A flotation recovery method for sulfide ore in cyanide tailings

Abstract

The present invention discloses a flotation recovery method for sulfide ore in cyanide tailings, which belongs to the technical field of cyanide tailings treatment and solves the problem that sulfide ore in cyanide tailings is difficult to recycle in the prior art. The flotation recovery method uses hydrophobic organic polyamine as a multidentate ligand to react with Fe in an aqueous solution. 2+ Cu + The stirring reaction is performed to obtain a hydrophobic organic polyamine-metal ion complex; the cyanide tailings are treated with the hydrophobic organic polyamine-metal ion complex and then flotated to obtain sulfide ore. The method of the present invention effectively realizes the recovery and utilization of sulfide ore in cyanide tailings.

Description

Technical Field

[0001] The invention belongs to the technical field of cyanidation tailings treatment, and in particular relates to a flotation recovery method for sulfide ore in cyanidation tailings. Background Art

[0002] Among the many methods and processes of gold smelting, cyanidation leaching is the main method of gold smelting in the world. However, the disadvantages of cyanidation are also obvious. The cyanidation gold extraction process produces a large amount of cyanidation tailings. The mineral composition of cyanidation tailings is complex. In addition to low-grade Au and Ag, it also contains a certain amount of valuable elements such as Fe, S, Cu, Pb, Zn, Sb, As, Si, and highly toxic CN- and residual polluting agents. It is a highly polluting but comprehensive utilization value of metallurgical waste slag.

[0003] The current treatment method for cyanide tailings in my country is simple storage or landfill, which wastes a large amount of valuable elements. The economic losses caused by dumping, pollution and treatment amount to hundreds of billions of yuan each year. The dumping of cyanide tailings is bound to have a serious impact on the environment, such as occupying a large amount of land, wasting mineral resources, and leaving highly toxic CN - It pollutes river soil and affects the ecological environment.

[0004] Although the cyanide tailings after multi-element recovery treatment still contain a large amount of sulfide ore (generally containing 19-30% sulfur), due to the spontaneous aggregation effect of fine-grained minerals and a large amount of CN - The presence of sulfide has an inhibitory effect on the floatability of sulfide ores, which brings great difficulties to the enrichment and separation of sulfide ores in cyanide tailings. At present, some domestic enterprises simply add sulfuric acid to the ore pulp for treatment. This method will produce toxic HCN gas, which will cause environmental pollution, and the treatment process is harmful to the health of workers. At present, there is also a method of using xanthate as a collector for flotation, but due to the inhibitory effect of cyanide on sulfide ores, the flotation effect is extremely poor; therefore, the recovery rate of sulfide ores is low, and the cost of enterprise treatment is high, which wastes a lot of resources and is not conducive to the efficient recovery of sulfide ores in cyanide tailings. Therefore, how to efficiently separate sulfide ores from cyanide tailings has become a problem that needs to be solved urgently. Summary of the invention

[0005] In view of the above analysis, the present invention aims to provide a flotation recovery method for sulfide ore in cyanide tailings, so as to solve the current problem that sulfide ore in cyanide tailings is difficult to recycle.

[0006] The purpose of the present invention is mainly achieved through the following technical solutions:

[0007] The present invention provides a flotation recovery method for sulfide ore in cyanide tailings, wherein the flotation recovery method uses hydrophobic organic polyamine as a multidentate ligand to prepare a hydrophobic organic polyamine-metal ion complex, wherein the metal ions include: Fe 2+ Cu + ; The cyanide tailings are treated with the hydrophobic organic polyamine-metal ion complex and then flotated to obtain sulfide ore.

