Method for strengthening flotation of copper cobalt oxide ore from magnesium-rich tailing water

Abstract

The invention belongs to the field of mineral flotation, and particularly relates to a method for intensifying magnesium-rich tailing water to float copper-cobalt oxide ores, which comprises the following steps: mixing the copper-cobalt oxide ores and the magnesium-rich tailing water preheated to 40-60 DEG C, grinding, then carrying out first roughing treatment by adopting a flotation reagent a containing a vulcanizing agent, a collecting agent (# imgabs0 #) and a foaming agent, and carrying out second roughing treatment by adopting a flotation reagent b containing a vulcanizing agent, a collecting agent (# imgabs0 #) and a foaming agent; two-stage roughing is carried out in a system containing a formula 1 and a formula 2 (# imgabs 1 #) and an auxiliary agent, wherein the auxiliary agent comprises at least one of NH4HCO3 and (NH4) 2CO3; and concentrate obtained after roughing is finely selected, and concentrate is obtained. On the basis of heating the magnesium-rich tailing water, the combination of a reagent mechanism of a flotation system is further matched, especially the combination of an auxiliary agent for second-stage roughing and a composite collecting agent type, synergy can be accidentally achieved, the flotation inhibition problem of the magnesium-rich tailing water on the copper cobalt oxide ore can be remarkably solved, and the flotation efficiency of the magnesium-rich tailing water is improved. Copper and cobalt can be obtained based on efficient flotation of the beneficiation and metallurgy wastewater.

Description

Technical Field

[0001] The invention relates to the field of nonferrous metal extraction technology and ore dressing, and in particular to the field of flotation of copper-cobalt oxide ore. Technical Background

[0002] Copper and cobalt, as important non-ferrous metal resources, play an important role in industrial production and application. Copper is widely used in electrical, mechanical manufacturing, construction development, aerospace and other fields due to its excellent conductivity and low price, while cobalt is widely used in the field of new energy materials, such as battery materials, heat-resistant alloys, magnetic materials, etc. As the demand for copper and cobalt resources in various countries in the world continues to increase, the copper and cobalt ore resources that are easy to mine and select are gradually decreasing, especially the sulfide ore resources with more copper and cobalt are further reduced, and the development and utilization of copper-cobalt oxide ores are gradually attracting people's attention. However, the composition of copper-cobalt oxide minerals is very complex, and the oxidation rate is extremely high. The high oxidation rate has brought great troubles to the development and utilization of copper-cobalt oxide ores, and conventional flotation methods are often inefficient and difficult to obtain high-grade copper-cobalt concentrates.

[0003] In addition, with the development of mineral resources, the discharge of high calcium and magnesium tail water during flotation and smelting has brought about a series of environmental problems and has received increasing attention. How to effectively reuse these tail waters is an important direction for solving mining water pollution. Especially for the production process of copper-cobalt oxide ore beneficiation and smelting, because calcium and magnesium ions are needed to regulate the precipitation of cobalt during the cobalt production process, the tail water contains a large amount of calcium and magnesium ions. Studies have shown that direct use of tail water will inhibit the flotation index of copper-cobalt oxide ore due to the high concentration of calcium and magnesium ions. Therefore, there is no mature and feasible method in the industry to enhance the reuse of magnesium-rich tailings water for flotation of copper-cobalt oxide ore. Summary of the invention

[0004] In view of the problem that magnesium-rich tailings water has an unsatisfactory effect in flotation of oxidized copper-cobalt ore, the present invention provides a method for enhancing the flotation of oxidized copper-cobalt ore with magnesium-rich tailings water, aiming to reuse magnesium-rich tailings water and efficiently flotate copper and cobalt.

