CN104016401A - Method for preparing copper oxide by recovering copper sulfate from micro-etching waste liquid - Google Patents
Method for preparing copper oxide by recovering copper sulfate from micro-etching waste liquid Download PDFInfo
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- CN104016401A CN104016401A CN201410289638.1A CN201410289638A CN104016401A CN 104016401 A CN104016401 A CN 104016401A CN 201410289638 A CN201410289638 A CN 201410289638A CN 104016401 A CN104016401 A CN 104016401A
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Abstract
The invention relates to a method for preparing copper oxide, and in particular relates to a method for preparing copper oxide by recovering copper sulfate from micro-etching waste liquid. The method for preparing copper oxide by recovering copper sulfate from micro-etching waste liquid is simple and convenient in operation, energy-saving, simple and feasible in subsequent wastewater treatment and good in product quality, and has economic benefits and wide social benefits. The method for preparing copper oxide by recovering copper sulfate from micro-etching waste liquid comprises the steps of concentrating micro-etching waste liquid, preparing a mixed crystal of copper sulfate and sodium sulfate, and preparing copper oxide. By adopting the preparation method disclosed by the invention, the treatment quantity of acidic waste liquid is reduced, the consumption of alkali is reduced, sulfuric acid can be recovered, the production cost of micro-etching is reduced, meanwhile, the treatment cost of waste liquid is also reduced, and the method is high in copper recovery efficiency and environment-friendly. The method disclosed by the invention is applied in the fields of treatment of micro-etching waste liquid and preparation of copper 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
Microetch waste liquid main methods has chemical precipitation method, copper sulfate method, cold method and electrolytic process at present.
One, chemical precipitation method is in microetch waste liquid, to add alkali to regulate pH value, makes cupric ion generate mantoquita, then makes mantoquita product through sedimentation, filtration.This law comparative maturity, but exist chemical precipitation method 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 difficulty easily produces secondary pollution problems.
Two, copper sulfate method is to add mantoquita in microetch waste liquid, in and free acid in waste liquid, waste liquid obtains copper sulfate through concentrated, crystallisation by cooling, the shortcoming of this method is that the acidity in waste liquid is higher, neutralization needs to consume a large amount of mantoquitas.
Three, cold method is by freezing microetch waste liquid, and cupric sulphate crystal is separated out.But the waste liquid that this method was processed, copper content is still higher, also needs further processing.
Four, electrolytic process is to use the method for electrolysis by copper reduction, the microetch waste liquid that reduces copper content is passed through to add regulating agent simultaneously, and indices value is reached to production necessary requirement, is reused for microetch operation.But along with the carrying out of reaction can be caused sodium ion accumulation, can not reach the complete-reclaiming of waste liquid.
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 economic benefit and widely the reclaim(ed) sulfuric acid copper from microetch waste liquid of social benefit 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, to copper ion concentration be 60～120g/L;
Two, the preparation of copper sulfate and sodium sulfate mixed crystal: the microetch waste liquid after concentrated is cooling, crystallization, filters, and gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: the copper sulfate that step 2 is made and the mixed crystallization of sodium sulfate mix with acidic copper chloride waste etching solution, making mixed copper content in reactor is 130～150g/L, be 30～50% NaOH to adding concentration in reactor, regulating pH value of solution in reactor is 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 of separating out copper sulfate and sodium sulfate is to remove sodium salt excessive in microetch system and mantoquita.
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 microetch waste liquid after concentrated is cooling, the temperature difference is controlled 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, is first that dilute 1:3～7 to adding pure water in filtrate by thinning ratio, 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, makes 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, has reduced 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, reduced the treatment capacity to acid waste liquid, reduced the consumption of alkali, reduced 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, reduced the quantity discharged of waste to environment, embodied the spirit of recycling economy, be the Waste recovery treatment process of the friendly type of a kind of environmental protection, 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 of processing, 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.
