An activation-flotation recovery method for sulfide minerals in cyanide tailings

Abstract

The invention discloses an activation-flotation recovery method for sulfide minerals in cyanide tailings, belongs to the technical field of cyanide tailings treatment, and solves the problem that sulfide minerals are deeply suppressed and difficult to be separated by flotation in the prior art cyanide tailings treatment method. The method adopts pre-mixing reaction of organic polyamine and metal ions to generate an activator for flotation of sulfide minerals, and then reacts the activator with the ore pulp prepared from the cyanide tailings to achieve surface activation of the sulfide minerals, and finally adds a collector to flotate and recover the sulfide minerals from the ore pulp. The method of the invention effectively realizes the recycling of sulfide minerals in cyanide tailings.

Description

Technical Field

[0001] The invention belongs to the technical field of cyanidation tailings treatment, and particularly relates to an activation-flotation recovery method for sulfide minerals in cyanidation tailings. Background Art

[0002] Cyanidation is the main method of gold extraction. Cyanidation has the advantages of low cost, mature technology, and high adaptability to ores. Since the cyanidation method was applied to gold production in the 1880s, it has gradually become the main method for extracting gold and silver from gold ore. At present, more than 80% of the companies in my country use cyanidation to extract gold. Cyanidation tailings are waste tailings produced in the cyanidation process. With the rapid development of my country's gold industry, my country's gold smelting companies will discharge a large amount of cyanidation tailings every year. According to incomplete statistics, in recent years, the annual cyanidation tailings discharged by my country's gold smelting companies have been more than 20 million tons.

[0003] In my country, gold is mainly associated with sulfide minerals, so "flotation of gold-containing sulfide minerals-cyanide leaching" is the main process of cyanide production in my country. After flotation, the sulfur content in the concentrate is enriched to between 10% and 35%, which leads to the fact that the cyanide tailings often contain a lot of sulfide minerals. The sulfide minerals are mainly pyrite, followed by chalcopyrite, galena, sphalerite, etc. Flotation is the main method for recovering sulfide minerals, but the sulfide minerals in the cyanide tailings are difficult to enrich through flotation technology. This is mainly because the surface properties of sulfide minerals change significantly under the long-term action of cyanide, making them difficult to be activated, and the difference in floatability between minerals is significantly reduced. Therefore, under current technical conditions, the sulfide minerals in the cyanide tailings are difficult to be effectively recovered and utilized.

[0004] Due to the lack of mature cyanide tailings treatment technology, most of the cyanide tailings are stored. This not only poses a great environmental safety hazard, but also causes a serious waste of valuable sulfide mineral resources in the cyanide tailings. In recent years, domestic and foreign scientific and technological workers have done a lot of experimental research on the comprehensive recovery and utilization of cyanide tailings, and have made certain progress. However, various methods have certain limitations, such as high cost, the cost of recovering gold and silver is much higher than the added value of cyanide tailings, poor adaptability, and not suitable for promotion and application.

[0005] Xanthate collectors (such as ethyl xanthate, butyl xanthate, isopentyl xanthate, etc.) are the main sulfide mineral collectors. During the flotation process, the collector is adsorbed on the surface of the mineral to make the mineral surface hydrophobic. During the flotation process, the hydrophobic sulfide mineral particles adhere to the bubbles and rise into the foam layer, while the hydrophilic gangue minerals cannot adhere to the bubbles and remain in the slurry. The flotation separation of sulfide minerals and gangue minerals is achieved through the above process. However, since sulfide minerals are deeply suppressed by cyanide in the cyanide gold extraction operation, xanthate is difficult to adsorb on the surface of sulfide minerals, resulting in poor flotation effect of sulfide minerals. Therefore, how to efficiently separate sulfide minerals from cyanide tailings has become a problem to be solved. Summary of the invention

[0006] In view of the above analysis, the present invention aims to provide an activation-flotation recovery method for sulfide minerals in cyanide tailings, so as to solve the problem that sulfide minerals are deeply suppressed and difficult to be separated by flotation in the existing cyanide tailings treatment methods.

[0007] The purpose of the present invention is mainly achieved through the following technical solutions:

[0008] The invention provides an activation-flotation recovery method for sulfide minerals in cyanide tailings. The method comprises pre-mixing an organic polyamine and a metal ion to generate an activator for the flotation of the sulfide minerals, then reacting the activator with a pulp prepared from the cyanide tailings to activate the surface of the sulfide minerals, and finally adding a collector to flotate and recover the sulfide minerals from the pulp.

