CN102190326A - Methods for recovering copper from copper-containing waste liquor - Google Patents
Methods for recovering copper from copper-containing waste liquor Download PDFInfo
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- CN102190326A CN102190326A CN 201010128252 CN201010128252A CN102190326A CN 102190326 A CN102190326 A CN 102190326A CN 201010128252 CN201010128252 CN 201010128252 CN 201010128252 A CN201010128252 A CN 201010128252A CN 102190326 A CN102190326 A CN 102190326A
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Abstract
The invention provides a method for recovering copper from copper-containing waste liquor to prepare copper-containing compounds. The invention also provides a method for recovering copper from copper-containing waste liquor to prepare copper hydroxide or a copper salt mixture comprising copper hydroxide, and the copper hydroxide or the copper salt mixture comprising copper hydroxide is prepared further into a copper-containing compound such as copper carbonate or copper oxide with reusable values. The invention also provides a method for preparing copper carbonate or copper oxide by copper hydroxide or a copper salt mixture comprising copper hydroxide.
Description
Technical field
The invention provides a kind of method from cupric waste liquid recovery copper, particularly prepare copper-containing compound from described contained waste liquid, especially copper carbonate and cupric oxide reclaim the method for utilizing purpose again that reaches to reach copper.
Background technology
Industrialized fast development brings many facilities in life for the mankind.Yet, also produced a large amount of trade wastes simultaneously.Along with the new line of environmental consciousness, how to reduce or efficient recovery utilizes the waste that is produced in the various industry to become the subject under discussion that gets most of the attention at present again.
Cupric waste main source has metal industry, electronic industry and chemical production etc.The cupric waste that present flourish electronic industry (for example printed circuit board industry) is produced has acid copper etching waste liquor and alkaline copper etching waste liquor etc.
The method of handling acid contained waste liquid in this technology comprises with aluminium substitution method generation copper precipitated metal; Or in the interpolation sodium hydroxide and waste liquid, the cupric ion in the waste liquid is separated out with copper hydroxide or cupric oxide form precipitation.The method of handling alkaline copper waste fluid in this technology comprises with sulphide precipitation recovery copper; Or add the alkali aeration with heating, generate the recyclable cupric oxide that utilizes again.Yet aforesaid method is not to be subject to the cost problem, is products therefrom foreign matter content height, or also has in the product that other not tractable impurity is present in the technology or recovery is made again.
Given this, the invention provides a kind of effective copper recovery process, to address the above problem.Method of the present invention can significantly reduce foreign matter content, so can select multifarious copper material source for use, and the operation facility has economic benefit, and the copper that is reclaimed can be prepared into the copper-containing compound (for example copper hydroxide, cupric oxide or copper carbonate) that possesses recycle value, and described copper-containing compound can be made various different gradess according to need, comprise the electronic-grade strict to impurity, not only the product flexibility ratio is high and meet the required of present environmental protection trend.
Summary of the invention
One aspect of the present invention provides a kind of method from cupric waste liquid recovery copper, and it comprises:
(a) add precipitation agent to contained waste liquid, adjust extremely about 2 to about 9 scope of pH value, make contamination precipitation and remove impurity, the control copper ion concentration is below 120 grams per liters; And
(b-1) with the formulations prepared from solutions copper-containing compound of step (a) gained.
Another aspect of the present invention provides a kind of method from cupric waste liquid recovery copper, and it comprises:
(a) add precipitation agent to contained waste liquid, adjust extremely about 2 to about 9 scope of pH value, make contamination precipitation and remove impurity, the control copper ion concentration is below 120 grams per liters; And
(b-2) the pH value of controlled step (a) gained solution is in about 3 to about 13 scope, and precipitation produces copper hydroxide or contains the mantoquita mixture of copper hydroxide.
Another aspect of the present invention provides a kind of and prepares the method for copper carbonate or cupric oxide from copper hydroxide or the mantoquita mixture that contains copper hydroxide, and it comprises:
(c) add acid to copper hydroxide or contain in the mantoquita mixture of copper hydroxide, it is dissolved as acid copper-containing solution;
(d-1) add carbonate to the prepared acid copper-containing solution of step (c), control pH value is in about 6 to about 7 scope, with the generation copper carbonate; And
(e), the prepared copper carbonate of step (d-1) is converted into cupric oxide optionally by conversion reaction.
