Copper deposition coagulant, preparation method and application thereof, and method for treating copper-containing waste liquid

Abstract

The invention provides a copper deposition coagulant, a preparation method and application thereof and a method for treating copper-containing waste liquid. The copper deposition coagulant comprises MyCOxS3-x, M (OH) z and water, M is at least one of Na, K and Mg, x is larger than or equal to 0 and smaller than 3, y is 1 or 2, and z is 2 or 1. Therefore, the copper precipitation coagulant has obvious action effect, copper-containing precipitates in the copper-containing waste liquid can be coagulated into copper-containing particles with larger particle size, the copper-containing particles can be separated out by direct filter pressing, and filter pressing can be carried out without adding PAM (polyacrylamide), so that the use of a flocculating agent PAM in the copper recovery process is eliminated, and the copper recovery efficiency is improved. And therefore, the treatment process of the copper-containing waste liquid is simplified, the treatment cost of the copper-containing waste liquid is reduced, and meanwhile, the copper recovery efficiency is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and in particular to a copper precipitation coagulant, a preparation method thereof, an application thereof, and a method for treating copper-containing waste liquid. Background Art

[0002] The electrolytic copper industry and the electroplating copper industry are industries with relatively serious water pollution. The presence of organic matter, copper, inorganic salts and other components in their wastewater poses great harm to humans and the ecology. On the other hand, the presence of a large amount of high-value metal elements such as copper in copper-containing wastewater is a valuable secondary resource. Therefore, from the perspective of environmental protection and resource recycling, it is necessary to recycle the copper in copper-containing wastewater. The commonly used methods for recycling copper-containing wastewater are electrolysis and chemical precipitation. Among them, the electrolysis method requires the solution to be acidic, and when the copper ion content in the solution is reduced to below 10g / L, the efficiency of electrolysis will drop significantly. Therefore, it is usually combined with membrane concentration technology and chemical precipitation technology to recover copper in the solution; the chemical precipitation method mainly uses sodium hydroxide to precipitate the copper ions in the copper-containing wastewater. During the precipitation process, a precipitate mainly composed of copper hydroxide or basic copper sulfate is generated. The generated precipitate can be filtered to obtain valuable copper-containing products. However, since the generated precipitate particles are very fine (nearly nanometer level), it is difficult to filter, which greatly affects the treatment efficiency of the copper-containing wastewater. Summary of the Invention

[0003] The present invention aims to solve, at least to some extent, one of the technical problems in the related art. To this end, one object of the present invention is to provide a copper precipitation coagulant that can effectively separate copper from copper-containing wastewater and improve the treatment efficiency of the copper-containing wastewater.

[0004] In one aspect of the present invention, the present invention provides a copper deposition coagulant. According to an embodiment of the present invention, the copper deposition coagulant comprises M y CO x S 3-x 、M(OH) z and water, wherein M is at least one of Na, Ka and Mg, 0≤x<3, y is 1 or 2, and z is 2 or 1. Thus, the effect of the copper precipitation coagulant is obvious: due to the M in the copper precipitation coagulant y CO x S 3-xThere is a strong interaction force between the sulfur in the copper-containing waste liquid and the copper in the copper-containing waste liquid, and the copper-precipitating coagulant is easily soluble in water, so that an interaction force occurs between the sulfur-containing group and the copper-containing precipitate. The interaction force will bond one or more particles to the periphery of the copper-precipitating coagulant like a bridge, and several or more particles will be condensed in a short time, resulting in a rapid increase in particle size, that is, the copper-containing precipitate in the copper-containing waste liquid will be condensed into copper-containing particles with a larger particle size, which can be directly separated by filter pressing. The copper-containing particles can be separated without adding PAM (polyacrylamide) for filter pressing, which eliminates the use of flocculant PAM in the copper recovery process, thereby simplifying the treatment process of the copper-containing waste liquid, reducing the treatment cost of the copper-containing waste liquid, and improving the efficiency of copper recovery. Moreover, the economic value of the separated copper-containing product is high, the copper-precipitating coagulant does not contain metal cations such as iron and aluminum, and the main body of the coagulant effect is a sulfur-containing anion group, so that no metal impurity ions are introduced into the product, thereby helping to improve the economic value of the separated copper-containing product. In addition, the sulfur in the product can be converted into sulfuric acid during smelting, further improving the economic value of the product.

[0005] According to an embodiment of the present invention, the copper deposition coagulant further includes at least one of ether and M2CO3.

[0006] According to an embodiment of the present invention, 0≤x≤1.

[0007] According to an embodiment of the present invention, based on the total mass of the copper deposition coagulant, the copper deposition coagulant comprises: 30% to 60% of M y CO x S 3-x ; 2% to 8% M(OH) z ; 0.5% to 1.5% ether; 0.5% to 1.5% M2CO3; and 29% to 67% water.

[0008] According to an embodiment of the present invention, the copper deposition coagulant comprises: 40% to 50% of M y CO x S 3-x ; 4% to 6% M(OH) z ; 0.8% to 1.2% ether; 0.8% to 1.2% M2CO3; and 41.6% to 54.4% water.

[0009] According to an embodiment of the present invention, based on the total mass of the copper deposition coagulant, the copper deposition coagulant further comprises: 0-5% N2S, where N is at least one of Na and K.

