A method for improving cobalt grade in a cobalt sulphide concentrate

Abstract

This invention provides a flotation method for improving the cobalt grade in cobalt-sulfur concentrate, comprising the following steps: S1: Adding a collector and a frother to the cobalt-sulfur concentrate obtained from vanadium-titanium magnetite, and performing cobalt-sulfur concentrate flotation to obtain high-grade cobalt-sulfur concentrate and tailings; S2: Adding a pH adjuster, a depressant, a collector, and a frother to the high-grade cobalt-sulfur concentrate obtained in S1 for a first cleaning process, and obtaining high-grade cobalt concentrate and tailings; S3: Adding a collector and a frother to the tailings obtained in S2, and performing scavenging to obtain sulfur concentrate; This invention achieves the separation of sulfur and cobalt in cobalt-sulfur concentrate, obtaining separate cobalt concentrate and sulfur concentrate, wherein the cobalt concentrate has a Co grade ≥1.0% and the sulfur concentrate has a S grade ≥32.0%, thereby improving the comprehensive utilization rate and value of vanadium-titanium magnetite resources; and the reagents used in this application are conventional reagents, which are easy to obtain, have stable components, and can be used for a long time.

Description

Technical Field

[0001] This invention relates to the field of cobalt grade flotation technology, and in particular to a flotation method for improving the cobalt grade in cobalt sulfide concentrate. Background Technology

[0002] The vanadium-titanium magnetite in Panzhihua is a polymetallic symbiotic mineral containing a variety of beneficial elements such as iron, vanadium, titanium, sulfur, and cobalt. Currently, the beneficiation process of vanadium-titanium magnetite mainly recovers iron concentrate, titanium concentrate, and a small amount of sulfur-cobalt concentrate. The sulfur-cobalt concentrate has an S grade of about 30% and a Co grade of about 0.3%.

[0003] As ore mining in the Panzhihua region continues to deepen, the content of sulfur and cobalt minerals in the ore is further increasing, and the demand for efficient recovery of sulfur and cobalt resources will be further enhanced. At the same time, with the increase in iron concentrate upgrading and desulfurization operations for the recovery of fine-grained ilmenite, the output of sulfur and cobalt concentrate is bound to increase. Therefore, there is an urgent need for a flotation reagent system that can improve the cobalt grade of sulfur and cobalt concentrate and form high-value separate sulfur and cobalt concentrates, thereby improving the utilization rate and value of sulfur and cobalt in vanadium-titanium magnetite in the Panzhihua-Xichang region.

[0004] According to current reports, flotation is the main method for recovering cobalt. However, common problems include low cobalt recovery rates and complex processes. Efficient and comprehensive recovery of valuable cobalt metal from cobalt sulfate concentrate is of great significance for improving the comprehensive utilization rate of mineral resources and significantly increasing the economic benefits of enterprises.

[0005] After a detailed search, the applicant did not find any existing technology regarding methods for extracting cobalt grade from cobalt sulfide concentrate obtained from vanadium-titanium magnetite.

[0006] Therefore, a new technical solution is needed to solve the above-mentioned technical problems. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention proposes a flotation method to improve the cobalt grade in cobalt-sulfur concentrate, which can produce separate cobalt concentrate and sulfur concentrate products with high Co and sulfur grades, thereby improving the comprehensive utilization rate of vanadium-titanium magnetite.

[0008] A flotation method for improving the cobalt grade in cobalt sulfide concentrate includes the following steps:

[0009] S1: Add collectors and frothers to the cobalt-sulfur concentrate obtained from vanadium-titanium magnetite, and carry out cobalt-sulfur concentrate flotation to obtain high-grade cobalt-sulfur concentrate and tailings.

[0010] S2: Add pH adjuster, inhibitor, collector and frother to the high-grade cobalt-sulfur concentrate obtained in S1 for the first cleaning process to obtain high-grade cobalt concentrate and tailings.

[0011] S3: Add collectors and frothers to the tailings obtained in S2 and perform scavenging to obtain sulfur concentrate.

[0012] As a preferred embodiment, the high-grade cobalt concentrate obtained from the first refining process is subjected to a second to fifth refining process, and the middlings generated from the second to fifth refining processes are recycled back to their corresponding previous refining process.

