CN102190326A - Method for recovering copper from copper-containing waste liquid - Google Patents

Abstract

The present invention provides a method for recovering copper from copper-containing waste liquid to prepare a copper-containing compound. The present invention also provides a method for recovering copper from copper-containing waste liquid to prepare copper hydroxide or a copper salt mixture containing copper hydroxide, which is further prepared into a copper-containing compound with recycling value, such as copper carbonate or copper oxide. The present invention further provides a method for preparing copper carbonate or copper oxide from copper hydroxide or a copper salt mixture containing copper hydroxide.

Description

Method for recovering copper from copper-containing waste liquid

technical field

The invention provides a method for recovering copper from copper-containing waste liquid, especially a method for preparing copper-containing compounds, especially copper carbonate and copper oxide, from the copper-containing waste liquid to achieve the purpose of copper recovery and reuse.

Background technique

The rapid development of industrialization has brought many conveniences to human life. However, it also produces a large amount of industrial waste. With the rising awareness of environmental protection, how to reduce or effectively recycle and reuse the waste generated in various industries has become an issue that has attracted much attention.

The main sources of copper-containing waste are metal industry, electronics industry, and chemical manufacturing industry. The copper-containing waste produced by the booming electronics industry (such as the printed circuit board industry) includes acidic copper etching waste liquid and alkaline copper etching waste liquid.

The method for treating acidic copper-containing waste liquid in this technology includes producing copper metal precipitation by aluminum replacement method; or adding sodium hydroxide to neutralize the waste liquid, so that the copper ions in the waste liquid are precipitated in the form of copper hydroxide or copper oxide. The method for treating alkaline copper-containing waste liquid in this technology includes recovering copper by sulfide precipitation; or generating recyclable copper oxide by heating and adding alkali aeration. However, the above-mentioned method is not limited by the cost problem, or the obtained product has high impurity content, or there are other difficult-to-handle impurities present in the process or in the recovered and remanufactured product.

In view of this, the present invention provides an effective copper recovery method to solve the above problems. The method of the present invention can greatly reduce the impurity content, so a variety of copper sources can be selected, and the operation is convenient and economical, and the recovered copper can be prepared into copper-containing compounds (such as copper hydroxide, Copper oxide or copper carbonate), and the copper-containing compound can be made into various grades as required, including electronic grade with strict requirements on impurities, which not only has high product flexibility but also meets the needs of current environmental protection trends.

Contents of the invention

One aspect of the present invention provides a method for recovering copper from copper-containing waste liquid, which comprises:

(a) adding a precipitant to the copper-containing waste liquid, adjusting the pH value to a range of about 2 to about 9, so as to precipitate and remove impurities, and control the concentration of copper ions below 120 g/L; and

(b-1) Prepare a copper-containing compound with the solution obtained in step (a).

Another aspect of the present invention provides a method for recovering copper from copper-containing waste liquid, comprising:

(a) adding a precipitant to the copper-containing waste liquid, adjusting the pH value to a range of about 2 to about 9, so as to precipitate and remove impurities, and control the concentration of copper ions below 120 g/L; and

(b-2) controlling the pH value of the solution obtained in step (a) in the range of about 3 to about 13, and precipitation produces copper hydroxide or a copper salt mixture containing copper hydroxide.

Yet another aspect of the present invention provides a method for preparing copper carbonate or copper oxide from copper hydroxide or a copper salt mixture containing copper hydroxide, comprising:

(c) adding an acid to copper hydroxide or a copper hydroxide-containing copper salt mixture to dissolve it into an acidic copper-containing solution;

(d-1) adding carbonate to the acidic copper-containing solution prepared in step (c), controlling the pH value in the range of about 6 to about 7, to generate copper carbonate; and

(e) converting the copper carbonate prepared in step (d-1) into copper oxide through a conversion reaction if necessary.

Description of drawings

Fig. 1 is the first implementation aspect of the method for recovering copper from copper-containing waste liquid of the present invention.

Fig. 2 is the second implementation aspect of the method for recovering copper from copper-containing waste liquid of the present invention.

3 is a schematic diagram of the method for preparing copper carbonate or copper oxide from copper hydroxide or a copper salt mixture containing copper hydroxide according to the present invention.

Fig. 4 is a schematic diagram of a method for preparing copper hydroxide or a copper salt mixture containing copper hydroxide from copper-containing waste liquid and then preparing copper carbonate or copper oxide according to the present invention.