[0010] In another aspect of the present invention, the present invention provides a method for preparing the copper deposition coagulant described above. According to an embodiment of the present invention, the method for preparing the copper deposition coagulant comprises: providing a raw material mixed solution, wherein the raw material mixed solution comprises M(OH) z , N2S and water, wherein M is at least one of Na, Li, Ka and Mg, N is at least one of Na and Ka, wherein z is 2 or 1; carbon disulfide gas is introduced into the raw material mixed solution, and the copper precipitation coagulant is obtained after the reaction. Thus, M in the copper precipitation coagulant prepared by the above method is y CO x S 3-x There is a strong interaction force between the sulfur in the copper-containing waste liquid and the copper in the copper-containing waste liquid, so that an interaction force occurs between the sulfur-containing group and the copper-containing precipitate, which can effectively agglomerate the copper-containing precipitate into copper-containing particles with a larger particle size, and then directly perform filter pressing to separate the copper-containing particles, thereby avoiding the use of a flocculant PAM (polyacrylamide), simplifying the treatment process of the copper-containing waste liquid, reducing the treatment cost of the copper-containing waste liquid, and improving the copper recovery efficiency; at the same time, the above-mentioned preparation method is simple, mild in conditions, cheap in raw materials, and low in preparation cost, thereby greatly reducing the treatment cost of the copper-containing waste liquid.

[0011] According to an embodiment of the present invention, the raw material mixed solution further includes at least one of diethyl ether and M2CO3.

[0012] According to an embodiment of the present invention, based on the total mass of the raw material mixed solution, the raw material mixed solution comprises: 25% of M(OH) z ; 1% ether; 1% M2CO3; 30% N2S; and the balance water.

[0013] According to an embodiment of the present invention, the molar amount of carbon disulfide is equal to the molar amount of M(OH) in the raw material solution. z The ratio of the molar amount of nitrogen to the sum of the molar amounts of N2S is 2.2:3 to 2.4:3.

[0014] In another aspect, the present invention provides a use of the aforementioned copper precipitation coagulant in the treatment of copper-containing wastewater, thereby effectively improving the efficiency of copper recovery from the copper-containing wastewater and reducing the recovery cost.

[0015] In another aspect, the present invention provides a method for treating copper-containing waste liquid using the copper-precipitating coagulant. According to an embodiment of the present invention, the method for treating copper-containing waste liquid using the copper-precipitating coagulant comprises: adjusting the pH of the copper-containing waste liquid to alkaline; adding the copper-precipitating coagulant to the copper-containing waste liquid and stirring to obtain a mixture of copper-containing particles; and filtering the mixture of copper-containing particles to obtain copper-containing particles and treated waste liquid. This method for treating copper-containing waste liquid is simple, requires mild conditions, has low implementation costs, and achieves high copper recovery efficiency.

[0016] According to an embodiment of the present invention, the copper-containing particles have a particle size of 40 to 100 micrometers.

[0017] According to an embodiment of the present invention, the filtration uses a filter cloth with a mesh size of 200 to 800. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the following description of the embodiments with reference to the accompanying drawings, in which:

[0019] Figure 1 This is a schematic diagram of the working principle of a copper precipitation flocculant in one embodiment of the present invention;

[0020] Figure 2 is a particle size distribution diagram of copper-containing particles before and after treatment with the copper precipitation flocculant in Example 1;

[0021] Figure 3 This is a diagram of the particle size distribution of copper-containing particles before and after treatment with the copper precipitation flocculant in Example 2. DETAILED DESCRIPTION

[0022] Below, the scheme of the present invention will be explained in conjunction with embodiment.It will be understood by those skilled in the art that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention.In the embodiment, if specific technology or conditions are not indicated, the technology or conditions described in the literature in this area or the product instructions are used.The reagents or instruments used are not indicated by the manufacturer, and are all conventional products that can be obtained by commercial purchase.

[0023] The present invention is described below with reference to specific examples. It should be noted that these examples are merely illustrative and do not limit the present invention in any way.

[0024] In one aspect of the present invention, the present invention provides a copper deposition coagulant. According to an embodiment of the present invention, the copper deposition coagulant comprises M y CO x S 3-x 、M(OH) zand water, wherein M is at least one of Na, Ka and Mg, 0≤x<3, y is 1 or 2, and z is 2 or 1. Thus, the effect of the copper precipitation coagulant is obvious: due to the M in the copper precipitation coagulant y CO x S 3-x There is a strong interaction force between the sulfur in the copper-containing waste liquid and the copper in the copper-containing waste liquid, and the copper-precipitating coagulant is easily soluble in water, so that an interaction force occurs between the sulfur-containing group and the copper-containing precipitate. The interaction force will bond one or more particles to the periphery of the copper-precipitating coagulant like a bridge, and several or more particles will be condensed in a short time, resulting in a rapid increase in particle size, that is, the copper-containing precipitate in the copper-containing waste liquid will be condensed into copper-containing particles with a larger particle size, which can be directly separated by filter pressing, and filter pressing can be performed without adding PAM (polyacrylamide), that is, the use of flocculant PAM in the copper recovery process is eliminated, thereby simplifying the treatment process of the copper-containing waste liquid, reducing the treatment cost of the copper-containing waste liquid, and improving the efficiency of copper recovery. Moreover, the economic value of the separated copper-containing product is high. The copper precipitation coagulant does not contain metal cations such as iron and aluminum, and the main body of the coagulant is the sulfur-containing anion group, so no metal impurity ions are introduced into the product, thereby helping to improve the economic value of the separated copper-containing product. In addition, the sulfur in the product can be converted into sulfuric acid during smelting, further improving the economic value of the product. Furthermore, M(OH) z Provide a certain alkaline environment for copper deposition coagulant to prevent M y CO x S 3-x Decomposed to produce hydrogen sulfide.

