Flotation method for activating minerals by using metal ion-containing waste liquid generated in circuit board preparation

Abstract

The invention belongs to the technical field of flotation reagents, and particularly relates to a method for activating mineral flotation by using metal ion-containing waste liquid generated by preparing a circuit board. The method comprises the following steps: by taking metal sulfide as a treatment object, preparing the metal sulfide into slurry, adding an inhibitor, an activating agent, a collecting agent and a foaming agent into the slurry, and carrying out flotation; the activating agent is metal ion-containing waste liquid generated in preparation of the circuit board; and the use amount of the flotation activating agent is 10-2200g / t. According to the method, the metal ion-containing waste liquid generated during circuit board preparation is used as the activating agent for the first time, the activating agent is used for flotation of metal sulfide and minerals thereof, meanwhile, mineral enrichment is achieved, and efficient and high-value utilization of the metal ion-containing waste liquid generated during circuit board preparation is preliminarily achieved.

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] With the rapid growth of my country's electronics industry, the printed circuit board (PCB) industry has developed rapidly. my country has become the world's largest printed circuit board production center. At present, there are many methods for manufacturing printed circuit boards, among which the most commonly used and practical is the copper foil etching method. The etching process of PCB using this production process includes cutting, drilling, copper deposition, pattern transfer, electroplating, film stripping, etching, tin-plated plate and molding. Etching liquid is mainly produced in the etching step. As the etching proceeds, the excess copper foil on the circuit board is continuously corroded by the etching liquid, and the copper ion concentration gradually increases. After approaching saturation, the etching speed will slowly decrease until there is no etching effect and it becomes waste liquid. According to statistics, on average, a large amount of copper-containing etching waste liquid can be generated in the etching process of each printed circuit board production, which is generally divided into acidic copper chloride etching waste liquid and alkaline copper ammonia etching waste liquid. The waste liquid generated in the copper plating and tin stripping process also contains a large amount of copper ions and various other ions. The content of metal ions in different types of waste liquid is also different, so the treatment methods of waste liquid are also varied. The waste liquid contains a high concentration of various heavy metal ions, usually copper, nickel, lead and other ions. If it is discharged directly without treatment, it will seriously affect the ecological environment. If the copper ions in the etching waste liquid are recycled and reused, it can avoid environmental pollution, save resources and create good economic benefits.

[0003] A search revealed that there are 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 method for activating the flotation of zinc-containing sulfide ore using circuit board waste liquid, using an activator with low cost, good activation effect and simple process, which can 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 purpose:

[0006] A method for activating mineral flotation by using waste liquid containing metal ions generated by preparing circuit boards, wherein metal sulfides are treated as the object, the metal sulfides are made into slurry, inhibitors, activators, collectors and frothers are added to the slurry, and flotation is performed to obtain the target product, wherein the activator is waste liquid containing metal ions generated by preparing 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 the waste liquid containing metal ions generated by the preparation of circuit boards. It can also be the product obtained by treating the waste liquid containing metal ions generated by the preparation of circuit boards. The reason for the treatment is to improve the flotation efficiency of the target mineral.

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

[0010] Solution 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 and adding acid, and fully stirring the reaction to obtain a solution A; the pH value of the solution A is 1.5-7.0, and the copper ion concentration is 0.1-2.0 mol / L;

[0012] Solution 2

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

[0014] Stirring the alkaline etching copper-containing waste liquid, adding water or hydrochloric acid to dilute it, and after stirring evenly, filtering and separating it; adding an extractant, stirring and taking out a precipitate, and adding an 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, react fully and separate the layers, 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 production process of circuit boards, the treatment method is:

[0020] The pH value 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 value 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, in scheme 1, the heating temperature is controlled at 60-90 degrees Celsius.

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

[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 factor in scheme 2 is controlled at about 40 to 60 times as the optimal dilution factor.

[0028] Preferably, in Option 2, adding waste activated carbon (which may come from the beverage industry) during filtration can effectively absorb the copper ions remaining 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 when the pH value is 2-4.

[0031] Preferably, the pH value of the solution in Scheme 3 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. Further preferably, the extractant concentration is 5-20% (by volume).

[0033] Preferably, the extraction time in Scheme 3 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 pyrosulfite is further preferred.

[0038] Preferably, the collector is at least one of xanthate, black medicine, nitrile ester, and sulfur-nitrogen. When flotating zinc-containing sulfide ores, N-allyl-O-isobutylthiocarbamate is further preferred. The collector has a strong selective collection effect on zinc-containing sulfide ores. It is easy to add in actual production, easy to use, and has strong stability. It can effectively capture fine iron-containing sphalerite, making the secondary utilization of resources better and having 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 2-8; more preferably 2-4, and even more preferably 2-3.

