CN103011253A - Method for preparing copper hydroxide with copper ammonia etching waste liquid - Google Patents
Method for preparing copper hydroxide with copper ammonia etching waste liquid Download PDFInfo
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- CN103011253A CN103011253A CN2012105630959A CN201210563095A CN103011253A CN 103011253 A CN103011253 A CN 103011253A CN 2012105630959 A CN2012105630959 A CN 2012105630959A CN 201210563095 A CN201210563095 A CN 201210563095A CN 103011253 A CN103011253 A CN 103011253A
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- etching waste
- cuprammonium
- copper
- waste liquor
- copper hydroxide
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Abstract
The invention discloses a method for preparing copper hydroxide with copper ammonia etching waste liquid. The method comprises the steps as follows: (1) stirring the copper ammonia etching waste liquid, adding copper chloride hydroxide and liquid alkali, controlling the pH value between 10 and 13 and the reaction time between 30min and 100min, obtaining a mixed solution, filtering the mixed solution, blow-drying an filtered supernatant, washing the supernatant with water, stopping washing when the pH value is between 9 and 12, blow-drying with air, adding a stabilizer to rinse, blow-drying, discharging, drying, and obtaining copper hydroxide. Wastes are changed into valuables by taking the copper ammonia etching waste liquid as a direct raw material; and as an ammonia solution in the copper ammonia etching waste liquid is taken as a carrier and a buffering agent during a reaction course, prepared copper hydroxide can be effectively prevented from being converted into copper oxide under the action of sodium hydroxide. Copper hydroxide prepared with the method is uniform in granule, and easy to rinse and dry; the quality can reach above 97%; the stability is good; copper hydroxide does not turn black at 80 DEG C for 2h; and filtered mother liquid can be recycled.
Description
Technical field
The present invention relates to the copper hydroxide preparing technical field, refer to especially a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide.
Background technology
The method of producing at present copper hydroxide has two kinds:
1, neutralizes under certain condition and get with the sodium hydroxide solution after the copper-bath after the dilution and the dilution.
2, with water-fast alkali type nantokite (basic copper chloride, basic copper nitrate, Basic Chrome Sulphate) under certain condition with dilution after sodium hydroxide solution reaction and get.
Above-mentioned two kinds of methods have following weak point:
(1), product is unstable, very easily occurs the problem (what in fact generate is the mixture of copper hydroxide and cupric oxide) of product blackout in the process of producing copper hydroxide;
(2), not environmental protection of technique, above-mentioned two kinds of methods all will be made with large water gaging the carrier of thinner and reaction, copper recovery is not high, wastewater treatment capacity is large;
(3), the quality of product is not high, first method especially is because separating and its copper hydroxide quality of washing difficulty seldom can reach more than 93%.
Summary of the invention
The present invention is directed to the problem of prior art, propose a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide, the method is simple, and cost is low, resource circulation utilization, environmental protection; And the copper hydroxide quality that makes can reach more than 97%, excellent stability.
Technical scheme of the present invention is achieved in that
A kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide comprises:
(1) stir the cuprammonium etching waste liquor, add afterwards basic copper chloride and liquid caustic soda, control pH is 10-13, and reaction 30-100min gets mixed solution;
(2) filter above-mentioned mixed solution, dry up the product after the filtration; Then wash product, when pH is 9-12, stop washing, air blow drying adds the stablizer rinsing, dry up, and discharging, oven dry namely gets copper hydroxide.
As preferred technical scheme, in the cuprammonium etching waste liquor in the described step (1), ammonia content is 10%～15%, and copper content is 9%～11%.
As preferred technical scheme, the basic copper chloride in the described step (1) is the complex body of copper hydroxide and cupric chloride, and its molecular formula is CuCl
23Cu (OH)
2XH
2O, X=1/2,1 or 2.
As preferred technical scheme, in the described step (1) use the cuprammonium etching waste liquor to prepare the method for copper hydroxide and the mass ratio of described basic copper chloride is 1.4-4:1.
As preferred technical scheme, the cuprammonium etching waste liquor in the described step (1) and the mass ratio of described basic copper chloride are 2-2.5:1.
