CN1307107C - Method for producing cuprous chloride by using waste copper chloride etching plate liquid - Google Patents

Abstract

A method for producing cuprous chloride using waste cupric chloride etching liquid comprises the following steps: (1) adding copper oxide to the waste cupric chloride etching liquid; (2) filtering the solution; (3) heating the clarified solution to 70°C-80°C, stirring the clarified solution while maintaining the temperature, and introducing sulfur dioxide gas into the clarified solution; (4) cooling the solution, filtering the precipitated crystals from the mother liquor; (5) washing the filtered crystals with dilute hydrochloric acid and ethanol in sequence, and drying the crystals to obtain cuprous chloride. The waste cupric chloride etching liquid and cupric oxide are used to generate cuprous chloride, and the process is simple and stable, with high yield and no secondary pollution.

Description

Method for Producing Cuprous Chloride Using Waste Cupric Chloride Etching Solution

technical field

The invention relates to a treatment method of waste copper chloride etching liquid, in particular to a method for producing cuprous chloride by using waste copper chloride etching liquid.

Background technique

Existing waste copper chloride etching liquid usually has four processing methods: one is to replace copper powder with waste copper chloride etching liquid and scrap iron; the second is to use waste copper chloride etching liquid and copper The ammonia etching liquid is used at the same time to produce copper sulfate; the third is to use the waste copper chloride etching liquid to directly evaporate, concentrate and crystallize to produce copper chloride dihydrate; the fourth is to use copper powder to reduce the copper chloride etching liquid to produce chlorine Cuprous oxide. The first is the most direct and simplest treatment method, but the benefit is poor. Because the waste liquid contains a large amount of hydrochloric acid, a considerable amount of iron is wasted in vain, resulting in serious waste; the second is to jointly treat the two waste liquids, but Gained product purity is low, and processing cost is higher; The 3rd kind consumes a lot of energy in the concentration process, and has a large amount of hydrochloric acid to volatilize, both pollutes environment and causes loss again, and the market demand of gained copper chloride dihydrate is few; The 3rd Four kinds are as described in patent 94113822.4. First, the waste copper chloride etching solution and scrap iron are directly replaced to produce copper powder, then water is added to reduce the acid and purified, and the obtained copper powder is reacted with copper chloride etching solution to form cuprous chloride. , due to the need for a large amount of water in the process of generating copper powder, and the hydrolysis of the cuprous chloride complex requires 4-6 times the volume of water, resulting in a great consumption of water resources, and a large amount of water produced in this process Iron-containing waste liquid has increased the burden of environmental protection treatment.

Japanese patent J56155020-A discloses a production method of cuprous oxide, the content of which is: when the copper chloride aqueous solution is eroded to treat the copper plate, the waste liquid discharged is converted into the cuprous chloride aqueous solution, and then the aqueous solution and the alkali solution At the same time, it is injected into the reactor and reacts to generate cuprous oxide under the condition of pH value of 8.5-12.5. Cuprous exists in a complex form, and a large amount of water is needed to obtain cuprous chloride products, and the steps are cumbersome, resulting in a waste of resources.

Contents of the invention

The purpose of the present invention is to provide a method for producing cuprous chloride by using waste copper chloride etching solution, the process is simple and stable, and the yield is high.

Technical scheme of the present invention is: a kind of method for producing cuprous chloride with waste cupric chloride etching board liquid, it comprises the steps:

(1), add copper oxide in waste copper chloride etching plate liquid, adjust the pH value of solution to 1-1.5;

(2), filter solution, remove insoluble matter, obtain clear solution;

(3) Heat the clear solution to 70°C-80°C, stir the clear solution while maintaining the temperature, and pass sulfur dioxide gas into the clear solution. When the solution changes from green to light brown, stop passing sulfur dioxide gas , to obtain the mother liquor;

(4), cooling described mother liquor, the crystallization of precipitation is filtered out from the mother liquor after cooling;

(5), wash the filtered crystals successively with dilute hydrochloric acid and ethanol, and dry the crystals to obtain cuprous chloride.

Compared with the prior art, the present invention has the following advantages: using waste copper chloride etching plate liquid and copper oxide to generate cuprous chloride, the process is simple and stable, the yield is high, and no secondary pollution occurs, which can not only solve the problem of etching The difficulty of waste liquid can also save copper resources and water resources, and more importantly, it can reduce the harm caused by copper to the natural environment. In the cuprous chloride product produced according to this method, the weight ratio of pure cuprous chloride is ≥98%, the weight ratio of high copper salt is ≤1%, the weight ratio of acid insoluble matter is ≤0.1%, and the weight ratio of iron is ≤0.1%. ≤0.005%, the weight ratio of sulfate ≤0.3%.

