A method for activating mineral flotation using waste liquid containing metal ions generated in the preparation of circuit boards

Abstract

The present invention belongs to the technical field of flotation reagents, and particularly relates to a method for activating mineral flotation using waste liquid containing metal ions generated during the manufacture of circuit boards. The present invention treats metal sulfides as the treatment target, converts the metal sulfides into a slurry, adds an inhibitor, an activator, a collector, and a frother to the slurry, and performs flotation to obtain the target product. The activator is waste liquid containing metal ions generated during the manufacture of circuit boards, and the amount of flotation activator used is 10 to 2200 g / t. This invention proposes, for the first time, using waste liquid containing metal ions generated during the manufacture of circuit boards as an activator for the flotation of metal sulfides and their minerals, simultaneously achieving mineral enrichment and preliminarily addressing the efficient and high-value utilization of waste liquid containing metal ions generated during the manufacture of circuit boards.

Description

Technical Field

[0001] The invention belongs to the technical field of flotation reagents, and in particular relates to a method for activating mineral flotation by utilizing waste liquid containing metal ions generated in the preparation of circuit boards. Background Art

[0002] The rapid growth of my country's electronics industry has driven the rapid development of the printed circuit board (PCB) industry. my country has become the world's largest PCB production center. Currently, there are many methods for manufacturing PCBs, the most common and practical of which is copper foil etching. The PCB etching process using this method includes cutting, drilling, copper deposition, pattern transfer, electroplating, film stripping, etching, tinning, and molding. Etching fluid is primarily produced during this etching step. As the etching process progresses, the excess copper foil on the PCB is continuously etched away by the etchant, gradually increasing the copper ion concentration. Once saturation is reached, the etching rate slowly decreases until the etching activity ceases and the solution becomes waste. Statistics show that the average PCB etching process generates a significant amount of copper-containing etching waste, generally classified as acidic copper chloride etching waste and alkaline copper ammonia etching waste. Wastewater generated during the copper plating and tin stripping processes also contains significant amounts of copper and various other ions. The metal ion content of different types of wastewater varies, resulting in a variety of wastewater treatment methods. Wastewater contains high concentrations of heavy metal ions, typically copper, nickel, and lead. Direct discharge without treatment can severely impact the ecological environment. Recycling copper ions from wastewater can avoid environmental pollution, conserve resources, and create significant economic benefits.

[0003] A search revealed that there are currently few reports on the technology of activating and flotating metal sulfides using waste liquid containing metal ions generated during the preparation of circuit boards. Summary of the Invention

[0004] The purpose of the present invention is to provide a recycling and reuse method for activating the flotation of zinc-containing sulfide ore using circuit board waste liquid. An activator with low cost, good activation effect and simple process is used to replace copper sulfate to activate the flotation of zinc-containing sulfide ore, thereby significantly reducing production costs.

[0005] The present invention adopts the following technical solutions to achieve the above-mentioned purpose:

[0006] A method for activating mineral flotation using wastewater containing metal ions generated during the production of printed circuit boards. Metal sulfides are processed by forming a slurry of the metal sulfides. An inhibitor, activator, collector, and frother are added to the slurry for flotation. The activator is the wastewater containing metal ions generated during the production of printed circuit boards. The amount of flotation activator used is 10-2200 g / t.

[0007] The present invention proposes for the first time to use waste liquid containing metal ions generated in the preparation of circuit boards as an activator, and to use the activator for the flotation of metal sulfides and minerals thereof.

[0008] In the present invention, the activator is a waste liquid containing metal ions generated during the production of printed circuit boards. Alternatively, the activator may be a product obtained by treating the waste liquid containing metal ions generated during the production of printed circuit boards. The purpose of this treatment is to improve the flotation efficiency of the target mineral.