[0005] In view of the problem that magnesium-rich tailings water easily inhibits copper and cobalt flotation and the recycling effect is not ideal, the present invention provides the following improvement scheme:

[0006] A method for enhancing the flotation of copper-cobalt oxide ores with magnesium-rich tailings water, comprising:

[0007] Step (1):

[0008] The oxidized copper-cobalt ore and the magnesium-rich tailings water preheated to 40-60° C. are mixed and ground, and then a flotation agent a containing a sulfiding agent, a collector of Formula 1 and a frother is used for a first roughing treatment to obtain a first roughing concentrate and a first roughing tailings slurry; the first roughing concentrate is subjected to a beneficiation treatment to obtain an oxidized concentrate I;

[0009] Formula 1

[0010] The R1 is a C2-C8 alkyl group; M is H, Na, K or NH4;

[0011] Step (2):

[0012] Adding flotation agent b to the first roughing tailings slurry of step (1) to perform second roughing to obtain second roughing concentrate and second roughing tailings slurry, and then adding flotation agent c to the second roughing tailings slurry to perform third roughing to obtain third roughing concentrate and third roughing tailings slurry;

[0013] The second-stage rougher concentrate and the third-stage rougher concentrate are combined and then subjected to fine scavenging using flotation reagent d to obtain oxidized concentrate II and fine scavenging tailings slurry;

[0014] The flotation reagent b, flotation reagent c and flotation reagent d contain a sulfiding agent and a composite collector; and the flotation reagent b and flotation reagent c also contain an auxiliary agent;

[0015] The flotation collector comprises a compound of formula 1 and a compound of formula 2; the auxiliary agent comprises at least one of NH4HCO3 and (NH4)2CO3;

[0016] Formula 2

[0017] The R2 is C2~C 10 alkyl, substituted alkyl, phenyl or substituted phenyl, wherein N is H, Na, K or NH4;

[0018] Step (3):

[0019] Adding flotation reagent e containing a sulfiding agent and a collector of formula 2 to the third-stage roughing tailings slurry for scavenging treatment to obtain final tailings and scavenging concentrate;

[0020] The scavenging concentrate and the fine scavenging tailings slurry of step (2) are combined and returned to the second roughing process.

[0021] In view of the problem that magnesium in magnesium-rich tailings water inhibits the flotation of copper and cobalt, the present invention previously tried to solve the problem of heating flotation, but did not achieve the expected effect. Instead, it amplified the inhibitory effect of magnesium-rich tailings water on oxidized copper and cobalt ore. In view of this problem, after in-depth research, on the basis of heating the magnesium-rich tailings water, the present invention further cooperates with the combination of the reagent mechanism of the flotation system, especially the combination of the auxiliary agent of the second roughing stage and the composite collector type, which can unexpectedly achieve synergy, can significantly solve the flotation inhibition problem of magnesium-rich tailings water on oxidized copper and cobalt ore, and can obtain copper and cobalt based on the efficient flotation of flotation wastewater.

[0022] In the present invention, the magnesium-rich tailings water is flotation wastewater containing magnesium ions.

[0023] In the present invention, there is no special requirement for the magnesium ion concentration of the magnesium-rich tailings water, but considering the good technical advantages of the method of the present invention, it can be applicable to magnesium-rich tailings water with a magnesium ion concentration of 0.3-2.5 g / L, and further 1.5-2 g / L.

[0024] In the present invention, calcium ions are also allowed to exist in the magnesium-rich tailings water. The presence of calcium ions will further inhibit the flotation of copper and cobalt oxides. However, thanks to the combined advantages of the flotation system and the tailings water heating mechanism, the present invention can also solve the copper and cobalt inhibition problem caused by the flotation reuse of calcium and magnesium-containing tailings water.

[0025] In the present invention, the calcium ion concentration in the magnesium-rich tailings water is 0.3-2.0 g / L, and can further be 1-1.5 g / L.

[0026] In the present invention, the copper grade in the oxidized copper-cobalt ore is 1.0% to 3.5% (or further 1.5 to 3.5%), the cobalt grade is above 0.07% (or further 0.1 to 0.15%), and the cobalt-copper oxidation rate is above 90%.

[0027] In the present invention, the cobalt oxide copper ore in step (1) has a crushing fineness of 2-4 mm; the product with a grinding fineness of less than 0.074 mm accounts for 55%-85% of the total mass (or further can be 65-80%); and the cobalt oxide copper ore slurry concentration in the grinding slurry is 30%-35%.