[0040] Formula 1

[0041] Preferably, the xanthate collector may 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 may 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 may 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 may 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 needs to be added, and the foaming agent is one of pine oil and MIBC, and pine oil is more preferably used.

[0043] Preferably, during the flotation process, minerals that need to be activated by copper ions include, but are not limited to, cassiterite, muscovite, fluorite, quartz, sphalerite, arsenopyrite, sphalerite and pyrite. The activator used should be several types of waste liquids treated or untreated in this patent, and any effective inhibitor, activator and other flotation reagents should be combined to form an effective flotation system for flotation.

[0044] Preferably, the solution treated in the above steps has removed 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] When used in industry, the inhibitor is first added to the ore pulp, and after it is fully stirred, the solution in the above step 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 sphalerite is: when the iron content in the sphalerite is less than 6%, the amount of the flotation activator is 10-1000 g / t; when the iron content in the sphalerite 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 sphalerite 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-containing sphalerite, during roughing, the amount of depressant can be optimized to 480~650g / t (including 500g / t~600g / t), and the amount of collector can be optimized to 45~110g / t (including 50g / t~100g / t). After the roughing is completed, the amount of collector added during scavenging can also be optimized to 50~55g / t.

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

[0051] The study found that: since the content of other impurity metal ions in the printed circuit etching waste liquid, tin stripping waste liquid and copper plating waste liquid is low, but it contains a large amount of copper ions with activation effect, the copper ions in these waste liquids can effectively activate copper ions to activate minerals such as cassiterite, muscovite, fluorite, quartz, sphalerite, arsenopyrite, sphalerite and pyrite, so that the collector can fully combine with the mineral surface, so that the mineral can effectively float into the foam and achieve the effect of separation from the gangue mineral. Unactivated minerals are difficult to effectively capture and have poor floatability. During the flotation process, it is often necessary to add an activator to promote the combination of the mineral surface and the collector, so as to effectively separate the zinc-containing minerals from the slurry and eliminate the harmful effects of inhibitory particles in the slurry. In the process of exploring this technology, it was first discovered that when the waste liquid containing metal ions generated by the preparation of circuit boards is directly or indirectly used as an activator to float zinc sulfide, its dosage is much lower than the dosage of copper sulfate in the prior art (the dosage of copper sulfate in the prior art is 1000~2000g / 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 can it have a good collection effect in flotation, but also can reduce the dosage of reagents, reduce environmental pollution, reduce production costs, make the secondary utilization of resources better, and significantly increase the economic benefits of the ore dressing 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 ore 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 with a wide range of raw materials, is green and environmentally friendly, and has a simple preparation process. It can replace activators such as copper sulfate in the mineral flotation process, saves reagent costs and reduces resource waste, realizes resource recycling, 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 embodiments. DETAILED DESCRIPTION

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

[0059] Solution 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 and adding acid, and fully stirring the reaction to obtain a solution A; the pH value of the solution A is 1.5-7.0, and the copper ion concentration is 0.1-2.0 mol / L;

[0061] Solution 2

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

[0063] Stirring the alkaline etching copper-containing waste liquid, adding water or hydrochloric acid to dilute it, and after stirring evenly, filtering and separating it; adding an extractant, stirring and taking out a precipitate, and adding an 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, react fully and separate the layers, 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 production process of circuit boards, the treatment method is:

[0069] The pH value 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 value 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 0.1-2.0 mol / L;

[0070] The above activator is specifically used, including: first adding the inhibitor to the ore pulp, after fully stirring it, adding the solution in the above step, and after a period of sufficient reaction, adding the collector and the frother in turn to carry out flotation;

[0071] The present invention also provides the use of the flotation activator in the above steps in the flotation of sphalerite. When the iron content in the sphalerite is less than 6%, the amount of the flotation activator is 10-1000 g / t; when the iron content in the sphalerite is 6-12%, the amount of the flotation activator is 10-1500 g / t; when the iron content in 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 in conjunction with 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 claimed invention, 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 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, containing about 5.3wt% zinc, about 11.5wt% iron, and about 14.2wt% sulfur.

[0074] Example 1

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

[0076] (1) Heat the acid 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 out the solution with a vacuum filter, take the precipitate in a container, add sulfuric acid and stir thoroughly to obtain implementation reagent 1 (solution A; the pH value of solution A is 4.0 and the copper ion concentration is 1.02 mol / L).