[0009] Preferably, the activator is selected from at least one of the following options;

[0010] Option 1

[0011] If the waste liquid containing metal ions is an acidic etching copper-containing waste liquid generated in the production process of a circuit board, the treatment method is as follows: stirring the acidic etching copper-containing waste liquid, adding alkali, filtering and washing after the reaction is completed, taking the precipitate, adding acid, and fully stirring to react to obtain solution A; the pH value of solution A is 1.5-7.0, and the copper ion concentration is 0.1-2.0 mol / L;

[0012] Option 2

[0013] If the waste liquid containing metal ions is the alkaline etching copper-containing waste liquid generated in the circuit board production process, the treatment method is:

[0014] Stirring the alkaline etching copper-containing waste liquid, adding water or hydrochloric acid to dilute it, stirring it evenly, and filtering it to separate it; adding an extractant, stirring it, taking the precipitate, and adding acid to obtain a solution B; the pH value of the solution B is 2.5-7.0, and the copper ion concentration is 0.1-2.0 mol / L;

[0015] Option 3

[0016] If the waste liquid containing metal ions is copper plating waste liquid generated in the production process of circuit boards, the treatment method is:

[0017] Adjust the pH value of the solution with acid or alkali, add an extractant, and after sufficient reaction and separation, take the extract layer, add sulfate and mix thoroughly, separate the extract, and obtain a residual solution C; the pH value of the solution C is 2.0-7.0, and the copper ion concentration is 0.05-2.0 mol / L;

[0018] Option 4

[0019] If the waste liquid containing metal ions is the tin stripping waste liquid generated in the circuit board production process, the treatment method is:

[0020] The pH of the solution is adjusted to be acidic, after suction filtration, an acid is added to the solution, the solution is fully stirred and then suction filtered, an alkali is added to adjust the pH of the solution, and after sufficient reaction, suction filtration is performed to obtain a solution D; the pH value of the solution D is 1.5-7.0, the tin ion concentration is less than 0.01 mol / L, and the copper ion concentration is 0.1-2 mol / L.

[0021] Preferably, the heating temperature in solution 1 is controlled at 60-90 degrees Celsius.

[0022] Preferably, the base in Scheme 1 is sodium hydroxide, calcium hydroxide, ammonia, etc., and is more preferably aqueous ammonia.

[0023] Preferably, the acid in Scheme 1 is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, etc., which can dissociate H + At least one of the acids, more preferably sulfuric acid.

[0024] Preferably, when adding alkali in scheme 1, the pH of the solution is controlled at 4.0-5.0.

[0025] Preferably, the main component of the precipitate in Scheme 2 is trihydroxycopper chloride CuCl2·3Cu(OH)2, containing a small amount of other impurities, and the reaction mechanism is:

[0026] .

[0027] Preferably, the dilution ratio in scheme 2 is controlled at about 40 to 60 times, which is the optimal dilution ratio.

[0028] Preferably, in Option 2, adding waste activated carbon (which may come from the beverage industry) during filtration can effectively absorb the residual copper ions in the solution.

[0029] Preferably, the acid in Scheme 2 is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, etc., which can dissociate H in aqueous solution. + At least one of the acids, more preferably hydrochloric acid.

[0030] Preferably, the copper chloride dihydrate solution in Scheme 2 can be recovered in the form of pure crystals at a pH of 2-4.

[0031] Preferably, the pH value of the solution in scheme three should be adjusted to about 3.5-4.5, and the acid used to adjust the pH value of the solution is sulfuric acid and the base is ammonia water.

[0032] Preferably, the extractant in Scheme 3 is Lix984N, and 240# kerosene can be used to dilute the extractant to achieve the target concentration. More preferably, the extractant concentration is 5-20% (by volume).

[0033] Preferably, the extraction time in scheme three is about 60 to 180 seconds.

[0034] Preferably, when the solution is adjusted to be acidic in Scheme 4, the pH value is controlled to be 1.0-2.0, and the main precipitated ion is tin.

[0035] Preferably, the acid in Scheme 4 is sulfuric acid, hydrochloric acid, nitric acid, acetic acid, etc., which can dissociate H in aqueous solution. + At least one of the acids, more preferably sulfuric acid, the ratio of sulfur to lead should be greater than 1.4 to ensure that lead ions can be effectively precipitated.