Fig. 5 is a schematic diagram of the method for preparing copper hydroxide or a copper salt mixture containing copper hydroxide from copper-containing waste liquid, and then preparing copper oxide according to the present invention.

Detailed ways

The source of the copper-containing waste liquid used in the present invention is not particularly limited, and it can be recycled from various industries or daily life waste, such as but not limited to acidic or alkaline copper-containing waste liquid, acidic or alkaline copper etching waste solution, electroplating waste solution, copper-containing sludge or metallic copper waste. For example, the acidic copper-containing waste liquid comprises a copper solution of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid or acetic acid or a combination thereof, and the alkaline copper-containing waste liquid comprises a copper ammonium salt solution of hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid or acetic acid or its combination. The collected copper waste liquid or waste material can be pretreated with any method familiar to those skilled in the art of the present invention, such as improving the copper ion content in the waste copper liquid by metal replacement, impregnating with acid or alkali The method is to dissolve copper from copper-containing sludge to form copper-containing waste liquid, or dissolve copper waste with acid or alkali to form copper-containing waste liquid, so that the copper content in copper-containing waste liquid will not be too low. For example, the copper content in the copper-containing waste liquid should be higher than 10 g/L. According to the present invention, solid copper such as copper powder, copper foil, copper shavings, copper ore, copper sludge, copper alloy or other copper scrap or its combination can be added when the copper content in the copper-containing waste liquid is low, to improve process efficiency. In addition, if the product to be prepared is a compound containing divalent copper, the monovalent copper ions in the waste liquid may be converted into divalent copper ions by redox method if necessary.

Generally speaking, in addition to copper ions, various metal ions may exist in copper-containing waste liquid, such as tin, lead, zinc, iron, calcium, magnesium, etc. The existence of these metal ions will increase the difficulty of conventional copper recycling methods. However, the inventors of this case have found through research that: in the step of preparing copper-containing compounds from copper-containing waste liquid, optionally adding a specific precipitant to the copper-containing waste liquid, and appropriately adding acid to the alkaline copper-containing waste liquid or Adding alkali to the acidic copper-containing waste liquid or its combination to adjust the pH value of the waste liquid can precipitate various metal impurities, and then remove the precipitated impurities through separation steps such as filtration, which can effectively purify the copper-containing waste liquid and reduce The ratio of undesired metal impurities in the waste liquid is used to control the concentration of copper ions in an appropriate range that is beneficial to the subsequent process. This purification step first removes undesired metal impurities such as tin, lead, zinc, calcium, magnesium, manganese, etc., thereby eliminating the steps required to remove such impurities in subsequent processes and reducing the cost of such impurities. The impact of similar impurities on the process. In addition, this purification step will not adversely affect the copper ions present in the solution, and can effectively purify the copper-containing waste liquid, reduce the proportion of undesired metal impurities in the waste liquid, thereby improving the recovery and remanufacturing. Purity of copper-containing compounds.

Therefore, in the method of the present invention, in the process of preparing the copper-containing compound, the aforementioned purification steps are used to remove the undesired metal impurities in the copper-containing waste liquid. In detail, the purification step is to add a specific precipitant (including but not limited to nitric acid, sulfuric acid, hydrochloric acid, tartaric acid, acetic acid, phosphoric acid, ammonium chloride, oxalic acid, sulfide, sodium hydroxide, potassium hydroxide, sodium carbonate, Potassium carbonate or ammonia or its mixture) in copper-containing waste liquid, adjust pH value to the scope of about 2 to about 9, preferably pH value is in the scope of about 2 to about 6, make impurity precipitate and remove impurity, control copper ion The concentration is below 120 g/L, and the preferred concentration range is below 80 g/L. The amount of the precipitating agent used in the present invention has no fixed range, and can be adjusted according to the needs of the amount of impurities. When there are many impurities, the relative amount of the precipitating agent also needs to be increased. For example, in one embodiment using typical normal waste streams, a precipitating agent may be used at a concentration ranging from about 0.2 to about 5 wt%. The acid and alkali used to adjust the pH value of the waste liquid are not particularly limited, and may be commonly used in this technology. For example, the acid may include nitric acid, sulfuric acid, hydrochloric acid, tartaric acid, acetic acid, phosphoric acid, ammonium chloride, Oxalic acid or mixtures thereof, the base may include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or ammonia or mixtures thereof.