[0077] (2) Before roughing, the sphalerite was ground with 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 by a flotation machine. After stirring for 3 minutes, 500g / t of inhibitor sodium metabisulfite was added, stirred for 3 minutes, and 500g / t of implementing reagent 1 was added, stirred for three minutes, and 50g / t of N-allyl-O-isobutylthiocarbamate was added, stirred for 3 minutes, and 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 scavenging concentrate was returned to the previous flotation operation in sequence; a blank selection was performed on the roughing concentrate to obtain a concentrate, and the selected middlings were returned to the roughing operation in sequence.

[0078]

[0079] Example 2

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

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

[0082] (2) Before roughing, the sphalerite was ground with 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 by a flotation machine. After stirring for 3 minutes, 400g / t of inhibitor sodium pyrosulfite 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 scavenging concentrate was returned to the previous flotation operation in sequence; a blank selection was performed on the roughing concentrate to obtain a concentrate, and the selected middlings were returned to the roughing operation in sequence.

[0083]

[0084] Example 3

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

[0086] (1) The copper plating waste liquid (whose components include 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, and 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 with 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 by a flotation machine. After stirring for 3 minutes, 500 g / t of inhibitor sodium metabisulfite was added, stirred for 3 minutes, and 500 g / t of reagent 3 was added, stirred for three minutes, and 50 g / t of N-allyl-O-isobutylthiocarbamate was added, stirred for 3 minutes, and aerated and foam was scraped off. After the roughing was completed, 50 g / t of flotation collector (N-allyl-O-isobutylthiocarbamate) was added to the roughing tailings, and two scavenging operations were performed. The scavenging concentrate was returned to the previous flotation operation in sequence; a blank selection was performed on the roughing concentrate to obtain a concentrate, and the selected middlings were returned to the roughing operation in sequence.

[0088]

[0089] Example 4

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

[0091] (1) Stir the tin stripping waste liquid (whose components include tin ions, copper ions, nitric acid, etc.) uniformly, measure the pH value of the solution with a pH meter, add hydrochloric acid to the solution to adjust the pH value to 1.5 to precipitate tin ions, add an appropriate amount of sulfuric acid to the solution after filtration to precipitate lead ions in the solution, filter, and add sodium hydroxide to the solution to adjust the pH value of the solution to 3, thereby obtaining the implementation reagent 4.

[0092] (2) Before roughing, use a ball mill to grind the sphalerite (grind until -200 particles account for 80±2%), add water to control the pulp concentration to 40%, and flotate through a flotation machine. After stirring for 3 minutes, add 500g / t of inhibitor sodium metabisulfite, stir for 3 minutes, add 500g / t of implementing reagent 4, stir for three minutes, add 50g / t of N-allyl-O-isobutylthiocarbamate, stir for 3 minutes, aerate and scrape off the foam. After the roughing is completed, add 50g / t of flotation collector to the roughing tailings, perform 2 scavenging operations, and the scavenging concentrate is returned to the previous flotation operation in sequence; perform a blank selection on the roughing concentrate to obtain a concentrate, and the selected middlings are returned to the roughing operation in sequence.

[0093]

[0094] Example 5

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

[0096] (1) Heat the acid 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 out the solution with a vacuum filter, take the precipitate in a container, add sulfuric acid and stir thoroughly to obtain the implementation reagent 1.

[0097] (2) Before roughing, use a ball mill to grind the iron-bearing sphalerite (grind until -200 particles account for 80±2%), add water to control the pulp concentration to 40%, and flotate through a flotation machine. After stirring for 3 minutes, add 500g / t of inhibitor sodium metabisulfite, stir for 3 minutes, add 500g / t of implementing reagent 1, stir for three minutes, add 50g / t of N-allyl-O-isobutylthiocarbamate, stir for 3 minutes, aerate and scrape off the foam. After the roughing is completed, add 50g / t of flotation collector (N-allyl-O-isobutylthiocarbamate) to the roughing tailings, perform 2 scavenging operations, and the scavenging concentrate is returned to the previous flotation operation in sequence; perform a blank selection on the roughing concentrate to obtain a concentrate, and the selected middlings are returned to the roughing operation in sequence.

[0098]

[0099] Comparative Example 1

[0100] Before roughing, the sphalerite was ground with a ball mill (grinding to -200 particles accounted for 80±2%), water was added to control the pulp concentration to 40%, and flotation was performed by a flotation machine. After stirring for 3 minutes, 500g / t of inhibitor sodium metabisulfite was added, stirred for 3 minutes, without adding any activator, 50g / t of N-allyl-O-isobutylthiocarbamate was added, stirred for 3 minutes, aerated and scraped off the foam. After the roughing is completed, 50g / t of flotation collector is added to the roughing tailings, and 2 scavenging operations are carried out. The scavenging concentrate is returned to the previous flotation operation in sequence; a blank selection is carried out on the roughing concentrate to obtain the concentrate, and the selected middlings are returned to the roughing operation in sequence.

