Composite collector for manganese extraction and sulfur collection from high-sulfur low-grade manganese carbonate ore and application thereof

Abstract

The application relates to the technical field of mineral processing, in particular to a composite collector for high-sulfur low-grade manganese carbonate ore and application thereof, and the composite collector is obtained by compounding a xanthate collector and a sulfonate collector; the xanthate collector comprises one of butyl xanthate and isobutyl xanthate; the sulfonate collector comprises at least one of alkyl sulfonate, alkyl benzene sulfonate and petroleum sulfonate. The composite collector can solve the problems of high grinding cost, poor manganese-sulfur separation effect and low comprehensive utilization rate of resources when high-sulfur low-grade manganese carbonate ore is processed at present, and provides an economical and feasible separation process with simple process and synchronous production of manganese concentrate and sulfur concentrate for high-sulfur low-grade manganese carbonate ore.

Description

Technical Field

[0001] This application relates to the field of mineral processing technology, specifically to a composite collector for manganese extraction and sulfur recovery from high-sulfur, low-grade manganese carbonate ore and its application. Background Technology

[0002] High-sulfur manganese carbonate ores are generally characterized by low primary manganese grade (usually around 10%, below the current industrial utilization threshold grade), high sulfur content (mainly in the form of pyrite, manganese sulfide and other sulfides, with a content of 6% to 8%), and complex intergrowth relationships between manganese minerals, sulfides and gangue.

[0003] Currently, the beneficiation process for this type of ore generally adopts a "full-size fine grinding - single magnetic separation or flotation" process, but there are still obvious shortcomings: because the mineral contains a large amount of coarse gangue that has reached the tailings standard, the grinding energy consumption during fine grinding is extremely high, which greatly increases the production cost and makes the economic feasibility of low-grade ore low; in addition, the high content of sulfides in the mineral will seriously interfere with the separation of manganese minerals. If single magnetic separation is used, the sulfur content of the obtained manganese concentrate will be seriously excessive and cannot meet the metallurgical requirements; in addition, in complex systems with low manganese and high sulfur, the use of single xanthate collectors has a strong collecting ability for pyrite, but insufficient selectivity for associated manganese sulfide minerals, and the effect is unstable in high mud or complex systems, resulting in unsatisfactory sulfur recovery rate, and manganese minerals may also be lost due to improper suppression or entrainment. Furthermore, in the current field, sulfides in high-sulfur manganese carbonate ores are usually regarded as impurities, and the focus is only on how to reduce the sulfur content in manganese concentrate. The process of "desulfurization" is actually the process of "removing impurities". The sulfides have not been recovered and enriched as a valuable symbiotic mineral resource, resulting in the waste of sulfur resources.

[0004] Therefore, a novel collector is needed for high-sulfur, low-grade manganese carbonate ore that efficiently enriches manganese while comprehensively recovering sulfur, in order to improve the overall utilization effect of high-sulfur, low-grade manganese carbonate ore. Summary of the Invention

[0005] The purpose of this application is to overcome the shortcomings of the existing technology and provide a composite collector for manganese and sulfur extraction from high-sulfur, low-grade manganese carbonate ore and its application, so as to solve the problems of high grinding cost, poor manganese-sulfur separation effect and low resource utilization rate when processing high-sulfur, low-grade manganese carbonate ore. It provides an economical, feasible, simple process for the beneficiation of high-sulfur, low-grade manganese carbonate ore that can simultaneously produce manganese concentrate and sulfur concentrate.

[0006] The objective of this application is achieved through the following technical solution: On the one hand, this application provides a composite collector for extracting manganese and sulfur from high-sulfur, low-grade manganese carbonate ore, wherein the composite collector is obtained by compounding xanthate collectors and sulfonate collectors; The xanthate collector includes one of butyl xanthate and isobutyl xanthate; The sulfonate collectors include at least one of alkyl sulfonates, alkylbenzene sulfonates, and petroleum sulfonates.

[0007] Furthermore, the weight ratio of the xanthate collector to the sulfonate collector is 1:(0.2~0.8).

[0008] On the other hand, this application provides a method for preparing the above-mentioned composite collector, comprising the following steps: The xanthate collector and the sulfonate collector are mixed and stirred at 15-80°C until completely dispersed to obtain the composite collector.