Detailed ways

A method for producing cuprous chloride with waste cupric chloride etching liquid, it comprises the steps:

(1), add copper oxide in the waste copper chloride etching plate liquid, the amount of the added copper oxide should make it enough to form insoluble matter in the waste copper chloride etching plate liquid, and the added copper oxide is copper oxide mud, Adjust the pH value of the solution to 1-1.5;

(2), filter solution, remove insoluble matter, obtain clear solution;

(3) Heat the clear solution to 70°C-80°C, stir the clear solution while maintaining the temperature, and pass sulfur dioxide gas into the clear solution. When the solution changes from green to light brown, stop passing sulfur dioxide gas , obtain mother liquor, the sulfur trioxide gas that produces absorbs sulfur trioxide gas with sodium carbonate solution, can obtain by-product sodium sulfate solution;

(4), cooling described mother liquor, the crystallization of precipitation is filtered out from the mother liquor after cooling, drop into sodium hydroxide in the mother liquor after the filtration, precipitate after reaction and obtain copper, and the copper that obtains is dropped into waste cupric chloride corrosion After plate solution, re-enter step (1);

(5) Wash the filtered crystals successively with dilute hydrochloric acid and ethanol, heat the washed crystals to 80°C-110°C, and keep them warm for 15-25 minutes to dry to obtain cuprous chloride, which is obtained after washing the crystals with ethanol After the waste liquid is dehydrated by lime and distilled, ethanol is regenerated.

After step (1), measure the proportion of copper ions in the solution, if the concentration of copper ions is less than 115 grams per liter, hydrochloric acid should be added in the solution and step (1) should be repeated, when the concentration of copper ions reaches 115-130 grams / liter, then enter step (2).

Using waste copper chloride etching plate liquid and copper oxide mud to produce cuprous chloride, using waste to make waste, the process is stable, the yield is high, and no secondary pollution occurs. The development of the board industry can also save a large amount of copper resources and reduce the harm caused by copper to the environment. Its economic benefits are high, and it can save the funds required for the treatment of waste copper chloride etching liquid. Below enumerate several embodiment and specifically illustrate this method:

Example 1

Use copper oxide mud or the copper produced in the above step (4) to adjust the pH value to 1 with the source waste copper chloride etching plate liquid, and measure the copper ion concentration to be 115 grams per liter, filter to remove insoluble substances, and heat the filtrate to a constant temperature of 70°C Stir, continuously feed sulfur dioxide gas into the filtrate, control the pressure of the sulfur dioxide gas cylinder to be 0.02Mpa, after 35 minutes, the solution turns from green to light brown, stop passing the sulfur dioxide gas, and cool the solution to form crystals and mother liquor, the produced trioxide The sulfur gas is absorbed by the sodium carbonate solution to obtain the by-product sodium sulfate solution.

Filter and separate the cuprous chloride crystals and mother liquor, wash the cuprous chloride crystals with dilute hydrochloric acid of pH=1 and ethanol respectively, dry at 80°C for 25 minutes, and then seal and pack. The mother liquor and the waste liquid after washing the crystallization of cuprous chloride with dilute hydrochloric acid are combined, neutralized with sodium hydroxide, and the copper sludge produced can be put into the waste cupric chloride etching liquid for reuse in production. After washing the cuprous chloride crystals with ethanol, the waste liquid is dehydrated and distilled with lime, and the regenerated ethanol is collected for reuse in production.

Example 2

Use copper oxide mud to adjust the pH value of the source waste copper chloride etching solution to 1.5, measure the copper ion concentration to be 120 g/L, and filter to remove impurities to obtain a clear solution. The obtained clear solution was heated to 73°C with constant temperature stirring, and sulfur dioxide gas was continuously introduced into the clear solution, and the pressure of the sulfur dioxide gas cylinder was controlled to be 0.03Mpa. After 30 minutes, the solution changed from green to yellow, and the sulfur dioxide gas was stopped, and the solution was stirred. After cooling, cuprous chloride crystals and mother liquor are formed, and the sulfur trioxide gas generated during this process is absorbed with sodium carbonate solution to obtain sodium sulfate solution as a by-product.

Filter and separate the cuprous chloride crystals and the mother liquor, wash the cuprous chloride crystals with dilute hydrochloric acid and ethanol at pH = 1, dry at 90°C for 20 minutes, then seal and pack, and wash and chlorinate the mother liquor with dilute hydrochloric acid The waste liquid after cuprous crystallization is combined and neutralized with sodium hydroxide, and the precipitated copper sludge can be reused for production. The waste liquid after washing the crystallization of cuprous chloride with ethanol is dehydrated and distilled with lime, and the regenerated ethanol can be reused in production.