[0009] Furthermore, the activation-flotation recovery method of sulfide minerals in the cyanide tailings comprises:

[0010] Step 1: stirring and mixing the organic polyamine and the metal ion in an aqueous solution in advance, and obtaining a reaction product which is a solution containing an organic polyamine-metal ion complex, and the reaction product is used as an activator;

[0011] Step 2: Prepare the cyanide tailings into a slurry with a mass concentration of 25%-45%, and adjust the pH of the slurry to 6.0-9.0;

[0012] Step 3: adding the activator obtained in step 1 to the slurry in step 2, stirring and reacting to obtain a mixed slurry;

[0013] Step 4: adding a collector for sulfide mineral flotation to the mixed slurry and stirring the mixture to react; the collector is adsorbed on the surface of the sulfide mineral to make the surface of the sulfide mineral hydrophobic;

[0014] Step 5: The mixed slurry is passed into the flotation equipment for aeration flotation. During the flotation process, the hydrophobic sulfide minerals on the surface float up with the bubbles into the concentrate, while the hydrophilic gangue minerals remain in the slurry and become tailings.

[0015] Furthermore, the main components of the cyanide tailings include: sulfide minerals and gangue minerals.

[0016] Furthermore, in step 1, the organic polyamine has the following characteristics: the organic polyamine is an organic substance containing two or more -NH2 and / or -NH- structures in the molecule.

[0017] Furthermore, in step 1, the organic polyamine is one or more of aliphatic amines, alcohol amines, aromatic amines, alicyclic amines, amides or naphthyl amines.

[0018] Furthermore, in step 1, the metal ion is Cu + or Fe 2+ .

[0019] Furthermore, in step 1, the organic polyamine and Fe 2+ or Cu + The molar ratio is 1-3:1.

[0020] Furthermore, in step 1, the stirring and mixing time is 2-15 minutes.

[0021] Furthermore, in step 3, the amount of activator added is 60-200 g / t 矿 .

[0022] Furthermore, in step 4, the collector is a xanthate agent.

[0023] Compared with the prior art, the present invention can achieve at least one of the following technical effects:

[0024] 1) The activation-flotation recovery method of sulfide minerals in cyanide tailings of the present invention utilizes a mixed reaction of metal ions and organic polyamines to generate an organic polyamine-metal ion complex, and one end of the ammonia / amine-metal ion in the organic polyamine-metal ion complex reacts with the cyanide component on the surface of the sulfide mineral to generate an organic polyamine-metal ion-cyanide complex on the mineral surface, thereby selectively adsorbing on the surface of the sulfide mineral, eliminating the inhibitory effect of cyanide on the flotation of the sulfide mineral; then, by adding a xanthate collector to make the surface of the sulfide mineral hydrophobic, the flotation separation of the sulfide mineral and the gangue mineral is achieved during the flotation process. The sulfur grade and recovery rate of the sulfide mineral obtained by the method of the present invention are both high, for example, the recovery rate is greater than 85%.

[0025] (2) The organic polyamine-metal ion complex of the present invention can also react with the free cyanide remaining in the ore pulp to form a precipitate, thereby eliminating the interference of the residual cyanide on the flotation of sulfide minerals and solving its harm to the environment.

[0026] (3) The activation-flotation recovery system of the present invention is provided with a reagent pre-mixing reaction stirring tank, Fe2+ or Cu + The organic polyamine is first introduced into the reagent pre-mixing reaction stirring barrel, and fully mixed and reacted under suitable conditions. The reaction product is then introduced into the slurry stirring barrel for slurry adjustment; the interference of the complex environment in the slurry on the reaction between reagents is avoided, and the efficiency of the flotation reagent is increased.

[0027] (4) The existing methods for recovering sulfide minerals from cyanide tailings often require the addition of sulfuric acid to the ore pulp, which will produce highly toxic cyanide gas (HCN). In the flotation method of the present invention, metal ions and organic polyamines react in a reagent pre-mixed reaction stirring tank to produce a flotation reagent organic polyamine-metal ion complex that can be selectively adsorbed on the surface of sulfide minerals, without generating any hazardous products. In addition, the reagent can also precipitate the residual cyanide in the original cyanide tailings, eliminating the original safety hazards of the cyanide tailings, and having high environmental friendliness.

[0028] (5) The reagent pre-mixing reaction stirring barrel, slurry stirring barrel and flotation equipment of the activation-flotation recovery system of the present invention are modularly arranged, which is convenient for combination and adjustment according to the actual production of different mines; a reasonable flotation process is designed to achieve efficient recovery of sulfide minerals. This system has the characteristics of less equipment, short process, low operating cost, less maintenance difficulty and less investment.

[0029] Other features and advantages of the present invention will be described in the following description, and part of them may become obvious from the description, or may be understood by practicing the present invention. The purpose and other advantages of the present invention may be realized and obtained by the contents particularly pointed out in the written description and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The drawings are only for the purpose of illustrating particular embodiments and are not to be considered limiting of the present invention. Like reference numerals refer to like components throughout the drawings.