[0009] Furthermore, this application provides the application of the above-mentioned composite collector or the composite collector prepared by the above method in the beneficiation of high-sulfur, low-grade manganese carbonate ore, including the following steps: S1. The high-sulfur, low-grade manganese carbonate ore is crushed to a particle size of -3 mm to -10 mm, and then dry magnetic separation is performed to remove coarse gangue mineral tailings to obtain dry magnetic concentrate. S2. The dry polished concentrate is finely ground, and then the obtained dry polished concentrate powder is subjected to strong magnetic separation to obtain manganese crude concentrate; S3. After adjusting the manganese crude concentrate into a slurry, the composite collector and frother are added for flotation separation and dewatering and drying to obtain manganese concentrate and sulfur concentrate; The foaming agent includes No. 2 oil.

[0010] In the above technical solution, the high-sulfur, low-grade manganese carbonate ore is first processed and crushed. The coarse-grained product is then immediately subjected to dry roughing, and tailings are pre-discarded. This significantly reduces the amount of material fed into the mill and the subsequent operational load, lowering energy consumption during fine grinding. Fine grinding of the dry-discarded concentrate ensures complete liberation of manganese minerals and sulfides, facilitating subsequent separation. After enrichment by strong magnetic separation, the finely ground product is then subjected to flotation desulfurization, simultaneously yielding qualified manganese concentrate with a manganese grade of over 18% and sulfur concentrate with a sulfur grade of over 30%.

[0011] Furthermore, in S1, the high-sulfur, low-grade manganese carbonate ore has a Mn grade of 8% to 10% and a S grade of 6% to 8%.

[0012] Furthermore, the feature is that, in S1, the magnetic field strength of the dry magnetic separation is 0.6~1.0 T.

[0013] Furthermore, in S2, after fine grinding, the dry-polished concentrate powder has a particle size of -0.074 mm and a content of 60% to 90%.

[0014] Furthermore, in S2, the magnetic field strength of the strong magnetic separation is 0.6~1.5 T.

[0015] Furthermore, in S3, the concentration of the slurry is 30%.

[0016] Furthermore, in S3, the flotation separation adopts a flotation process of one roughing, one scavenging, and two cleaning steps.

[0017] Furthermore, based on the weight of the manganese crude concentrate, the amount of the composite collector is 100~500 g / t, and the amount of the frother is 40 g / t.

[0018] The principle of this application is: The composite collector of this application is obtained by compounding xanthate collectors and sulfonate collectors. The two collectors can produce a significant synergistic effect. The introduction of sulfonate enhances the adsorption strength and coverage uniformity of the reagent on the mineral surface, making up for the problem of insufficient collection ability of xanthate for some manganese sulfides. At the same time, sulfonate itself also has certain collection and foaming properties, improving the overall collection ability and selectivity for complex sulfide minerals, and is especially suitable for the flotation environment of high-sulfur and low-grade manganese carbonate ores.

[0019] The beneficial effects of this application are: 1. Highly innovative reagent: The composite collector provided in this application, through a specific ratio of xanthate and sulfonate, produces an excellent synergistic effect, significantly improving the collection capacity and selectivity for complex sulfide minerals in high-sulfur, low-grade manganese carbonate ores, ensuring both sulfur recovery rate and manganese concentrate grade. 2. Significant economic benefits: This application innovatively constructs a new beneficiation process for high-sulfur, low-grade manganese carbonate ore, using dry magnetic separation for pre-tailing after coarse crushing. This process discards approximately 30% to 35% of the tailings at the source, significantly reducing the amount of ore required for subsequent fine grinding. This lowers grinding energy consumption and production costs, enabling the economical development of low-grade manganese carbonate ore. Then, through a precise combination of "intense magnetic separation" and "flotation," manganese is first enriched, followed by targeted desulfurization. The process is smooth and has minimal interference, ultimately yielding qualified manganese concentrate with a manganese grade of not less than 18%, and high-quality sulfur concentrate with a sulfur grade of not less than 30%. This achieves efficient separation and enrichment of manganese and sulfur elements.