[0036] Preferably, the base in Scheme 4 is sodium hydroxide, calcium hydroxide, ammonia, etc., more preferably sodium hydroxide, and the pH value is controlled to be 1.5~3.5.

[0037] Preferably, the inhibitor is an organic inhibitor or an inorganic inhibitor. If the gangue mineral is pyrite, sodium metabisulfite is further preferred.

[0038] Preferably, the collector is at least one of xanthate, black powder, nitrile ester, and sulfur-nitrogen. In the flotation of zinc-containing sulfide ores, N-allyl-O-isobutylthiocarbamate is further preferred. This collector has a strong selective capture effect on zinc-containing sulfide ores, is easy to add in actual production, is convenient to use, and has strong stability. It can effectively capture fine-grained iron-containing sphalerite, resulting in better resource secondary utilization and broad application prospects. It also has a certain foaming property, which can reduce the amount of foaming agent used in the production process and significantly reduce production costs.

[0039] Further preferably, in the preparation of N-allyl-O-isobutylthiocarbamate, the nitrobenzene organic compound is an organic compound having a structure of Formula 1, wherein R is C n H 2n wherein n is preferably 2 to 8, more preferably 2 to 4, and even more preferably 2 to 3.

[0040] Formula 1

[0041] Preferably, the xanthate collector can be any xanthate collector known in the industry, for example, including but not limited to at least one of butyl xanthate, ethyl xanthate, isobutyl xanthate, etc.; the black drug collector can be any black drug collector known in the industry, for example, including but not limited to at least one of butyl ammonium black drug, No. 25 black drug, and amine black drug; the nitrile ester collector can be any nitrile ester collector known in the industry, for example, including but not limited to at least one of ethyl nitrile ester and butyl yellow nitrile ester; the sulfur nitrogen collector can be any sulfur nitrogen collector known in the industry, for example, including but not limited to at least one of ethyl nitrogen, butyl sulfur nitrogen, and sulfur nitrogen ester.

[0042] Preferably, when the collector has excellent foaming performance, no foaming agent is needed, and the foaming agent is one of pine oil and MIBC, more preferably pine oil.

[0043] Preferably, during the flotation process, minerals requiring copper ion activation, including but not limited to cassiterite, muscovite, fluorite, quartz, sphalerite, arsenopyrite, sphalerite, and pyrite, can be selected. The activator used should be the treated or untreated waste liquids of this patent, combined with any effective inhibitors, activators, and other flotation agents to form an effective flotation system for flotation.

[0044] Preferably, the solution treated in the above steps removes a variety of metal ion impurities, and can effectively activate copper ions and / or tin ions. The mineral flotation that is less affected by metal ions can simplify the waste liquid treatment method and be directly used in mineral flotation.

[0045] In industrial applications, the inhibitor is first added to the ore pulp, and after it is fully stirred, the solution in the above steps is added. After a period of sufficient reaction, the collector and frother are added in sequence for flotation.

[0046] The metal sulfide is preferably zinc sulfide.

[0047] The present invention also provides the use of the flotation activator in the above steps in the flotation of sphalerite.

[0048] Preferably, the amount of the flotation activator in the flotation of marmatite is: when the iron content in the marmatite is less than 6%, the amount of the flotation activator is 10-1000 g / t; when the iron content in the marmatite is 6-12%, the amount of the flotation activator is 10-1500 g / t, preferably 450-650 g / t; when the iron content in the marmatite is greater than 12%, the amount of the flotation activator is 100-2000 g / t.

[0049] In industrial applications, when the mineral is sphalerite or iron-bearing sphalerite, the depressant dosage can be optimized to 480-650 g / t (including 500-600 g / t) and the collector dosage can be optimized to 45-110 g / t (including 50-100 g / t) during roughing. After roughing, the collector dosage can also be optimized to 50-55 g / t during scavenging.

[0050] In industrial applications, when the mineral is sphalerite or iron-containing sphalerite, during roughing, the inhibitor is selected from at least one of sodium sulfite, sodium metabisulfite, lime, and cyanide. The collector is selected from at least one of N-allyl-O-isobutylthiocarbamate and butyl xanthate.