According to the present invention, the above-mentioned purification steps may optionally be followed by removal of impurities in any manner known to those skilled in the art to which the present invention pertains. For example, ion exchange resins can be used to remove calcium and magnesium ions; or activated carbon can be used to remove organic impurities; or oxidants can be added, such as chlorate, hypochlorite, perchlorate, H ₂ O ₂ , air or oxygen or a combination thereof to remove metal ions, such as iron ions, etc. The concentration of the oxidizing agent is in the range of about 0.005wt% to about 20wt%, preferably in the range of about 0.01wt% to about 0.5wt%, and the preferred oxidizing agent is hypochlorite, such as sodium hypochlorite.

In the method of the present invention, after the above purification steps, the purified copper-containing waste liquid can be used to prepare copper-containing compounds with reuse value by any method well known to those skilled in the art of the present invention. The above-mentioned copper-containing compound is not particularly limited, and is preferably copper hydroxide, copper carbonate or copper oxide. Copper carbonate as described herein refers to copper carbonate in a broad sense, which includes copper carbonate products well known to those skilled in the art of the present invention, such as basic copper carbonate, CuCO ₃ .Cu(OH) ₂ compounds, verdigris wait.

1 and 2 are used to illustrate two implementation aspects of the method for recovering copper from copper-containing waste liquid of the present invention, but not to limit the scope of the present invention. Any modifications and changes that can be easily achieved by those skilled in the technical field to which the present invention belongs are included in the description and claims of this application.

Fig. 1 shows the first implementation aspect of the method for recovering copper from copper-containing waste liquid of the present invention, the copper-containing compound obtained in this implementation aspect is copper carbonate or copper oxide. As shown in Figure 1, the method of the present invention is to prepare copper carbonate or copper oxide with the spray drying method after first purifying the copper-containing waste liquid.

In detail, according to the first implementation aspect of the present invention, the present invention provides a method for recovering copper from copper-containing waste liquid, which comprises:

(a) adding a precipitating agent to the copper-containing waste liquid, adjusting the pH value to the range of about 2 to about 9, preferably the pH value is in the range of about 2 to about 6, so that impurities are precipitated and removed, and the concentration of copper ions is controlled at Below 120 g/l, preferably in the concentration range below 80 g/l; and

(b-1) Prepare copper carbonate or copper oxide by spray drying the solution obtained in step (a).

The preparation of copper carbonate or copper oxide by spray drying is well known to those skilled in the art of the present invention, and its detailed steps can be found in US 3,607,023.

According to the present invention, the change of the above-mentioned first embodiment includes: when the product obtained in step (b-1) is copper carbonate, it may be converted into copper oxide through a conversion reaction if necessary. The above-mentioned conversion reactions can be known to those skilled in the art to which the present invention belongs. For example, copper carbonate can be heated to an appropriate temperature (for example: 200°C to 500°C) in an environment of sufficient oxygen to make it react with oxygen to form copper oxide, and then filter, wash with water, and dry as needed Become a specific copper oxide product.

Figure 2 shows the second implementation aspect of the method for recovering copper from copper-containing waste liquid of the present invention. The method of the present invention is to first purify the copper-containing waste liquid, and then carry out the neutralization step, and precipitate to generate copper hydroxide or hydrogen-containing Copper salt mixture of copper oxide.

In detail, according to the second implementation aspect of the present invention, the present invention provides a method for recovering copper from copper-containing waste liquid, which comprises:

(a) adding a precipitating agent to the copper-containing waste liquid, adjusting the pH value to the range of about 2 to about 9, preferably the pH value is in the range of about 2 to about 6, so that impurities are precipitated and removed, and the concentration of copper ions is controlled at Below 120 g/l, preferably in the concentration range below 80 g/l; and

(b-2) controlling the pH value of the solution obtained in step (a) in the range of about 3 to about 13, and precipitation produces copper hydroxide or a copper salt mixture containing copper hydroxide.

Since there may be other unremoved ions in the copper-containing waste liquid, such as ammonium ions, chloride ions, etc., the copper hydroxide produced in step (b-2) of the second aspect may exist in the form of a copper salt mixture , such as Cu(OH) ₂ ·CuCl ₂ or Cu(OH) ₂ ·Cu(NH ₃ ) ₄ Cl ₂ and other forms.