[0028] In the present invention, the sulfiding agent includes at least one of sodium sulfide and sodium hydrogen sulfide.

[0029] In the present invention, the foaming agent includes at least one of 2# oil and methyl isobutyl carbinol.

[0030] In the present invention, in step (1), the amount of the sulfiding agent added is 500-1000 g / ton of ore, the amount of the collector added in formula 1 is 400-800 g / ton of ore, and the amount of the foaming agent added is 20-40 g / ton of ore. Further, the amount of the sulfiding agent added is 800-1000 g / ton of ore, the amount of the collector added in formula 1 is 600-800 g / ton of ore, and the amount of the foaming agent added is 20-40 g / ton of ore.

[0031] In the present invention, the scraping time of the first rough selection is 3 to 5 minutes.

[0032] In the present invention, in step (1), the concentration step includes two concentration processes, and the steps are, for example: subjecting the first roughing concentrate to a first concentration (also called first concentration) to obtain a first concentration concentrate and a first concentration medium pulp; subjecting the first concentration concentrate to a second concentration (also called second concentration) to obtain a second concentration ore and a second concentration medium pulp; the second concentration concentrate is the oxidized concentrate I; the first concentration medium pulp is returned to the previous flotation process (for example, the first concentration medium pulp is heated to 40-60°C and then returned to the first roughing process), and the second concentration medium pulp is subjected to the fine scavenging process.

[0033] In the present invention, the first concentrating stage allows the addition of an inhibitor, wherein the inhibitor includes at least one of water glass and CMC.

[0034] Preferably, the dosage of the inhibitor is 200-400 g / ton of ore.

[0035] Preferably, the selected scraping time is 2 to 3 minutes.

[0036] In the present invention, in step (2), a roughing tailing is subjected to flotation in a system comprising the auxiliary agent and the composite collector, and the temperature of the tailing is controlled (the heating temperature of the tailing water is basically maintained). This can solve the problem of copper and cobalt flotation inhibition caused by heating and recycling magnesium-rich tailing water, and can also significantly enhance the flotation index of the tailing wastewater recycling.

[0037] In the present invention, an auxiliary agent containing ethylenediamine phosphate can be added to the auxiliary agent. The present invention shows that adding a certain auxiliary agent to the auxiliary agent can cooperate with the further combination of the tailings water heating and the flotation system, and can further solve the problem of further inhibition of degradation of copper-cobalt oxide ore caused by tailings water heating and reuse.

[0038] Preferably, the content of the auxiliary additive accounts for 10% to 30% of the additive.

[0039] In the present invention, in step (2), the sulfiding agent includes at least one of sodium sulfide and sodium hydrogen sulfide.

[0040] In the present invention, in step (2), in the composite collector, the weight ratio of the compound of formula 1 to the compound of formula 2 is 1:0.1-0.5.

[0041] In the present invention, in the second roughing process of step (2), the amount of sulfiding agent added is 400-600 g / ton of ore, the amount of auxiliary agent added is 300-500 g / ton of ore; and the amount of composite collector used is 350-700 g / ton of ore.

[0042] In the present invention, in the third roughing process of step (2), the dosage of each component in the flotation reagent c is 0.5 to 1.5 times the dosage of the flotation reagent b, and can further be 0.5 to 1 times;

[0043] In the present invention, in step (2), during the fine scavenging process, the amount of the sulfiding agent used is 200-400 g / ton of ore; and the amount of the composite collector used is 150-400 g / ton of ore.

[0044] In the present invention, the scraping time of the second rough selection and the third rough selection is 3 to 5 minutes, and the scraping time of the fine sweeping selection is 2 to 3 minutes.

[0045] In the present invention, in step (3), the amount of the sulfiding agent is 200-400 g / ton of ore; the amount of the collector of formula 2 is 20-100 g / ton of ore.

[0046] In the present invention, the scraping time of the sweeping selection is 3 to 5 minutes.

[0047] In the present invention, the scavenging concentrate and the fine scavenging tailings slurry are mixed and heated to 40-60° C. and then recycled to the second roughing process.