Brief description of the drawings
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, to copper ion concentration be 60g/L;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: by 25 DEG C of the microetch waste liquid coolings after concentrated, crystallization, filters, and gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: the copper sulfate that step 2 is made and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, making mixed copper content in reactor is 130g/L, be 30% NaOH to adding concentration in reactor, regulating pH value of solution in reactor is 9, temperature is 80 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
Be that 1:4 dilutes to adding pure water in the gained filtrate in step 2 by thinning ratio, then join in microetch tank liquor blend tank, regulating sulfuric acid volumetric concentration is 3%, and copper ion concentration is 15g/L, and Sodium Persulfate concentration is 75g/L, makes 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, to copper ion concentration be 100g/L;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: by 30 DEG C of the microetch waste liquid coolings after concentrated, crystallization, filters, and gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: the copper sulfate that step 2 is made and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, making mixed copper content in reactor is 140g/L, be 45% NaOH to adding concentration in reactor, regulating pH value of solution in reactor is 13, temperature is 65 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
Be that 1:5 dilutes to adding pure water in the gained filtrate in step 2 by thinning ratio, then join in microetch tank liquor blend tank, regulating sulfuric acid volumetric concentration is 2.5%, and copper ion concentration is 14g/L, and Sodium Persulfate concentration is 102g/L, makes 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, to copper ion concentration be 90g/L;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: by 60 DEG C of the microetch waste liquid coolings after concentrated, crystallization, filters, and gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: the copper sulfate that step 2 is made and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, making mixed copper content in reactor is 150g/L, be 50% NaOH to adding concentration in reactor, regulating pH value of solution in reactor is 12, temperature is 75 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
Be that 1:7 dilutes to adding pure water in the gained filtrate in step 2 by thinning ratio, then join in microetch tank liquor blend tank, regulating sulfuric acid volumetric concentration is 4%, and copper ion concentration is 10g/L, and Sodium Persulfate concentration is 90g/L, makes 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, to copper ion concentration be 80g/L;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: by 65 DEG C of the microetch waste liquid coolings after concentrated, crystallization, filters, and gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: the copper sulfate that step 2 is made and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, making mixed copper content in reactor is 145g/L, be 35% NaOH to adding concentration in reactor, regulating pH value of solution in reactor is 8, temperature is 60 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
Be that 1:3 dilutes to adding pure water in the gained filtrate in step 2 by thinning ratio, then join in microetch tank liquor blend tank, regulating sulfuric acid volumetric concentration is 3.5%, and copper ion concentration is 9g/L, and Sodium Persulfate concentration is 110g/L, makes 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, to copper ion concentration be 120g/L;
Two, the preparation of the mixed crystal of copper sulfate and sodium sulfate: by 40 DEG C of the microetch waste liquid coolings after concentrated, crystallization, filters, and gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: the copper sulfate that step 2 is made and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, making mixed copper content in reactor is 135g/L, be 40% NaOH to adding concentration in reactor, regulating pH value of solution in reactor is 11, temperature is 55 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
Be that 1:6 dilutes to adding pure water in the gained filtrate in step 2 by thinning ratio, then join in microetch tank liquor blend tank, regulating sulfuric acid volumetric concentration is 2%, and copper ion concentration is 12g/L, and Sodium Persulfate concentration is 125g/L, makes micro etching solution.
Quantity of alkali consumption and the copper recovery for the treatment of process 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 that every recovery makes the alkali number that 100g cupric oxide consumes, 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 obviously improve.
In embodiment 1-5, the filtrate of separating out after copper sulfate is further processed to recycling, easy to operation, have advantages of energy-conservation, economic benefit is high.
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 more than described 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 limited by appended claims.Those skilled in the art is not deviating under the prerequisite of principle of the present invention and essence, can make various changes or modifications to these embodiments, but these changes and amendment all fall 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, to copper ion concentration be 60～120g/L;
Two, the preparation of copper sulfate and sodium sulfate mixed crystal: the microetch waste liquid after concentrated is cooling, filters, and gained solid is the mixed crystal of copper sulfate and sodium sulfate;
Three, the preparation of cupric oxide: the copper sulfate that step 2 is made and the mixed crystal of sodium sulfate mix with acidic copper chloride waste etching solution, making mixed copper content in reactor is 130～150g/L, be 30～50% NaOH to adding concentration in reactor, regulating pH value of solution in reactor is 8～13, temperature is 55～80 DEG C, after 1h, cooling, filter, gained solid is cupric oxide.
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, when microetch waste liquid after concentrated is cooling, the temperature difference is 30～60 DEG C.
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, be first that dilute 1:3～7 to adding pure water in filtrate by thinning ratio, join in microetch tank liquor blend tank, being adjusted to sulfuric acid volumetric concentration is 2～4% again, and copper ion concentration is 9～15g/L, Sodium Persulfate concentration is 75～125g/L, makes micro etching solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437277A (en) * | 2018-11-05 | 2019-03-08 | 上海交通大学 | A kind of method of green high-efficient recycling copper ion |
| CN114702058A (en) * | 2022-04-25 | 2022-07-05 | 惠州市东江环保技术有限公司 | Process for comprehensively recycling micro-etching waste liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437277A (en) * | 2018-11-05 | 2019-03-08 | 上海交通大学 | A kind of method of green high-efficient recycling copper ion |
| CN109437277B (en) * | 2018-11-05 | 2020-07-14 | 上海交通大学 | Method for green and efficient recovery of copper ions |
| CN114702058A (en) * | 2022-04-25 | 2022-07-05 | 惠州市东江环保技术有限公司 | Process for comprehensively recycling micro-etching waste liquid |
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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. |