Description of drawings
Fig. 1 is the first enforcement aspect that reclaims copper method from the cupric waste liquid of the present invention.
Fig. 2 is the second enforcement aspect that reclaims copper method from the cupric waste liquid of the present invention.
Fig. 3 is the synoptic diagram for preparing the method for copper carbonate or cupric oxide from copper hydroxide or the mantoquita mixture that contains copper hydroxide of the present invention.
Fig. 4 prepares copper hydroxide or contains the mantoquita mixture of copper hydroxide from the cupric waste liquid for of the present invention, prepares the synoptic diagram of the method for copper carbonate or cupric oxide by it again.
Fig. 5 prepares copper hydroxide or contains the mantoquita mixture of copper hydroxide from the cupric waste liquid for of the present invention, and then prepares the synoptic diagram of the method for cupric oxide.
Embodiment
The source of the contained waste liquid that the present invention is used there is no particular restriction, can be the waste of recovery from various industry or daily life, it is such as but not limited to acidity or alkaline copper waste fluid, acidity or alkaline copper etching waste liquor, electroplating effluent, copper-contained sludge or metallic copper waste material.For example, acid contained waste liquid comprises copper solutions or its combination of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid or acetic acid, and alkaline copper waste fluid comprises cuprammonium salts solution or its combination of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid or acetic acid.Collected next copper waste liquid or waste material can carry out pre-treatment with the method that any the technical staff in the technical field of the invention was had the knack of earlier, for example improve content of copper ion in the waste copper liquid, from cupric mud the copper stripping formed contained waste liquid or forms contained waste liquid with acid or alkali dissolution copper junk, make that the copper content in the contained waste liquid is unlikely to too low with acid or alkali steeping method with the metal replacement method.For example, the copper content in the contained waste liquid should be higher than 10 grams per liters.According to the present invention, when copper content in the contained waste liquid is low, can add solid-state copper such as copper powder, Copper Foil, copper scale, copper ore, copper mud, copper alloy or other copper junk or its combination, to improve process efficiency.In addition, if the product of desire preparation when containing cupric compound, also can form bivalent cupric ion with the univalent copper ion in the waste liquid with oxidation reduction process optionally earlier.
In general, except cupric ion, also may there be various metal ion in the contained waste liquid, as tin, lead, zinc, iron, calcium, magnesium etc.The existence of these metal ions can increase known copper and reclaim the degree of difficulty of making method again.Yet, this case the contriver find after deliberation: prepared by contained waste liquid in the step of copper-containing compound, randomly add specific precipitation agent to contained waste liquid, and appropriateness add in the acid-to-alkaline contained waste liquid or add alkali to acid contained waste liquid or its combination to adjust the pH value of waste liquid, can make multiple metallic impurity precipitation, again via after removing precipitated impurities such as separation steps such as filtrations, effective purifying contained waste liquid, reduce the metallic impurity ratio of not expected in the waste liquid, helping the proper range of subsequent technique with the control copper ion concentration.This purification step can remove the metallic impurity of not expecting earlier, and therefore for example tin, lead, zinc, calcium, magnesium, manganese etc. can be omitted in the subsequent technique to remove the required step of this type of impurity, and can reduce the influence of this class impurity to technology.In addition, this purification step can not cause adverse influence to existing cupric ion in the solution, and effectively the purifying contained waste liquid reduces the metallic impurity ratio of not expected in the waste liquid, promotes the purity that reclaims the copper-containing compound of making and getting thus.
