CN104016401B - A kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide - Google Patents
A kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide Download PDFInfo
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Abstract
The present invention a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper relate to a kind of preparation method of cupric oxide for the method for cupric oxide, particularly relate to a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide.Its objective is in order to provide a kind of easy and simple to handle, energy-conservation, subsequent wastewater treatment is simple, good product quality, have the reclaim(ed) sulfuric acid copper from microetch waste liquid of economic benefit and social benefit widely for the method for cupric oxide.The present invention a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper comprise the following steps for the method for cupric oxide: concentrated microetch waste liquid; Prepare copper sulfate and sodium sulfate mixed crystal; Prepare cupric oxide.Preparation method of the present invention decreases the treatment capacity to acid waste liquid, reduces the consumption of alkali, and all right reclaim(ed) sulfuric acid, reduce the production cost of microetch, decrease the processing cost of waste liquid simultaneously, and copper organic efficiency is high, environmentally friendly.The present invention is used for the process of microetch waste liquid and the preparation field of cupric oxide.
Description
Technical field
The present invention relates to a kind of preparation method of cupric oxide, particularly relate to a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide.
Background technology
Current microetch waste liquid main methods has chemical precipitation method, copper sulfate method, cold method and electrolytic process.
One, chemical precipitation method adds alkali adjust ph in microetch waste liquid, makes cupric ion generate mantoquita, then make mantoquita product through sedimentation, filtration.This law comparative maturity, but there is chemical precipitation method and need to consume a large amount of alkali, processing cost is higher.Consumption of chemical agent is large, and in discharge water, solvability salt concn is too high, and waste water cannot recycle, and sludge yield is large, and sludge dispoal is difficult, easily produces secondary pollution problems.
Two, copper sulfate method adds mantoquita in microetch waste liquid, in and free acid in waste liquid, waste liquid obtains copper sulfate through concentrated, crystallisation by cooling, and the shortcoming of this method is that the acidity in waste liquid is higher, and neutralization need consume a large amount of mantoquita.
Three, cold method is by freezing for microetch waste liquid, and cupric sulphate crystal is separated out.But the waste liquid of this method process, copper content is still higher, also needs further process.
Four, electrolytic process uses the method for electrolysis by copper reduction, simultaneously by reducing the microetch waste liquid of copper content by adding regulating agent, indices value being reached to production necessary requirement, is reused for microetch operation.But along with the carrying out of reaction can cause sodium ion to accumulate, the complete-reclaiming of waste liquid can not be reached.
Summary of the invention
The present invention will solve above technical problem, and provide a kind of easy and simple to handle, energy-conservation, subsequent wastewater treatment is simple, good product quality, have the reclaim(ed) sulfuric acid copper from microetch waste liquid of economic benefit and social benefit widely for the method for cupric oxide.
The present invention a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, comprise the following steps:
One, microetch waste liquid is concentrated: evaporation concentration microetch waste liquid is 60 ~ 120g/L to copper ion concentration;
Two, the preparation of copper sulfate and sodium sulfate mixed crystal: the microetch waste liquid cooling after concentrated, crystallization, filter, gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: copper sulfate step 2 obtained and the mixed crystallization of sodium sulfate mix with acidic copper chloride waste etching solution, mixed copper content in reactor is made to be 130 ~ 150g/L, the NaOH that concentration is 30 ~ 50% is added in reactor, pH value of solution in reactor is regulated to be 8 ~ 13, temperature is 55 ~ 80 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
Wherein, in described step 2, the microetch waste liquid after cooling concentration, the object separating out copper sulfate and sodium sulfate is excessive sodium salt and mantoquita in removing microetch system.
In preparation method of the present invention, reaction process is as follows:
CuCl
2+2NaOH→Cu(OH)
2+2NaCl(1)
CuSO
4+2NaOH→Cu(OH)
2+Na
2SO
4(2)
Optionally, the present invention is a kind of, and from microetch waste liquid, reclaim(ed) sulfuric acid copper is for the method for cupric oxide, and in described step 2, when the microetch waste liquid after concentrated cools, the temperature difference controls at 30 ~ 60 DEG C.
Optionally, the present invention a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, in described step 2, gained filtrate is the vitriol oil, and first in filtrate, adding pure water by thinning ratio is that 1:3 ~ 7 are diluted, then joins in microetch tank liquor blend tank, being adjusted to sulfuric acid volumetric concentration is 2 ~ 4%, copper ion concentration is 9 ~ 15g/L, and Sodium Persulfate concentration is 75 ~ 125g/L, i.e. obtained micro etching solution.