[0048] In the present invention, the temperature of the ore pulp in the flotation stage is controlled between 40 and 60° C. by heated magnesium-rich tailings water and / or recycled ore pulp in the grinding, first roughing, second roughing and third roughing stages.

[0049] Beneficial effects:

[0050] The present invention innovatively combines the flotation system by heating the magnesium-rich tailings water, which can unexpectedly and significantly solve the flotation inhibition problem of copper-cobalt oxide ores caused by the reuse of magnesium-containing tailings water, and can obtain copper and cobalt based on the magnesium-rich tailings flotation wastewater by efficient flotation.

[0051] The present invention can enhance the flotation effect of recycled magnesium-rich tailings water on copper and cobalt oxides, can effectively shorten the flotation system, and can also obtain high copper and cobalt recovery rate and selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 It is a process flow chart of the enhanced flotation of copper-cobalt ore oxidized by tailings water of the present invention. DETAILED DESCRIPTION

[0053] In order to make the technical problems to be solved, technical solutions and advantages of the present invention more clear, they are described in detail below in conjunction with specific embodiments.

[0054] Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art; unless otherwise specified, the reagents used in the examples are commercially available.

[0055] The present invention provides a method for strengthening the flotation of copper-cobalt oxide ores by magnesium-rich tailings water, comprising the following steps:

[0056] (1) Tailings pond return water heating: The tailings pond return water is heated through pipelines and pumped back to the flotation operation section

[0057] (2) Grinding and slurrying: The raw cobalt oxide copper ore is crushed, mixed with the heated tailings return water, ground and slurried to obtain the raw ore slurry.

[0058] (3) Oxidized ore roughing I: a sulfiding agent, formula 1, and a frother are sequentially added to the raw ore pulp in step (1) and then aerated flotation is performed to obtain a first roughing concentrate and a first roughing tailing. The first roughing concentrate is subjected to two rounds of concentration to obtain an oxidized concentrate I, wherein water glass is added as an inhibitor in the concentration operation I; the first concentrated middling is heated and returned to the roughing operation I.

[0059] (4) Second and third roughing of oxide ore: adding a sulfiding agent and an auxiliary agent and a combination of Formula 1 and Formula 2 to the first roughing tailings slurry in step (3) in sequence, and then performing aeration flotation to obtain a second roughing concentrate and a second roughing tailings of the oxide ore; then adding a sulfiding agent and an auxiliary agent and a combination of Formula 1 and Formula 2 to the second roughing tailings slurry in sequence, and then performing aeration flotation to obtain a third roughing concentrate and a third roughing tailings of the oxide ore.

[0060] (5) Fine scavenging of oxidized ore: After the second rougher concentrate and the third rougher concentrate are combined with the concentrated middling ore pulp, sulfiding agent and the combination of formula 1 and formula 2 are added in sequence, and then aeration flotation is carried out to obtain oxidized concentrate II and fine scavenging middling ore.

[0061] (6) Scavenging of oxide ore: adding sulfidizing agent and formula 2 to the third rougher tailings slurry in sequence, and then performing aeration flotation to obtain scavenging concentrate and tailings; the scavenging concentrate is combined with the fine scavenging ore in step (5), and returned to the second rougher after being heated through a pipeline.

[0062] Furthermore, in the step (1), the heating is performed by wrapping the boiler steam pipe with cloth and laying the pipe on the return water pipe, and the return water is heated to 40-60°C.

[0063] Furthermore, the cobalt oxide copper ore in step (2) has a crushing fineness of 2-4 mm. The product with a grinding fineness of less than 0.074 mm accounts for 55%-85% of the total mass.

[0064] Furthermore, the concentration of the cobalt oxide copper ore pulp in step (2) is 30% to 35%.

[0065] Furthermore, the amount of the sulfiding agent added in step (3) is 500-1000 g / ton of ore, and the amount added in formula 1 is 400-800 g / ton of ore.

[0066] Furthermore, in the step (3), the heating is performed by wrapping the boiler steam pipe with cloth and laying the pipe on the slurry flow pipe, and the slurry is heated to 40-60°C.

[0067] Furthermore, in the above step (3), the amount of inhibitor added in the first operation of the selection process is 200-400 g / ton of ore.