Therefore, method of the present invention is in the program of preparation copper-containing compound, uses as the aforementioned purification step to remove the metallic impurity of not expecting in the contained waste liquid earlier.Specifically, described purification step is to add specific precipitation agent (including but not limited to nitric acid, sulfuric acid, hydrochloric acid, tartrate, acetic acid, phosphoric acid, ammonium chloride, oxalic acid, sulfide, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammonia or its mixture) to contained waste liquid, adjust extremely about 2 to about 9 scope of pH value, preferred pH value is in about 2 to about 6 scope, make contamination precipitation and remove impurity, the control copper ion concentration is below 120 grams per liters, and preferred concentration range for is below 80 grams per liters.The amount of the used precipitation agent of the present invention there is no fixed range, can optionally adjust according to the amount of impurity, impurity for a long time, relatively precipitation agent also need cooperate increase.For example, in an embodiment who uses general normal waste liquid, but the working concentration scope is between about precipitation agent of 0.2 to about 5wt%.Bronsted lowry acids and bases bronsted lowry in order to the pH value of adjusting waste liquid there is no particular restriction, can be bronsted lowry acids and bases bronsted lowry commonly used in this technology, for example, acid can comprise nitric acid, sulfuric acid, hydrochloric acid, tartrate, acetic acid, phosphoric acid, ammonium chloride, oxalic acid or its mixture, and alkali can comprise sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammonia or its mixture.
According to the present invention, can after above-mentioned purification step, remove impurity in the known mode of any the technical staff in the technical field of the invention.For instance, can optionally remove calcium, magnesium plasma with ion exchange resin; Or remove organic impurity with activated carbon; Or adding oxygenant, for example oxymuriate, hypochlorite, perchlorate, H
2O
2, air or oxygen or its combination, remove metal ion, as iron ion etc.The concentration of above-mentioned oxygenant is between the scope of about 0.005wt% to about 20wt%, and preferably between about scope of 0.01 to about 0.5wt%, preferred oxygenant is hypochlorite, for example clorox.
Method of the present invention can with described purified contained waste liquid, have the copper-containing compound of recycle value by the known method preparation of any the technical staff in the technical field of the invention behind above-mentioned purification step.Above-mentioned copper-containing compound there is no particular restriction, is preferably copper hydroxide, copper carbonate or cupric oxide.Described herein copper carbonate is meant the generalized copper carbonate, promptly comprises the known copper carbonate product of the technical staff in the technical field of the invention, for example comprises ventilation breather, CuCO
3Cu (OH)
2Compound, verdigris etc.
Below now cooperate explanation, further specify and of the present inventionly reclaim two enforcement aspects of the method for copper from the cupric waste liquid with Fig. 1 and 2, but not in order to limit the scope of the invention.Modification that any the technical staff in the technical field of the invention can reach easily and change are included in the content of this case specification sheets and claims.
Figure 1 shows that and of the present inventionly reclaim the first enforcement aspect of the method for copper from the cupric waste liquid, aspect this enforcement in the copper-containing compound of gained be copper carbonate or cupric oxide.As shown in Figure 1, method of the present invention is earlier with behind the contained waste liquid purifying, again with spray drying method for preparation copper carbonate or cupric oxide.
Specifically, according to the first enforcement aspect of the present invention, the invention provides a kind of method from cupric waste liquid recovery copper, it comprises:
(a) add precipitation agent to contained waste liquid, adjust the scope of pH value to about 2 to about 9, preferred pH value makes contamination precipitation and removes impurity in about 2 to about 6 scope, controls copper ion concentration below 120 grams per liters, and preferred concentration range for is below 80 grams per liters; And
(b-1) with the solution of step (a) gained with spray drying method for preparation copper carbonate or cupric oxide.
With spray drying method for preparation copper carbonate or cupric oxide is to be the technical staff in the technical field of the invention institute well known, and its detailed step can be referring to US 3,607,023 content that is disclosed.
According to the present invention, the variation of the above-mentioned first enforcement aspect comprises: when the product of step (b-1) gained is copper carbonate, can be translated into cupric oxide optionally by conversion reaction.Above-mentioned conversion reaction can be any the technical staff in the technical field of the invention institute well known.For instance, can under the sufficient oxygen environment, copper carbonate be heated to proper temperature (for example: 200 ℃ to 500 ℃), the reaction of itself and oxygen be transformed form cupric oxide, and can be according to need more after filtration, washing, oven dry become specific cupric oxide product.