[0025] According to some embodiments of the present invention, the copper deposition coagulant further comprises at least one of ether and M2CO3. Among them, ether is used as a catalyst to accelerate the generation of MCO3 in the process of synthesizing the copper deposition coagulant. x S 3-x catalyst, thereby improving the efficiency of preparing copper precipitation coagulant; in the process of filter pressing to separate copper-containing particles, M2CO3 can make the flow rate of the filtrate in the filter pressing faster, so that the dehydration effect of the copper-containing particles (or copper mud) is better, and the water content in the obtained copper-containing particles (or copper mud) is less.

[0026] Among them, in some embodiments of the present invention, M y CO x S 3-x 、M(OH) z The metal M elements in M2CO3 are independent of each other, that is, the metal elements M in the three can be the same or different. y CO x S 3-x The M element is sodium, M(OH) zThe metal M in M2CO3 is potassium, the metal M in M2CO3 is sodium; or the element M in the above three materials is sodium or potassium.

[0027] In some embodiments of the present invention, M is preferably at least one of Na or K, which can ensure that MCO in the copper deposition coagulant is x S 3-x The good water solubility of solutes such as MOH and M2CO3 makes it difficult to produce precipitation or crystallization, thus ensuring the good chemical stability of the copper precipitation coagulant, which is beneficial to the coagulation effect of the copper precipitation coagulant. If other cations are selected, the water solubility of the copper precipitation coagulant will be affected, thereby affecting the coagulation effect of the coagulant, that is, affecting the separation effect of copper in copper-containing wastewater.

[0028] According to some embodiments of the present invention, 0≤x≤1, M y CO x S 3-x M y CS3 or M y The above two substances have better condensation effects on copper-containing precipitates and are easier to obtain during the preparation process.

[0029] According to some embodiments of the present invention, based on the total mass of the copper deposition coagulant, the copper deposition coagulant includes: 30% to 60% (for example, 30%, 33%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 57%, 60%, etc.) of M y CO x S 3-x ; 2% to 8% (e.g., 2%, 3%, 4%, 5%, 6%, 7%, 8%, etc.) of M(OH) z ; 0.5% to 1.5% (e.g., 0.5%, 0.7%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc.) of ether; 0.5% to 1.5% (e.g., 0.5%, 0.7%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc.) of M2CO3; and 29% to 67% of water. y CO x S 3-x As the main coagulant component of copper deposition coagulant, if M y CO x S 3-x The concentration is too low, MCO per unit volume x S 3-x The concentration of M is relatively low, which is not conducive to the agglomeration of copper-containing precipitates into large particles; if M y CO x S 3-xIf the concentration is too high, it may cause excessive sulfur content in the local area when added to the reaction vessel, and there is a risk of hydrogen sulfide precipitation; y CO x S 3-x The content is 30% to 60%, which can effectively make the copper precipitate condense into large-sized copper-containing particles, while ensuring that the risk of hydrogen sulfide precipitation in the reaction vessel is not likely to occur, thereby improving the safety of the implementation. z It is mainly used to provide synthetic raw materials and alkaline environment for the synthesis process of copper precipitation coagulant. The alkaline environment is mainly used to prevent the overflow of hydrogen sulfide in the synthesis process and after synthesis. Therefore, if it is alkaline M(OH) z If the concentration is too low, the pH of the solution after the copper precipitation coagulant is synthesized will be low, and the risk of hydrogen sulfide precipitation will increase significantly; if the alkali concentration is too high, the cost of preparing the copper precipitation coagulant will increase, and excessive hydroxide may also cause the copper-containing precipitate to dissolve back into the aqueous solution, reducing the particle size of the copper-containing precipitate, which is not conducive to the coagulation of the copper-containing precipitate; M(OH) z The content of 2% to 8% provides a certain alkaline environment for the copper precipitation coagulant aqueous solution, avoids the precipitation of hydrogen sulfide, and at the same time improves the coagulation effect of copper-containing precipitation, which is conducive to obtaining coagulated large-size copper-containing particles. Ether is used as a catalyst to accelerate the generation of M in the process of synthesizing copper precipitation coagulants. y CO x S 3-x If the ether concentration is low, the reaction acceleration effect is not obvious; if the ether concentration is high, there is a risk of ether volatilization. In the process of filter press separation of copper-containing particles, M2CO3 can make the flow rate of the filtrate in the filter press faster, the dehydration effect of the copper-containing particles (or copper mud) is better, and the water content of the obtained copper-containing particles (or copper mud) is less; if the M2CO3 concentration is too low, the promoting effect on the filter press of the copper-containing mud is low; if the M2CO3 concentration is too high, the processing cost will increase; the M2CO3 content is 0.5% to 1.5%, while improving the dehydration effect of the copper-containing particles, it tries to reduce the overall cost of the copper precipitation coagulant.

[0030] According to some embodiments of the present invention, the copper deposition coagulant comprises: 40% to 50% of M y CO x S 3-x ; 4% to 6% M(OH) z ; 0.8% to 1.2% ether; 0.8% to 1.2% M2CO3; and 41.6% to 54.4% water. The copper precipitation coagulant with the above ratio has a better copper precipitation and coagulation effect.

[0031] According to some embodiments of the present invention, based on the total mass of the copper deposition coagulant, the copper deposition coagulant further comprises: 0-5% N2S, where N is at least one of Na and Ka.2- In the process of treating copper-containing wastewater, S 2- It can further combine with the copper ions in the supernatant, so that the content of copper ions in the supernatant is further reduced, and the copper content in the copper mud is increased; in addition, the interaction force between copper and sulfur is much greater than the interaction force between copper and organic matter. Therefore, the presence of N2S can make this coagulant have a certain ability to break the complexation between copper and organic matter, that is, the ability to break the complexation, thereby improving its ability to condense copper.

