Method for enhancing flotation of copper-cobalt oxide ores with magnesium-rich tailings water

Abstract

The present invention belongs to the field of mineral flotation and specifically relates to a method for enhancing the flotation of copper-cobalt oxide ore using magnesium-rich tailings water. The method comprises mixing the copper-cobalt oxide ore with magnesium-rich tailings water preheated to 40-60°C, grinding the ore, and then performing a first roughing treatment using a flotation reagent a containing a sulfiding agent, a collector of Formula 1 (#imgabs0#), and a frother. A two-stage roughing treatment is then performed in a system containing Formulas 1 and 2 (#imgabs1#) and an auxiliary agent, the auxiliary agent comprising at least one of NH4HCO3 and (NH4)2CO3. The roughing concentrate is then subjected to beneficiation to produce a concentrate. By heating the magnesium-rich tailings water and further combining the reagent mechanisms of the flotation system, particularly the auxiliary agent in the second roughing stage and a composite collector type, a surprising synergy is achieved, significantly resolving the problem of magnesium-rich tailings water inhibiting the flotation of copper-cobalt oxide ore. This allows for efficient flotation of copper and cobalt from smelting wastewater.

Description

Technical Field

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

[0002] Copper and cobalt, as important non-ferrous metal resources, play a vital role in industrial production and applications. Copper, due to its excellent electrical conductivity and low price, is widely used in electrical engineering, machinery manufacturing, construction development, aerospace and other fields, while cobalt is widely used in new energy materials such as battery materials, heat-resistant alloys, and magnetic materials. As the global demand for copper and cobalt resources continues to increase, the resources of copper and cobalt ores that are easy to mine and separate are gradually decreasing, especially the sulfide ores with high copper and cobalt reserves. The development and utilization of copper-cobalt oxide ores has gradually attracted attention. However, the mineral composition of copper-cobalt oxide is very complex, and its oxidation rate is extremely high. This high oxidation rate has brought great difficulties to the development and utilization of copper-cobalt oxide ores. Conventional flotation methods are often inefficient, making it difficult to obtain high-grade copper-cobalt concentrates.

[0003] In addition, with the development of mineral resources, the discharge of high-calcium and magnesium tailwater during flotation and smelting has brought about a series of environmental problems and has received increasing attention. How to effectively reuse this tailwater is an important direction for solving mining water pollution. This is especially true for the production process of combined beneficiation and smelting of copper-cobalt oxide ores. Because calcium and magnesium ions are required to regulate the precipitation of cobalt during cobalt production, the tailwater contains a large amount of calcium and magnesium ions. Studies have shown that directly using tailwater will inhibit the flotation indicators of copper-cobalt oxide ores 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 ores. Summary of the Invention

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

[0005] To address the problem that magnesium-rich tailings water easily inhibits copper and cobalt flotation and the recycling effect is unsatisfactory, the present invention provides the following improvement scheme:

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

[0007] Step (1):

[0008] The copper-cobalt oxide ore and magnesium-rich tailings water preheated to 40-60° C. are mixed and ground, and then a first roughing treatment is performed using a flotation reagent a containing a sulfiding agent, a collector of formula 1, and a frother 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 oxide concentrate I;