Figure 2 shows that and of the present inventionly reclaim the second enforcement aspect of the method for copper from the cupric waste liquid, method of the present invention is earlier with behind the contained waste liquid purifying, carries out neutralization procedure, and precipitation generates copper hydroxide or contains the mantoquita mixture of copper hydroxide.
Specifically, according to the second enforcement aspect of the present invention, the invention provides a kind of method from cupric waste liquid recovery copper, it comprises:
(a) add precipitation agent to contained waste liquid, adjust the scope of pH value to about 2 to about 9, preferred pH value makes contamination precipitation and removes impurity in about 2 to about 6 scope, controls copper ion concentration below 120 grams per liters, and preferred concentration range for is below 80 grams per liters; And
(b-2) the pH value of controlled step (a) gained solution is in about 3 to about 13 scope, and precipitation produces copper hydroxide or contains the mantoquita mixture of copper hydroxide.
Owing to may still there be in the contained waste liquid other ion that does not remove to exist, for example ammonium ion, chlorion etc., so the prepared copper hydroxide of second aspect step (b-2) may exist with the form of mantoquita mixture, for example Cu (OH)
2CuCl
2Or Cu (OH)
2Cu (NH
3)
4Cl
2Etc. form.
The adjustment of the pH value of above-mentioned steps (b-2) can be with the acid contained waste liquid of gained after the purified step and alkaline copper waste fluid with the suitable proportion intermingling, or adding acid or alkali are adjusted.There is no particular restriction in order to acid and the alkali of adjusting, can be acid and alkali commonly used in this technology, for example, acid can comprise nitric acid, sulfuric acid, hydrochloric acid, tartrate, acetic acid, phosphoric acid, ammonium chloride or oxalic acid or its combination, and alkali can comprise sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammonia or its combination.
Be to promote the usefulness of utilizing of cupric product, the present invention provides a kind of method for preparing copper carbonate or cupric oxide from copper hydroxide or the mantoquita mixture that contains copper hydroxide in addition.Above-mentioned copper hydroxide or contain the mantoquita mixture of copper hydroxide can be obtained from the method (for example above-mentioned second enforcement aspect) that the cupric waste liquid reclaims copper by the present invention, or obtained by any prior art method.
Specifically, the invention provides and a kind ofly prepare the method for copper carbonate or cupric oxide from copper hydroxide or the mantoquita mixture that contains copper hydroxide, it comprises:
(c) add acid to copper hydroxide or contain in the mantoquita mixture of copper hydroxide, it is dissolved as acid copper-containing solution;
(d-1) add carbonate to the prepared acid copper-containing solution of step (c), control pH value is in about 6 to about 7 scope, with the generation copper carbonate; And
(e), the prepared copper carbonate of step (d-1) is converted into cupric oxide optionally by conversion reaction.
The employed acid of above-mentioned steps (c) there is no particular restriction, is preferably mineral acid, for example hydrochloric acid, sulfuric acid or nitric acid or its combination.Adding the amount of acid or the pH of solution does not have special restriction, as long as addition is enough to make the solid-state copper compound (for example copper hydroxide) in the acid copper-containing solution to dissolve fully.The conversion reaction of above-mentioned steps (e) such as this paper previous narration.
The employed carbonate of above-mentioned steps (d-1) includes but not limited to yellow soda ash, salt of wormwood, volatile salt, bicarbonate of ammonia or its analogue or its combination, is preferably yellow soda ash or salt of wormwood.Specifically, this carbonic acid reactions steps is with via the cupric acidic solution of above-mentioned steps (c) the gained carbonate contact reacts with alkalescence, and appropriateness is adjusted the adding proportion of yellow soda ash, and control pH value is in about 6 to about 7 scope.
Preferably, this case contriver finds carrying out step (d-1) before, also can carry out mixing soon (or claiming premix) with a small amount of cupric acidic solution and carbonate earlier in batches.In this mixed soon, temperature there is no specific limited.Owing to carrying out step of the present invention (d-1) before, can carry out earlier mixing soon, so the present invention can prepare copper carbonate under lower pH value scope, reduce amount because of the alkali of the required interpolation of control pH value, thus the quality of may command products obtained therefrom; In addition, owing to fast mixing can be reacted in lower temperature range, thereby can save the energy waste in the technology.