[0031] Figure 1 Schematic diagram of the principle of the present invention; wherein (a) represents that the surfaces of the unactivated sulfide mineral particles and the gangue mineral particles are unable to adsorb the collector; (b) represents that the surfaces of the activated sulfide minerals can adsorb the collector to make the mineral surfaces hydrophobic; (c) represents that the sulfide minerals adsorbing the collector after activation and becoming hydrophobic on the surface adhere to the bubbles during the flotation process and float with the bubbles, while the hydrophilic gangue minerals remain in the slurry;

[0032] Figure 2 It is a schematic diagram of the overall structure of the activation-flotation recovery system of the present invention;

[0033] Figure 3 It is a schematic diagram of the overall structure of the flotation device of the present invention;

[0034] Figure 4 This is a schematic diagram of the flotation process of Example 2 of the present invention.

[0035] Reference numerals:

[0036] 1-precision doser, 2-reagent pre-mixing reaction stirring barrel, 3-peristaltic pump, 4-slurry stirring barrel, 5-slurry pump, 6-flotation equipment, 7-overflow port, 8-underflow port, 9-feeding port, 10-bubble generator. DETAILED DESCRIPTION

[0037] The following is a further detailed description of an activation-flotation recovery method for sulfide minerals in cyanide tailings in conjunction with specific examples. These examples are only for comparison and explanation purposes, and the present invention is not limited to these examples.

[0038] At present, xanthate collectors (such as ethyl xanthate, butyl xanthate, isopentyl xanthate, etc.) are the main sulfide mineral collectors. During the flotation process, the collectors are adsorbed on the mineral surface to make the mineral surface hydrophobic. During the flotation process, the hydrophobic sulfide mineral particles adhere to the bubbles and rise into the foam layer, while the hydrophilic gangue minerals cannot adhere to the bubbles and remain in the pulp; the flotation separation of sulfide minerals and gangue minerals can be achieved through the above process. However, since the sulfide minerals in the cyanide tailings are deeply suppressed by cyanide in the cyanide gold extraction operation, xanthate is difficult to adsorb on the surface of the sulfide minerals, resulting in poor flotation effect of sulfide minerals. Therefore, after in-depth research, the inventors proposed a new activation-flotation recovery method for sulfide minerals in cyanide tailings: an activator for sulfide mineral flotation is generated by pre-mixing an organic polyamine and a metal ion, and the activator reacts with the cyanide-containing components exposed on the surface of the sulfide mineral to eliminate the interference of cyanide on the adsorption of the collector on the mineral surface, and then the sulfide minerals are recovered from the cyanide tailings by flotation using a xanthate collector.

[0039] The invention provides an activation-flotation recovery method for sulfide minerals in cyanide tailings, wherein organic polyamines and metal ions are pre-mixed and reacted to generate an activator for sulfide mineral flotation, and then the activator is reacted with a pulp prepared from the cyanide tailings to achieve surface activation of the sulfide minerals, and finally a collector is added to flotate and recover the sulfide minerals from the pulp.

[0040] The present invention provides an activation-flotation recovery method for sulfide minerals in cyanide tailings, comprising:

[0041] Step 1: stirring and mixing the organic polyamine and the metal ion in an aqueous solution in advance, and obtaining a reaction product which is a solution containing an organic polyamine-metal ion complex, and the reaction product is used as an activator;

[0042] Step 2: Prepare the cyanide tailings into a slurry with a mass concentration of 25%-45%, and adjust the pH of the slurry to 6.0-9.0;

[0043] Step 3: adding the activator obtained in step 1 to the slurry in step 2, stirring and reacting to obtain a mixed slurry;

[0044] Step 4: Add a collector for sulfide mineral flotation to the mixed slurry and stir to react for 3-10 minutes; the collector is adsorbed on the surface of the sulfide mineral to make the surface of the sulfide mineral hydrophobic;

[0045] Step 5: The mixed slurry is passed into the flotation equipment for aeration flotation. During the flotation process, the hydrophobic sulfide minerals on the surface float up with the bubbles into the concentrate, while the hydrophilic gangue minerals remain in the slurry and become tailings.

[0046] Specifically, the main components of the cyanide tailings include pyrite, chalcopyrite, galena, sphalerite and other sulfide minerals and gangue minerals, wherein the sulfur content is 10% to 35%, for example, 15% to 20%.

[0047] Specifically, in the above step 1, the organic polyamine has the following characteristics:

[0048] Organic polyamines are organic substances that contain two or more -NH2 (i.e., amino) and / or -NH- (i.e., amine) structures in their molecules.

[0049] Specifically, in the above step 1, the organic polyamine can be one or more of aliphatic amines, alcohol amines, aromatic amines, alicyclic amines, amides or naphthyl amines, for example, triethylenetetramine, diethylenetriamine, ethylenediaminetetraacetate, tetraethylenepentamine, and the like.