[0013] As a preferred embodiment, the process includes five refining processes. The middlings obtained from the second refining process are recycled back to the first refining process, and the cobalt concentrate obtained from the second refining process is subjected to a third refining process. The middlings obtained from the third refining process are recycled back to the second refining process, and the cobalt concentrate obtained from the third refining process is subjected to a fourth refining process. The middlings obtained from the fourth refining process are recycled back to the third refining process, and the cobalt concentrate obtained from the fourth refining process is subjected to a fifth refining process. The middlings obtained from the fifth refining process are recycled back to the fourth refining process, and the cobalt concentrate obtained from the fifth refining process is the final cobalt concentrate.

[0014] As a preferred option, an inhibitor is added during the 2nd to 5th selection process.

[0015] As a preferred approach, the dosage of the inhibitor gradually increases with the number of selections, increasing by 1 / 4 to 3 / 4 of the dosage of the inhibitor used in the previous selection.

[0016] As a preferred embodiment, the number of sweeps in S3 is 1-5 times, and the middlings obtained from the 2nd to 5th sweeps are recycled back to the previous sweep.

[0017] As a preferred embodiment, the scavenging process involves five stages. The first scavenging yields a high-grade sulfur concentrate, which is then subjected to a second scavenging. The middlings from the second scavenging are recycled back to the first scavenging stage. The sulfur concentrate from the second scavenging stage is then subjected to a third scavenging stage. The middlings from the third scavenging stage are recycled back to the second scavenging stage. The sulfur concentrate from the third scavenging stage is then subjected to a fourth scavenging stage. The middlings from the fourth scavenging stage are recycled back to the third scavenging stage. The sulfur concentrate from the fourth scavenging stage is then subjected to a fifth scavenging stage. The middlings from the fifth scavenging stage are recycled back to the fourth scavenging stage. The sulfur concentrate obtained from the fifth scavenging stage is the final sulfur concentrate.

[0018] As a preferred option, the number of scavenging cycles is 2-5. The dosage of the collector and frother gradually increases with the number of scavenging cycles, increasing by 1 / 4 to 3 / 4 of the dosage of the collector and frother used in the previous scavenging cycle.

[0019] As a preferred embodiment, the collector is butyl xanthate.

[0020] As a preferred embodiment, the amount of the collector is 20-100 g / t.

[0021] As a preferred embodiment, the foaming agent is methyl isobutyl methanol or pine oil.

[0022] As a preferred embodiment, the amount of foaming agent used is 10-80 g / t.

[0023] As a preferred option, the pH adjuster is lime.

[0024] As a preferred embodiment, the amount of the pH adjuster is 100-1000 g / t.

[0025] As a preferred option, the pH value of the pulp of high-grade cobalt-sulfur concentrate after adding a pH adjuster is greater than or equal to 9.

[0026] As a preferred embodiment, the inhibitor is at least one of lime, sodium sulfite, and sodium metabisulfite.

[0027] As a preferred embodiment, the inhibitor is sodium sulfite and sodium metabisulfite, wherein the mass ratio of sodium sulfite to sodium metabisulfite is 20%:80%-50%:50%.

[0028] As a preferred embodiment, the amount of the sodium sulfite and sodium metabisulfite mixture is 100-1000 g / t.

[0029] As a preferred embodiment, the high-grade sulfur-cobalt concentrate in S1 has a sulfur grade of ≥35% and a cobalt grade of ≥0.3%.

[0030] In summary, this invention achieves the separation of sulfur and cobalt in cobalt-sulfur concentrate, yielding separate cobalt concentrate and sulfur concentrate, wherein the cobalt concentrate has a Co grade ≥1.0% and the sulfur concentrate has a S grade ≥32.0%, thereby improving the comprehensive utilization rate and value of vanadium-titanium magnetite resources. Furthermore, the reagents used in this application are conventional reagents, which are easy to obtain, have stable components, and can be used for a long time. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 This is a flowchart illustrating the flotation method of the present invention. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be further described in detail below with reference to specific examples and the accompanying drawings.