In addition, the present invention can add copper carbonate crystal grain as crystal seed in above-mentioned steps (d-1), become step (d-3), generate to quicken the copper carbonate crystalline, wherein the copper carbonate particulate weight of Tian Jiaing is between the scope of about 0.005wt% to 5wt%, preferably between about 0.01wt% to 0.1wt%.Above-mentioned crystal seed can be selected kind commonly used in the art for use, such as but not limited to ventilation breather.Preferably, this grows brilliant reaction times of reacting at least about 20 minutes to about 60 minutes, and the scope of controlled temperature between about 30 ℃ to about 70 ℃ is preferably the scope between 50 ℃ to about 60 ℃.
Fig. 3 is the synoptic diagram for preparing the method for copper carbonate or cupric oxide from copper hydroxide or the mantoquita mixture that contains copper hydroxide of the present invention.
Fig. 4 prepares copper hydroxide or contains the mantoquita mixture of copper hydroxide from the cupric waste liquid for of the present invention, prepares the synoptic diagram of the method for copper carbonate or cupric oxide again via it.
The present invention provides a kind of method for preparing cupric oxide from copper hydroxide or the mantoquita mixture that contains copper hydroxide in addition.This method can be further with prepared copper hydroxide or the mantoquita mixture (for example above-mentioned second enforcement aspect) that contains copper hydroxide are prepared as cupric oxide according to the present invention.Specifically, this method comprises:
(c) add acid to copper hydroxide or contain in the mantoquita mixture of copper hydroxide, it is dissolved as acid copper-containing solution; And
(d-2) add alkali to the prepared acid copper-containing solution of step (c), control pH value is in about 9 to about 14 scope, and preferably pH is in about 12 to about 14 scope, and temperature is controlled at the scope between about 80 ℃ to about 105 ℃, preferably the scope between about 90 ℃ to about 100 ℃ generates cupric oxide.The alkali kind of wherein being added there is no particular restriction, is preferably sodium hydroxide.
Fig. 5 prepares copper hydroxide or contains the mantoquita mixture of copper hydroxide from the cupric waste liquid for of the present invention, and then prepare the synoptic diagram of the method for cupric oxide, and it is the first mantoquita mixture for preparing copper hydroxide or contain copper hydroxide by method of the present invention.
Following examples are to be used for that the invention will be further described, but not in order to limit the scope of the invention.Modification that any those skilled in the art can reach easily and change are included in the scope of this case specification sheets disclosure and appended claims.
Embodiment 1
Add phosphoric acid to alkaline copper waste fluid (copper content is 99.38 grams per liters), adjusting the pH value is between about 2 to about 6, the metal ion of not expecting can form the difficultly-soluble phosphates class with the phosphate radical effect, make contamination precipitation and filter to remove impurity, cupric liquid behind the purifying and the foreign matter content in the stoste are shown in following table one:
Table one
| Composition | Cu | Al | Ca | Cd | Cr | Fe |
| Stoste | (99.38 grams per liter) | (3.04 mg/litre) | (8.009 mg/litre) | (0.149 mg/litre) | (0.654 mg/litre) | (0.455 mg/litre) |
| Refined solution | (99.38 grams per liter) | (1.96 mg/litre) | (2.545 mg/litre) | (0.076 mg/litre) | (0.456 mg/litre) | (0.242 mg/litre) |
| Purifying % | 0 | 35.52 | 68.22 | 48.89 | 30.28 | 46.81 |
(the continuous table of going up)
| Composition | Mg | Mn | Ni | Pb | Sn | Zn |
| Stoste | (4.5 mg/litre) | (3.258 mg/litre) | (17.54 mg/litre) | (4.89 mg/litre) | (5.5 mg/litre) | 164 (mg/litre) |
| Refined solution | (0.73 mg/litre) | (1.666 mg/litre) | (6.341 mg/litre) | (3.8 mg/litre) | (1.41 mg/litre) | (7.06 mg/litre) |
| Purifying % | 83.7 | 48.86 | 63.85 | 22.2 | 74.4 | 95.7 |
By data in the table as can be known, add phosphoric acid and to contained waste liquid, can make multiple metallic impurity precipitation, help removing the metallic impurity of not expecting, purifying contained waste liquid, the metallic impurity ratio that effectively reduces in the waste liquid not expected.