[0101]

[0102] Comparative Example 2

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

[0104]

[0105] Comparative Example 3

[0106] The other conditions of this comparative example are consistent with 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 solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for activating mineral flotation using waste liquid containing metal ions generated during the preparation of circuit boards, characterized in that: Taking metal sulfide as the treatment object, the metal sulfide is made into slurry, and inhibitor, activator, collector and frother are added into the slurry for flotation; The target product is obtained, wherein the activator is waste liquid containing metal ions generated by preparing circuit boards; and the amount of the flotation activator used is 10-2200 g / t.

2. A method for activating mineral flotation using waste liquid containing metal ions generated during the preparation of circuit boards, characterized in that: The activator is selected from at least one of the following schemes; Solution 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 and adding acid, and fully stirring the reaction to obtain a solution A; the pH value of the solution A is 1.5-7.0, and the copper ion concentration is 0.1-2.0 mol / L; Solution 2 If the waste liquid containing metal ions is the alkaline etching copper-containing waste liquid generated in the production process of circuit boards, the treatment method is: Stirring the alkaline etching copper-containing waste liquid, adding water or hydrochloric acid to dilute it, and after stirring evenly, filtering and separating it; adding an extractant, stirring and taking out a precipitate, and adding an 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, react fully and separate the layers, 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 production process of circuit boards, the treatment method is: The pH value 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 value 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.

3. The method for activating mineral flotation by using waste liquid containing metal ions generated in the preparation of circuit boards according to claim 2, characterized in that: In scheme 1, the heating temperature is controlled at 60-90 degrees Celsius; Preferably, the base in Scheme 1 is sodium hydroxide, calcium hydroxide, ammonia, etc., and is more preferably aqueous ammonia; 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; Preferably, when adding alkali in Scheme 1, the pH of the solution is controlled at 4.0-5.

0.

4. The method for activating mineral flotation by using waste liquid containing metal ions generated in the preparation of circuit boards according to claim 2, characterized in that: In scheme 2, the dilution multiple is controlled at about 40 to 60 times, which is the best dilution multiple; In scheme 2, waste activated carbon is added during filtration; 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; The copper chloride dihydrate solution in Scheme 2 can be recovered in the form of pure crystals at a pH of 2 to 4.

5. The method for activating mineral flotation by using waste liquid containing metal ions generated in the preparation of circuit boards according to claim 2, characterized in that: In scheme 3, the pH value of the solution should be adjusted to about 3.5-4.

5. 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 can be used to dilute the extractant to achieve the target concentration. Preferably, the extractant concentration is 5-20V%; The extraction time in scheme three is 60~180 seconds.

6. The method for activating mineral flotation by using waste liquid containing metal ions generated in the preparation of circuit boards according to claim 2, characterized in that: When the solution is adjusted to be acidic in scheme 4, the pH value is controlled to be 1.0~2.0; 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; In scheme 4, the alkali is sodium hydroxide, calcium hydroxide, ammonia, etc., and sodium hydroxide is more preferably used. At this time, the pH value is controlled to be 1.5~3.

5.

7. The method for activating mineral flotation by using waste liquid containing metal ions generated in the preparation of circuit boards according to claim 2, characterized in that: The inhibitor is an organic inhibitor or an inorganic inhibitor. If the gangue mineral is pyrite, sodium pyrosulfite is further preferred; The collector is at least one of xanthate, black medicine, nitrile ester, and sulfur-nitrogen. When flotation is performed on zinc-containing sulfide ores, N-allyl-O-isobutylthiocarbamate is further preferred.

8. The method for activating mineral flotation by using waste liquid containing metal ions generated in the preparation of circuit boards according to claim 2, 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 An alkyl group, n≥1; wherein n is preferably 2 to 8; more preferably 2 to 4, and even more preferably 2 to 3; Formula 1.

9. The method for activating mineral flotation by using waste liquid containing metal ions generated in the preparation of circuit boards according to claim 2, characterized in that: The amount of the flotation activator used in the flotation of sphalerite is: when the iron content in the sphalerite is less than 6%, the amount of the flotation activator is 10-1000 g / t; When the iron content in sphalerite is 6-12%, the amount of flotation activator is 10-1500 g / t, preferably 450-650 g / t; When the iron content in marmatite is greater than 12%, the dosage of flotation activator is 100~2000g / t.

10. The method for activating mineral flotation by using waste liquid containing metal ions generated in the preparation of circuit boards according to claim 2, characterized in that: When the mineral is sphalerite or iron-containing sphalerite, the dosage of the depressant is 480~650g / t and the dosage of the collector is 45~110g / t during roughing. After the roughing is completed, the amount of the collector added during scavenging can also be optimized to 50~55g / t.

Images