[0051] Research has found that while wastewater from printed circuit etching, tin stripping, and copper plating processes contains relatively low levels of other impurity metal ions, it contains significant amounts of copper ions, which have an activating effect. The copper ions in these wastewaters can effectively activate minerals such as cassiterite, muscovite, fluorite, quartz, sphalerite, arsenopyrite, sphalerite, and pyrite, allowing the collector to fully bind to the mineral surface, allowing the minerals to float into the froth and separate from the gangue minerals. Unactivated minerals are difficult to capture effectively and have poor floatability. During flotation, an activator is often added to promote binding between the mineral surface and the collector, effectively separating the zinc-containing minerals from the slurry and eliminating the harmful effects of inhibitory particles in the slurry. This technological exploration has for the first time demonstrated that using metal ion-containing wastewater generated directly or indirectly from circuit board manufacturing as an activator for zinc sulfide flotation can achieve a significantly lower dosage than the copper sulfate used in existing techniques (which typically ranges from 1000 to 2000 g / t).

[0052] Beneficial effects:

[0053] (1) The mineral activator of the present invention can effectively activate part of the ore, so that it can better combine with the collector, not only having a good collection effect in flotation, but also reducing the amount of reagents used, reducing environmental pollution, reducing production costs, making the secondary utilization of resources better, and significantly increasing the economic benefits of the mineral processing plant.

[0054] (2) The activator prepared by the present invention has a good activation effect on minerals, which is beneficial to the separation of minerals from the slurry, improves the effect of the collector on the minerals and the quality of the concentrate, and improves the production indicators of the concentrator.

[0055] (3) The present invention utilizes an activator whose raw materials are widely available, environmentally friendly, and has a simple preparation process. It can replace activators such as copper sulfate in the mineral flotation process, saving reagent costs and reducing resource waste, thus realizing resource recycling and utilization, and has practical application value.

[0056] (4) The implementation method of the present invention can effectively remove impurity ions such as iron ions and nickel ions in the waste etching solution, and the copper ions in the waste etching solution can be effectively preserved in the solution. The purity of the purified solution is high, which is convenient for subsequent recycling and utilization, and the copper ion loss rate is small.

[0057] The technical solution of the present invention is further described in detail below through examples. DETAILED DESCRIPTION

[0058] The present invention provides a recycling and reuse method using copper-containing waste liquid from circuit boards to activate mineral flotation, comprising the following steps:

[0059] Option 1

[0060] If the waste liquid containing metal ions is an acidic etching copper-containing waste liquid generated in the production process of a circuit board, the treatment method is as follows: stirring the acidic etching copper-containing waste liquid, adding alkali, filtering and washing after the reaction is completed, taking the precipitate, adding acid, and fully stirring to react to obtain solution A; the pH value of solution A is 1.5-7.0, and the copper ion concentration is 0.1-2.0 mol / L;

[0061] Option 2

[0062] If the waste liquid containing metal ions is the alkaline etching copper-containing waste liquid generated in the circuit board production process, the treatment method is:

[0063] Stirring the alkaline etching copper-containing waste liquid, adding water or hydrochloric acid to dilute it, stirring it evenly, and filtering it to separate it; adding an extractant, stirring it, taking the precipitate, and adding acid to obtain a solution B; the pH value of the solution B is 2.5-8.0, and the copper ion concentration is 0.1-2.0 mol / L;

[0064] Option 3

[0065] If the waste liquid containing metal ions is copper plating waste liquid generated in the production process of circuit boards, the treatment method is:

[0066] Adjust the pH value of the solution with acid or alkali, add an extractant, and after sufficient reaction and separation, take the extract layer, add sulfate and mix thoroughly, separate the extract, and obtain a residual solution C; the pH value of the solution C is 2.0-7.0, and the copper ion concentration is 0.05-2.0 mol / L;

[0067] Option 4

[0068] If the waste liquid containing metal ions is the tin stripping waste liquid generated in the circuit board production process, the treatment method is:

[0069] Adjusting the pH of the solution to be acidic, filtering the solution with suction, adding acid, stirring thoroughly, and filtering with suction, adding alkali to adjust the pH of the solution, and filtering thoroughly after reaction to obtain a solution D; wherein the pH value of the solution D is 1.5-7.0, the tin ion concentration is less than 0.01 mol / L, and the copper ion concentration is 0.1-2.0 mol / L;

[0070] The above activator is specifically used in the following steps: first, the inhibitor is added to the ore pulp, and after it is fully stirred, the solution in the above step is added, and after a period of sufficient reaction, the collector and the frother are added in sequence to carry out flotation;

[0071] The present invention also provides the use of a flotation activator in the flotation of sphalerite in the above steps. When the iron content of the sphalerite is less than 6%, the amount of the flotation activator is 10-1000 g / t; when the iron content of the sphalerite is 6-12%, the amount of the flotation activator is 10-1500 g / t; when the iron content of the sphalerite is greater than 12%, the amount of the flotation activator is 100-2000 g / t;

[0072] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the scope of the invention claimed for protection, but merely represent selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0073] The ore raw materials are taken from the tailings after lead selection in a lead-zinc mine in Chenzhou, Hunan Province, containing about 5.3wt% zinc, about 11.5wt% iron, and about 14.2wt% sulfur.

[0074] Example 1

[0075] The present invention provides a recycling and reuse method using copper-containing waste liquid from circuit boards to activate mineral flotation, comprising the following steps:

[0076] (1) Heat the acidic copper chloride etching waste liquid (its components are: copper ions, cuprous chloride, nickel ions, zinc ions, etc.) in a water bath at 60 degrees Celsius, use a pH meter to measure the pH value of the solution, add ammonia water and stir continuously during heating, and control the pH value of the solution at 4.5. Filter the solution with a vacuum filter, take the precipitate into a container, add sulfuric acid and stir thoroughly to obtain the implementation reagent 1 (solution A; the pH value of the solution A is 4.0 and the copper ion concentration is 1.02 mol / L).

[0077] (2) Before roughing, the sphalerite was ground in a ball mill (grinded to 80±2% of -200 particles), water was added to control the pulp concentration to 40wt%, and flotation was performed on a flotation machine. After stirring for 3 minutes, 500g / t of sodium metabisulfite inhibitor was added, stirred for 3 minutes, 500g / t of reagent 1 was added, stirred for three minutes, 50g / t of N-allyl-O-isobutylthiocarbamate was added, stirred for 3 minutes, aerated and the foam was scraped off. After the roughing was completed, 50g / t of flotation collector (N-allyl-O-isobutylthiocarbamate) was added to the roughing tailings, and two scavenging operations were performed. The scavenged concentrate was returned to the previous flotation operation in sequence; the roughing concentrate was subjected to a blank selection to obtain concentrate, and the selected middlings were returned to the roughing operation in sequence.

[0078]

[0079] Example 2

[0080] The present invention provides a recycling and reuse method using copper-containing waste liquid from circuit boards to activate mineral flotation, comprising the following steps:

[0081] (1) Add hydrochloric acid to alkaline copper ammonia etching waste liquid (its components include ammonia water, copper ammonia complex, etc.) and stir thoroughly. Measure the pH value of the solution with a pH meter. The final dilution ratio is controlled at 50 times and the pH value is controlled at 3.6. After filtration, the precipitate is taken, and the extractant ethanol is added and stirred thoroughly. After filtration, the precipitate is taken and sulfuric acid is added to obtain the implementation reagent 2 (solution B; the pH value of the solution B is 3.9 and the copper ion concentration is 0.89 mol / L).

[0082] (2) Before roughing, the sphalerite was ground in a ball mill (grinded to -200 particles accounting for 80±2%), water was added to control the pulp concentration to 40wt%, and flotation was performed on a flotation machine. After stirring for 3 minutes, 400g / t of sodium metabisulfite inhibitor was added, stirred for 3 minutes, 600g / t of Example Reagent 2 was added, stirred for three minutes, 100g / t of butyl xanthate was added, stirred for 3 minutes, aerated and the foam was scraped off. After the roughing was completed, 50g / t of flotation collector (butyl xanthate) was added to the roughing tailings, and two scavenging operations were performed. The scavenged concentrate was sequentially returned to the previous flotation operation; a blank selection was performed on the roughing concentrate to obtain concentrate, and the selected middlings were sequentially returned to the roughing operation.

