50 ℃;

2) and cooling to 10-20 ℃, precipitating solids, filtering, mechanically using filtrate, washing the solids with dilute hydrochloric acid for 2-3 times, washing with water, and drying to obtain white to light green solid cuprous chloride.

Preferably, the base is potassium hydroxide or sodium hydroxide solution, preferably sodium hydroxide solution.

Preferably, the reducing agent is a water-soluble reducing agent, preferably sodium sulfite.

Preferably, the reducing agent: the ammonia-containing wastewater is 0.1-5: 100, preferably 0.5-3: 100.

Preferably, the stirring time at room temperature is 1-8 hours, preferably 2-5 hours.

Preferably, the cooling temperature range is 0-30 ℃, and preferably 10-20 ℃.

Preferably, the concentration of the dilute hydrochloric acid for washing is 1-20%, and preferably 2-10%.

The invention has the advantages that: the method for recycling and treating the cuprous chloride in the ammonia-containing wastewater by using the novel method does not relate to organic solvents and other complex materials, is simple and convenient in treatment method, high in recycling rate, capable of effectively reducing the content of heavy metals in the wastewater, reasonable and efficient in recycling the cuprous chloride by using the difference between the PH and the solubility, and low in cost.

Detailed Description

For the purpose of enhancing understanding of the present invention, the following detailed description will be given in conjunction with examples, which are provided for illustration only and do not limit the scope of the present invention.

Example 1

Adding 1000 g of ammonia-containing wastewater (1% of cuprous chloride), adjusting the pH (potential of Hydrogen) to be =6 by using 30% sodium hydroxide solution under stirring, adding 1 g of sodium sulfite into the reaction flask, stirring and dissolving, and continuing stirring at 50 ℃ for 2 hours; cooling to 30 ℃, precipitating solids, filtering, washing the solids with 5% dilute hydrochloric acid for 3 times, washing with water, and drying to obtain 9.0 g of white to light green solid cuprous chloride, wherein the detection content is as follows: 96%, recovery rate: 86.4 percent.

Example 2

Adding 1000 g of ammonia-containing wastewater (1% of cuprous chloride), adjusting the pH to be =6 by using 30% sodium hydroxide solution under the condition of stirring, adding 5 g of sodium sulfite into the reaction flask after the completion of the adjustment, stirring and dissolving, and continuing stirring for 5 hours at 50 ℃; cooling to 10 ℃, precipitating solids, filtering, washing the solids with 5% dilute hydrochloric acid for 3 times, washing with water, and drying to obtain 9.7 g of white to light green solid cuprous chloride, wherein the content is detected as follows: 97%, recovery rate: 94.09 percent.

Example 3

Adding 1000 g of ammonia-containing wastewater (1% of cuprous chloride), adjusting the pH to =7 by using 30% potassium hydroxide solution under stirring, adding 30 g of sodium sulfite into the reaction flask, stirring and dissolving, and continuing stirring for 5 hours at 30 ℃; cooling to 20 ℃, precipitating solids, filtering, washing the solids with 5% dilute hydrochloric acid for 3 times, washing with water, and drying to obtain 9.6 g of white to light green solid cuprous chloride, wherein the content is detected as follows: 97%, recovery rate: 93.12 percent.

Example 4:

adding 1000 g of ammonia-containing wastewater (1% of cuprous chloride), adjusting the pH to =7 by using 30% sodium hydroxide solution under stirring, adding 5 g of sodium sulfite into the reaction flask, stirring and dissolving, and continuing stirring at 50 ℃ for 5 hours; cooling to 10 ℃, precipitating solids, filtering, washing the solids with 20% dilute hydrochloric acid for 3 times, washing with water, and drying to obtain 8.9 g of white to light green solid cuprous chloride, wherein the content is detected as follows: 96.9%, recovery: 86.24 percent.

Example 5:

adding 1000 g of ammonia-containing wastewater (1% of cuprous chloride), adjusting the pH to be =6 by using 30% sodium hydroxide solution under the condition of stirring, adding 5 g of sodium sulfite into the reaction flask after the completion of the adjustment, stirring and dissolving, and continuing stirring for 1 hour at 30 ℃; cooling to 10 ℃, precipitating solids, filtering, washing the solids with 10% dilute hydrochloric acid for 3 times, washing with water, and drying to obtain 8.5 g of white to light green solid cuprous chloride, wherein the content is detected as follows: 96.8%, recovery: 82.28 percent.

Example 6:

adding 1000 g of ammonia-containing wastewater (1% of cuprous chloride), adjusting the pH to be =6 by using 30% sodium hydroxide solution under the condition of stirring, adding 5 g of sodium sulfite into the reaction flask after the completion of the adjustment, stirring and dissolving, and continuing stirring for 5 hours at 50 ℃; cooling to 0 ℃, precipitating solids, filtering, washing the solids with 5% dilute hydrochloric acid for 3 times, washing with water, and drying to obtain 9.3 g of white to light green solid cuprous chloride, wherein the content is detected as follows: 96%, recovery rate: 89.28 percent.