[0050] Specifically, in the above step 1, the metal ion can be Cu + or Fe 2+ .

[0051] Specifically, in the above step 1, the organic polyamine and Fe 2+ or Cu + If the molar ratio of organic polyamine to Fe is too small, the complexing reaction will be incomplete and the activator dosage will be insufficient; if the molar ratio is too large, the metal ions will be excessive and the collector will be consumed in the subsequent reaction, which will deteriorate the flotation effect. 2+ or Cu + The molar ratio is 1-3:1.

[0052] Specifically, in the above step 1, Fe 2+ The source can be FeCl2, Cu + The source may be CuCl.

[0053] Specifically, in the above step 1, the mass fraction of the organic polyamine in water is 1%-20%.

[0054] Specifically, in the above step 1, too short a stirring and mixing time will result in incomplete reaction, and too long a stirring and reaction time will result in increased energy consumption. Therefore, the stirring and mixing time is controlled to be 2-15 minutes; for example, 3 minutes, 5 minutes, 7 minutes, 10 minutes, 12 minutes, and 15 minutes.

[0055] Specifically, in the above step 2, if the mass concentration of the ore pulp is too high, it will be difficult for the flotation reagents (for example, activators, collectors) to disperse and react effectively in the ore pulp, and cause serious gangue entrainment in the subsequent flotation process; if the ore pulp concentration is too low, it will lead to a decrease in the system processing capacity and a decrease in the flotation recovery rate. Therefore, the mass concentration of the ore pulp is controlled to be 25%-45%; for example, 25%, 30%, 35%, 40%, 45%.

[0056] Specifically, in the above step 2, the pH is controlled to be 6.0-9.0 (e.g., 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0) in order to provide a suitable solution environment for the interaction between the flotation reagent (e.g., activator, collector) and the mineral surface.

[0057] Specifically, in the above step 3, the amount of activator added is 60-200g / t 矿 , for example, 60g / t 矿 , 80g / t 矿 , 100g / t 矿 , 120g / t 矿 , 140g / t 矿 , 160g / t 矿 , 180g / t 矿 , 200g / t ore.

[0058] Specifically, in the above step 3, the purpose of the stirring reaction is to allow the activator to react with the exposed cyanide-containing components on the surface of the sulfide mineral to form a complex reaction so as to be adsorbed on the surface of the sulfide mineral, thereby eliminating the interference of the original exposed cyanide on the surface of the sulfide mineral with the adsorption of the collector. If the stirring time is too long, some of the organic polyamine-metal ion complexes that have been adsorbed on the surface of the sulfide mineral will be desorbed, and the energy consumption of mechanical stirring will also increase; while if the stirring time is too short, it will affect the full adsorption of the organic polyamine-metal ions on the mineral surface. Therefore, the stirring reaction time is controlled to be 3-15 minutes, for example, 3 minutes, 5 minutes, 7 minutes, 10 minutes, 12 minutes, and 15 minutes.

[0059] Specifically, in the above step 4, the collector is a xanthate agent, for example, butyl xanthate, isopentyl xanthate, etc.

[0060] Specifically, the principle of the activation-flotation recovery method of sulfide minerals in the cyanide tailings is as follows:

[0061] In the cyanide gold extraction operation, under the long-term action of cyanide, the surface of the sulfide mineral reacts with cyanide, causing cyanide to adsorb on the surface of the sulfide mineral. During the flotation process, the cyanide-containing components on the surface of the sulfide mineral seriously hinder the adsorption of xanthate collectors on the surface of the sulfide mineral, thereby inhibiting the flotation of the sulfide mineral. In the above step 1, Fe 2+ or Cu + It can accept lone pairs of electrons. In organic polyamines, the N atom of -NH2 or -NH- contains unshared electron pairs and can give out lone pairs of electrons. Therefore, the two can react chemically to form organic polyamine-metal ion complexes (e.g. [Cu(H2N-CH2-CH2-NH2)] + , [Cu(H2N-CH2-CH2-NH2)2] + The organic polyamine-metal ion complex is added to the pulp of cyanide tailings as an activator for sulfide mineral flotation. The activator reacts with the exposed cyanide-containing components on the surface of the sulfide mineral and adsorbs on the mineral surface, eliminating the barrier of the original exposed cyanide on the surface of the sulfide mineral to the adsorption of xanthate collectors; the xanthate collectors selectively adsorb on the surface of the sulfide mineral to make the surface of the sulfide mineral hydrophobic, while the surface of the gangue mineral cannot adsorb xanthate and remains hydrophilic. During the flotation process, the hydrophobic sulfide mineral particles adhere to the bubbles and rise into the concentrate, while the gangue minerals are difficult to adhere to the bubbles due to their hydrophilic surface and remain in the pulp. The flotation separation of sulfide minerals and gangue minerals is achieved through the above process.