Example 3

The copper oxide mud and the copper mud produced in the above step (4) are used to adjust the pH value to 1 with the source waste copper chloride etching plate liquid, and the measured copper ion concentration is 125 grams per liter, and the insoluble matter is removed by filtration to obtain a clarified filtrate. Heat the clarified filtrate to 75°C and stir at a constant temperature, continuously feed sulfur dioxide gas into the clarified filtrate, control the pressure of the sulfur dioxide gas cylinder to 0.04Mpa, and after 35 minutes, the solution changes from green to light brown, stop feeding the sulfur dioxide gas, and cool the solution to obtain The mother liquor and the cuprous chloride precipitated in the mother liquor are crystallized, and the sulfur trioxide gas generated in the process is absorbed with sodium carbonate solution to obtain a by-product sodium sulfate solution.

After filtering, washing the obtained cuprous chloride crystals with dilute hydrochloric acid of pH=2 and ethanol respectively, drying the cuprous chloride crystals at 100° C. for 15 minutes, and then sealing and packaging the obtained cuprous chloride crystals.

Other steps are the same as in Example 1.

Example 4

The copper oxide mud and the copper mud produced in the above-mentioned steps (4) are used to adjust the pH value to 1.5 with the source waste copper chloride etching plate liquid, and the measured copper ion concentration is 130 grams per liter, and the insoluble matter is removed by filtration. Heat the obtained filtrate to 80°C and stir at a constant temperature, continuously feed sulfur dioxide gas into the filtrate, control the pressure of the sulfur dioxide gas cylinder to 0.05Mpa, after 30 minutes, the solution changes from green to light brown, stop the flow of sulfur dioxide gas, cool down Brown solution, the mother liquor and the cuprous chloride crystals precipitated in the mother liquor are obtained, and the sulfur trioxide gas generated in the process is absorbed by the sodium carbonate solution to obtain the by-product sodium sulfate solution.

Separate the cuprous chloride crystals by filtration, wash the cuprous chloride crystals with dilute hydrochloric acid of pH=2.5 and ethanol respectively, then dry the cuprous chloride crystals at 105°C for 15 minutes, and seal the obtained cuprous chloride Package.

Other steps are the same as in Example 1.

Claims (8)

1, a kind of method with producing cuprous chloride form deposed copper chloride fluid of etching board, it is characterized in that: it comprises the steps:

(1), in useless cupric chloride etching liquid, add cupric oxide, the pH value of regulator solution is to 1-1.5;

(2), filtering solution, remove insoluble substance, obtain settled solution;

(3), settled solution is heated to 70 ℃-80 ℃, under the condition that keeps temperature, stir settled solution, and in this settled solution, feed sulfur dioxide gas, when solution becomes light brown by green, stop logical sulfur dioxide gas, obtain mother liquor;

(4), cool off described mother liquor, sedimentary crystallization is filtered out from cooled mother liquor;

(5), with the crystallization that dilute hydrochloric acid, ethanol washing and filtering successively go out, after the dry described crystallization, obtain cuprous chloride.

2, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: in step (1), the amount of the cupric oxide of adding should make it be enough to form insoluble substance in useless cupric chloride etching liquid.

3, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: afterwards in step (1), measure cupric ion proportion in solution, if copper ion concentration is less than 115 grams per liters, then should in solution, add hydrochloric acid and repeating step (1), when copper ion concentration reaches the 115-130 grams per liter, enter step (2) again.

4, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: in step (1), the cupric oxide of adding is the oxidation copper sludge.

5, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: produce sulfur trioxide gas after in settled solution, feeding sulfur dioxide gas in the step (3), absorb sulfur trioxide gas with sodium carbonate solution, obtain byproduct sulfite solution.

6, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1, it is characterized in that: drop into sodium hydroxide in the mother liquor after in step (4), filtering, the reaction postprecipitation obtains copper, behind the useless cupric chloride etching liquid of the copper input that obtains, reenters step (1).

7, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1 is characterized in that: in step (5), behind the washing with alcohol crystallisate waste liquid of gained after lime dehydration and distillation, regeneration ethanol.

8, the method with producing cuprous chloride form deposed copper chloride fluid of etching board according to claim 1 is characterized in that: in step (5), crystallize to 80 ℃-110 ℃ behind the heated scrub, and after 15-25 minute drying of insulation, obtain cuprous chloride.