[0008] Furthermore, the flotation recovery method comprises:

[0009] Step 1: Using hydrophobic organic polyamine as a multidentate ligand, react with Fe 2+ Cu + The reaction is carried out by stirring, and the reaction product is a solution containing a hydrophobic organic polyamine-metal ion complex;

[0010] Step 2: Prepare the cyanide tailings into a slurry with a mass concentration of 20%-45%, and adjust the slurry to a pH of 7-9;

[0011] Step 3: adding the reaction product of step 1 to the slurry of step 2, stirring and reacting to obtain a mixed slurry;

[0012] Step 4: Pass the mixed ore pulp into the flotation equipment for flotation to obtain the floated sulfide ore.

[0013] Furthermore, the main components of the cyanide tailings include: sulfide minerals and gangue minerals.

[0014] Furthermore, the hydrophobic organic polyamine has the following characteristics:

[0015] The molecular structure contains more than two -NH2 and / or -NH- structures;

[0016] The molecular structure also contains a hydrophobic structure, which includes an aromatic group or a C4-C20 alkyl group.

[0017] Furthermore, the hydrophobic organic polyamine is alkyl polyamine ether or tetradecyl diamine.

[0018] Furthermore, in step 1, the hydrophobic organic polyamine and Fe 2+ Cu + The molar ratio is 1-3:1.

[0019] Furthermore, in step 3, the amount of the reaction product added is 80-200 g / t 矿 .

[0020] Furthermore, in step 3, the stirring reaction time is 3-15 min.

[0021] Furthermore, the flotation recovery method adopts a flotation recovery system for sulfide ores in cyanide tailings, and the flotation recovery system for sulfide ores in cyanide tailings includes a precise dosing device, a reagent pre-mixing reaction stirring barrel, a slurry stirring barrel and a flotation device; a peristaltic pump is provided between the reagent pre-mixing reaction stirring barrel and the slurry stirring barrel; a slurry pump is provided between the slurry stirring barrel and the flotation device.

[0022] Furthermore, the precision doser includes a first precision doser and a second precision doser; the first precision doser is used to add metal ions into the reagent premixing reaction stirring barrel, and the second precision doser is used to add organic polyamines into the reagent premixing reaction stirring barrel.

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

[0024] 1) The flotation recovery method of sulfide ore in cyanide tailings of the present invention utilizes a mixed reaction of metal ions and hydrophobic organic polyamines to produce a hydrophobic organic polyamine-metal ion complex, and one end of the ammonia / amine group-metal ion in the hydrophobic organic polyamine-metal ion complex reacts with the cyanide component on the surface of the sulfide mineral to generate an organic polyamine-metal ion-metal 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; and one end of the hydrophobic group faces the solution, making the mineral surface hydrophobic, and realizing the flotation separation of the sulfide mineral and the gangue mineral in the flotation process. The sulfur grade and recovery rate of the sulfide mineral obtained by the method of the present invention are both high.

[0025] 2) The hydrophobic 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 ore and solving its harm to the environment.

[0026] 3) The flotation recovery system of the present invention is provided with a reagent pre-mixing reaction stirring tank, Fe 2+ or Cu + Ions and hydrophobic 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.

[0027] 4) The existing method of recovering sulfide ore 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, the 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 the sulfide ore, and no dangerous products are generated; and the reagent can also precipitate the residual cyanide in the original cyanide tailings, eliminating the original safety hazards of the cyanide tailings, and has high environmental friendliness.

[0028] 5) The reagent pre-mixing reaction stirring barrel, slurry stirring barrel and flotation equipment of the 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 ores. 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 It is a schematic diagram of the overall structure of the flotation recovery system of the present invention;

[0032] Figure 2 It is a schematic diagram of the overall structure of the flotation device of the present invention;

[0033] Figure 3 is one of the structural formulas of the hydrophobic organic polyamine of the present invention;

[0034] Figure 4 is the second structural formula of the hydrophobic organic polyamine of the present invention;

[0035] Figure 5 This is the third structural formula of the hydrophobic organic polyamine of the present invention.