[0062] Furthermore, in the above step 3, the organic polyamine-metal ion complex can also react with the residual free cyanide in the ore pulp to generate a solid precipitate, thereby eliminating the inhibitory effect of cyanide on sulfide minerals, improving the floatability of sulfide minerals, and improving the recovery rate of sulfide minerals.

[0063] Specifically, in the above step 4, if the amount of collector is too much, it will lead to waste of reagents and excessive production costs; if it is too little, it will lead to insufficient hydrophobicity of the mineral surface; therefore, the mass of the collector is controlled to be 200-500g / t 矿 (e.g. 200g / t 矿 , 250g / t 矿 、300g / t 矿 、350g / t 矿 , 400g / t 矿 , 450g / t 矿 ).

[0064] Specifically, in the above step 4, if the stirring reaction time is too long, it will lead to an increase in the mechanical stirring cost and even cause the adsorbed reagent to fall off from the mineral surface; if it is too short, it will lead to an incomplete reaction; therefore, the stirring reaction is controlled to 3-10 minutes.

[0065] Specifically, in the above step 5, during the flotation process, the concentration of the mixed pulp is 25%-45%, and the flotation time is 10-25 minutes.

[0066] On the other hand, the present invention also provides an activation-flotation recovery system used in the above-mentioned activation-flotation recovery method of sulfide minerals in cyanide tailings, comprising a precision doser 1, a reagent pre-mixing reaction stirring barrel 2, a slurry stirring barrel 4 and a flotation device 6; a peristaltic pump 3 is provided between the reagent pre-mixing reaction stirring barrel 2 and the slurry stirring barrel 4; a slurry pump 5 is provided between the slurry stirring barrel 4 and the flotation device 6; the precision doser 1 comprises a first precision doser and a second precision doser; the first precision doser is used to add metal ions to the reagent pre-mixing reaction stirring barrel 2, and the second precision doser is used to add organic polyamines to the reagent pre-mixing reaction stirring barrel 2, and the metal ions and the organic polyamines can react in the reagent pre-mixing reaction stirring barrel 2 to form organic polyamine-metal ion complexes.

[0067] Specifically, the flotation device 6 includes a flotation column and / or a flotation machine. Figure 3 As shown, a flotation column is used as an example: an overflow port 7 and a feed port 9 are provided at the top of the flotation device 6 , an underflow port 8 is provided at the bottom, and a bubble generator 10 is provided at the lower part of the flotation device 6 .

[0068] Specifically, in the above step 1, the first precision doser and the second precision doser are respectively used to add Fe 2+ or Cu + Ions and hydrophobic organic polyamines are added to a reagent containing water and pre-mixed in a reaction stirring tank 2 for stirring reaction to obtain a reaction product which is a solution containing a hydrophobic organic polyamine-metal ion complex.

[0069] Specifically, in the above step 2, the cyanide tailings are configured into a slurry with a mass concentration of 20%-45% in the slurry stirring barrel 4.

[0070] Specifically, in the above step 3, the organic polyamine-metal ion complex can be added into the slurry stirring barrel 4 through the peristaltic pump 3 as an activator. In the slurry stirring barrel 4, the activator and the mineral particles are fully mixed and reacted to prepare the slurry. In this process, the organic polyamine-metal ion complex is selectively adsorbed on the surface of the sulfide minerals in the cyanide tailings.

[0071] Specifically, in the above step 5, the mixed slurry is fed into the flotation device 6 through the slurry pump 5. During the flotation process of the flotation device 6, the hydrophobic sulfide mineral particles adhere to the bubbles and rise into the foam layer, and then overflow from the overflow port 7; the hydrophilic gangue particles cannot float up and become tailings and are discharged from the underflow port 8 at the bottom of the flotation device 6.

[0072] Specifically, in the above step 5, according to different flotation processes, multiple flotation equipment can be used in combination, for example, the roughing concentrate enters the second flotation equipment for concentrating, and the roughing tailings enter the third flotation equipment for scavenging. In order to achieve the best economic and technical indicators, for different cyanide tailings, it is generally necessary to determine the best flotation process in advance through mineral processing tests, such as a roughing process, a roughing-scavenging open-circuit process, a roughing-scavenging-scavenging closed-circuit process, etc.

[0073] Compared with the prior art, the activation-flotation recovery method of sulfide minerals in cyanide tailings of the present invention utilizes the mixed reaction of metal ions and organic polyamines to generate organic polyamine-metal ion complexes, and one end of the ammonia / amine-metal ion in the organic polyamine-metal ion complexes reacts with the cyanide component on the surface of the sulfide mineral to generate organic polyamine-metal ion-metal cyanide complexes on the mineral surface, thereby selectively adsorbing on the surface of the sulfide mineral, eliminating the inhibitory effect of cyanide on the flotation of the sulfide mineral; then, by adding a xanthate collector, the surface of the sulfide mineral is made hydrophobic, and the flotation separation of the sulfide mineral and the gangue mineral is achieved during the flotation process. The sulfur grade and recovery rate of the sulfide mineral obtained by the method of the present invention are both high.