[0032] In another aspect of the present invention, the present invention provides a method for preparing the copper deposition coagulant described above. According to an embodiment of the present invention, the method for preparing the copper deposition coagulant comprises:

[0033] S100: Providing a raw material mixed solution, the raw material mixed solution includes M(OH) z , N2S and water, wherein M is at least one of Na, Li, Ka and Mg, N is at least one of Na and Ka, and z is 2 or 1.

[0034] According to some embodiments of the present invention, the raw material mixed solution further comprises at least one of ether and M2CO3. Among them, ether is used as a catalyst to accelerate the generation of M2CO3 in the process of synthesizing the copper precipitation coagulant. y CO x S 3-x The catalyst can improve the efficiency of preparing copper precipitation coagulant, that is, compared with the reaction without adding ether, after adding ether, M y CO x S 3-x The rate is greatly improved; in the process of filter pressing to separate copper-containing particles, M2CO3 can make the flow rate of the filtrate in the filter pressing faster, so that the dehydration effect of the copper-containing particles (or copper mud) is better, and the water content in the obtained copper-containing particles (or copper mud) is less.

[0035] According to some embodiments of the present invention, based on the total mass of the raw material mixed solution, the raw material mixed solution includes: 20%-30% of M(OH) z ; 0.5%-1.5% ether; 0.5%-1.5% M2CO3; 25%-35% N2S; and the balance water. In some specific embodiments, the raw material mixed solution includes: 25% MOH; 1% ether; 1% M2CO3; 30% M2S; and the balance water.

[0036] S200: introducing carbon disulfide gas into the raw material mixed solution to obtain a copper deposition coagulant after reaction.

[0037] According to some embodiments of the present invention, the molar amount of carbon disulfide is equal to the molar amount of M(OH) in the raw material solution. zThe ratio of the sum of the molar amounts of carbon disulfide and N2S is 2.2:3 to 2.4:3, such as 2.2:3, 2.25:3, 2.3:3, 2.35:3, and 2.4:3. This can effectively ensure the full reaction of carbon disulfide and avoid the waste of raw materials; ensure that M(OH) z With sufficient amount of M2S, it further provides a good alkaline environment for the reflection environment and the obtained copper precipitation coagulant, avoiding the generation of hydrogen sulfide.

[0038] After carbon disulfide gas is introduced into the raw material mixed solution, carbon disulfide reacts with M(OH) z Reacts with N2S (taking M and N as metallic sodium as an example, the reaction includes: 2NaOH+CS2=Na2COS2+H2O; Na2S+CS2=Na2CS3), and the solution after the reaction is MCxO 3-x , M2CO3, ether, M(OH) z The mixed aqueous solution is the copper precipitation flocculant. z and N2S as the reaction raw materials, while M(OH) z It also provides an alkaline environment for the synthesis process of copper precipitation coagulant, which can effectively prevent the overflow of hydrogen sulfide in the synthesis process and after synthesis; ether is used as a catalyst to accelerate the generation of M in the process of preparing synthetic copper precipitation coagulant. y CO x S 3-x The catalyst accelerates the reaction of carbon disulfide with M(OH) z , N2S reaction; M2CO3 does not participate in the reaction process, but in the subsequent process of filter pressing to separate copper-containing particles, M2CO3 can make the flow rate of the filtrate in the filter pressing faster, the dehydration effect of the copper-containing particles (or copper mud) is better, and the water content in the obtained copper-containing particles (or copper mud) is less.

[0039] Furthermore, N2S can be excessive in the above raw materials, so that the copper precipitation coagulant obtained will also include a certain amount of N2S. In the process of treating copper-containing waste liquid, the S in the copper precipitation coagulant 2- It can further combine with the copper ions in the supernatant, so that the content of copper ions in the supernatant is further reduced, and the copper content in the copper mud is increased; in addition, the interaction force between copper and sulfur is much greater than the interaction force between copper and organic matter. Therefore, the presence of N2S can make this coagulant have a certain ability to break the complexation between copper and organic matter, that is, the ability to break the complexation, thereby improving its ability to condense copper.

[0040] In some embodiments, carbon disulfide and M(OH) z The reaction of N2S can be carried out at room temperature. It can be seen that the process conditions for preparing the copper precipitation coagulant by the above method are mild, which is conducive to further reducing the process cost.

[0041] According to some embodiments of the present invention, the copper deposition coagulant prepared by the above method has obvious effects: due to the M in the copper deposition coagulant y CO x S 3-x There is a strong interaction force between the sulfur in the copper-containing waste liquid and the copper in the copper-containing waste liquid, and the copper-precipitating coagulant is easily soluble in water, so that an interaction force occurs between the sulfur-containing group and the copper-containing precipitate. The interaction force will bond one or more particles to the periphery of the copper-precipitating coagulant like a bridge, and several or more particles will be condensed in a short time, resulting in a rapid increase in particle size, that is, the copper-containing precipitate in the copper-containing waste liquid will be condensed into copper-containing particles with a larger particle size, which can be directly separated by filter pressing. The copper-containing particles can be separated without adding PAM (polyacrylamide) for filter pressing, which eliminates the use of flocculant PAM in the copper recovery process, thereby simplifying the treatment process of the copper-containing waste liquid, reducing the treatment cost of the copper-containing waste liquid, and improving the efficiency of copper recovery. Moreover, the economic value of the separated copper-containing product is high, the copper-precipitating coagulant does not contain metal cations such as iron and aluminum, and the main body of the coagulant effect is a sulfur-containing anion group, so that no metal impurity ions are introduced into the product, thereby helping to improve the economic value of the separated copper-containing product. In addition, the sulfur in the product can be converted into sulfuric acid during smelting, further improving the economic value of the product. Furthermore, the process for preparing the copper precipitation coagulant by the above method has cheap synthetic raw materials, simple synthetic process, mild synthetic conditions and low synthetic cost. The obtained copper precipitation coagulant plays a role in the copper recycling process, and the utilization rate of the synthesized product is high, so that the copper precipitation coagulant of the present invention has a high cost performance.