As preferred technical scheme, the reaction times in the described step (1) is 30-100min.
As preferred technical scheme, described step (1) temperature is controlled at 30-40 ℃.
As preferred technical scheme, the washing in the described step (2) adopts stage pump that tap water is pressed into.
As preferred technical scheme, the stablizer in the described step (2) is glycerine or tributyl phosphate.
As preferred technical scheme, filtrate and copper chloride etching waste liquid neutralization reaction after described step (2) is filtered prepare basic copper chloride.
The present invention compared with prior art has following beneficial effect:
(1) utilizes cupric ion in the cuprammonium etching waste liquor as the direct material of producing copper hydroxide, turn waste into wealth;
(2) utilize ammonia solution in the cuprammonium etching waste liquor can effectively prevent the copper hydroxide that generated under the effect of sodium hydroxide as the carrier in the reaction process and buffer reagent and change into cupric oxide;
(3) copper hydroxide that generates of this method, uniform particles, easily rinsing oven dry, quality can reach more than 97%, and stablizer is good, can blackening behind 80 ℃ of lower 2h;
(4) a small amount of copper, ammonia and alkali is fully used resource for the production of basic copper chloride in the mother liquor after filtering.
Description of drawings
In order to be illustrated more clearly in embodiment of the present invention or technical scheme of the prior art, the below will do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art, apparently, accompanying drawing in the following describes only is embodiments more of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 process flow sheet of the present invention.
Embodiment
The below will be clearly and completely described the technical scheme in the embodiment of the invention, and obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The material of mentioning in following examples is commercially available material.The cuprammonium etching waste liquor is turned waste into wealth in the present invention, takes full advantage of resource, environmentally-friendly sanitary.Basic copper chloride among the present invention is a complex body of copper hydroxide and cupric chloride, and its molecular formula is CuCl
23Cu (OH)
2XH
2O (X=1/2,1,2).Do not have the requirement of concentration aspect among the present invention for liquid caustic soda, this also is one of advantage of the present invention.Preparation method's process of the present invention is easily controlled, and the copper hydroxide stability that makes is high, can blackening behind 80 ℃ of 2h of high temperature.Waste liquid in the preparation process can utilize again simultaneously, produces basic copper chloride.Therefore so that resource find application to greatest extent.
Embodiment 1
A kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide comprises:
(1) in 3000L plastics reactor, adds 1.5m
3The cuprammonium etching waste liquor starts stirring, and temperature remains on 30-40 ℃.The cuprammonium etching waste liquor adds the complete 330kg basic copper chloride that adds afterwards.Complete rear adding 0.8m feeds intake
3Liquid caustic soda, control pH is 10-13, reaction 30min gets mixed solution; The interior most copper of still this moment are precipitated as copper hydroxide, and the liquid copper content is below 0.1%.Ammonia content is 10%～15% in the cuprammonium etching waste liquor, and copper content is 9%～11%.
(2) prepare this moment to filter, check pressure filter, mortar pump, open corresponding each valve of bottom valve and press, start mortar pump.Begin to filter, the from front to back evenly water outlet of each outlet valve, material should once have been pressed in the still, otherwise the blackening of clout possibility affects quality product.After material has been pressed in the still, shut mortar pump, open air compressor machine and related valve and dry up material in the pressure filter.Next step washing is adjusted valve and with stage pump tap water is pressed into, and water outlet is thin out gradually from indigo plant, when pH is down to 9 ~ 12, stops washing, and then air blow drying adds the rinsing of phosphoric acid tri-n-butyl, air blow drying, and discharging is to pneumatic drier oven dry, packing.
The copper hydroxide that makes not blackening behind 80 ℃ of lower 2h.
Embodiment 2
A kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide comprises:
(1) in 3000L plastics reactor, adds 1.7m
3Ton cuprammonium etching waste liquor starts stirring, and temperature remains on 30-40 ℃.The cuprammonium etching waste liquor adds the complete 300kg basic copper chloride that adds afterwards.Complete rear adding 0.9m feeds intake
3Liquid caustic soda, control pH is 10-13, reaction 100min gets mixed solution; The interior most copper of still this moment are precipitated as copper hydroxide, and the liquid copper content is below 0.1%.Ammonia content is 10%～15% in the cuprammonium etching waste liquor, and copper content is 9%～11%.