[0036] Reference numerals:

[0037] 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

[0038] The following is a further detailed description of a flotation recovery method for sulfide ore in cyanide tailings in conjunction with specific examples. These examples are only used for comparison and explanation purposes, and the present invention is not limited to these examples.

[0039] The present invention provides a flotation recovery method for sulfide ore in cyanide tailings. The flotation recovery method uses hydrophobic organic polyamine as a multidentate ligand to prepare a hydrophobic organic polyamine-metal ion complex. The metal ions include: Fe 2+ or Cu + The cyanide tailings are treated with a hydrophobic organic polyamine-metal ion complex and then flotated to obtain sulfide ore.

[0040] Specifically, the flotation recovery method of sulfide ore in the cyanide tailings comprises:

[0041] Step 1: Using hydrophobic organic polyamine as a multidentate ligand, react with Fe 2+ or Cu + The reaction is carried out by stirring, and the reaction product is a solution containing a hydrophobic organic polyamine-metal ion complex;

[0042] Step 2: Prepare the cyanide tailings into a slurry with a mass concentration of 20%-45%, and adjust the slurry to a pH of 7-9;

[0043] Step 3: Add the reaction product of step 1 to the slurry of step 2. The amount of the reaction product of step 1 added is 80-200g / t. 矿 ; Stirring the reaction to obtain a mixed slurry;

[0044] Step 4: Pass the mixed slurry into the flotation equipment, ventilate and perform flotation to obtain the floated sulfide ore.

[0045] Specifically, the main components of the cyanide tailings include sulfide minerals such as pyrite, chalcopyrite, galena, sphalerite, and gangue minerals such as quartz and aluminosilicate, wherein the sulfur content is 10%-35%.

[0046] Specifically, in the above step 1, the hydrophobic organic polyamine includes the following characteristics:

[0047] 1. The molecular structure contains more than two -NH2 and / or -NH- structures;

[0048] 2. The molecular structure also contains a hydrophobic structure, which includes a C4-C20 alkyl or aromatic group.

[0049] Specifically, the hydrophobic organic polyamine may be an alkyl polyamine ether, wherein the alkyl group may be a hydrocarbon chain containing four to twenty carbon atoms and one to four amino groups in the molecule; specifically, the alkyl polyamine ether may be dodecyl diamine ether or hexadecyl triamine ether. 1 -(2-(Decyloxy)ethyl)-1,2-ethylenediamine, N 1 -(2-aminoethyl)-N 2 -(3-tridecyloxy)propyl)-1,2-ethylenediamine, etc.

[0050] Specifically, in the above step 1, the hydrophobic organic polyamine may also be N-tetradecyl-1,3-propyldiamine or the like.

[0051] Specifically, in the above step 1, the hydrophobic organic polyamine may be:

[0052] CH3-(CH2)9-O-(CH2)2-NH-(CH2)2-NH2

[0053] or

[0054] CH3-(CH2) 12 -O-(CH2)3-NH-(CH2)2-NH-(CH2)2-NH2

[0055] or

[0056] CH3-(CH2) 13 -NH-(CH2)3-NH2

[0057] Specifically, in the above step 1, the hydrophobic organic polyamine and Fe 2+ or Cu + Too large a molar ratio of Fe leads to incomplete complexation and low complex yield; too small a molar ratio leads to excessive metal ions, interfering with subsequent flotation. 2+ or Cu + The molar ratio is 1-3:1.

[0058] Specifically, in the above step 1, Fe 2+ The source can be FeCl2, Cu + The source may be CuCl.

[0059] Specifically, in the above step 1, the mass fraction of the hydrophobic organic polyamine in water is 1%-20%.

[0060] Specifically, in the above step 1, too short a stirring reaction time will result in incomplete reaction, and too long a stirring reaction time will result in increased energy consumption. Therefore, the stirring reaction time is controlled to be 2-15 minutes; illustratively, such as 3 minutes, 5 minutes, 7 minutes, 10 minutes, 12 minutes, and 15 minutes.