[0020] 3. High degree of comprehensive utilization of resources: This application achieves the simultaneous production of qualified manganese concentrate and sulfur concentrate from a single high-sulfur, low-grade manganese carbonate ore through the combination of magnetic-levitation technology and specific reagents. It transforms "desulfurization" from an impurity that increases costs into a profitable mineral product. By actively recovering sulfur as one of the products, it achieves the full-component recovery of resources, creates more economic value, and meets the requirements for the construction of green mines.

[0021] 4. Stable and reliable process with strong adaptability: This application successfully solves the problem of beneficiation of difficult-to-process high-sulfur and low-grade manganese carbonate ore, providing a reliable and efficient technical option for the development and utilization of similar mineral resources, and has good prospects for industrial application. Attached Figure Description

[0022] Figure 1 This is a process flow diagram for the beneficiation of high-sulfur, low-grade manganese carbonate ore using a composite collector, as described in this application. Detailed Implementation

[0023] The technical solution of this application is described in further detail below with reference to the accompanying drawings, but the scope of protection of this invention is not limited to the following description.

[0024] Example 1

[0025] Prepare the composite collector according to the following steps: Butyl xanthate and sodium petroleum sulfonate were mixed at a weight ratio of 1:0.5 and then added to water. The mixture was stirred at 60°C until completely dispersed to obtain the composite collector with a mass concentration of 10%.

[0026] Using a high-sulfur, low-grade manganese carbonate ore from a region in northeastern Sichuan as the target manganese carbonate ore, dry magnetic tailings removal-flotation desulfurization was carried out using the aforementioned composite sulfide ore collector. The mineral composition was as follows: Mn grade 9.52%, S grade 7.58%, TFe grade 6.00%, SiO2 grade 30.65%, and CaO grade 12.63%. Mn mainly exists in the form of manganese dolomite, and sulfur mainly exists in the form of pyrite, with a small amount of manganese sulfide. The beneficiation process is as follows: S1. The high-sulfur, low-grade manganese carbonate ore is crushed to a particle size of -3 mm, and then dry magnetic separation is performed in a dry magnetic separator with a magnetic field strength of 0.8T to remove coarse gangue mineral tailings with a yield of about 35%, and dry-dissolved concentrate is obtained. S2. The dry polished concentrate is finely ground to -0.074 mm (75%) using a ball mill, and then the dry polished concentrate powder is subjected to strong magnetic separation using a SLon-500 type strong magnetic separator under a magnetic field strength of 1.2 T to obtain manganese rough concentrate; S3. After adjusting the manganese crude concentrate to a slurry concentration of 30%, add 300 g / t of the composite sulfide mineral collector and 40 g / t of pine oil by weight of the manganese crude concentrate, and adjust the pH to 7. Then, use a flotation process of "one roughing, one scavenging, and two cleaning" to separate the ore by flotation and dehydrate and dry it to obtain manganese concentrate and sulfur concentrate.

[0027] After analyzing the obtained manganese concentrate and sulfur concentrate by chemical titration, the yield of manganese concentrate was 38.12%, the grade of manganese was 18.52%, the recovery rate of manganese was 74.16%, and the sulfur content was 0.89%; the yield of sulfur concentrate was 16.22%, the grade of sulfur was 33.41%, and the recovery rate of sulfur was 71.49%.

[0028] Example 2

[0029] Prepare the composite collector according to the following steps: Isobutyl xanthate and sodium dodecylbenzenesulfonate were mixed at a weight ratio of 1:0.4, and then water was added. The mixture was stirred at 60°C until it was completely dispersed to obtain the composite collector with a mass concentration of 5%.