Embodiment 2
Add in the acid contained waste liquid (copper content is 31.43 grams per liters) with sodium hydroxide, adjust the pH value and extremely about 4.2 be settled out impurity, question response is finished and is added clorox 0.5wt% continuation precipitation again, filters in the lump and removes impurity, and cupric liquid behind the purifying and the foreign matter content in the stoste are shown in following table two:
Table two
| Composition | Cu | Al | Ca | Cd | Cr | Fe |
| Stoste | (31.43 grams per liter) | (0.5116 mg/litre) | (39.68 mg/litre) | ND | (0.139 mg/litre) | (24.53 mg/litre) |
| PH adjusts refined solution | 31.32 | 0.585 | 30.94 | ND | 0.1125 | 12.92 |
| (grams per liter) | (mg/litre) | (mg/litre) | (mg/litre) | (mg/litre) | ||
| The oxygenant purifying | (31.32 grams per liter) | (0.272 mg/litre) | (26.41 mg/litre) | ND | (0.101 mg/litre) | (11.44 mg/litre) |
| Purifying % | 0.34 | 53.5 | 33.4 | - | 19.1 | 53.4 |
(the continuous table of going up)
| Composition | Mg | Mn | Ni | Pb | Sn | Zn |
| Stoste | (8.445 mg/litre) | (0.926 mg/litre) | (0.219 mg/litre) | ND | ND | (28.97 mg/litre) |
| PH adjusts refined solution | (6.857 mg/litre) | (0.776 mg/litre) | (0.1641 mg/litre) | ND | ND | (12.77 mg/litre) |
| The oxygenant purifying | (6.385 mg/litre) | (0.6928 mg/litre) | (0.1536 mg/litre) | ND | ND | (1.64 mg/litre) |
| Purifying % | 6.9 | 10.7 | 6.4 | - | - | 87.2 |
By data in the table as can be known, adjust pH value and add oxygenant and to alkaline copper waste fluid, multiple metallic impurity are precipitated, help removing the metallic impurity of not expecting, purifying contained waste liquid, the metallic impurity ratio that effectively reduces in the waste liquid not expected.
Claims (29)
1. one kind is reclaimed the method for copper from the cupric waste liquid, and it comprises:
(a) add precipitation agent to contained waste liquid, adjust extremely about 2 to about 9 scope of pH value, make contamination precipitation and remove impurity, the control copper ion concentration is below 120 grams per liters; And
(b-1) with the formulations prepared from solutions copper-containing compound of step (a) gained.
2. the method for claim 1, it further comprises at least a purification step that is selected from the following group that forms afterwards in above-mentioned steps (a): carry out purifying with ion exchange resin, carry out purifying with activated carbon, carry out purifying with oxygenant.
3. method as claimed in claim 2, the concentration of wherein said oxygenant between about 0.005wt% to the scope of about 20wt%.
4. method as claimed in claim 2, the chloride hydrochlorate of wherein said oxidant package, hypochlorite, perchlorate, H
2O
2, air or oxygen or its combination.
5. method as claimed in claim 4, wherein said oxygenant are clorox.
6. as the described method of arbitrary claim in the claim 1 to 5, wherein precipitation agent comprises nitric acid, sulfuric acid, hydrochloric acid, tartrate, acetic acid, phosphoric acid, ammonium chloride, oxalic acid, sulfide, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammonia or its combination.
7. the method for claim 1, wherein said step (b-1) are that solution with step (a) gained is with spray drying method for preparation copper carbonate or cupric oxide.
8. method as claimed in claim 7 wherein when the product of step (b-1) gained is copper carbonate, can be converted into cupric oxide with copper carbonate optionally by conversion reaction.