[0042] In another aspect, the present invention provides a use of the aforementioned copper precipitation coagulant in the treatment of copper-containing wastewater, thereby effectively improving the efficiency of copper recovery from the copper-containing wastewater and reducing the recovery cost.

[0043] According to embodiments of the present invention, the copper precipitation coagulant of the present invention can be applied to the treatment of copper-containing waste liquid in any industry. In some embodiments, the copper precipitation coagulant of the present invention can be applied to the treatment of copper-containing waste liquid in the PCB industry, copper-containing waste liquid in the electroplating copper industry, copper-containing waste liquid in the electrolytic copper industry, and copper-containing waste liquid in the lithium battery copper foil industry. Thus, the application field of the copper precipitation coagulant of the present invention has no special restrictions and has a relatively broad application field.

[0044] In another aspect of the present invention, the present invention provides a method for treating copper-containing waste liquid using the copper precipitation coagulant. According to an embodiment of the present invention, the method for treating copper-containing waste liquid using the copper precipitation coagulant comprises:

[0045] T100: Adjust the pH of copper-containing wastewater to alkaline.

[0046] In some embodiments, the pH of the copper-containing waste liquid can be adjusted to 8-9 using an alkali such as sodium hydroxide or potassium hydroxide. This is conducive to the generation of copper-containing precipitates such as basic copper sulfate, copper hydroxide, or a mixture of the two from the copper-containing waste liquid.

[0047] T200: Add copper precipitation coagulant to the copper-containing waste liquid and stir to obtain a copper-containing particle mixture.

[0048] In this process, if Figure 1 As shown ( Figure 1 Taking M2CO1S2 as an example), due to the M y CO x S 3-x The interaction between the sulfur-containing groups and copper is extremely strong. The sulfur-containing groups act like bridges, connecting one or more copper-containing particles together, causing the copper-containing particles to rapidly increase in size. After adding the coagulant, the D50 of the copper hydroxide or basic copper sulfate particles can rapidly increase from a few microns to tens of microns. In some embodiments of the present invention, the particle size D50 of the copper-containing particles can reach 40 to 100 microns, for example, 40 to 50 microns, 50 to 60 microns, 60 to 70 microns, 70 to 80 microns, 80 to 90 microns, and 90 to 100 microns.

[0049] The dosage and concentration of the copper precipitation coagulant can be flexibly adjusted according to actual conditions such as the copper content in the copper-containing waste liquid and the volume of the copper-containing waste liquid to be treated, and no limitation is imposed here.

[0050] T300: Filter the copper-containing particle mixture to obtain copper-containing particles and treated waste liquid.

[0051] In some embodiments of the present invention, due to the rapid increase in the particle size of the copper-containing particles, the precipitate can be directly subjected to filter pressing, thereby avoiding the problem of the introduction of copper mud impurities caused by the addition of polyferric chloride / polyaluminum chloride and PAM, while reducing the processing cost and reducing the processing steps of copper-containing waste mud.

[0052] Moreover, since the copper precipitation coagulant also contains some sodium carbonate, the flow rate of the filtrate in the filter press is faster, the dehydration effect of the copper mud is better, the water content in the copper mud is less, and the transportation cost of the copper mud is reduced. At the same time, if the copper precipitation coagulant further contains S 2- , S 2-It is also possible to further combine with copper ions in the supernatant to cause the content of copper ions in the supernatant to further decrease, thereby increasing the content of copper in the copper mud. In addition, when N2S is further included in the copper precipitation coagulant, since the force between copper and sulphur is much greater than the force between copper and organic matter, the presence of N2S can make this coagulant also have the ability to certain break the complexation of copper and organic matter, i.e., broken network ability, and then promote the ability of its condensation of copper. In addition, the method for the above-mentioned treatment of copper-containing waste liquid is simple, mild conditions, low implementation cost, and high copper recovery efficiency.

[0053] According to some embodiments of the present invention, in step T300, a filter cloth of 200 to 800 mesh (such as 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, 550 mesh, 600 mesh, 650 mesh, 700 mesh, 750 mesh, 800 mesh, etc.) is used for filtration. The particle size of the copper-containing particles obtained in the present invention is relatively large, and a filter cloth of a lower mesh number can be used for filtration and collection, thereby greatly reducing the difficulty of filtration and shortening the duration of filtration. In some specific embodiments, a filter cloth of 300 to 600 mesh can be used to filter and recycle the copper-containing particles. If the copper precipitation coagulant of the present invention is not used, that is, the pH is adjusted to 10 to 11 in step T100, the copper-containing waste liquid generates copper-containing precipitates such as basic copper sulfate, copper hydroxide or a mixture of the two, and then directly filters, it is necessary to filter the copper-containing precipitate for several hours (such as more than 4 hours) with a filter cloth of more than 2000 mesh (such as 2500 mesh). Moreover, in comparison of the above two treatment methods, it was found that the copper content in the wet copper mud obtained without adding the copper precipitation coagulant was about 29%. After adding the copper precipitation coagulant, the copper content in the wet copper mud increased to about 35%, and the water content decreased from about 47.29% without adding the copper precipitation coagulant to about 44.99%, greatly improving the economic value of the copper-containing sludge.