The pH value adjustment of the above step (b-2) can be adjusted by mixing the acidic copper-containing waste liquid and the alkaline copper-containing waste liquid in an appropriate proportion after the purification step, or by adding acid or alkali. The acid and base used for adjustment are not particularly limited, and may be acids and bases commonly used in this technology. For example, the acid may include nitric acid, sulfuric acid, hydrochloric acid, tartaric acid, acetic acid, phosphoric acid, ammonium chloride or oxalic acid or combinations thereof, The base may include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or ammonia or combinations thereof.

In order to improve the utilization efficiency of copper-containing products, the present invention further provides a method for preparing copper carbonate or copper oxide from copper hydroxide or a copper salt mixture containing copper hydroxide. The above-mentioned copper hydroxide or copper salt mixture containing copper hydroxide can be produced by the method of the present invention for recovering copper from copper-containing waste liquid (such as the second embodiment mentioned above), or by any known method.

In detail, the present invention provides a method for preparing copper carbonate or copper oxide from copper hydroxide or a copper salt mixture containing copper hydroxide, which comprises:

(c) adding an acid to copper hydroxide or a copper hydroxide-containing copper salt mixture to dissolve it into an acidic copper-containing solution;

(d-1) adding carbonate to the acidic copper-containing solution prepared in step (c), controlling the pH value in the range of about 6 to about 7, to generate copper carbonate; and

(e) converting the copper carbonate prepared in step (d-1) into copper oxide through a conversion reaction if necessary.

The acid used in the above step (c) is not particularly limited, and is preferably an inorganic acid, such as hydrochloric acid, sulfuric acid or nitric acid or a combination thereof. The amount of added acid or the pH of the solution is not particularly limited, as long as the added amount is sufficient to completely dissolve the solid copper compound (such as copper hydroxide) in the acidic copper-containing solution. The conversion reaction of the above step (e) is as described previously herein.

The carbonates used in the above step (d-1) include but are not limited to sodium carbonate, potassium carbonate, ammonium carbonate, ammonium bicarbonate or the like or combinations thereof, preferably sodium carbonate or potassium carbonate. Specifically, the carbonic acid reaction step is to contact the copper-containing acidic solution obtained through the above step (c) with alkaline carbonate, moderately adjust the addition ratio of sodium carbonate, and control the pH value at about 6 to about 7 scope.

Preferably, the inventors of the present case found that before step (d-1), a small amount of copper-containing acidic solution and carbonate can be quickly mixed (or pre-mixed) in batches. In this fast mixing, the temperature is not particularly limited. Because before carrying out step (d-1) of the present invention, can carry out rapid mixing earlier, so the present invention can prepare copper carbonate under the range of lower pH value, reduce the amount of the alkali that needs to add because of controlling pH value, thereby The quality of the resulting product can be controlled; moreover, energy consumption in the process can be saved as fast mixing allows the reaction to be carried out at a lower temperature range.

In addition, the present invention may add copper carbonate grains as crystal seeds in the above-mentioned step (d-1) as required, and become step (d-3), to accelerate the generation of copper carbonate crystals, wherein the weight of the copper carbonate particles added is between In the range of about 0.005wt% to 5wt%, preferably about 0.01wt% to 0.1wt%. The above-mentioned seed crystals can be those commonly used in this technical field, such as but not limited to basic copper carbonate. Preferably, the reaction time of the crystal growth reaction is at least about 20 minutes to about 60 minutes, and the controlled temperature is in the range of about 30°C to about 70°C, preferably in the range of 50°C to about 60°C.

3 is a schematic diagram of the method for preparing copper carbonate or copper oxide from copper hydroxide or a copper salt mixture containing copper hydroxide according to the present invention.

Fig. 4 is a schematic diagram of a method for preparing copper hydroxide or a copper salt mixture containing copper hydroxide from copper-containing waste liquid, and then preparing copper carbonate or copper oxide through the method of the present invention.