[0068] Furthermore, in step (4), the amount of vulcanizing agent added is 400-600 g / ton of ore, and the amount of auxiliary agent added is 300-500 g / ton of ore.

[0069] Furthermore, in the step (4), the amount of formula 1 added is 300-500 g / ton of ore; and the amount of formula 2 added is 50-200 g / ton of ore.

[0070] Furthermore, in step (5), the amount of the sulfiding agent used is 200-400 g / ton of ore.

[0071] Furthermore, in the step (5), the amount of formula 1 added is 100-300 g / ton of ore; and the amount of formula 2 added is 50-100 g / ton of ore.

[0072] Furthermore, in step (6), the amount of sulfiding agent added is 200-400 g / ton of ore.

[0073] Furthermore, the amount of formula 2 added in step (6) is 20-100 g / ton of ore.

[0074] Furthermore, in the step (6), the heating is performed by wrapping the boiler steam pipe with cloth and laying the pipe on the slurry flow pipe, and the slurry is heated to 40-60°C.

[0075] Furthermore, the scraping time for the rough selection and sweeping selection operations is 3 to 5 minutes, and the scraping time for the fine selection operation and the precise sweeping selection operation is 2 to 3 minutes.

[0076] Furthermore, it is used to process oxidized copper-cobalt ore, in which the copper grade is 1.0% to 3.5%, the cobalt grade is not less than 0.07%, and the cobalt-copper oxidation rate is greater than 90%.

[0077] Furthermore, the water used in the mineral processing process comes from tailings water, which is characterized by high calcium and magnesium ion concentrations, with calcium ion concentrations of 0.3~2.0 g / L and magnesium ion concentrations of 0.3~2.5 g / L.

[0078] In the present invention, the formula 1 used in the flotation stage can be a single compound or a combination of compounds having the structure shown. As a typical example, the formula 1 can be a formula 1A, a formula 1B, etc., wherein the formula 1A is a formula 1 compound in which R1 is n-butyl and M is Na; the formula 1B is a formula 1 compound in which R1 is n-pentyl and M is Na.

[0079] The formula 2 used in the flotation stage can be a single compound or a combination of compounds having the structure shown. As a typical example, the formula 2 can be a formula 2A, a formula 2B, etc., wherein the formula 2A is a formula 2 compound in which R2 is phenyl and N is H; the formula 2B is a formula 2 compound in which R2 is 2-hydroxyphenyl and N is H.

[0080] In the flotation stage of the present invention, the temperature of the flotation stage is controlled between 40 and 60° C. by heating tailings water or heating recycled ore pulp.

[0081] In the following cases, the dosage of reagents mentioned refers to the weight of reagents used per ton of ore (the actual unit is g / t).

[0082] Example 1

[0083] The test sample of this embodiment is a raw ore of a copper-cobalt oxide ore, wherein the cobalt grade is 0.11%, the copper grade is 1.80%, the ore oxidation rate is 92.5%, the water used for flotation is the tailings pond smelting drainage, the calcium ion concentration is 1.25 g / L, the magnesium ion concentration is 1.70 g / L, and the flotation process is as follows:

[0084] (1) Tailings pond return water heating: The tailings pond return water is heated to 50°C through pipes and pumped back to the flotation operation

[0085] (2) Grinding and slurrying: The test sample ore is ground to a fineness of less than 0.074 mm and the product accounts for 70% of the total weight. The tail water is then heated and slurried to a concentration of 33% to obtain ore slurry.

[0086] (3) Sodium hydrosulfide 800 g / t, formula 1A 300 g / t, formula 1B 300 g / t, and 2# oil 30 g / t were added to the pulp in sequence, and stirred. The easily floatable copper and cobalt minerals were subjected to aeration flotation to obtain the first roughing concentrate and the first roughing tailings. The first roughing concentrate was subjected to two concentration operations to obtain oxidized concentrate I. The first concentrated middling pulp was heated to 50°C and returned to the first roughing.