[0054] Example

[0055] Example 1

[0056] First, 4 mol of CS2 is passed into a solution containing 2 mol of NaOH, 0.5% ether by mass, 0.5 mol / L of sodium carbonate and 4 mol of Na2S, and reacted at room temperature for 5 minutes to obtain a copper precipitation coagulant. At this time, the solution after the reaction is a copper precipitation coagulant A composed of Na2COS2 as the main component, Na2CS3 as the auxiliary component, 0.5% ether, 0.5% sodium carbonate and other substances. The copper precipitation coagulant A is configured to a concentration of 30% for standby use, that is, a copper precipitation coagulant mixed solution B, which includes 30% Na2CO x S 3-x , 4% NaOH, 0.5% ether and 0.5% sodium carbonate.

[0057] Second, copper-containing waste liquid was tested. The copper content in the copper-containing waste liquid was 8960 mg / L, COD was 1095 mg / L, pH was 0.13, and the main anion was SO4 2- A certain amount of alkali NaOH is added to adjust the pH of the copper-containing waste liquid to 9. At this time, the copper-containing precipitate generated in the copper-containing waste liquid is a mixture of basic copper sulfate and copper hydroxide, and its particle size distribution is as follows: Figure 2 As shown in (a), the D50 of the copper-containing precipitate is 6.5 μm, the copper content of the wet mud containing the copper precipitate is 29.51%, and the copper content of the supernatant is 65.43 ppm (the original solution contains some complexed copper, and adding alkali cannot precipitate the copper in the complexed copper).

[0058] Third, 270 mg / L of the copper precipitation coagulant mixed solution B was added (i.e., 270 mg of the copper precipitation coagulant mixed solution B was used in 1 liter of copper-containing waste liquid). The pH of the copper-containing waste liquid increased from 9 to 10.5. After stirring for 4 minutes, the particle size of the copper-containing particles increased significantly. At this time, the D50 of the copper-containing particles increased rapidly from 6.5 μm to 69 μm, an increase of 9.61 times (its particle size distribution is shown in FIG. Figure 2 Under these conditions, copper particles can be filtered and recovered using a 300-mesh filter cloth. After 2 hours of filtration through a 300-mesh filter cloth, the resulting wet copper sludge contained 35.12% copper by mass, a 19.01% increase compared to the pre-filtered copper flocculant, significantly increasing the value of the copper sludge. The copper content of the filtered supernatant was 7.97 ppm, an 87.82% decrease compared to the pre-filtered copper flocculant, reducing the difficulty of subsequent supernatant processing.

[0059] Example 2

[0060] First, 4 mol of CS2 is passed into a solution containing 2 mol of KaOH, 1.5% of ether, 2 mol / L of potassium carbonate and 5 mol of Ka2S, and reacted at room temperature for 4 minutes to obtain a copper precipitation coagulant. At this time, the solution after the reaction is a copper precipitation coagulant A composed of Ka2CS3 as the main component, Ka2COS2 as the auxiliary component, 1.5% of ether, 1.5% of potassium carbonate and other substances. The copper precipitation coagulant A is configured to a concentration of 60% for standby use, that is, a copper precipitation coagulant mixed solution B, which includes 60% of Ka2CO x S 3-x , 6% KaOH, 1.5% ether and 1.5% potassium carbonate.

[0061] Second, the copper-containing waste liquid from the PCB factory was tested. The copper content in the copper-containing waste liquid was 23142 mg / L, COD was 456 mg / L, pH was 0.05, and the main anion was Cl -A certain amount of alkali KaOH is added to adjust the pH of the copper-containing waste liquid to 9. At this time, the copper-containing precipitate generated in the copper-containing waste liquid is copper oxide (due to the large amount of alkali added and the high solution temperature, copper hydroxide is converted into copper oxide). Its particle size distribution is as follows: Figure 3 As shown in (a), at this time, the D50 of the copper-containing precipitate is 5 μm, the copper content of the wet mud of the copper-containing precipitate is 31.25%, and the copper content of the supernatant is 31.31 ppm.

[0062] Third, 540 mg / L of the copper precipitation coagulant mixed solution B was added (i.e., 540 mg of the copper precipitation coagulant mixed solution B was used in 1 liter of copper-containing waste liquid). The pH of the copper-containing waste liquid increased from 9 to 10.7. After stirring for 3 minutes, the particle size of the copper-containing particles increased significantly. At this time, the D50 of the copper-containing particles increased rapidly from 5 μm to 75 μm, an increase of 15 times (the particle size distribution is shown in FIG. Figure 3 (b) Under these conditions, a 250-mesh filter cloth can be used to filter and recover copper particles. After 1.5 hours of filtration through a 250-mesh filter cloth, the resulting wet copper sludge has a copper content of 35.79%, a 14.53% increase compared to the pre-filtered copper flocculant, significantly increasing the value of the copper sludge. The copper content of the filtered supernatant is 5.13 ppm, an 83.61% decrease compared to the pre-filtered copper flocculant, reducing the difficulty of subsequent supernatant processing.