[0061] Specifically, in the above step 2, if the mass concentration of the ore pulp is too high, it will make it difficult for the flotation reagent to be effectively dispersed and reacted 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 20%-45%; for example, 20%, 25%, 30%, 35%, 40%, 45%.

[0062] Specifically, in the above step 2, the pH is controlled to be 7-9 (eg, 7, 7.5, 8, 8.5, 9) in order to provide a suitable solution environment for the interaction between the flotation reagent and the mineral surface.

[0063] Specifically, in the above step 3, if the stirring time is too long, part of the organic polyamine-metal ion complex adsorbed on the surface of the sulfide ore will be desorbed, and the energy consumption of mechanical stirring will be increased; while if the stirring time is too short, the organic polyamine-metal ion will be fully adsorbed on the surface of the mineral. 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.

[0064] Specifically, the principle of the flotation recovery method of sulfide ore in the cyanide tailings is as follows:

[0065] In the above step 1, the N atom in -NH2 or -NH- in the organic polyamine contains an unshared electron pair, so the organic polyamine can give up a lone pair of electrons in the chemical reaction; metal ions such as Fe 2+ or Cu + can accept lone pairs of electrons; therefore, organic polyamines as multidentate ligands bind Fe as the central atom. 2+ or Cu + Can react and form organic polyamine-metal ion complexes, such as [Fe(C 14 H 32 N2O)] + , [Cu(C 20 H 45 N3O)2] + , [Cu(C 17 H 38 N2)2] + wait.

[0066] In the above step 3, the organic polyamine-metal ion complex is added to the slurry of the cyanide tailings, and can react with the hydrophilic cyanide component on the surface of the sulfide mineral (in the cyanide gold extraction operation, cyanide changes the surface properties of the sulfide mineral and produces cyanide-containing components on the surface of the sulfide mineral), and an organic polyamine-metal ion-cyanide complex is generated on the mineral surface. Among them, 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, so that the complex is adsorbed on the surface of the sulfide mineral, and the hydrophobic end faces the solution, making the mineral surface hydrophobic.

[0067] Specifically, in the untreated cyanide tailings, the surfaces of all mineral particles (including sulfide minerals and gangue minerals) are hydrophilic. In the above step 3, the hydrophilic cyanide component (such as [Fe(CN)6] 4- , Fe4[Fe(CN)6]3, etc.) reacts with the hydrophobic organic polyamine-metal ion complex produced in step 1 to make it adsorbed on the surface of the sulfide ore, thereby making the surface of the sulfide ore hydrophobic; therefore, in the flotation process in step 4, the hydrophobic sulfide ore can adhere to the bubbles and rise with the bubbles into the foam layer, while the hydrophilic gangue minerals remain in the slurry, thereby achieving the flotation separation of the sulfide ore and the gangue minerals. On the other hand, a trace amount of free cyanide remains in the flotation slurry of the cyanide tailings. Although the concentration of free cyanide is extremely low (mg / L level), it can significantly inhibit the flotation of the sulfide ore; the hydrophobic organic polyamine-metal ion complex can also react with the residual free cyanide in the slurry to generate a solid precipitate, thereby eliminating the inhibitory effect of cyanide on the sulfide ore, improving the floatability of the sulfide ore, and improving the recovery rate of the sulfide ore.

[0068] On the other hand, the present invention also provides a flotation recovery system for sulfide ores 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 generate organic polyamine-metal ion complexes.

[0069] 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 .

[0070] In order to provide bubbles and water flow to the greatest extent, if the height H1 of the bubble generator 10 from the bottom flow port 8 is too large, the rising path of the bubbles from the bubble generator 10 will be too small, the probability of collision between the bubbles and the particles in the slurry will be reduced, and the flotation effect will be reduced; if H1 is too small, the high-concentration slurry at the bottom will hinder the rising water flow and bubbles, reducing the sorting effect; therefore, the height H1 of the bubble generator 10 from the bottom flow port 8 is controlled to be 1 / 4 to 1 / 3 of the total height H of the flotation equipment 6, and preferably, H1 is 1 / 3H.