[0030] Using a high-sulfur, low-grade manganese carbonate ore from a region in northeastern Sichuan as the target manganese carbonate ore, dry magnetic tailings removal-flotation desulfurization was carried out using the aforementioned composite sulfide ore collector. The mineral composition was as follows: Mn grade 9.52%, S grade 7.58%, TFe grade 6.00%, SiO2 grade 30.65%, and CaO grade 12.63%. Mn mainly existed as manganese carbonate, and sulfur mainly existed as pyrite, with a small amount of manganese sulfide. The beneficiation process is as follows: S1. The high-sulfur, low-grade manganese carbonate ore is crushed to a particle size of -8 mm, and then dry magnetic separation is performed in a dry magnetic separator with a magnetic field strength of 0.7T to remove coarse gangue mineral tailings with a yield of about 30%, and dry-dissolved concentrate is obtained. S2. The dry polished concentrate is finely ground to -0.074 mm (85%) using a ball mill, and then the dry polished concentrate powder is subjected to strong magnetic separation using a SLon-500 type strong magnetic separator under a magnetic field strength of 0.9 T to obtain manganese rough concentrate. S3. After adjusting the manganese crude concentrate to a slurry concentration of 30%, add 250 g / t of the composite sulfide mineral collector and 35 g / t of pine oil by weight of the manganese crude concentrate, and adjust the pH to 7. Then, use a flotation process of "one roughing, one scavenging, and two cleaning" to separate the ore by flotation and dehydrate and dry it to obtain manganese concentrate and sulfur concentrate.

[0031] After analyzing the obtained manganese concentrate and sulfur concentrate by chemical titration, the yield of manganese concentrate was 38.87%, the grade of manganese was 18.34%, the recovery rate of manganese was 74.88%, and the sulfur content was 0.93%; the yield of sulfur concentrate was 16.15%, the grade of sulfur was 32.48%, and the recovery rate of sulfur was 69.20%.

[0032] Example 3

[0033] Prepare the composite collector according to the following steps: Butyl xanthate and alkyl sulfonate (C12~C14) were mixed at a weight ratio of 1:0.6 and then water was added. The mixture was stirred at 60°C until it was completely dispersed to obtain the composite collector with a mass concentration of 10%.

[0034] Using high-sulfur, low-grade manganese carbonate ore from a certain mining area as the target manganese carbonate ore, dry magnetic tailings removal-flotation desulfurization was carried out using the aforementioned composite sulfide ore collector. The mineral composition was as follows: Mn grade 9.23%, S grade 6.87%, TFe grade 5.72%, SiO2 grade 33.65%, and CaO grade 10.63%. Mn mainly existed as manganese carbonate, and sulfur mainly existed as pyrite, with a small amount of manganese sulfide. The beneficiation process is as follows: S1. The high-sulfur, low-grade manganese carbonate ore is crushed to a particle size of -3 mm, and then dry magnetic separation is carried out in a dry magnetic separator with a magnetic field strength of 1.0T to remove coarse gangue mineral tailings with a yield of about 30%, and dry-dissolved concentrate is obtained. S2. The dry polished concentrate is finely ground to -0.074 mm (65%) using a ball mill, and then the dry polished concentrate powder is subjected to strong magnetic separation using a SLon-500 type strong magnetic separator under a magnetic field strength of 1.5 T to obtain manganese rough concentrate. S3. After adjusting the manganese crude concentrate to a slurry concentration of 30%, add 400 g / t of the composite sulfide mineral collector and 35 g / t of pine oil by weight of the manganese crude concentrate, and adjust the pH to 7. Then, use a flotation process of "one roughing, one scavenging, and two cleaning" to separate the ore by flotation and dehydrate and dry it to obtain manganese concentrate and sulfur concentrate.

[0035] After analyzing the obtained manganese concentrate and sulfur concentrate by chemical titration, the yield of manganese concentrate was 36.64%, the grade of manganese was 18.21%, the recovery rate of manganese was 72.29%, and the sulfur content was 1.05%; the yield of sulfur concentrate was 15.37%, the grade of sulfur was 31.74%, and the recovery rate of sulfur was 71.01%.

[0036] Comparative Example 1 Using the same high-sulfur, low-grade manganese carbonate ore as in Example 1 as the candidate manganese carbonate ore, and referring to the steps of Example 1, only butyl xanthate was used as the collector at a dosage of 300 g / t. Other operations were the same as in Example 1, and the final minerals were analyzed.

[0037] The results showed that the final manganese concentrate yield was 38.26%, the manganese grade was 16.53%, the manganese recovery rate was 66.43%, and the sulfur content was 2.81%; the sulfur concentrate yield was 16.38%, the sulfur grade was 28.57%, and the sulfur recovery rate was 61.74%.