[0009] Formula 1

[0010] 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 stage roughing tailings slurry of step (1) to perform a second stage roughing to obtain a second stage roughing concentrate and a second stage roughing tailings slurry, and then adding flotation agent c to the second stage roughing tailings slurry to perform a third stage roughing to obtain a third stage roughing concentrate and a third stage 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 reagents b, c and d contain a sulfiding agent and a composite collector; and the flotation reagents b and 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 order to solve the problem of magnesium in magnesium-rich tailings water inhibiting the flotation of copper and cobalt, the present invention previously attempted to solve the problem of temperature flotation, but did not achieve the expected effect. Instead, it amplified the inhibitory effect of magnesium-rich tailings water on oxidized copper and cobalt ores. To solve this problem, the present invention conducted in-depth research. On the basis of heating the magnesium-rich tailings water, the present invention further combined 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 unexpectedly achieved synergy, significantly solved the problem of magnesium-rich tailings water inhibiting the flotation of oxidized copper and cobalt ores, and obtained 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 permitted in the magnesium-rich tailings water. The presence of calcium ions can further inhibit the flotation of copper and cobalt oxides. However, thanks to the combined advantages of the flotation system and tailings water heating mechanism, the present invention can also address the copper and cobalt inhibition issue 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 copper-cobalt oxide ore is 1.0% to 3.5% (may further be 1.5 to 3.5%), the cobalt grade is above 0.07% (may further be 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 (and can further 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. Furthermore, 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 stages of concentration processes, and the steps are, for example: the first stage roughing concentrate is subjected to the first stage concentration (also called the first stage concentration) in advance to obtain the first stage concentrated concentrate and the first stage concentrated middling pulp; the first stage concentrated concentrate is subjected to the second stage concentration (also called the second stage concentration) to obtain the second stage concentrated ore and the second stage concentrated middling pulp; the second stage concentrated concentrate is the oxidized concentrate I; the first stage concentrated middling pulp is returned to the previous flotation process (for example, the first stage concentrated middling pulp is heated to 40-60°C and then returned to the first stage roughing process), and the second stage concentrated middling pulp is subjected to the fine scavenging process.

[0033] In the present invention, an inhibitor is allowed to be added in the first concentrating stage, 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 tailing temperature is controlled (substantially maintaining the heating temperature of the tailing water). 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 reuse.

[0037] In the present invention, an auxiliary agent containing ethylenediamine phosphate may be added to the auxiliary agent. Research in the present invention has shown that the addition of a certain auxiliary agent to the auxiliary agent can be combined with the tailings water heating and flotation system to further solve the problem of further inhibiting the 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, during 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, during 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; 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 and third roughing selections 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 sweeping 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 using 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 above-mentioned flotation system by heating the magnesium-rich tailings water, thereby unexpectedly and significantly solving 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 efficient flotation of magnesium-rich tailings flotation wastewater.

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

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

[0053] In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, a detailed description will be given below with reference to 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 enhanced flotation of copper-cobalt oxide ores from magnesium-rich tailings water, comprising the following steps:

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

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

[0058] (3) Oxide ore roughing I: sulfiding agent, formula 1, and frother are added to the raw ore pulp in step (1) in sequence, and then aeration flotation is carried out to obtain the first roughing concentrate and the first roughing tailings. The first roughing concentrate is subjected to two rounds of concentration to obtain oxidized concentrate I, wherein water glass is added as an inhibitor in the concentration operation I; the first concentrated middlings are returned to the roughing operation I after being heated.

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

[0060] (5) Fine scavenging of oxidized ore: After the second rougher concentrate and the third rougher concentrate are combined with the selected 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.

[0061] (6) Oxide ore scavenging: sulfiding agent and formula 2 are added to the third rougher tailings slurry in sequence, and then aeration flotation is performed 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 in the pipeline.

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

[0063] Furthermore, the cobalt oxide copper ore in step (2) is crushed to a 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 cobalt oxide copper ore pulp concentration 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 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 said step (3), the amount of inhibitor added in the first operation 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 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, the amount of the sulfiding agent in step (5) is 200-400 g / ton of ore.

[0071] Furthermore, in 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, the amount of sulfiding agent added in step (6) 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 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 and precise sweeping selection operations is 2 to 3 minutes.

[0076] Furthermore, it is used to process copper-cobalt oxide 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 compound of Formula 1 used in the flotation stage may be a single compound or a combination of compounds having the structure shown. As a typical example, Formula 1 may be a compound of Formula 1A, Formula 1B, etc., wherein Formula 1A is a compound of Formula 1 in which R1 is n-butyl and M is Na; and Formula 1B is a compound of Formula 1 in which R1 is n-pentyl and M is Na.