[0034] It should be noted that all expressions using "1", "2", etc. in the embodiments of the present invention are for the purpose of distinguishing two entities with the same name but different names or different parameters. It can be seen that "1", "2", etc. are only for the convenience of expression and should not be construed as a limitation on the embodiments of the present invention. Subsequent embodiments will not explain this in detail.

[0035] like Figure 1 As shown, an embodiment of the present invention provides a flotation method for improving the cobalt grade in cobalt sulfide concentrate, comprising the following steps:

[0036] S1: A collector and a frother are added to the cobalt-sulfur concentrate obtained from vanadium-titanium magnetite to perform flotation of the cobalt-sulfur concentrate, resulting in high-grade cobalt-sulfur concentrate and tailings; wherein the sulfur (S) grade in the cobalt-sulfur concentrate is about 30% and the cobalt (Co) grade is about 0.3%, and the high-grade cobalt-sulfur concentrate obtained has a sulfur grade greater than or equal to 35% and a cobalt grade greater than or equal to 0.3%; the collector is butyl xanthate, and the dosage of the collector is 20-100 g / t; the frother is methyl isobutyl methanol (MIBC) or No. 2 oil (pine oil), and the dosage of the frother is 10-80 g / t;

[0037] S2: A pH adjuster, inhibitor, collector, and frother are added to the high-grade cobalt-sulfur concentrate obtained in S1 for the first cleaning process, yielding high-grade cobalt concentrate and tailings. The pH adjuster is lime, and the dosage is 100-1000 g / t. The pH value of the high-grade cobalt-sulfur concentrate slurry after adding the pH adjuster is greater than or equal to 9. Lime can be used not only as a pH adjuster but also as an inhibitor. The inhibitor is at least one of lime, sodium sulfite, and sodium metabisulfite. When lime is added as a pH adjuster, it can... It is sufficient to act as an inhibitor; adding one part lime is enough, and there is no need to add it repeatedly. Sodium sulfite and sodium metabisulfite are preferably a mixture, with a mass ratio of sodium sulfite to sodium metabisulfite of 20%:80%-50%:50%, and the amount of the sodium sulfite and sodium metabisulfite mixture is 100-1000 g / t. The collector is butyl xanthate, and the amount of the collector is 20-100 g / t. The frother is methyl isobutyl methanol (MIBC) or No. 2 oil (pine oil), and the amount of the frother is 10-80 g / t.

[0038] The high-grade cobalt concentrate after the first cleaning can also be cleaned a second to fifth time. The middlings produced by the second to fifth cleaning are recycled back to the previous cleaning. Only lime, sodium sulfite, and sodium metabisulfite inhibitors are added for the second to fifth cleaning.

[0039] This embodiment uses a 5-stage refining process as an example. The first refining process yields high-grade cobalt concentrate and tailings. The high-grade cobalt concentrate undergoes a second refining process. The middlings from the second refining process are recycled back to the first refining process. The cobalt concentrate from the second refining process undergoes a third refining process. The middlings from the third refining process are recycled back to the second refining process. The cobalt concentrate from the third refining process undergoes a fourth refining process. The middlings from the fourth refining process are recycled back to the third refining process. The cobalt concentrate from the fourth refining process undergoes a fifth refining process. The middlings from the fifth refining process are recycled back to the third refining process. Returning to the 4th and 5th refining processes, the resulting cobalt concentrate is the final cobalt concentrate. When refining 2-5 times, the dosage of the inhibitor gradually increases with the number of refining processes, increasing by 1 / 4 to 3 / 4 of the dosage of the inhibitor used in the previous refining process. For example, if the dosage of sodium sulfite and sodium metabisulfite mixture as inhibitor in the 1st refining process is 200 g / t, then the dosage of collector in the 2nd refining process is 250 g / t to 350 g / t. Other details are not elaborated here, and technicians can make appropriate selections according to specific circumstances.

[0040] S3: Add collectors and frothers to the tailings obtained in S2 and perform scavenging to obtain sulfur concentrate; the type and amount of collectors and frothers are as described above and will not be repeated here; the number of scavenging in S3 is 1-5 times, and the middlings obtained from the 2nd-5th scavenging are recycled back to the previous scavenging.