[0083]

[0084] Example 3

[0085] The present invention provides a recycling and reuse method using copper-containing waste liquid from circuit boards to activate mineral flotation, comprising the following steps:

[0086] (1) The pH value of the copper plating waste liquid (its components are: copper ions, lead ions, ammonia water, nickel ions, etc.) is measured with a pH meter, and the pH value of the solution is adjusted to 4 with sulfuric acid or ammonia water. The extractant Lix984N and 240# kerosene are added to dilute the extractant concentration to 15%. After sufficient reaction, the extract layer is taken and sulfuric acid is added to be fully mixed. The sulfuric acid layer is taken as the implementation agent 3 (the pH value of the solution C is 4.0 and the copper ion concentration is 0.93 mol / L).

[0087] (2) Before roughing, the sphalerite was ground in a ball mill (grinded to -200 particles accounting for 80±2%), water was added to control the pulp concentration to 40%, and flotation was performed on a flotation machine. After stirring for 3 minutes, 500g / t of sodium metabisulfite inhibitor was added, stirred for 3 minutes, and 500g / t of reagent 3 was added and stirred for three minutes. 50g / t of N-allyl-O-isobutylthiocarbamate was added and stirred for 3 minutes. The mixture was aerated and the foam was scraped off. After the roughing was completed, 50g / t of flotation collector (N-allyl-O-isobutylthiocarbamate) was added to the roughing tailings and two scavenging operations were performed. The scavenged concentrate was sequentially returned to the previous flotation operation; a blank selection was performed on the roughing concentrate to obtain concentrate, and the selected middlings were sequentially returned to the roughing operation.

[0088]

[0089] Example 4

[0090] The present invention provides a recycling and reuse method using copper-containing waste liquid from circuit boards to activate mineral flotation, comprising the following steps:

[0091] (1) Stir the tin stripping waste liquid (its components are: tin ions, copper ions, nitric acid, etc.) evenly, use a pH meter to measure the pH value of the solution, add hydrochloric acid to the solution to adjust the pH value to 1.5 to precipitate the tin ions, and add an appropriate amount of sulfuric acid to the solution after filtration to precipitate the lead ions in the solution. Filter, and add sodium hydroxide to the solution to adjust the pH value of the solution to 3 to obtain the implementation reagent 4.

[0092] (2) Before roughing, the sphalerite was ground in a ball mill (grinded to 80±2% of -200 particles), water was added to control the pulp concentration to 40%, and flotation was performed on a flotation machine. After stirring for 3 minutes, 500g / t of sodium metabisulfite inhibitor was added, stirred for 3 minutes, and 500g / t of reagent 4 was added and stirred for three minutes. 50g / t of N-allyl-O-isobutylthiocarbamate was added and stirred for 3 minutes. The mixture was aerated and the foam was scraped off. After the roughing was completed, 50g / t of flotation collector was added to the roughing tailings and scavenged twice. The scavenged concentrate was returned to the previous flotation operation in sequence. A blank selection was performed on the roughing concentrate to obtain concentrate, and the selected middlings were returned to the roughing operation in sequence.

[0093]

[0094] Example 5

[0095] The present invention provides a recycling and reuse method using copper-containing waste liquid from circuit boards to activate mineral flotation, comprising the following steps:

[0096] (1) Heat the acidic copper chloride etching waste liquid (its components are: copper ions, cuprous chloride, nickel ions, zinc ions, etc.) in a water bath at 60 degrees Celsius. Use a pH meter to measure the pH value of the solution. Add ammonia water and stir continuously during heating to control the pH value of the solution at 4.5. Filter the solution with a vacuum filter, take the precipitate in a container, add sulfuric acid and stir thoroughly to obtain the working reagent 1.