9. one kind is reclaimed the method for copper from the cupric waste liquid, and it comprises:
(a) add precipitation agent to contained waste liquid, adjust extremely about 2 to about 9 scope of pH value, make contamination precipitation and remove impurity, the control copper ion concentration is below 120 grams per liters; And
(b-2) the pH value of controlled step (a) gained solution is in about 3 to about 13 scope, and precipitation produces copper hydroxide or contains the mantoquita mixture of copper hydroxide.
10. method as claimed in claim 9, it further comprises at least a purification step that is selected from the following group that forms afterwards in above-mentioned steps (a): carry out purifying with ion exchange resin, carry out purifying and carry out purifying with oxygenant with activated carbon.
11. method as claimed in claim 10, the concentration of wherein said oxygenant is between the scope of about 0.005wt% to about 20wt%.
12. method as claimed in claim 10, the chloride hydrochlorate of wherein said oxidant package, hypochlorite, perchlorate, H
2O
2, air or oxygen or its combination.
13. method as claimed in claim 12, wherein said oxygenant are clorox.
14. method as claimed in claim 9, wherein precipitation agent comprises nitric acid, sulfuric acid, hydrochloric acid, tartrate, acetic acid, phosphoric acid, ammonium chloride, oxalic acid, sulfide, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood or ammonia or its combination.
15. as the method for arbitrary claim in the claim 9 to 14, it further comprises the following step:
(c) add acid to the prepared copper hydroxide of step (b-2) or contain in the mantoquita mixture of copper hydroxide, it is dissolved as acid copper-containing solution.
16. method as claimed in claim 15, wherein the described acid of step (c) is hydrochloric acid, sulfuric acid or nitric acid or its combination.
17. method as claimed in claim 15, it further comprises the following step:
(d-1) add carbonate to the prepared acid copper-containing solution of step (c), control pH value is in about 6 to about 7 scope, with the generation copper carbonate; And
(e), the prepared copper carbonate of step (d-1) is converted into cupric oxide optionally by conversion reaction.
18. method as claimed in claim 17, wherein the described carbonate of step (d-1) is yellow soda ash, salt of wormwood, volatile salt, bicarbonate of ammonia or these analogue or its combination.
19. method as claimed in claim 17, can in above-mentioned steps (d-1), add the copper carbonate particle as crystal seed, wherein the copper carbonate particulate weight of Tian Jiaing is between about 0.005wt% to 5wt%, about 20 minutes to about 60 minutes reaction times, the scope of controlled temperature between about 30 ℃ to about 70 ℃.
20. method as claimed in claim 15, it further comprises the following step:
(d-2) add alkali to the prepared acid copper-containing solution of step (c), generate cupric oxide.
21. method as claimed in claim 20, wherein the described alkali of step (d-2) is sodium hydroxide.
22. method as claimed in claim 20, wherein the pH value of step (d-2) is about 9 to about 14 the scope of being controlled at.
23. method as claimed in claim 20, wherein the temperature of step (d-2) is the scope that is controlled between about 80 ℃ to about 105 ℃.
24. as the described method of arbitrary claim in the claim 1,7 and 9, wherein the copper of contained waste liquid source is to comprise acid contained waste liquid, alkaline copper waste fluid, solid-state copper or its mixture.
25. method as claimed in claim 24, wherein
Acid contained waste liquid comprises copper solutions or its combination of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid or acetic acid;
Alkaline copper waste fluid comprises cuprammonium salts solution or its combination of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid or acetic acid; And
Solid-state copper-clad contains copper powder, Copper Foil, copper scale, copper ore, copper mud or copper alloy or its combination.
26. one kind prepares the method for copper carbonate or cupric oxide from copper hydroxide or the mantoquita mixture that contains copper hydroxide, it comprises:
(c) add acid to copper hydroxide or contain in the mantoquita mixture of copper hydroxide, it is dissolved as acid copper-containing solution.