[0071] Specifically, the organic polyamine-metal ion complex can be added into the slurry stirring barrel 4 through the peristaltic pump 3, and the slurry stirring barrel 4 is filled with cyanide tailings slurry with a mass concentration of 20%-45% (such as 25%, 30%, 35%, 40%, 45%), which is a mixture of cyanide tailings and added clean water; the organic polyamine-metal ion complex and other flotation reagents such as pH adjusters are fully mixed with mineral particles in the slurry stirring barrel 4 to react and adjust the slurry. In this process, the organic polyamine-metal ion complex is selectively adsorbed on the surface of the sulfide ore in the cyanide tailings.

[0072] Specifically, the cyanide tailings slurry that has been slurried in the slurry stirring barrel 4 is fed into the flotation device 6 through the slurry pump 5. During the flotation process of the flotation device 6, the hydrophobic sulfide ore 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.

[0073] On the other hand, the present invention also provides a flotation recovery method for sulfide ore in cyanide tailings using the above flotation recovery system, comprising:

[0074] Step S1: Use the first precision doser and the second precision doser 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;

[0075] Step S2: in the slurry stirring barrel 4, the cyanide tailings are prepared into a slurry with a mass concentration of 20%-45%, and the slurry is adjusted to a pH of 7-9;

[0076] Step S3: Use peristaltic pump 3 to add the reaction product of step S1 to the slurry of step S2. The amount of the reaction product of step S1 added is 80-200 g / t. 矿 ; Stirring the reaction to obtain a mixed slurry;

[0077] Step S4: passing the mixed slurry into the flotation equipment 6 for aeration flotation to obtain the floated sulfide ore.

[0078] Specifically, in the above step S4, the step of aeration flotation includes:

[0079] Step S401, the slurry in the slurry mixing barrel 4 is introduced into the flotation device 6 through the slurry pump 5, and air is introduced into the slurry in the flotation device through the self-priming of the flotation device or the inflation of the air compressor, and a large number of bubbles are generated through the bubble generator 10 or mechanical stirring;

[0080] Step S402: After ventilation, the sulfide mineral particles adhere to the bubbles due to their hydrophobic surface and rise with the bubbles into the foam layer, while the gangue mineral particles cannot adhere to the bubbles due to their hydrophobic surface and remain in the slurry. The selected sulfide minerals are discharged from the overflow port 7, and the gangue minerals are discharged as tailings through the underflow port 8.

[0081] Specifically, in the above step S402, the pulp concentration is 20%-45%, and the flotation time is 10-25 minutes.

[0082] Specifically, in the above step S402, according to different flotation processes, multiple flotation equipments can be used in combination, for example, the concentrate from roughing is sent to the second flotation equipment for concentrating, and the tailings from roughing are sent to 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 flow in advance through mineral processing tests, such as a roughing process, a roughing process, a scavenging process, a closed-circuit process, etc.

[0083] Compared with the prior art, the flotation recovery system of the present invention is provided with a reagent pre-mixing reaction stirring tank, Fe 2+ or Cu + Ions and hydrophobic 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.

[0084] The existing method of recovering sulfide ore 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 the sulfide ore, 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.

[0085] The reagent pre-mixing reaction stirring barrel, slurry stirring barrel and flotation equipment of the flotation 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 ore. The system has the characteristics of less equipment, short process, low operating cost, less maintenance difficulty and less investment.