[0074] The organic polyamine-metal ion complex of the present invention can also react with the free cyanide remaining in the ore pulp to generate precipitation, thereby eliminating the interference of the residual cyanide on the flotation of sulfide minerals and solving the harm to the environment.

[0075] The activation-flotation recovery system of the present invention is provided with a reagent pre-mixing reaction stirring tank, Fe 2+ or Cu + Ions and organic polyamines are first introduced into a pre-mixed reaction stirring barrel for reagents, and fully mixed and reacted under suitable conditions. The reaction products are then introduced into a slurry stirring barrel for slurry adjustment. This avoids the interference of the complex environment in the slurry on the reaction between reagents and increases the efficiency of the flotation reagents.

[0076] The existing method of recovering sulfide minerals from cyanide tailings often requires adding sulfuric acid to the ore pulp, and this process will produce highly toxic cyanide gas (HCN); while in the flotation method of the present invention, metal ions and organic polyamines react in a reagent pre-mixed reaction stirring tank to produce a flotation reagent organic polyamine-metal ion complex that can be selectively adsorbed on the surface of sulfide minerals, and no dangerous products are generated; and the reagent can also precipitate residual cyanide in the original cyanide tailings, eliminating the original safety hazards of the cyanide tailings, and has high environmental friendliness.

[0077] The reagent pre-mixing reaction stirring barrel, slurry stirring barrel and flotation equipment of the activation-flotation recovery system of the present invention are arranged in a modular manner, which is convenient for combination and adjustment according to the actual production of different mines; a reasonable flotation process is designed to achieve efficient recovery of sulfide minerals. The system has the characteristics of less equipment, short process, low operating cost, less maintenance difficulty and less investment.

[0078] Example 1

[0079] This embodiment provides an activation-flotation recovery method for sulfide minerals in cyanide tailings, the sulfur grade in the cyanide tailings is 15.66%, the sulfide minerals mainly include pyrite, and the gangue minerals mainly include quartz, feldspar, kaolin, etc. The method comprises the following steps:

[0080] (1) FeCl2 and triethylenetetramine are mixed in water in a molar ratio of 1:2, and stirred for 10 minutes to obtain a sulfide mineral flotation activator; wherein the mass concentration of the triethylenetetramine is 5%;

[0081] (2) adjusting the concentration of cyanide tailings slurry to 38% and the pH of the slurry to 8.0;

[0082] (3) Add activator (80g / t 矿 ) is added to the slurry of (2), stirred to react and obtain a mixed slurry; 300 g / t butyl xanthate is added to the mixed slurry. 矿 , stirring reaction for 3 min;

[0083] (4) The mixed pulp is passed into a flotation machine for aeration flotation to obtain sulfur concentrate (sulfide minerals). The flotation pulp concentration is 38% and the flotation time is 15 minutes; the sulfide minerals float up with the bubbles and overflow as concentrate, while the gangue minerals remain in the pulp and are subsequently discharged from the discharge port.

[0084] Through the above method, after one roughing, a sulfur concentrate with a sulfur grade of 36.65% and a recovery rate of 85.04% can be obtained, and the sulfur grade of the tailings is reduced to 3.68%.

[0085] Example 2

[0086] This embodiment provides an activation-flotation recovery method for sulfide minerals in cyanide tailings, wherein the sulfur grade in the cyanide tailings is 17.83%, the sulfide minerals mainly include pyrite, chalcopyrite, a small amount of sphalerite and a small amount of galena, and the gangue minerals are mainly quartz and aluminosilicate, etc. The method comprises the following steps:

[0087] (1) CuCl and triethylenetetramine are mixed in water in a molar ratio of 1:3, and stirred for 15 minutes to obtain a sulfide mineral flotation activator; wherein the mass concentration of the triethylenetetramine is 10%;

[0088] (2) adjusting the concentration of cyanide tailings slurry to 40% and the slurry pH to 8.0;

[0089] (3) Add activator (120g / t 矿 ) is added to the slurry of (2), and stirred to react to obtain a mixed slurry; 400g / t butyl xanthate is added to the mixed slurry 矿 , stirring and reacting for 5 min;

[0090] (4) The mixed pulp is passed into the flotation column and aerated flotation is performed to obtain sulfur concentrate (sulfide minerals). The flotation pulp concentration is 40% and the flotation time is 15 minutes; the sulfide minerals float up with the bubbles and overflow as concentrate, while the gangue minerals remain in the pulp and are subsequently discharged from the tailings discharge pipe at the bottom of the flotation column.