The present invention a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, there is following beneficial effect:
1, of the present invention from microetch waste liquid, reclaim(ed) sulfuric acid copper, can reclaim(ed) sulfuric acid for the method for cupric oxide, reduces the production cost of microetch operation.
2, of the present invention from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, decrease the treatment capacity to acid waste liquid, reduce the consumption of alkali, decrease the processing cost of waste liquid.
3, of the present invention from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, decrease the quantity discharged of waste to environment, embody the spirit of recycling economy, be a kind of Waste recovery treatment process of environmental protection friendly, have obvious environmental benefit.
4, from microetch waste liquid, reclaim(ed) sulfuric acid copper is for the method for cupric oxide in the present invention, and in the waste liquid processed, copper organic efficiency is high.
5, of the present invention from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide is easy and simple to handle, energy-conservation, subsequent wastewater treatment is simple, good product quality, there is economic benefit and social benefit widely.
Accompanying drawing explanation
Fig. 1 be the present invention a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the process flow sheet of the method for cupric oxide.
Embodiment
By following examples, the present invention is further detailed.
Embodiment 1
The present embodiment a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, carry out according to the following steps:
One, microetch waste liquid is concentrated: evaporation concentration microetch waste liquid is 60g/L to copper ion concentration;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: the microetch waste liquid after concentrated is lowered the temperature 25 DEG C, crystallization, and filter, gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: copper sulfate step 2 obtained and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, mixed copper content in reactor is made to be 130g/L, the NaOH that concentration is 30% is added in reactor, pH value of solution in reactor is regulated to be 9, temperature is 80 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
In the gained filtrate in step 2, adding pure water by thinning ratio is that 1:4 dilutes, then joins in microetch tank liquor blend tank, and regulate sulfuric acid volumetric concentration to be 3%, copper ion concentration is 15g/L, and Sodium Persulfate concentration is 75g/L, i.e. obtained micro etching solution.
Embodiment 2
The present embodiment a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, carry out according to the following steps:
One, microetch waste liquid is concentrated: evaporation concentration microetch waste liquid is 100g/L to copper ion concentration;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: the microetch waste liquid after concentrated is lowered the temperature 30 DEG C, crystallization, and filter, gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: copper sulfate step 2 obtained and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, mixed copper content in reactor is made to be 140g/L, the NaOH that concentration is 45% is added in reactor, pH value of solution in reactor is regulated to be 13, temperature is 65 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
In the gained filtrate in step 2, adding pure water by thinning ratio is that 1:5 dilutes, then joins in microetch tank liquor blend tank, and regulate sulfuric acid volumetric concentration to be 2.5%, copper ion concentration is 14g/L, and Sodium Persulfate concentration is 102g/L, i.e. obtained micro etching solution.
Embodiment 3
The present embodiment a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, carry out according to the following steps:
One, microetch waste liquid is concentrated: evaporation concentration microetch waste liquid is 90g/L to copper ion concentration;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: the microetch waste liquid after concentrated is lowered the temperature 60 DEG C, crystallization, and filter, gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: copper sulfate step 2 obtained and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, mixed copper content in reactor is made to be 150g/L, the NaOH that concentration is 50% is added in reactor, pH value of solution in reactor is regulated to be 12, temperature is 75 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
In the gained filtrate in step 2, adding pure water by thinning ratio is that 1:7 dilutes, then joins in microetch tank liquor blend tank, and regulate sulfuric acid volumetric concentration to be 4%, copper ion concentration is 10g/L, and Sodium Persulfate concentration is 90g/L, i.e. obtained micro etching solution.
Embodiment 4
The present embodiment a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, carry out according to the following steps:
One, microetch waste liquid is concentrated: evaporation concentration microetch waste liquid is 80g/L to copper ion concentration;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: the microetch waste liquid after concentrated is lowered the temperature 65 DEG C, crystallization, and filter, gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: copper sulfate step 2 obtained and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, mixed copper content in reactor is made to be 145g/L, the NaOH that concentration is 35% is added in reactor, pH value of solution in reactor is regulated to be 8, temperature is 60 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
In the gained filtrate in step 2, adding pure water by thinning ratio is that 1:3 dilutes, then joins in microetch tank liquor blend tank, and regulate sulfuric acid volumetric concentration to be 3.5%, copper ion concentration is 9g/L, and Sodium Persulfate concentration is 110g/L, i.e. obtained micro etching solution.