[0079] The compound of Formula 2 employed in the flotation stage can be a single compound or a combination of compounds having the structure shown. As a typical example, Formula 2 can be represented by Formula 2A, Formula 2B, and the like, wherein Formula 2A represents a compound of Formula 2 in which R2 is phenyl and N is H; and Formula 2B represents a compound of Formula 2 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 the tailings water or heating the 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 flotation water is the tailings pond smelting drainage, the calcium ion concentration is 1.25 g / L, and the magnesium ion concentration is 1.70 g / L. The flotation process is as follows:

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

[0085] (2) Grinding and slurrying: The test sample ore was ground to a fineness of less than 0.074 mm and the product accounted for 70% of the total weight. Then, the tail water was heated and slurried to a concentration of 33% to obtain the 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 rougher concentrate and the first rougher tailings. The first rougher concentrate was subjected to two rounds of concentrating operations to obtain oxidized concentrate I. The first concentrating middling pulp was heated to 50°C and returned to the first rougher.

[0087] (4) Sodium sulfide 500 g / t, auxiliary agent (ammonium bicarbonate) 400 g / t, formula 1A 200 g / t, formula 1B 200 g / t, and formula 2A 80 g / t are added to the first rougher tailings slurry in sequence, and the hard-floating copper-cobalt ore is aerated and floated (second rougher) to obtain a second rougher concentrate and a second rougher tailings. Sodium sulfide 500 g / t, auxiliary agent (ammonium bicarbonate) 400 g / t, formula 1A 200 g / t, formula 1B 200 g / t, and formula 2A 80 g / t are added to the second rougher tailings in sequence, and the hard-floating copper-cobalt ore is aerated and floated (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 pulp, 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 aeration flotation was performed to obtain oxidized concentrate II.

[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 in a pipeline.

[0089] Comparative Example 1:

[0090] Compared with Example 1, the only difference is that in step 1, the tailings water and the recycled slurry in the process are not heated, and the temperature is room temperature (20-25° C.). 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 of 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 flotation water is the tailings pond smelting drainage, the calcium ion concentration is 1.25 g / L, and the magnesium ion concentration is 1.70 g / L. The flotation process is as follows:

[0097] (1) Tailings pond return water heating: The tailings pond return water is heated to 55°C through the pipeline 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. Then, the tail water is heated and the slurry is adjusted to a concentration of 35% to obtain the ore slurry.

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

[0100] (4) Sodium sulfide 600 g / t, auxiliary agent (ammonium bicarbonate) 500 g / t, formula 1A 250 g / t, formula 1B 250 g / t, and formula 2A 140 g / t were added to the first rougher tailings slurry in sequence, and the hard-floating copper-cobalt ore was aerated and floated to obtain a second rougher concentrate and a second rougher tailings. Sodium sulfide 600 g / t, auxiliary agent (ammonium bicarbonate) 500 g / t, formula 1A 250 g / t, formula 1B 250 g / t, and formula 2A 140 g / t were added to the second rougher tailings in sequence, and the hard-floating copper-cobalt ore was aerated and floated 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 pulp, and 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 aeration flotation was performed to obtain oxidized concentrate II.

[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 in 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 further 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] As shown in Table 1, on the basis of heating the magnesium-rich tailings water, further coordinating with 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, unexpected synergy can be achieved, 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 by efficient flotation based on smelting wastewater.

Claims

1. A method for enhancing the flotation of copper-cobalt oxide ores from magnesium-rich tailings, characterized in that the steps include: Step (1): The copper-cobalt oxide ore and magnesium-rich tailings water preheated to 40-60° C. are mixed and ground, and then a first roughing treatment is performed using a flotation reagent a containing a sulfiding agent, a collector of formula 1, and a frother 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 oxide concentrate I; Formula 1 R1 is a C2~C8 alkyl group; M is H, Na, K or NH4; Step (2): Adding flotation agent b to the first stage roughing tailings slurry of step (1) to perform a second stage roughing to obtain a second stage roughing concentrate and a second stage roughing tailings slurry, and then adding flotation agent c to the second stage roughing tailings slurry to perform a third stage roughing to obtain a third stage roughing concentrate and a third stage 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 reagents b, c and d contain a sulfiding agent and a composite collector; and the flotation reagents b and c also contain an auxiliary agent; The composite 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 enhancing the flotation of copper-cobalt oxide ores from magnesium-rich tailings water as claimed in claim 1, wherein: The magnesium-rich tailings water is flotation wastewater containing magnesium ions.