[0087] (4) To the first rougher tailings slurry, 500 g / t of sodium sulfide, 400 g / t of auxiliary agent (ammonium bicarbonate), 200 g / t of formula 1A, 200 g / t of formula 1B, and 80 g / t of formula 2A are added in sequence, and the hard-floating copper-cobalt ore is subjected to aeration flotation (second rougher) to obtain a second rougher concentrate and a second rougher tailings. To the second rougher tailings, 500 g / t of sodium sulfide, 400 g / t of auxiliary agent (ammonium bicarbonate), 200 g / t of formula 1A, 200 g / t of formula 1B, and 80 g / t of formula 2A are added in sequence, and the hard-floating copper-cobalt ore is subjected to aeration flotation (third rougher) to obtain a third rougher concentrate and a third rougher tailings. The second rougher concentrate and the third rougher concentrate were combined with the second concentrated tailings slurry, and then 300 g / t of sodium sulfide, 100 g / t of formula 1A, 100 g / t of formula 1B, and 50 g / t of formula 2A were added, and oxidized concentrate II was obtained by aeration flotation.

[0088] (5) Sodium sulfide 200 g / t and formula 2A 50 g / t are added to the third rougher tailings slurry in sequence, and then aeration flotation is carried out to obtain scavenger concentrate and tailings; the scavenger concentrate is combined with the fine scavenger concentrate, and returned to the second rougher after being heated through a pipeline.

[0089] Comparative Example 1:

[0090] Compared with Example 1, the only difference is that in step 1, the tailings water in the process and the recycled slurry are not heated, and the temperature is room temperature (20-25° C.), and the other operations and parameters are the same as in Example 1.

[0091] Comparative Example 2

[0092] Compared with Example 1, the only difference is that the additive is added in the flotation process of step 3, but not in the flotation process of step 4. Other operations and parameters are the same as those in Example 1.

[0093] Comparative Example 3

[0094] Compared with Example 1, the only difference is that in the second roughing and third roughing stages of step 4, Formula 2A is replaced by Formula 1A in equal amounts, and other operations and parameters are the same as those in Example 1.

[0095] Example 2

[0096] The test sample of this embodiment is a raw ore of a copper-cobalt oxide ore, wherein the cobalt grade is 0.13%, the copper grade is 2.12%, the ore oxidation rate is 95%, the water used for flotation is the tailings pond smelting drainage, the calcium ion concentration is 1.25 g / L, the magnesium ion concentration is 1.70 g / L, and the flotation process is as follows:

[0097] (1) Tailings pond return water heating: The tailings pond return water is heated to 55°C through pipes and pumped back to the flotation operation

[0098] (2) Grinding and slurrying: The test sample ore is ground to a fineness of less than 0.074 mm and the product accounts for 75% of the total weight. The tail water is then heated and slurried to a concentration of 35% to obtain ore slurry.

[0099] (3) Sodium hydrosulfide 1000 g / t, formula 1A 400 g / t, formula 1B 400 g / t, 2# oil 30 g / t were added to the pulp in sequence, and stirred. The easily floatable copper-cobalt minerals were subjected to aeration flotation to obtain the first roughing concentrate and the first roughing tailings. The first roughing concentrate was subjected to two concentration operations to obtain oxidized concentrate I. The first concentrated middling pulp was heated to 50°C and returned to the first roughing.

[0100] (4) To the first rougher tailings slurry, 600 g / t of sodium sulfide, 500 g / t of auxiliary agent (ammonium bicarbonate), 250 g / t of formula 1A, 250 g / t of formula 1B, and 140 g / t of formula 2A are added in sequence to aerate the hard-floating copper-cobalt ore to obtain a second rougher concentrate and a second rougher tailings. To the second rougher tailings, 600 g / t of sodium sulfide, 500 g / t of auxiliary agent (ammonium bicarbonate), 250 g / t of formula 1A, 250 g / t of formula 1B, and 140 g / t of formula 2A are added in sequence to aerate the hard-floating copper-cobalt ore to obtain a third rougher concentrate and a third rougher tailings. The second rougher concentrate and the third rougher concentrate were combined with the second concentrated tailings slurry, and then 400 g / t of sodium sulfide, 100 g / t of formula 1A, 100 g / t of formula 1B, and 50 g / t of formula 2A were added, and oxidized concentrate II was obtained by aeration flotation.