Embodiment 5
The present embodiment a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, carry out according to the following steps:
One, microetch waste liquid is concentrated: evaporation concentration microetch waste liquid is 120g/L to copper ion concentration;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: the microetch waste liquid after concentrated is lowered the temperature 40 DEG C, crystallization, and filter, gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: copper sulfate step 2 obtained and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, mixed copper content in reactor is made to be 135g/L, the NaOH that concentration is 40% is added in reactor, pH value of solution in reactor is regulated to be 11, temperature is 55 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
In the gained filtrate in step 2, adding pure water by thinning ratio is that 1:6 dilutes, then joins in microetch tank liquor blend tank, and regulate sulfuric acid volumetric concentration to be 2%, copper ion concentration is 12g/L, and Sodium Persulfate concentration is 125g/L, i.e. obtained micro etching solution.
The quantity of alkali consumption for the treatment of process and copper recovery in the common microetch method for treating waste liquid of table 1 and embodiment
| Usual way | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Quantity of alkali consumption (g) | 451.7 | 350.5 | 354.6 | 360.0 | 353.2 | 355.5 |
| Alkali consumes reduction (%) | / | 22.4％ | 21.5％ | 20.3％ | 21.8％ | 21.3％ |
| Copper recovery (%) | 99.2％ | 99.992％ | 99.993％. | 99.993％ | 99.993％ | 99.993％ |
Table 1 is the alkali number often reclaiming obtained 100g cupric oxide consumption, and the data of copper recovery.As shown in Table 1, adopt the reclaim(ed) sulfuric acid copper from microetch waste liquid of embodiment 1-5 to be starkly lower than common microetch method for treating waste liquid for the alkali lye consumption of the method for cupric oxide, and copper organic efficiency significantly improve.
In embodiment 1-5, further recycling is processed to the filtrate after precipitation copper sulfate, easy to operation, there is advantage that is energy-conservation, high financial profit.
Table 2 the inventive method difference with the prior art
As shown in Table 2, the present invention can process microetch waste liquid, and reclaims Waste Sulfuric Acid, can save sulfuric acid, produces higher economic benefit.
Although the foregoing describe the specific embodiment of the present invention, it will be understood by those of skill in the art that these only illustrate, protection scope of the present invention is defined by the appended claims.Those skilled in the art, under the prerequisite not deviating from principle of the present invention and essence, can make various changes or modifications to these embodiments, but these change and amendment all falls into protection scope of the present invention.
Claims (3)
1. from microetch waste liquid, reclaim(ed) sulfuric acid copper, for a method for cupric oxide, is characterized in that comprising the following steps:
One, microetch waste liquid is concentrated: evaporation concentration microetch waste liquid is 60 ~ 120g/L to copper ion concentration;
Two, the preparation of copper sulfate and sodium sulfate mixed crystal: the microetch waste liquid cooling after concentrated, filter, gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: copper sulfate step 2 obtained and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, mixed copper content in reactor is made to be 130 ~ 150g/L, the NaOH that concentration is 30 ~ 50% is added in reactor, pH value of solution in reactor is regulated to be 8 ~ 13, temperature is 55 ~ 80 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
2. according to claim 1 a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, it is characterized in that: in described step 2, during microetch waste liquid cooling after concentrated, the temperature difference is 30 ~ 60 DEG C.
3. according to claim 1 a kind of from microetch waste liquid reclaim(ed) sulfuric acid copper for the method for cupric oxide, it is characterized in that: in described step 2, gained filtrate is the vitriol oil, first in filtrate, adding pure water by thinning ratio is that 1:3 ~ 7 are diluted, join in microetch tank liquor blend tank, being adjusted to sulfuric acid volumetric concentration is 2 ~ 4%, and copper ion concentration is 9 ~ 15g/L again, Sodium Persulfate concentration is 75 ~ 125g/L, i.e. obtained micro etching solution.
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| CN101935062A (en) * | 2010-09-02 | 2011-01-05 | 昆山联鼎环保科技有限公司 | Method for preparing high-purity copper oxide by adopting acidic etching waste liquor |
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Effective date of registration: 20190705 Address after: 518105 Building A, No. 18 Industrial Avenue, Third Industrial Zone, Bitou Community, Songgang Street, Baoan District, Shenzhen City, Guangdong Province Patentee after: SHENZHEN SHENTOU ENVIRONMENT TECHNOLOGY Co.,Ltd. Address before: Southern Gushiyu Village, Shimenzhai, Funing County, Qinhuangdao City, Hebei Province Patentee before: QINHUANGDAO RUISIKE ENVIRONMENTAL PROTECTION TECHNOLOGY CO.,LTD. |
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Address after: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address before: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee before: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address after: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee after: Shenzhen Environmental Protection Technology Group Co.,Ltd. Address before: 518105 building a, No.18, Industrial Avenue, third industrial zone, Bitou community, Songgang street, Bao'an District, Shenzhen City, Guangdong Province Patentee before: SHENZHEN SHENTOU ENVIRONMENT TECHNOLOGY Co.,Ltd. |