3. The method for enhancing the flotation of copper-cobalt oxide ores from magnesium-rich tailings water as claimed in claim 2, wherein: The magnesium ion concentration of magnesium-rich tailings water is 0.3~2.5 g / L.

4. The method for enhancing the flotation of copper-cobalt oxide ores from magnesium-rich tailings water as claimed in claim 3, wherein: Calcium ions also exist in the magnesium-rich tailings water.

5. The method for enhancing the flotation of copper-cobalt oxide ores from magnesium-rich tailings water as claimed in claim 4, wherein: The calcium ion concentration in the magnesium-rich tailings water is 0.3-2.0 g / L.

6. The method for enhancing the flotation of copper-cobalt oxide ores from magnesium-rich tailings water according to claim 1, wherein: The copper grade in copper-cobalt oxide ore is 1.0%~3.5%, the cobalt grade is above 0.07%, and the cobalt-copper oxidation rate is above 90%.

7. The method for enhancing the flotation of copper-cobalt oxide ores from magnesium-rich tailings water according to claim 1, wherein: 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 pulp concentration in the grinding pulp is 30%-35%.

8. The method for enhancing the flotation of copper-cobalt oxide ores from magnesium-rich tailings water according to claim 1, wherein: The sulfiding agent includes at least one of sodium sulfide and sodium hydrogen sulfide.

9. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: The foaming agent includes at least one of 2# oil and methyl isobutyl carbinol.

10. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: In step (1), the amount of sulfiding agent added is 500-1000 g / ton of ore, the amount of collector added in formula 1 is 400-800 g / ton of ore; and the amount of foaming agent added is 20-40 g / ton of ore.

11. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water according to claim 10, wherein: The scraping time for the first rough selection is 3~5min.

12. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: In step (1), the beneficiation step includes two stages of beneficiation processes, wherein an inhibitor is added in the first stage of beneficiation, the middling slurry of the first stage of beneficiation is heated to 40-60°C and then returned to the first stage of roughing process; the concentrate of the second stage of beneficiation is the oxidized concentrate I, and the middling slurry of the second stage of beneficiation participates in the fine scavenging process.

13. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water according to claim 12, wherein: The inhibitor includes at least one of water glass and CMC.

14. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water according to claim 12, wherein: The dosage of the inhibitor is 200-400 g / ton of ore.

15. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 12, characterized in that: The best scraping time is 2~3min.

16. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, characterized in that: In step (2), an auxiliary agent containing ethylenediamine phosphate may be added to the auxiliary agent.

17. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water according to claim 16, wherein: The content of auxiliary additives accounts for 10%~30% of the total additives.

18. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: The sulfiding agent includes at least one of sodium sulfide and sodium hydrogen sulfide.

19. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, characterized in that: 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.

20. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, characterized in that: During the second roughing process of step (2), the amount of sulfiding agent added is 400~600g / ton of ore, the amount of auxiliary agent added is 300~500g / ton of ore; and the amount of composite collector added is 350~700g / ton of ore.

21. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 20, characterized in that: During the third roughing process of step (2), the dosage of each component in flotation reagent c is 0.5 to 1.5 times the dosage of flotation reagent b.

22. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: In step (2), during the fine sweeping process, the dosage of the sulfiding agent is 200-400 g / ton of ore; the dosage of the composite collector is 150-400 g / ton of ore.

23. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: The scraping and foaming time for the second and third rough selections is 3 to 5 minutes, and the scraping and foaming time for fine sweeping selection is 2 to 3 minutes.

24. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: 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.

25. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 24, characterized in that: In step (3), the scraping time of the sweeping selection is 3 to 5 minutes.

26. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: The scavenging concentrate and the fine scavenging tailings slurry are mixed and heated to 40~60℃ and then reused in the second roughing process.

27. The method for enhancing the flotation of copper-cobalt oxide ores using magnesium-rich tailings water as claimed in claim 1, wherein: 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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