[0038] As can be seen, butyl xanthate alone has a decent ability to collect pyrite, but a weak ability to collect manganese sulfide minerals associated with the ore. This results in some manganese sulfide being lost in the manganese concentrate, leading to a high sulfur content in the manganese concentrate. At the same time, the total sulfur recovery rate is low, failing to achieve efficient separation and simultaneous high recovery of manganese and sulfur.

[0039] Comparative Example 2 Using the same high-sulfur, low-grade manganese carbonate ore as in Example 1 as the candidate manganese carbonate ore, and referring to the steps of Example 1, using butyl xanthate and sodium petroleum sulfonate in a 1:1 weight ratio as a composite collector at a dosage of 300 g / t, other operations were the same as in Example 1, and the final minerals were analyzed.

[0040] The results showed that the final manganese concentrate yield was 38.51%, the manganese grade was 16.18%, the manganese recovery rate was 65.45%, and the sulfur content was 1.50%; the sulfur concentrate yield was 17.26%, the sulfur grade was 30.03%, and the sulfur recovery rate was 68.38%.

[0041] As can be seen, although the sulfur recovery rate is high, the sulfur content of the manganese concentrate (1.50%) is significantly higher than that of Example 1 (0.89%). At the same time, with the total consumption of collector remaining unchanged, the excessively high proportion of sulfonate leads to a slight decrease in reagent selectivity, and the collection of sulfide minerals is too strong. This may have resulted in the inclusion of a small amount of extremely fine manganese minerals or increased foam viscosity, thus affecting the quality of the manganese concentrate.

[0042] Comparative Example 3 Using the same high-sulfur, low-grade manganese carbonate ore as in Example 1 as the manganese carbonate ore to be beneficiated, the beneficiation process is as follows: S1. The high-sulfur, low-grade manganese carbonate ore is crushed to a particle size of -8 mm, and then dry magnetic separation is performed in a dry magnetic separator with a magnetic field strength of 0.7T to remove coarse gangue mineral tailings with a yield of about 30%, and dry-dissolved concentrate is obtained. S2. The dry polished concentrate is finely ground to -0.074 mm (85%) using a ball mill. The resulting dry polished concentrate powder is then adjusted to a 30% slurry. Based on the weight of the dry polished concentrate powder, 250 g / t of the composite sulfide mineral collector and 35 g / t of pine oil are added, and the pH is adjusted to 7. Then, a flotation separation is performed using a "one roughing, one scavenging, two cleaning" flotation process, followed by dewatering and drying to obtain desulfurized tailings and crude sulfur concentrate. S3. Use a SLon-500 high-intensity magnetic separator to perform high-intensity magnetic separation on the obtained dry desulfurization tailings under a magnetic field strength of 0.9 T to obtain manganese concentrate.

[0043] The results showed that the final manganese concentrate yield was 45.29%, the manganese grade was 14.38%, the manganese recovery rate was 68.41%, and the sulfur content was 1.80%; the crude sulfur concentrate yield was 22.38%, the sulfur grade was 23.18%, and the sulfur recovery rate was 68.44%.

[0044] As can be seen, without pre-enrichment through magnetic separation, a large amount of gangue minerals enters the flotation system, resulting in severe mud formation in the pulp. This significantly interferes with the selective collection of sulfide minerals by the composite collector, leading to decreased flotation efficiency and unsatisfactory sulfur concentrate grade and recovery rate. Simultaneously, the mud also affects the recovery of fine-grained manganese carbonate by subsequent high-intensity magnetic separation, resulting in significantly lower manganese grade and recovery rate compared to Example 1. This process is energy-intensive and produces poor performance.