The present invention further provides a method for preparing copper oxide from copper hydroxide or a copper salt mixture containing copper hydroxide. This method can further prepare the copper hydroxide or the copper salt mixture containing copper hydroxide prepared according to the present invention (such as the above-mentioned second embodiment) into copper oxide. In detail, this method contains:

(c) adding an acid to copper hydroxide or a copper salt mixture containing copper hydroxide to dissolve it into an acidic copper-containing solution; and

(d-2) adding alkali to the acidic copper-containing solution prepared in step (c), controlling the pH value in the range of about 9 to about 14, preferably in the range of about 12 to about 14, and controlling the temperature at about 80°C In the range between about 105°C and preferably between about 90°C and about 100°C, copper oxide is formed. The type of alkali added therein is not particularly limited, preferably sodium hydroxide.

Fig. 5 is a schematic diagram of the method for preparing copper hydroxide or a copper salt mixture containing copper hydroxide from copper-containing waste liquid according to the present invention, and then preparing copper oxide, which is first prepared by the method of the present invention. A copper salt mixture of copper.

The following examples are used to further illustrate the present invention, but not to limit the scope of the present invention. Any modifications and changes that can be easily achieved by those skilled in the art are included within the scope of the disclosure of this specification and the scope of the appended claims.

Example 1

Add phosphoric acid to the alkaline copper-containing waste liquid (copper content is 99.38 grams per liter), adjust the pH value between about 2 and about 6, undesired metal ions will react with phosphate to form insoluble phosphates, making Impurities are precipitated and filtered to remove impurities. The impurity contents in the purified copper-containing solution and the original solution are shown in Table 1 below:

Table I

Element Cu Al Ca Cd Cr Fe stock solution 99.38 (g/L) 3.04 (mg/L) 8.009(mg/L) 0.149(mg/L) 0.654(mg/L) 0.455(mg/L) Purified solution 99.38 (g/L) 1.96(mg/L) 2.545(mg/L) 0.076(mg/L) 0.456(mg/L) 0.242(mg/L) Purified% 0 35.52 68.22 48.89 30.28 46.81

(Continued from the above table)

Element Mg Mn Ni Pb Sn Zn stock solution 4.5 (mg/L) 3.258(mg/L) 17.54 (mg/L) 4.89 (mg/L) 5.5 (mg/L) 164 (mg/L) Purified solution 0.73(mg/L) 1.666(mg/L) 6.341 (mg/L) 3.8 (mg/L) 1.41 (mg/L) 7.06 (mg/L) Purified% 83.7 48.86 63.85 22.2 74.4 95.7

It can be seen from the data in the table that adding phosphoric acid to copper-containing waste liquid can precipitate various metal impurities, which is beneficial to remove undesired metal impurities, purify copper-containing waste liquid, and effectively reduce the proportion of undesired metal impurities in waste liquid .

Example 2

Sodium hydroxide is added to the acidic copper-containing waste liquid (copper content is 31.43 g/L), the pH value is adjusted to about 4.2 to precipitate impurities, and after the reaction is completed, 0.5 wt% sodium hypochlorite is added to continue the precipitation, and the impurities are removed by filtration. The impurity content in the purified copper-containing liquid and the stock solution is shown in Table 2 below:

Table II

Element Cu Al Ca Cd Cr Fe stock solution 31.43 (g/L) 0.5116(mg/L) 39.68 (mg/L) ND 0.139(mg/L) 24.53 (mg/L) pH adjusted purification solution 31.32 0.585 30.94 ND 0.1125 12.92 (g/L) (mg/L) (mg/L) (mg/L) (mg/L) Oxidant purification 31.32 (g/L) 0.272(mg/L) 26.41 (mg/L) ND 0.101(mg/L) 11.44 (mg/L) Purified% 0.34 53.5 33.4 - 19.1 53.4

(Continued from the above table)

Element Mg Mn Ni Pb Sn Zn stock solution 8.445(mg/L) 0.926(mg/L) 0.219(mg/L) ND ND 28.97(mg/L)

pH adjusted purification solution 6.857(mg/L) 0.776(mg/L) 0.1641(mg/L) ND ND 12.77 (mg/L) Oxidant purification 6.385(mg/L) 0.6928(mg/L) 0.1536(mg/L) ND ND 1.64 (mg/L) Purified% 6.9 10.7 6.4 - - 87.2

From the data in the table, it can be seen that adjusting the pH value and adding oxidants to the alkaline copper-containing waste liquid can precipitate various metal impurities, which is beneficial to remove undesired metal impurities, purify the copper-containing waste liquid, and effectively reduce the amount of impurities in the waste liquid. Undesirable ratio of metal impurities.

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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