[0097] (2) Before roughing, the iron-containing sphalerite was ground using a ball mill (grinding to -200 particles accounting for 80±2%), water was added to control the pulp concentration to 40%, and flotation was performed using a flotation machine. After stirring for 3 minutes, 500g / t of sodium metabisulfite inhibitor was added, stirred for 3 minutes, and 500g / t of reagent 1 was added and stirred for three minutes. 50g / t of N-allyl-O-isobutylthiocarbamate was added and stirred for 3 minutes. The mixture was aerated and the foam was scraped off. After the roughing was completed, 50g / t of flotation collector (N-allyl-O-isobutylthiocarbamate) was added to the roughing tailings and two scavenging operations were performed. The scavenged concentrate was sequentially returned to the previous flotation operation; a blank selection was performed on the roughing concentrate to obtain concentrate, and the selected middlings were sequentially returned to the roughing operation.

[0098]

[0099] Comparative Example 1

[0100] Before roughing, the sphalerite was ground in a ball mill (to a particle size of 80 ± 2% -200 g). Water was added to control the pulp concentration to 40%, and flotation was performed on a flotation cell. After stirring for 3 minutes, 500 g / t of sodium metabisulfite, a depressant, was added and stirred for 3 minutes. No activator was added, and 50 g / t of N-allyl-O-isobutylthiocarbamate was added and stirred for 3 minutes. The mixture was aerated and froth was removed by scraping. After the roughing, 50 g / t of flotation collector was added to the roughing tailings, and two scavenging operations were performed. The scavenged concentrate was then returned to the previous flotation process. The roughing concentrate was then subjected to a blank cleaning process to obtain a concentrate, and the selected middlings were returned to the roughing process.

[0101]

[0102] Comparative Example 2

[0103] The other conditions of this comparative example are the same as those of Example 1, except that no inhibitor is added.

[0104]

[0105] Comparative Example 3

[0106] The other conditions of this comparative example are the same as those of Example 1, except that the activator is an equal amount of chemically pure copper sulfate;

[0107]

[0108] It can be seen from Example 1 and Comparative Example 3 that, compared with chemically pure copper sulfate, the activator used in the present invention can also improve the yield of the concentrate and the grade of zinc to a certain extent.

[0109] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention can still be modified or replaced by equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for activating mineral flotation using wastewater containing metal ions generated during the production of circuit boards, characterized by: Taking metal sulfide as the treatment object, the metal sulfide is made into slurry, and inhibitors, activators, collectors and frothers are added to the slurry for flotation; The target product is obtained, wherein the activator is waste liquid containing metal ions generated in the preparation of circuit boards; the amount of the flotation activator is 10-2200 g / t; The activator is selected from at least one of the following options; Option 1 If the waste liquid containing metal ions is an acidic etching copper-containing waste liquid generated in the production process of a circuit board, the treatment method is as follows: stirring the acidic etching copper-containing waste liquid, adding alkali, filtering and washing after the reaction is completed, taking the precipitate, adding acid, and fully stirring to react to obtain solution A; the pH value of solution A is 1.5-7.0, and the copper ion concentration is 0.1-2.0 mol / L; Option 2 If the waste liquid containing metal ions is the alkaline etching copper-containing waste liquid generated in the circuit board production process, the treatment method is: Stirring the alkaline etching copper-containing waste liquid, adding water or hydrochloric acid to dilute it, stirring it evenly, and filtering it to separate it; adding an extractant, stirring it, taking the precipitate, and adding acid to obtain a solution B; the pH value of the solution B is 2.5-7.0, and the copper ion concentration is 0.1-2.0 mol / L; Option 3 If the waste liquid containing metal ions is copper plating waste liquid generated in the production process of circuit boards, the treatment method is: Adjust the pH value of the solution with acid or alkali, add an extractant, and after sufficient reaction and separation, take the extract layer, add sulfate and mix thoroughly, separate the extract, and obtain a residual solution C; the pH value of the solution C is 2.0-7.0, and the copper ion concentration is 0.05-2.0 mol / L; Option 4 If the waste liquid containing metal ions is the tin stripping waste liquid generated in the circuit board production process, the treatment method is: The pH of the solution is adjusted to be acidic, after suction filtration, an acid is added to the solution, the solution is fully stirred and then suction filtered, an alkali is added to adjust the pH of the solution, and after sufficient reaction, suction filtration is performed to obtain a solution D; the pH value of the solution D is 1.5-7.0, the tin ion concentration is less than 0.01 mol / L, and the copper ion concentration is 0.1-2 mol / L.