[0041] This embodiment uses a 5-stage scavenging process as an example. The first scavenging yields high-grade sulfur concentrate, which is then subjected to a second scavenging. The middlings from the second scavenging are recycled back to the first scavenging, and the sulfur concentrate from the second scavenging is subjected to a third scavenging. The middlings from the third scavenging are recycled back to the second scavenging, and the sulfur concentrate from the third scavenging is subjected to a fourth scavenging. The middlings from the fourth scavenging are recycled back to the third scavenging, and the sulfur concentrate from the fourth scavenging is subjected to a fifth scavenging. The middlings from the fifth scavenging are recycled back to the fourth scavenging, and the sulfur concentrate from the fifth scavenging is the final sulfur concentrate. The number of scavenging stages is 2-5. The dosage of collectors and frothers gradually increases with the number of scavenging stages, increasing by 1 / 4 to 3 / 4 of the dosage of collectors and frothers used in the previous scavenging.

[0042] This embodiment achieves the separation of sulfur and cobalt in cobalt-sulfur concentrate, resulting in separate cobalt concentrate and sulfur concentrate, wherein the cobalt concentrate has a Co grade ≥1.0% and the sulfur concentrate has a S grade ≥32.0%, thereby improving the comprehensive utilization rate and value of vanadium-titanium magnetite resources; moreover, the reagents used in this application are conventional reagents, which are easy to obtain, have stable components, and can be used for a long time.

[0043] Example 1:

[0044] This embodiment provides a specific application scenario, specifically:

[0045] This embodiment uses vanadium-titanium magnetite tailings from a beneficiation plant in Panzhihua. The tailings contain 30.47% sulfur, 15.80% TiO2, and 0.367% Co. Specific composition is shown in Table 1.

[0046]

[0047] Table 1 Chemical composition analysis of cobalt-sulfur concentrate from a mineral processing plant in Panzhihua

[0048] This example uses the following steps for flotation:

[0049] S1: A cobalt-sulfur concentrate with an S grade of 30.47% was roughed by adding butyl xanthate as a collector and MIBC as a frother to obtain a high-grade cobalt-sulfur concentrate and tailings with an S grade of 36.20% and a Co grade of 0.382%; the dosage of butyl xanthate was 60 g / t and the dosage of MIBC was 20 g / t.

[0050] S2: Lime is added as a pH adjuster and inhibitor to the high-grade cobalt-sulfur concentrate obtained from S1, which has a sulfur grade of 36.20% and a cobalt grade of 0.382%. A mixture of sodium sulfite and sodium metabisulfite is added as an inhibitor, butyl xanthate is added as a collector, and MIBC is added as a frother for the first cleaning process to obtain high-grade cobalt-sulfur concentrate and tailings. The amount of lime used is 1000 g / t, the mass ratio of sodium sulfite to sodium metabisulfite is 20%:80% and the amount of sodium sulfite used is 500 g / t, the amount of butyl xanthate used is 50 g / t, and the amount of MIBC used is 20 g / t.

[0051] The high-grade cobalt concentrate obtained from the first refining process is subjected to a second and third refining process. In the second and third refining processes, only depressants such as lime, sodium sulfite, and sodium metabisulfite are added. The amount of depressant used in the third refining process is increased by 1 / 4 compared to the second refining process, and the amount of depressant used in the second refining process is increased by 1 / 4 compared to the first refining process. The middlings obtained from the third refining process are returned to the second refining process, and the middlings obtained from the second refining process are returned to the first refining process. The high-grade cobalt concentrate obtained from the third refining process is used as the final concentrate.

[0052] S3: Add butyl xanthate as a collector and MIBC as a frother to the tailings obtained in S2 for scavenging to obtain sulfur concentrate; the amount of collector and frother is the same as in S1; the tailings are scavenged 3 times, the amount of collector and frother used in the third scavenging is increased by 1 / 4 compared with the amount of collector and frother used in the second scavenging, and the amount of collector and frother used in the second scavenging is increased by 1 / 4 compared with the amount of collector and frother used in the first scavenging; the middlings obtained from the third scavenging are returned to the second scavenging, the middlings obtained from the second scavenging are returned to the first scavenging, and the high-grade sulfur ore obtained from the third scavenging is used as the final tailings. The final product indicators are shown in Table 2.