[0063] Example 3

[0064] First, 4 mol of CS2 is passed into a solution containing 2 mol of NaOH, 1% ether, 1 mol / L of sodium carbonate and 5 mol of Na2S, and reacted at room temperature for 4 minutes to obtain a copper precipitation coagulant. At this time, the solution after the reaction is a copper precipitation coagulant A composed of Na2CS3 as the main component, Na2COS2 as the auxiliary component, 1% ether, 1% sodium carbonate and other substances. The copper precipitation coagulant A is configured to a concentration of 45% for standby use, that is, a copper precipitation coagulant mixed solution B, which includes 45% Na2CO x S 3-x , 5% NaOH, 1% ether and 1% sodium carbonate.

[0065] Second, the copper-containing waste liquid from the electroplating copper foil factory was tested. The copper content in the copper-containing waste liquid was 1156 mg / L, COD was 695 mg / L, pH was 0.05, and the main anion was SO4 2- A certain amount of alkali NaOH was added to adjust the pH of the copper-containing waste liquid to 9. At this time, the copper-containing precipitate generated in the copper-containing waste liquid was a mixture of basic copper sulfate and copper hydroxide. At this time, the D50 of the copper-containing precipitate was 6.92 μm, the copper content of the wet mud of the copper-containing precipitate was 30.16%, and the copper content of the supernatant was 54.31 ppm (the original solution contained some complexed copper, and the addition of alkali could not precipitate the copper in the complexed copper).

[0066] Third, 135 mg / L of the above-mentioned copper-precipitating coagulant mixed solution B was added (i.e., 135 mg of copper-precipitating coagulant mixed solution B was used in 1 liter of copper-containing waste liquid). The pH of the copper-containing waste liquid rose from 9 to 10. After stirring for 4 minutes, the particle size of the copper-containing particles increased significantly. At this time, the D50 of the copper-containing particles rapidly increased from 6.92 μm to 65 μm, an increase of 8.39 times. Under this condition, the copper-containing particles can be filtered and recovered using a 300-mesh filter cloth. The mass content of copper in the wet copper mud obtained after 2 hours of pressure filtration with a 300-mesh filter cloth was 33.74%, an increase of 11.87% over that before the addition of the copper-precipitating coagulant, which greatly increased the value of the copper mud. Among them, the copper content of the supernatant after filtration was 10.96 ppm, a decrease of 79.82% over that before the addition of the copper-precipitating coagulant, which reduced the difficulty of subsequent supernatant treatment.

[0067] Example 4

[0068] First, 4 mol of CS2 is passed into a solution containing 2 mol of NaOH and 4 mol of Na2S, and the reaction is carried out at room temperature for 30 minutes to obtain a copper precipitation coagulant. At this time, the solution after the reaction is a copper precipitation coagulant A mainly composed of Na2COS2 and Na2CS3. The copper precipitation coagulant A is configured to a concentration of 30% for standby use, that is, a copper precipitation coagulant mixed solution B, which includes 30% Na2CO x S 3-x and 4% NaOH.

[0069] Second, the same copper-containing waste liquid as in Example 1 was tested. The copper content in the copper-containing waste liquid was 8960 mg / L, COD was 1095 mg / L, pH was 0.13, and the main anion was SO4 2- A certain amount of alkali NaOH was added to adjust the pH of the copper-containing waste liquid to 9. At this time, the copper-containing precipitate generated in the copper-containing waste liquid was a mixture of basic copper sulfate and copper hydroxide. At this time, the D50 of the copper-containing precipitate was 5.9 μm, the copper content of the wet mud of the copper-containing precipitate was 28.31%, and the copper content of the supernatant was 67.21 ppm (the original solution contained some complexed copper, and the addition of alkali could not precipitate the copper in the complexed copper).

[0070] Third, 270 mg / L of the above-mentioned copper-precipitating coagulant mixed solution B (i.e., 270 mg of copper-precipitating coagulant mixed solution B is used in 1 liter of copper-containing waste liquid) is added. The pH of the copper-containing waste liquid rises from 9 to 10.1. After stirring for 4 minutes, the particle size of the copper-containing particles increases significantly. At this time, the D50 of the copper-containing particles rises rapidly from 5.9 μm to 65 μm, an increase of 10.02 times. The supernatant copper content is reduced to 9.53 ppm. Under this condition, the copper-containing particles can be filtered and recovered using a 300-mesh filter cloth. The content of copper in the wet copper mud obtained after 2 hours of filter press filtration using a 300-mesh filter cloth is 32.01%.

[0071] Comparative Example 1

[0072] The copper-containing waste liquid in Example 1 was tested. The copper content in the copper-containing waste liquid was 8931 mg / L, COD was 995 mg / L, pH was 0.13, and the main anion was SO4 2- The pH of the solution was adjusted to 10.5 by adding a certain amount of alkali. The copper precipitate produced under these conditions had a D50 of 6.46 μm. The solution was filtered for 4.5 hours using a 2500-mesh filter cloth. The resulting copper sludge had a copper content of 29.32%, and the supernatant had a copper content of 65.51 ppm.

[0073] Comparative Example 2

[0074] The copper-containing waste liquid in Example 2 was tested. The copper content in the copper-containing waste liquid was 23187 mg / L, COD was 431 mg / L, pH was 0.08, and the main anion was Cl - The pH of the solution was adjusted to 10.7 by adding a certain amount of alkali. Under these conditions, the copper-containing precipitated copper oxide produced had a D50 of 5.2 μm. The solution was filtered using a 3000-mesh filter cloth for 5.5 hours. The resulting copper sludge had a copper content of 30.14%, and the supernatant had a copper content of 29.56 ppm.