2. The method for activating mineral flotation using waste liquid containing metal ions generated during the production of circuit boards according to claim 1, characterized in that: In scheme 1, the reaction temperature is controlled at 60-90 degrees Celsius; In scheme 1, the base is at least one of sodium hydroxide, calcium hydroxide, and ammonia; In the first solution, the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, and acetic acid; When adding alkali in Scheme 1, the pH of the solution is controlled at 4.0~5.

0.

3. The method for activating mineral flotation using waste liquid containing metal ions generated in the production of circuit boards according to claim 1, characterized in that: In scheme 2, the dilution ratio is controlled at 40-60 times; In option 2, waste activated carbon is added during filtration; In the second scheme, the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid and acetic acid.

4. The method for activating mineral flotation using waste liquid containing metal ions generated during the production of circuit boards according to claim 1, characterized in that: In scheme 3, the pH value of the solution is adjusted to 3.5-4.5, and the acid used to adjust the pH value of the solution is sulfuric acid and the base is ammonia water; In scheme 3, the extractant is Lix984N, and 240# kerosene is used to dilute the extractant to achieve the target concentration, which is 5~20V%; The extraction time in scheme three is 60~180 seconds.

5. The method for activating mineral flotation using waste liquid containing metal ions generated in the production of circuit boards according to claim 1, characterized in that: When the solution is adjusted to acid in Scheme 4, the pH value is controlled to be 1.0~2.0; In scheme 4, the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, and acetic acid. In scheme 4, the alkali is at least one of sodium hydroxide, calcium hydroxide, and ammonia.

6. The method for activating mineral flotation using waste liquid containing metal ions generated in the production of circuit boards according to claim 1, characterized in that: The inhibitor is at least one of an organic inhibitor and an inorganic inhibitor, The collector is at least one of xanthate, black medicine, nitrile ester, and sulfur nitrogen.

7. The method for activating mineral flotation using waste liquid containing metal ions generated during the production of circuit boards according to claim 6, characterized in that: If the gangue mineral is pyrite, the inhibitor is sodium metabisulfite; When flotating zinc-containing sulfide ores, the collector is N-allyl-O-isobutylthiocarbamate.

8. The method for activating mineral flotation using waste liquid containing metal ions generated in the production of circuit boards according to claim 6, characterized in that: In the preparation of N-allyl-O-isobutylthiocarbamate, the nitrobenzene organic compound is an organic compound having a structure of Formula 1, wherein R is C n H 2n Alkyl, wherein n is 2 to 8; Formula 1.

9. The method for activating mineral flotation using waste liquid containing metal ions generated in the production of circuit boards according to claim 2, characterized in that: The dosage of flotation activator in sphalerite flotation is: when the iron content in sphalerite is less than 6%, the dosage of flotation activator is 10~1000g / t; When the iron content in sphalerite is 6-12%, the dosage of flotation activator is 10-1500g / t; When the iron content in sphalerite is greater than 12%, the dosage of flotation activator is 100~2000g / t.

10. The method for activating mineral flotation using waste liquid containing metal ions generated in the production of circuit boards according to claim 9, characterized in that: When the iron content in sphalerite is 6~12%, the dosage of flotation activator is 450~650g / t.

11. The method for activating mineral flotation using waste liquid containing metal ions generated in the production of circuit boards according to claim 2, characterized in that: When the mineral is sphalerite or iron-containing sphalerite, the dosage of the inhibitor is 480~650g / t and the dosage of the collector is 45~110g / t during roughing; after the roughing is completed, the dosage of the collector during scavenging is 50~55g / t.

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