[0053]

[0054] Table 2 Results of Implementation of Improving Cobalt Grade in Cobalt Sulfide Concentrate at a Mineral Processing Plant in Panzhihua

[0055] This method successfully separated sulfur and cobalt in cobalt-sulfur concentrate, yielding separate cobalt and sulfur concentrates. Table 2 shows that the cobalt concentrate had a yield of 15.832%, a sulfur grade of 39.450%, and a recovery rate of 20.486%; a cobalt grade of 1.170% and a recovery rate of 50.443%. The sulfur concentrate had a yield of 65.076%, a sulfur grade of 32.760%, and a recovery rate of 69.966%; a cobalt grade of 0.256% and a recovery rate of 45.443%. This improved the comprehensive utilization rate and value of vanadium-titanium magnetite resources.

[0056] Example 2:

[0057] This embodiment provides another specific application scenario, specifically:

[0058] This embodiment uses vanadium-titanium magnetite tailings from a mineral processing plant in Yunnan Province. The tailings contain 29.87% sulfur, 14.85% TiO2, and 0.342% Co. Specific composition is shown in Table 3.

[0059]

[0060] Table 3 Chemical composition analysis of cobalt-sulfur concentrate from a mineral processing plant in Yunnan Province

[0061] This example uses the following steps for flotation:

[0062] S1: Butyl xanthate was added as a collector and MIBC as a frother to cobalt sulfide concentrate with an S grade of 29.87% for roughing to obtain high-grade cobalt sulfide concentrate and tailings with an S grade of 36.10% and a Co grade of 0.375%; the dosage of butyl xanthate was 80 g / t and the dosage of MIBC was 20 g / t.

[0063] S2: Lime is added as a pH adjuster and inhibitor to the high-grade cobalt-sulfur concentrate obtained from S1, which has a sulfur grade of 36.10% and a cobalt grade of 0.375%. Sodium sulfite and sodium metabisulfite are added as inhibitors, as well as a mixture of sodium sulfite and sodium metabisulfite as inhibitors. Butyl xanthate is added as a collector, and MIBC is added as a frother for the first cleaning process to obtain high-grade cobalt-sulfur concentrate and tailings. Among them, the amount of lime is 800g / t, the mass ratio of sodium sulfite to sodium metabisulfite is 50%:50% and the amount of sodium sulfite is 400g / t, the amount of butyl xanthate is 50g / t, and the amount of MIBC is 20g / t.

[0064] The high-grade cobalt concentrate obtained from the first refining process is subjected to a second and third refining process. In the second and third refining processes, only depressants such as lime, sodium sulfite, and sodium metabisulfite are added. The amount of depressant used in the third refining process is increased by 1 / 4 compared to the second refining process, and the amount of depressant used in the second refining process is increased by 1 / 4 compared to the first refining process. The middlings obtained from the third refining process are returned to the second refining process, and the middlings obtained from the second refining process are returned to the first refining process. The high-grade cobalt concentrate obtained from the third refining process is used as the final concentrate.

[0065] S3: Add butyl xanthate as a collector and MIBC as a frother to the tailings obtained in S2 for scavenging to obtain sulfur concentrate; the amount of collector and frother is the same as in S1; the tailings are scavenged 3 times, the amount of collector and frother used in the third scavenging is increased by 1 / 4 compared with the amount of collector and frother used in the second scavenging, and the amount of collector and frother used in the second scavenging is increased by 1 / 4 compared with the amount of collector and frother used in the first scavenging; the middlings obtained from the third scavenging are returned to the second scavenging, the middlings obtained from the second scavenging are returned to the first scavenging, and the high-grade sulfur ore obtained from the third scavenging is used as the final tailings. The final product indicators are shown in Table 4.