[0086] In the flotation recovery method of the present invention, the hydrophobic organic polyamine-metal ion complex generated by the mixed reaction of metal ions and hydrophobic organic polyamines can react with the metal cyanide on the surface of the sulfide ore to generate an organic polyamine-metal ion-metal cyanide complex on the surface of the mineral, thereby selectively adsorbing on the surface of the sulfide ore, eliminating the inhibitory effect of cyanide on the flotation of the sulfide ore. In addition, the flotation reagent can also react with the residual cyanide in the ore pulp to generate precipitation, eliminating the interference of the residual cyanide on the flotation of the sulfide ore and solving its harm to the environment.

[0087] Example 1

[0088] This embodiment provides a flotation recovery method for sulfide ore in cyanide tailings, wherein the sulfur grade in the cyanide tailings is 19.89%, wherein the main sulfide mineral is pyrite, and also contains a small amount of chalcopyrite; the gangue minerals are mainly quartz and silicate minerals. The method comprises the following steps:

[0089] (1) FeCl2 and alkyl polyamine (N-tetradecyl-1,3-propyldiamine) are mixed in an aqueous solution at a molar ratio of 1:1, and stirred for reaction for 10 minutes; the reaction product is a solution containing a hydrophobic organic polyamine-metal ion complex;

[0090] (2) adjusting the mass concentration of the cyanide tailings slurry to 30% and the slurry pH to 8.5;

[0091] (3) Add the reaction product in (1) to the cyanide tailings slurry, and the dosage of the reaction product is 120g / t 矿 , stirring and reacting in a stirring barrel for 10 minutes to obtain a mixed slurry;

[0092] (4) The mixed pulp is passed into the flotation column and aerated flotation is performed to obtain sulfur concentrate. The flotation pulp concentration is 30% and the flotation time is 15 minutes. The sulfide ore floats up with the bubbles, while the gangue minerals remain in the pulp and are subsequently discharged from the underflow port 8 at the bottom of the flotation column.

[0093] Through the above method, after one roughing, a sulfur concentrate with a sulfur grade of 38.44% and a recovery rate of 87.64% can be obtained, and the sulfur grade of the tailings is reduced to 4.50%.

[0094] Specifically, the above steps can all be carried out in the flotation recovery system of the sulfide ore in the cyanidation tailings, and the specific steps will not be repeated here.

[0095] Example 2

[0096] This embodiment provides a flotation recovery method for sulfide ore in cyanidation tailings, wherein the sulfur grade in the cyanidation tailings is 23.38%, the main metal minerals are pyrite, followed by chalcopyrite, and also contain a small amount of galena and sphalerite; the gangue minerals, in addition to quartz, also contain sericite, plagioclase, calcite, etc. The method comprises the following steps:

[0097] (1) CuCl and alkyl polyamine ether (N 1 -(2-(decyloxy)ethyl)-1,2-ethylenediamine) in a molar ratio of 1:2 in an aqueous solution, and stirred for reaction for 10 minutes; the reaction product is a solution containing a hydrophobic organic polyamine-metal ion complex;

[0098] (2) adjusting the mass concentration of the cyanide tailings slurry to 35% and the slurry pH to 8.0;

[0099] (3) Add the reaction product in (1) to the cyanide tailings slurry at a dosage of 100 g / t 矿 , stir the reaction in a stirring barrel for 10 minutes;

[0100] (4) The slurry is passed into an aerated flotation machine and aerated flotation is performed to obtain sulfur concentrate. The concentration of the flotation slurry is 35% and the flotation time is 20 minutes. The sulfide ore floats up with the bubbles, while the gangue minerals remain in the slurry and are subsequently discharged from the underflow port 8 at the bottom of the flotation column.

[0101] Through the above method, after one roughing, a sulfur concentrate with a sulfur grade of 36.28% and a recovery rate of 87.89% can be obtained, and the sulfur grade of the tailings is reduced to 6.53%.

[0102] Specifically, the above steps can all be carried out in the flotation recovery system of the sulfide ore in the cyanidation tailings, and the specific steps will not be repeated here.