(d-3) add carbonate to the prepared acid copper-containing solution of step (c), control pH value is in about 6 to about 7 scope, and add the copper carbonate particle as crystal seed, wherein the copper carbonate particulate weight of Tian Jiaing is between about 0.005wt% to 5wt%, about 20 minutes to about 60 minutes reaction times, the scope of controlled temperature between about 30 ℃ to about 70 ℃ is to generate copper carbonate; And
(e), the prepared copper carbonate of step (d-3) is converted into cupric oxide optionally by conversion reaction.
27. method as claimed in claim 26, wherein the described acid of step (c) is hydrochloric acid, sulfuric acid or nitric acid or its combination.
28. method as claimed in claim 26, wherein the described carbonate of step (d-3) is yellow soda ash, salt of wormwood, volatile salt, bicarbonate of ammonia or its combination.
29. as the described method of arbitrary claim in the claim 26 to 28, wherein said copper hydroxide or the mantoquita mixture that contains copper hydroxide are by making as the described method of arbitrary claim in the claim 9 to 16.
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| CN106064826A (en) * | 2016-06-02 | 2016-11-02 | 东莞市广华化工有限公司 | A kind of method and apparatus utilizing wiring board acidic etching waste liquid to reclaim copper resource |
| CN106756091A (en) * | 2016-12-19 | 2017-05-31 | 长江大学 | A kind of extracting method of Metals of Discarded Printed Circuit Boards copper |
| CN107176713A (en) * | 2017-06-02 | 2017-09-19 | 绍兴上虞微益再生资源有限公司 | The copper smelting method of cupric industrial wastes |
| CN107381746A (en) * | 2017-08-23 | 2017-11-24 | 华南理工大学 | A kind of method for being removed in waste water and reclaiming copper |
| CN109280773A (en) * | 2018-10-22 | 2019-01-29 | 瑞安市浩通铜材有限公司 | Use copper scrap for the pouring molding method of the copper profile of base-material |
| CN110357142A (en) * | 2019-07-29 | 2019-10-22 | 深圳市海文环保技术有限公司 | Copper-containing etching waste solution processing method and system |
| CN111634912A (en) * | 2020-06-30 | 2020-09-08 | 中国林业科学研究院林产化学工业研究所 | Process method for reducing ash content of phosphoric acid method activated carbon |
| CN114836631A (en) * | 2022-06-15 | 2022-08-02 | 蜂巢能源科技股份有限公司 | Recycling method of copper-manganese solution generated by extracting and recycling battery material |
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| CN106064826A (en) * | 2016-06-02 | 2016-11-02 | 东莞市广华化工有限公司 | A kind of method and apparatus utilizing wiring board acidic etching waste liquid to reclaim copper resource |
| CN106756091A (en) * | 2016-12-19 | 2017-05-31 | 长江大学 | A kind of extracting method of Metals of Discarded Printed Circuit Boards copper |
| CN107176713A (en) * | 2017-06-02 | 2017-09-19 | 绍兴上虞微益再生资源有限公司 | The copper smelting method of cupric industrial wastes |
| CN107381746A (en) * | 2017-08-23 | 2017-11-24 | 华南理工大学 | A kind of method for being removed in waste water and reclaiming copper |
| CN109280773A (en) * | 2018-10-22 | 2019-01-29 | 瑞安市浩通铜材有限公司 | Use copper scrap for the pouring molding method of the copper profile of base-material |
| CN110357142A (en) * | 2019-07-29 | 2019-10-22 | 深圳市海文环保技术有限公司 | Copper-containing etching waste solution processing method and system |
| CN110357142B (en) * | 2019-07-29 | 2022-02-01 | 深圳市海文环保技术有限公司 | Method and system for treating copper-containing etching waste liquid |
| CN111634912A (en) * | 2020-06-30 | 2020-09-08 | 中国林业科学研究院林产化学工业研究所 | Process method for reducing ash content of phosphoric acid method activated carbon |
| CN114836631A (en) * | 2022-06-15 | 2022-08-02 | 蜂巢能源科技股份有限公司 | Recycling method of copper-manganese solution generated by extracting and recycling battery material |
| CN114836631B (en) * | 2022-06-15 | 2023-12-01 | 蜂巢能源科技股份有限公司 | Recycling method of copper-manganese liquid generated by extraction and recovery of battery materials |
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