[0066]

[0067] Table 4 Results of Implementation of Improving Cobalt Grade in Cobalt Sulfide Concentrate at a Mineral Processing Plant in Yunnan

[0068] This method successfully separated sulfur and cobalt in cobalt-sulfur concentrate, yielding separate cobalt and sulfur concentrates. Table 4 shows that the cobalt concentrate had a yield of 15.564%, a sulfur grade of 38.550%, and a recovery rate of 20.087%; a cobalt grade of 1.010% and a recovery rate of 45.964%. The sulfur concentrate had a yield of 60.451%, a sulfur grade of 32.690%, and a recovery rate of 66.158%; a cobalt grade of 0.270% and a recovery rate of 47.725%. This improved the comprehensive utilization rate and value of vanadium-titanium magnetite resources.

[0069] It should be noted that the components or steps in the above embodiments can be interchanged, substituted, added, or deleted. Therefore, the combinations formed by these reasonable permutations and transformations should also fall within the protection scope of this invention, and the protection scope of this invention should not be limited to the above embodiments.

[0070] The above are exemplary embodiments disclosed in this invention. The order of the disclosed embodiments is merely for descriptive purposes and does not represent the superiority or inferiority of the embodiments. However, it should be noted that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the disclosed embodiments of this invention (including the claims) is limited to these examples. Various changes and modifications can be made without departing from the scope defined by the claims. The functions, steps, and / or actions of the methods according to the disclosed embodiments described herein do not need to be performed in any particular order. Furthermore, although the elements disclosed in the embodiments of this invention may be described or claimed individually, they may be understood as multiple unless explicitly limited to a singular.

[0071] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention (including the claims) is limited to these examples. Within the framework of the invention, technical features of the above embodiments or different embodiments can be combined, and many other variations of the different aspects of the invention as described above exist, which are not provided in the details for the sake of brevity. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the invention should be included within the protection scope of the invention.

Claims

1. A flotation method for improving the cobalt grade in cobalt-sulfur concentrate, characterized in that, Includes the following steps: S1: Add collectors and frothers to the cobalt-sulfur concentrate obtained from vanadium-titanium magnetite, and carry out cobalt-sulfur concentrate flotation to obtain high-grade cobalt-sulfur concentrate and tailings. S2: Add pH adjuster, inhibitor, collector, and frother to the high-grade cobalt-sulfur concentrate obtained in S1 for the first cleaning process, to obtain high-grade cobalt concentrate and tailings; perform the second to fifth cleaning processes on the high-grade cobalt concentrate obtained in the first cleaning process. The middlings produced in the second to fifth cleaning processes are recycled back to their corresponding previous cleaning process. In the second to fifth cleaning processes, only inhibitor is added. The amount of inhibitor gradually increases with the number of cleaning processes, increasing by 1 / 4 to 3 / 4 of the amount of inhibitor used in the corresponding previous cleaning process. Lime is used for both pH adjuster and inhibitor. S3: Add collector and frother to the tailings obtained in S2 and perform scavenging to obtain sulfur concentrate; the number of scavenging in S3 is 1-5 times, and the middlings obtained from the 2nd-5th scavenging are recycled back to the previous scavenging. The number of scavenging times is 2-5 times, and the amount of collector and frother used gradually increases with the number of scavenging times, increasing by 1 / 4-3 / 4 of the amount of collector and frother used in the previous scavenging. The collector used in steps S1-S3 is butyl xanthate.

2. The flotation method for improving the cobalt grade in cobalt-sulfur concentrate according to claim 1, characterized in that, The high-grade sulfur-cobalt concentrate in S1 has a sulfur grade of ≥35% and a cobalt grade of ≥0.3%.

3. The flotation method for improving the cobalt grade in cobalt-sulfur concentrate according to claim 1, characterized in that, The pH value of the pulp of high-grade cobalt-sulfur concentrate after adding pH adjuster is greater than or equal to 9.

4. The flotation method for improving the cobalt grade in cobalt-sulfur concentrate according to claim 1, characterized in that, The inhibitor is at least one of lime, sodium sulfite, and sodium metabisulfite.

5. The flotation method for improving the cobalt grade in cobalt-sulfur concentrate according to claim 4, characterized in that, The inhibitors are sodium sulfite and sodium metabisulfite, with a mass ratio of 20%:80%-50%:50%.

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