[0103] Example 3

[0104] This embodiment provides a flotation recovery method for sulfide ore in cyanide tailings, wherein the sulfur grade in the cyanide tailings is 29.54%, the main metal mineral is pyrite, and the gangue minerals are quartz, feldspar, chlorite, kaolinite, etc. The method comprises the following steps:

[0105] (1) FeCl2 and alkyl polyamine ether (N 1 -(2-aminoethyl)-N 2-(3-tridecyloxy)propyl)-1,2-ethylenediamine) in a molar ratio of 1:2 in an aqueous solution, and stirred for reaction for 10 minutes; the reaction product is a solution containing a hydrophobic organic polyamine-metal ion complex;

[0106] (2) adjusting the mass concentration of the cyanide tailings slurry to 40% and the slurry pH to 8.5;

[0107] (3) Add the reaction product in (1) to the cyanide tailings slurry at a dosage of 125 g / t 矿 , stir the reaction in a stirring barrel for 15 minutes;

[0108] (4) The ore pulp is passed into the flotation column and aerated flotation is performed to obtain sulfur concentrate. The flotation pulp concentration is 40% and the flotation time is 15 minutes. The sulfide ore floats up with the bubbles, while the gangue minerals remain in the pulp and are subsequently discharged from the bottom flow port 8 at the bottom of the flotation column.

[0109] Through the above method, after one roughing, a sulfur concentrate with a sulfur grade of 40.86% and a recovery rate of 91.45% can be obtained, and the sulfur grade of the tailings is reduced to 7.45%.

[0110] Example 4

[0111] This embodiment provides a flotation recovery method for sulfide ore in cyanide tailings, wherein the sulfur grade in the cyanide tailings is 27.66%, wherein the main sulfide mineral is pyrite, and the main gangue minerals are quartz, plagioclase, etc. The method comprises the following steps:

[0112] (1) CuCl and alkyl polyamine ether (N 1 -(2-(decyloxy)ethyl)-1,2-ethylenediamine) in a molar ratio of 1:2 in an aqueous solution, and stirred for reaction for 15 minutes; the reaction product is a solution containing a hydrophobic organic polyamine-metal ion complex;

[0113] (2) adjusting the mass concentration of the cyanide tailings slurry to 40% and the slurry pH to 8.5;

[0114] (3) Add the reaction product in (1) to the cyanide tailings slurry at a dosage of 150 g / t 矿 , stirring reaction for 15 min;

[0115] (4) The slurry is passed through the flotation equipment, and the sulfur concentrate is obtained by aeration flotation. The flotation process is a closed-circuit process of one stage of roughing, one stage of scavenging and one stage of concentrating. The flotation equipment adopts a cyclone-static microbubble flotation column. The slurry is first passed through a roughing flotation column with a diameter of 4.5m. The roughing concentrate enters the concentrating, and the roughing tailings enter the scavenging; 70g / t of flotation reagent is added to the scavenging section, and 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; no additional flotation reagent is added to the concentrating section, and a flotation column with a diameter of 4m is used. The concentrating tailings and the scavenging concentrate are returned to the roughing, and the concentrating concentrate is used as the final concentrate.

[0116] Comparative Example 1

[0117] This comparative example provides a method for recovering sulfide ore in cyanide tailings, comprising the following steps:

[0118] (1) preparing cyanide tailings into a slurry with a mass concentration of 40%;

[0119] (2) Add 25 kg / t of sulfuric acid to the slurry 矿 After stirring for 20 minutes, 500 g / t of collector butyl xanthate was added to the slurry and stirred for 3 minutes;

[0120] (3) The ore pulp is passed into a cyclone-static microbubble flotation column. The flotation process is the same as that in Example 4. 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.