[0091] Through the above method, after one roughing, a sulfur concentrate with a sulfur grade of 38.30% and a recovery rate of 85.86% can be obtained, and the sulfur grade of the tailings is reduced to 4.20%.

[0092] Example 3

[0093] This embodiment provides an activation-flotation recovery method for sulfide minerals in cyanide tailings, wherein the sulfur grade in the cyanide tailings is 20.34%, the sulfide minerals are mainly pyrite, and the gangue minerals are mainly silicate minerals, quartz, etc. The method comprises the following steps:

[0094] (1) FeCl2 and diethylenetriamine are mixed in water in a molar ratio of 1:1, and stirred for reaction for 8 minutes to obtain a sulfide mineral flotation activator; wherein the mass concentration of triethylenetetramine is 10%;

[0095] (2) adjusting the concentration of cyanide tailings slurry to 35% and the slurry pH to 7.5;

[0096] (3) Add activator (100g / t 矿 ) is added to the slurry of (2), and stirred to react to obtain a mixed slurry; 400g / t butyl xanthate is added to the mixed slurry 矿 , stirring reaction for 3 min;

[0097] (4) The mixed pulp is passed into the flotation column and aerated flotation is performed to obtain sulfur concentrate (sulfide minerals). The flotation pulp concentration is 35% and the flotation time is 15 minutes; the sulfide minerals float up with the bubbles and overflow as concentrate, while the gangue minerals remain in the pulp and are subsequently discharged from the tailings discharge pipe at the bottom of the flotation column.

[0098] Through the above method, after one roughing, a sulfur concentrate with a sulfur grade of 38.45% and a recovery rate of 88.55% can be obtained, and the sulfur grade of the tailings is reduced to 4.38%.

[0099] Example 4

[0100] This embodiment provides an activation-flotation recovery method for sulfide minerals in cyanide tailings, the sulfur grade in the cyanide tailings is 22.20%, the sulfide minerals mainly include pyrite and chalcopyrite, and the gangue minerals are mainly quartz, etc. The method comprises the following steps:

[0101] (1) CuCl and tetraethylenepentamine are mixed in water in a molar ratio of 1:2, and stirred for 5 minutes to obtain a sulfide mineral flotation activator; wherein the mass concentration of triethylenetetramine is 5%;

[0102] (2) adjusting the concentration of cyanide tailings slurry to 40% and the slurry pH to 8.5;

[0103] (3) Add activator (200g / t 矿 ) is added to the slurry of (2), stirred to react and obtain a mixed slurry; 250g / t butyl xanthate is added to the mixed slurry 矿 , stirring reaction for 3 min;

[0104] (4) The mixed pulp is passed into the flotation machine, and aeration flotation is performed to obtain sulfur concentrate (sulfide minerals). The flotation pulp concentration is 40%, and the flotation time is 15 minutes; the sulfide minerals float up with the bubbles and overflow as concentrate, while the gangue minerals remain in the pulp and are subsequently discharged from the tailings discharge pipe at the bottom of the flotation column.

[0105] Through the above method, after one roughing, a sulfur concentrate with a sulfur grade of 42.35% and a recovery rate of 87.57% can be obtained, and the sulfur grade of the tailings is reduced to 5.10%.

[0106] Example 5

[0107] This embodiment provides an activation-flotation recovery method for sulfide minerals in cyanide tailings, wherein the sulfur grade in the cyanide tailings is 19.39%, the sulfide minerals are mainly pyrite, and also contain a small amount of chalcopyrite; the gangue minerals are mainly silicate minerals such as quartz and feldspar. The method comprises the following steps:

[0108] (1) CuCl and tetraethylenepentamine were mixed in a molar ratio of 1:1, and stirred for 10 minutes to obtain a sulfide mineral flotation activator;

[0109] (2) adjusting the concentration of cyanide tailings slurry to 40% and the slurry pH to 8.5;

[0110] (3) Add activator (100g / t 矿 ) is added to the slurry of (2), stirred to react and obtain a mixed slurry; 450g / t butyl xanthate is added to the mixed slurry 矿 , stirring reaction for 3 min;

[0111] (4) The mixed pulp is passed into the flotation equipment, and the sulfur concentrate (sulfide mineral) is obtained by aeration flotation. Specifically, the flotation process is a roughing process, a scavenging process and a cleaning process (such as Figure 4 As shown in the figure, the flotation equipment uses a cyclone-static microbubble flotation column. The slurry is first passed into a roughing flotation column with a diameter of 4.5m. The roughing concentrate enters the fine separation, and the roughing tailings enter the scavenging separation. The flotation reagent dosage of the scavenging section is 1 / 2 of that of the roughing section. A flotation column with a diameter of 4m is used. The scavenging tailings are used as the final tailings, and the scavenging concentrate is returned to the roughing section. No additional flotation reagent is added in the fine separation section. A flotation column with a diameter of 4m is used. The fine tailings and the scavenging concentrate are returned to the roughing section together, and the fine concentrate is used as the final concentrate.