[0101] (5) Sodium sulfide 400 g / t and formula 2A 80 g / t are added to the third rougher tailings slurry in sequence, and then aeration flotation is carried out to obtain scavenger concentrate and tailings; the scavenger concentrate is combined with the fine scavenger concentrate, and returned to the second rougher after being heated through a pipeline.

[0102] Comparative Example 4:

[0103] Compared with Example 2, the only difference is that in step 4, no auxiliary agent is added, and the other operations and parameters are the same as those in Example 2.

[0104] Comparative Example 5

[0105] Compared with Example 2, the only difference is that in step 4, an equal amount of sodium carbonate is used as an auxiliary agent, and other operations and parameters are the same as those in Example 2.

[0106] Example 3

[0107] Compared with Example 2, the only difference is that the auxiliary agent also contains ethylenediamine phosphoric acid, which accounts for 15% of the weight of the auxiliary agent. The total amount of the auxiliary agent and other operations and parameters are the same as those in Example 2.

[0108]

[0109] It can be seen from Table 1 that on the basis of heating the magnesium-rich tailings water, the combination of the reagent mechanism of the flotation system, especially the combination of the auxiliary agent in the second roughing stage and the composite collector type, can unexpectedly achieve synergy, which can significantly solve the flotation inhibition problem of magnesium-rich tailings water on oxidized copper-cobalt ore, and copper and cobalt can be obtained based on efficient flotation of smelting wastewater.

Claims

1. A method for strengthening the flotation of copper-cobalt ore from magnesium-rich tailings, characterized in that the steps include: Step (1): The oxidized copper-cobalt ore and the magnesium-rich tailings water preheated to 40-60° C. are mixed and ground, and then a flotation agent a containing a sulfiding agent, a collector of Formula 1 and a frother is used for a first roughing treatment to obtain a first roughing concentrate and a first roughing tailings slurry; the first roughing concentrate is subjected to a beneficiation treatment to obtain an oxidized concentrate I; Formula 1 The R1 is a C2-C8 alkyl group; M is H, Na, K or NH4; Step (2): Adding flotation agent b to the first roughing tailings slurry of step (1) to perform second roughing to obtain second roughing concentrate and second roughing tailings slurry, and then adding flotation agent c to the second roughing tailings slurry to perform third roughing to obtain third roughing concentrate and third roughing tailings slurry; The second-stage rougher concentrate and the third-stage rougher concentrate are combined and then subjected to fine scavenging using flotation reagent d to obtain oxidized concentrate II and fine scavenging tailings slurry; The flotation reagent b, flotation reagent c and flotation reagent d contain a sulfiding agent and a composite collector; and the flotation reagent b and flotation reagent c also contain an auxiliary agent; The flotation collector comprises a compound of formula 1 and a compound of formula 2; the auxiliary agent comprises at least one of NH4HCO3 and (NH4)2CO3; Formula 2 The R2 is C2~C 10 alkyl, substituted alkyl, phenyl or substituted phenyl, wherein N is H, Na, K or NH4; Step (3): Adding flotation reagent e containing a sulfiding agent and a collector of formula 2 to the third-stage roughing tailings slurry for scavenging treatment to obtain final tailings and scavenging concentrate; The scavenging concentrate and the fine scavenging tailings slurry of step (2) are combined and returned to the second roughing process.

2. The method for strengthening the flotation of copper-cobalt oxide ores by magnesium-rich tailings water as claimed in claim 1, characterized in that: The magnesium-rich tailings water is flotation wastewater containing magnesium ions; Preferably, the magnesium ion concentration of the magnesium-rich tailings water is 0.3-2.5 g / L; Preferably, calcium ions also exist in the magnesium-rich tailings water; Preferably, the calcium ion concentration in the magnesium-rich tailings water is 0.3-2.0 g / L.

3. The method for strengthening the flotation of copper-cobalt oxide ores by magnesium-rich tailings water as claimed in claim 1, characterized in that: The copper grade in oxidized copper-cobalt ore is 1.0%~3.5%, the cobalt grade is above 0.07%, and the cobalt-copper oxidation rate is above 90%.