[0075] Comparative Example 3

[0076] The copper-containing waste liquid in Example 3 was tested. The copper content in the copper-containing waste liquid was 1156 mg / L, COD was 652 mg / L, pH was 0.05, and the main anion was SO4 2- The solution's pH was adjusted to 10 by adding a certain amount of alkali. The resulting copper precipitate was a mixture of basic copper sulfate and copper hydroxide, with a D50 of 6.13 μm. The solution was filtered for 4.5 hours using a 2500-mesh filter press. The resulting copper sludge had a copper content of 30.03%, and the supernatant had a copper content of 53.43 ppm.

[0077] The test data in the above embodiments and comparative examples can be found in Table 1.

[0078] Table 1

[0079]

[0080] It can be seen from the data of the examples and comparative examples in Table 1 above that the copper precipitation coagulant of the present invention has significant effects in reducing the copper content of the supernatant, increasing the copper content in the copper mud, and increasing the particle size of copper-containing particles.

[0081] By comparing Example 4 with Example 1, it can be seen that the addition of an appropriate amount of ether can greatly accelerate the preparation process of the copper precipitation flocculant (the reaction order in Example 1 is 5 minutes, while the reaction in Example 4 is 30 minutes). At the same time, the addition of sodium carbonate can increase the copper mud content after filter pressing. The copper precipitation flocculant in Example 1 increased by 3.11% compared with that in Example 4 in which sodium carbonate was added.

[0082] Among them, the parameter test method is:

[0083] Copper content: The copper content of the copper sludge and the supernatant in the above embodiment was tested by ICP (equipment model: PerkinElmer AVi200). A certain amount of supernatant was taken, the solution was diluted a certain number of times so that the copper content in the solution was within the range of the ICP standard solution, and the sample was injected for measurement; a certain amount of copper-containing sludge was dissolved in aqua regia, and after dissolution, the supernatant was filtered to obtain the supernatant, and the supernatant was diluted a certain number of times so that the copper content in the supernatant was within the range of the ICP standard solution, and the sample was injected for measurement.

[0084] COD test: COD test adopts potassium dichromate method (equipment model: Lianhua Technology LH-T600), and the measurement method is GB11914-89.

[0085] Particle size test: The particle size was determined using a laser particle size analysis method (equipment model: Mastersize 4000). The copper-containing precipitate was dispersed in water, ultrasonic waves and stirring were used to maintain the copper-containing precipitate in suspension, and the particle size of the copper-containing precipitate was measured by sampling.

[0086] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

[0087] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A copper deposition coagulant, characterized in that Including M y CO x S 3-x 、M(OH) z and water, wherein M is at least one of Na, Ka and Mg, 0≤x<3, y is 1 or 2, and z is 2 or 1.

2. The copper precipitation coagulant according to claim 1, characterized in that It also includes at least one of diethyl ether and M2CO3.

3. The copper precipitation coagulant according to claim 1, characterized in that 0≤x≤1。 4. The copper precipitation coagulant according to claim 2, characterized in that Based on the total mass of the copper deposition coagulant, the copper deposition coagulant comprises: 30% to 60% of M y CO x S 3-x ; 2% to 8% M(OH) z ; 0.5% to 1.5% ether; 0.5% to 1.5% M2CO3; and 29% to 67% water.

5. The copper deposition coagulant according to claim 4, characterized in that The copper deposition coagulant comprises: 40% to 50% of M y CO x S 3-x ; 4% to 6% M(OH) z ; 0.8% to 1.2% ether; 0.8% to 1.2% M2CO3; and 41.6% to 54.4% water.

6. The copper deposition coagulant according to any one of claims 1 to 5, characterized in that Based on the total mass of the copper deposition coagulant, the copper deposition coagulant further comprises: 0-5% N2S, where N is at least one of Na and K.

7. A method for preparing the copper deposition coagulant according to any one of claims 1 to 6, characterized in that: include: Providing a raw material mixed solution, the raw material mixed solution includes M(OH) z , N2S and water, wherein M is at least one of Na, Li, Ka and Mg, N is at least one of Na and Ka, and z is 2 or 1; Carbon disulfide gas is introduced into the raw material mixed solution to obtain the copper precipitation coagulant after reaction.

8. The method according to claim 7, characterized in that The raw material mixed solution further includes at least one of ether and M2CO3.

9. The method according to claim 8, characterized in that Based on the total mass of the raw material mixed solution, the raw material mixed solution comprises, by mass percentage: 20%-30% M(OH) z ; 0.5%-1.5% ether; 0.5%-1.5%% M2CO3; 25%-35% N2S; and the balance water.

10. The method according to any one of claims 7 to 9, characterized in that The molar amount of carbon disulfide is equal to the molar amount of M(OH) in the raw material solution. z The ratio of the molar amount of nitrogen to the sum of the molar amounts of N2S is 2.2:3 to 2.4:

3.

11. Use of the copper precipitation coagulant according to any one of claims 1 to 6 in the treatment of copper-containing waste liquid.

12. A method for treating copper-containing wastewater using the copper precipitation coagulant according to any one of claims 1 to 6, characterized in that: include: Adjusting the pH of the copper-containing waste liquid to alkaline; adding the copper precipitation coagulant to the copper-containing waste liquid and stirring to obtain a copper-containing particle mixture; The copper-containing particle mixture is filtered to obtain copper-containing particles and treated waste liquid.

13. The method according to claim 12, characterized in that The copper-containing particles have a particle size of 40 to 100 microns.

14. The method according to claim 12 or 13, characterized in that The filtration adopts filter cloth with 200-800 meshes.

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