[0112] Comparative Example 1

[0113] The treatment object of Comparative Example 1 is the same as that of Example 5, and the same flotation process and flotation equipment as those of Example 5 are used, but the traditional sulfide mineral flotation reagent system is used. The following steps are included:

[0114] (1) preparing cyanide tailings into a slurry with a mass concentration of 40%;

[0115] (2) Adjust the pH of the slurry to 5.5 and add 80 g / t copper sulfate to the slurry. 矿 After stirring for 5 minutes, add 350g / t of butyl xanthate as collector 矿 , stirring reaction for 3 min;

[0116] (3) The ore pulp is passed into a cyclone-static microbubble flotation column. The flotation process is the same as that in Example 5. The amount of reagent added in the scavenging section is 1 / 2 of that in the coarse section, and no reagent is added in the cleaning section.

[0117] Comparative Example 2

[0118] Comparative Example 2 treats the same object as Example 5, and uses the same flotation process and flotation equipment as Example 5, but uses a traditional sulfide mineral flotation reagent system. It includes the following steps:

[0119] (1) preparing cyanide tailings into a slurry with a mass concentration of 40%;

[0120] (2) Add 20 kg / t of sulfuric acid to the slurry 矿 After stirring for 20 minutes, add 350g / t of butyl xanthate collector to the slurry. 矿 , stirring reaction for 3 min;

[0121] (3) The ore pulp is passed into a cyclone-static microbubble flotation column. The flotation process is the same as that in Example 5. The amount of reagent added in the scavenging section is 1 / 2 of that in the coarse section, and no reagent is added in the cleaning section.

[0122] Table 1 below shows the test results of Example 5, Comparative Example 1 and Comparative Example 2. As shown in Table 1 below, the concentrate grade and recovery rate of Comparative Example 1 and Comparative Example 2 using the traditional sulfide mineral flotation method are both low, and the sulfide minerals cannot be effectively floated and separated from the cyanide tailings; while Example 5 using the method of the present invention can effectively activate the flotation of sulfide minerals, and the sulfur grade and recovery rate of its concentrate are higher than those of Comparative Examples 1-2, achieving ideal indicators.

[0123] Table 1 Test results of Example 5 and Comparative Examples 1-2

[0124]

[0125] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. An activation-flotation recovery method for sulfide minerals in cyanide tailings, characterized in that: The method comprises pre-mixing an organic polyamine and a metal ion to generate an activator for flotation of sulfide minerals, then reacting the activator with a pulp prepared from cyanide tailings to activate the surface of the sulfide minerals, and finally adding a collector to flotate and recover the sulfide minerals from the pulp. The organic polyamine comprises the following features: the organic polyamine is an organic substance containing two or more -NH2 and / or -NH- structures in the molecule; The organic polyamine is one or more of aliphatic amines, alcohol amines, aromatic amines, alicyclic amines, amides or naphthyl amines; The metal ion is Cu + or Fe 2+ .

2. The activation-flotation recovery method of sulfide minerals in cyanide tailings according to claim 1, characterized in that: include: Step 1: stirring and mixing the organic polyamine and the metal ion in an aqueous solution in advance, and obtaining a reaction product which is a solution containing an organic polyamine-metal ion complex, and the reaction product is used as an activator; Step 2: Prepare the cyanide tailings into a slurry with a mass concentration of 25%-45%, and adjust the pH of the slurry to 6.0-9.0; Step 3: adding the activator obtained in step 1 to the slurry in step 2, stirring and reacting to obtain a mixed slurry; Step 4: adding a collector for sulfide mineral flotation to the mixed slurry and stirring the mixture to react; the collector is adsorbed on the surface of the sulfide mineral to make the surface of the sulfide mineral hydrophobic; Step 5: The mixed slurry is passed into the flotation equipment for aeration flotation. During the flotation process, the hydrophobic sulfide minerals on the surface float up with the bubbles into the concentrate, while the hydrophilic gangue minerals remain in the slurry and become tailings.

3. The activation-flotation recovery method of sulfide minerals in cyanide tailings according to claim 2, characterized in that: The main components of the cyanide tailings include: sulfide minerals and gangue minerals.

4. The activation-flotation recovery method of sulfide minerals in cyanide tailings according to claim 2, characterized in that: In the step 1, the organic polyamine and Fe 2+ or Cu + The molar ratio is 1-3:

1.

5. The activation-flotation recovery method of sulfide minerals in cyanide tailings according to claim 2, characterized in that: In the step 1, the stirring and mixing time is 2-15 minutes.

6. The activation-flotation recovery method of sulfide minerals in cyanide tailings according to any one of claims 2 to 5, characterized in that: In the step 4, the collector is a xanthate agent.

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