[0121] Comparative Example 2

[0122] This comparative example provides a method for recovering sulfide ore in cyanide tailings, comprising the following steps:

[0123] (1) preparing cyanide tailings into a slurry with a mass concentration of 40%;

[0124] (2) adding sulfuric acid to the slurry to adjust the pH value of the slurry to 5.5, stirring and reacting for 20 minutes, adding 350 g / t of butyl xanthate as a collector to the slurry, stirring and reacting for 3 minutes;

[0125] (3) The ore pulp is passed into a cyclone-static microbubble flotation column. The flotation process is the same as that in Example 4. 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.

[0126] Comparative Example 3

[0127] This comparative example provides a method for recovering sulfide ore in cyanide tailings, comprising the following steps:

[0128] (1) preparing cyanide tailings into a slurry with a mass concentration of 40%;

[0129] (2) Add 40 kg / t of sulfuric acid to the slurry, stir and react for 20 minutes, then add 300 g / t of butyl xanthate and 200 g / t of butylamine black medicine as collector to the slurry, stir and react for 3 minutes;

[0130] (3) The ore pulp is passed into a cyclone-static microbubble flotation column. The flotation process is the same as that in Example 4. 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.

[0131] Table 1 below shows the test results of Example 4 and Comparative Examples 1-3.

[0132] Table 1 Test results of Example 4 and Comparative Examples 1-3

[0133]

[0134] As shown in Table 1 above, in Comparative Examples 1-3, after acid decyanation, the conventional sulfide ore collector (xanthate, xanthate + black medicine) failed to efficiently recover the sulfide ore from the cyanide tailings. However, in Example 4 using the method of the present invention, the sulfur grade and recovery rate of the concentrate were higher than those of Comparative Examples 1-3.

[0135] 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. A flotation recovery method for sulfide ore in cyanide tailings, characterized in that: The flotation recovery method uses hydrophobic organic polyamine as a multidentate ligand to prepare a hydrophobic organic polyamine-metal ion complex, wherein the metal ions include: Fe 2+ Cu + ; The cyanide tailings are treated with the hydrophobic organic polyamine-metal ion complex and then flotated to obtain sulfide ore; The hydrophobic organic polyamine has the following characteristics: The molecular structure contains more than two -NH2 and / or -NH- structures; The molecular structure also contains a hydrophobic structure, which includes an aromatic group or a C4-C20 alkyl group; The hydrophobic organic polyamine is alkyl polyamine ether or tetradecyl diamine.

2. The flotation recovery method of sulfide ore in cyanide tailings according to claim 1, characterized in that: The flotation recovery method comprises: Step 1: Use hydrophobic organic polyamine as multidentate ligand to bind Fe 2+ Cu + Stirring and reacting, the reaction product is a solution containing a hydrophobic organic polyamine-metal ion complex; Step 2: Prepare the cyanide tailings into a slurry with a mass concentration of 20%-45%, and adjust the slurry to a pH of 7-9; Step 3: adding the reaction product of step 1 to the slurry of step 2, stirring and reacting to obtain a mixed slurry; Step 4: Pass the mixed ore pulp into the flotation equipment for flotation to obtain the floated sulfide ore.

3. The flotation recovery method of sulfide ore in cyanide tailings according to claim 1, characterized in that: The main components of the cyanide tailings include: sulfide minerals and gangue minerals.

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

1.

5. The flotation recovery method of sulfide ore in cyanide tailings according to claim 2, characterized in that: In step 3, the stirring reaction time is 3-15 min.

6. The flotation recovery method of sulfide ore in cyanide tailings according to any one of claims 2 to 5, characterized in that: The flotation recovery method adopts a flotation recovery system for sulfide ore in cyanide tailings, and the flotation recovery system for sulfide ore in cyanide tailings comprises a precise dosing device (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); and a slurry pump (5) is provided between the slurry stirring barrel (4) and the flotation device (6).

7. The flotation recovery method of sulfide ore in cyanide tailings according to claim 6, characterized in that: 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 a reagent premixing reaction stirring barrel (2), and the second precision doser is used to add organic polyamines to a reagent premixing reaction stirring barrel (2).

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