4. The method for strengthening the flotation of copper-cobalt oxide ores with magnesium-rich tailings water as claimed in claim 1, characterized in that: The cobalt oxide copper ore in step (1) has a crushing fineness of 2-4 mm; the product with a grinding fineness of less than 0.074 mm accounts for 55%-85% of the total mass; and the cobalt oxide copper ore slurry concentration in the grinding slurry is 30%-35%.

5. The method for strengthening the flotation of copper-cobalt oxide ores with magnesium-rich tailings water as claimed in claim 1, characterized in that: The vulcanizing agent includes at least one of sodium sulfide and sodium hydrogen sulfide; Preferably, the foaming agent includes at least one of 2# oil and methyl isobutyl carbinol; Preferably, in step (1), the amount of the sulfiding agent added is 500-1000 g / ton of ore, the amount of the collector of formula 1 added is 400-800 g / ton of ore; the amount of the foaming agent added is 20-40 g / ton of ore; Preferably, the scraping time of the first rough selection is 3 to 5 minutes.

6. The method for strengthening the flotation of copper-cobalt oxide ores by magnesium-rich tailings water according to claim 1 or 5, characterized in that: In step (1), the beneficiation step includes two beneficiation processes, wherein an inhibitor is added in the first beneficiation stage, and the middling slurry of the first beneficiation is heated to 40-60°C and then returned to the first roughing process; the concentrate of the second beneficiation is the oxidized concentrate I, and the middling slurry of the second beneficiation participates in the fine scavenging process; Preferably, the inhibitor comprises at least one of water glass and CMC; Preferably, the dosage of the inhibitor is 200-400 g / ton of ore; Preferably, the selected scraping time is 2 to 3 minutes.

7. The method for strengthening the flotation of copper-cobalt oxide ores with magnesium-rich tailings water as claimed in claim 1, characterized in that: In step (2), the auxiliary agent may further include an auxiliary agent containing ethylenediamine phosphate; Preferably, the content of auxiliary additives accounts for 10% to 30% of the additives; Preferably, the sulfiding agent includes at least one of sodium sulfide and sodium hydrogen sulfide; Preferably, in the composite collector, the weight ratio of the compound of formula 1 to the compound of formula 2 is 1:0.1-0.5; Preferably, in the second roughing process of step (2), the amount of sulfiding agent added is 400-600 g / ton of ore, the amount of auxiliary agent added is 300-500 g / ton of ore; the amount of composite collector added is 350-700 g / ton of ore; Preferably, in the third roughing process of step (2), the dosage of each component in the flotation reagent c is 0.5 to 1.5 times the dosage of the flotation reagent b, and can further be 0.5 to 1 times; Preferably, in step (2), during the fine scavenging process, the amount of the sulfiding agent used is 200-400 g / ton of ore; the amount of the composite collector used is 150-400 g / ton of ore; Preferably, the scraping time for the second and third rough selections is 3 to 5 minutes, and the scraping time for the fine sweeping selection is 2 to 3 minutes.

8. The method for strengthening the flotation of copper-cobalt oxide ores with magnesium-rich tailings water as claimed in claim 1, characterized in that: In step (3), the dosage of the sulfiding agent is 200-400 g / ton of ore; the dosage of the collector of formula 2 is 20-100 g / ton of ore; Preferably, the scraping time of the sweeping selection is 3 to 5 minutes.

9. The method for strengthening the flotation of copper-cobalt oxide ores by magnesium-rich tailings water according to claim 1 or 8, characterized in that: The scavenging concentrate and the fine scavenging tailings slurry are mixed and heated to 40-60°C and then reused in the second roughing process.

10. The method for strengthening the flotation of copper-cobalt oxide ores with magnesium-rich tailings water as claimed in claim 1, characterized in that: The temperature of the slurry in the flotation stage is controlled between 40 and 60°C by heated magnesium-rich tailings water and / or recycled slurry in the grinding, first roughing, second roughing and third roughing stages.

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