(2) prepare this moment to filter, check pressure filter, mortar pump, open corresponding each valve of bottom valve and press, start mortar pump.Begin to filter, the from front to back evenly water outlet of each outlet valve, material should once have been pressed in the still, otherwise the blackening of clout possibility affects quality product.After material has been pressed in the still, shut mortar pump, open air compressor machine and related valve and dry up material in the pressure filter.Next step washing is adjusted valve and with stage pump tap water is pressed into, and water outlet is thin out gradually from indigo plant, when pH is down to 9 ~ 12, stops washing, air blow drying, and then glycerol adding rinsing, air blow drying, discharging is to pneumatic drier oven dry, packing.
The copper hydroxide that makes not blackening behind 80 ℃ of lower 2h.
Embodiment 3
A kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide comprises:
(1) in 3000L plastics reactor, adds 1.8m
3The cuprammonium etching waste liquor starts stirring, and temperature remains on 30-40 ℃.The cuprammonium etching waste liquor adds the complete 280kg basic copper chloride that adds afterwards.Complete rear adding 0.8m feeds intake
3Liquid caustic soda, control pH is 10-13, reaction 40-60min gets mixed solution; The interior most copper of still this moment are precipitated as copper hydroxide, and the liquid copper content is below 0.1%.Ammonia content is 10%～15% in the cuprammonium etching waste liquor, and copper content is 9%～11%.
(2) prepare this moment to filter, check pressure filter, mortar pump, open corresponding each valve of bottom valve and press, start mortar pump.Begin to filter, the from front to back evenly water outlet of each outlet valve, material should once have been pressed in the still, otherwise the blackening of clout possibility affects quality product.After material has been pressed in the still, shut mortar pump, open air compressor machine and related valve and dry up material in the pressure filter.Next step washing is adjusted valve and with stage pump tap water is pressed into, and water outlet is thin out gradually from indigo plant, when pH is down to 9 ~ 12, stops washing, air blow drying, and then glycerol adding rinsing, air blow drying, discharging is to pneumatic drier oven dry, packing.
The copper hydroxide that makes not blackening behind 80 ℃ of lower 2h.
Embodiment 4
A kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide comprises:
(1) in 3000L plastics reactor, adds 1.5m
3The cuprammonium etching waste liquor starts stirring.The cuprammonium etching waste liquor adds the complete 340kg basic copper chloride that adds afterwards.Complete rear adding 0.6m feeds intake
3Liquid caustic soda, control pH is 10-13, reaction 40-60min gets mixed solution; The interior most copper of still this moment are precipitated as copper hydroxide, and the liquid copper content is below 0.1%.Ammonia content is 10%～15% in the cuprammonium etching waste liquor, and copper content is 9%～11%.
(2) prepare this moment to filter, check pressure filter, mortar pump, open corresponding each valve of bottom valve and press, start mortar pump.Begin to filter, the from front to back evenly water outlet of each outlet valve, material should once have been pressed in the still, otherwise the blackening of clout possibility affects quality product.After material has been pressed in the still, shut mortar pump, open air compressor machine and related valve and dry up material in the pressure filter.Next step washing, water outlet is thin out gradually from indigo plant, when pH is down to 9 ~ 12, stops washing, air blow drying, then glycerol adding rinsing, air blow drying, discharging is to pneumatic drier oven dry, packing.
The copper hydroxide that makes not blackening behind 80 ℃ of lower 2h.
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. method of using the cuprammonium etching waste liquor to prepare copper hydroxide comprises:
(1) stir the cuprammonium etching waste liquor, add afterwards basic copper chloride and liquid caustic soda, control pH is 10-13, and reaction 30-100min gets mixed solution;
(2) filter above-mentioned mixed solution, dry up the upper strata product after the filtration; Then wash product, when pH is 9-12, stop washing, air blow drying adds the stablizer rinsing, dry up, and discharging, oven dry namely gets copper hydroxide.
2. a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide according to claim 1 is characterized in that, the basic copper chloride in the described step (1) is the complex body of copper hydroxide and cupric chloride, and its molecular formula is CuCl
23Cu (OH)
2XH
2O, X=1/2,1 or 2.
3. a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide according to claim 1 and 2 is characterized in that, the cuprammonium etching waste liquor in the described step (1) and the mass ratio of described basic copper chloride are 1.4-4:1.
4. a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide according to claim 1 and 2 is characterized in that, the cuprammonium etching waste liquor in the described step (1) and the mass ratio of described basic copper chloride are 2-2.5:1.
5. a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide according to claim 3 is characterized in that, the reaction times in the described step (1) is 30-100min.
6. a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide according to claim 3 is characterized in that, described step (1) temperature is controlled at 30-40 ℃.
7. a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide according to claim 3 is characterized in that, the washing in the described step (2) adopts stage pump that tap water is pressed into.
8. a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide according to claim 1 and 2 is characterized in that, the stablizer in the described step (2) is glycerine or tributyl phosphate.
9. a kind of method of using the cuprammonium etching waste liquor to prepare copper hydroxide according to claim 1 and 2 is characterized in that, filtrate and copper chloride etching waste liquid neutralization reaction after described step (2) is filtered prepare basic copper chloride.
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| CN2012105630959A CN103011253A (en) | 2012-12-21 | 2012-12-21 | Method for preparing copper hydroxide with copper ammonia etching waste liquid |
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| CN2012105630959A CN103011253A (en) | 2012-12-21 | 2012-12-21 | Method for preparing copper hydroxide with copper ammonia etching waste liquid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936052A (en) * | 2014-04-02 | 2014-07-23 | 西安交通大学 | Device with pH regulation function for preparing copper hydroxide from etching waste liquid |
| CN106661738A (en) * | 2014-04-01 | 2017-05-10 | 西格玛工程集团 | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
| CN111847496A (en) * | 2020-06-23 | 2020-10-30 | 吴江市威士达铜业科技有限公司 | Preparation method of stable-state copper hydroxide |
| CN114516654A (en) * | 2022-02-09 | 2022-05-20 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by same |
| CN114684847A (en) * | 2020-12-25 | 2022-07-01 | 广州科城环保科技有限公司 | Copper hydroxide, preparation method and application thereof, and bactericide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195497A (en) * | 2006-12-04 | 2008-06-11 | 沈祖达 | Process for producing cupric hydroxide or cupric oxide |
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2012
- 2012-12-21 CN CN2012105630959A patent/CN103011253A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195497A (en) * | 2006-12-04 | 2008-06-11 | 沈祖达 | Process for producing cupric hydroxide or cupric oxide |
Non-Patent Citations (1)
| Title |
|---|
| 郑淑玉 等: "从印刷电路板蚀刻废液中回收氢氧化铜", 《化工给排水设计》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661738A (en) * | 2014-04-01 | 2017-05-10 | 西格玛工程集团 | Oxidation of copper in a copper etching solution by the use of oxygen and/or air as an oxidizing agent |
| CN106661738B (en) * | 2014-04-01 | 2019-11-19 | 西格玛工程集团 | By using oxygen and/or air as oxidant the copper oxide in copper etching solution |
| CN103936052A (en) * | 2014-04-02 | 2014-07-23 | 西安交通大学 | Device with pH regulation function for preparing copper hydroxide from etching waste liquid |
| CN111847496A (en) * | 2020-06-23 | 2020-10-30 | 吴江市威士达铜业科技有限公司 | Preparation method of stable-state copper hydroxide |
| CN114684847A (en) * | 2020-12-25 | 2022-07-01 | 广州科城环保科技有限公司 | Copper hydroxide, preparation method and application thereof, and bactericide |
| CN114684847B (en) * | 2020-12-25 | 2023-11-10 | 广州科城环保科技有限公司 | Copper hydroxide, preparation method and application thereof, and bactericide |
| CN114516654A (en) * | 2022-02-09 | 2022-05-20 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by same |
| CN114516654B (en) * | 2022-02-09 | 2024-02-27 | 广州科城环保科技有限公司 | Preparation method of modified copper hydroxide and modified copper hydroxide prepared by preparation method |
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Application publication date: 20130403 |