[0045] In summary, compared to a single xanthate (Comparative Example 1), the specific ratio compound reagent of this application (Example 1) significantly enhances the recovery capacity of manganese sulfide minerals while ensuring effective pyrite collection. This results in a substantial increase in sulfur recovery rate (from 61.74% to 71.49%) and an effective reduction in sulfur content of manganese concentrate (from 2.81% to 0.89%) at the same dosage, truly achieving a balance between "manganese extraction" and "sulfur recovery." Comparative Example 2 shows that compound ratios exceeding the preferred range of this application (1:0.4-0.6), although the sulfur recovery rate... The ratio is still relatively high, but it will impair the separation selectivity and lead to a decline in the quality of manganese concentrate, which proves the technical advancement and necessity of the ratio range limited by this application. As can be seen from Comparative Example 3, the "dry magnetic separation tailings removal-strong magnetic separation manganese extraction-flotation sulfur recovery" process pioneered by this application has an inherent logical advantage. First, manganese is pre-enriched by magnetic separation and a large amount of waste rock and mud are removed, which creates ideal feeding conditions of "rich, clean and uniform" for subsequent flotation, greatly improving the flotation efficiency. This sequential design is not a simple step superposition, but a deep coupling based on the differences in mineral properties, which is the key to achieving leading overall technical indicators.

[0046] In other words, the composite collector and its combined beneficiation method provided in this application, through the synergistic innovation of reagents and the optimization and integration of process flow, have synergistically solved the core technical problems of "difficult separation of manganese and sulfur, low product indicators, and uneven recovery" in the resource utilization of high-sulfur and low-grade manganese carbonate ore, demonstrating significant technological progress and outstanding substantive features.

[0047] The above description is merely a preferred embodiment of this application. It should be understood that this application is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. It can be used in various other combinations, modifications, and environments, and can be altered within the scope of the concept described herein through the above teachings or the technology or knowledge in related fields. Modifications and variations made by those skilled in the art that do not depart from the spirit and scope of this invention should be within the protection scope of the appended claims.

Claims

1. A composite collector for manganese extraction and sulfur recovery from high-sulfur, low-grade manganese carbonate ore, characterized in that, The composite collector is obtained by combining xanthate collectors and sulfonate collectors; The xanthate collector includes one of butyl xanthate and isobutyl xanthate; The sulfonate collectors include at least one of alkyl sulfonates, alkylbenzene sulfonates, and petroleum sulfonates.

2. The composite collector according to claim 1, characterized in that, The weight ratio of the xanthate collector to the sulfonate collector is 1:(0.2~0.8).

3. A method for preparing the composite collector as described in any one of claims 1 to 2, characterized in that, Includes the following steps: The xanthate collector and the sulfonate collector are mixed and stirred at 15-80°C until completely dispersed to obtain the composite collector.

4. The application of the composite collector as described in any one of claims 1-2 or the composite collector prepared according to claim 3 in the beneficiation of high-sulfur, low-grade manganese carbonate ore, characterized in that, Includes the following steps: S1. The high-sulfur, low-grade manganese carbonate ore is crushed to a particle size of -3 mm to -10 mm, and then dry magnetic separation is performed to remove coarse gangue mineral tailings to obtain dry magnetic concentrate. S2. The dry polished concentrate is finely ground, and then the obtained dry polished concentrate powder is subjected to strong magnetic separation to obtain manganese crude concentrate; S3. After adjusting the manganese crude concentrate into a slurry, the composite collector and frother are added for flotation separation and dewatering and drying to obtain manganese concentrate and sulfur concentrate; The foaming agent includes No. 2 oil.

5. The dry magnetic tailings removal-flotation desulfurization method for high-sulfur, low-grade manganese carbonate ore according to claim 4, characterized in that, In S1, the high-sulfur, low-grade manganese carbonate ore has a Mn grade of 8% to 10% and a S grade of 6% to 8%.

6. The dry magnetic tailings removal-flotation desulfurization method for high-sulfur, low-grade manganese carbonate ore according to claim 4, characterized in that, In S1, the magnetic field strength of the dry magnetic separation is 0.6~1.0 T.

7. The dry magnetic tailings removal-flotation desulfurization method for high-sulfur, low-grade manganese carbonate ore according to claim 4, characterized in that, In S2, after fine grinding, the dry-polished concentrate powder has a particle size of -0.074 mm and a content of 60% to 90%. And / or, in S2, the magnetic field strength of the strong magnetic separation is 0.6~1.5 T.

8. The dry magnetic tailings removal-flotation desulfurization method for high-sulfur, low-grade manganese carbonate ore according to claim 4, characterized in that, In S3, the concentration of the slurry is 30%.

9. The dry magnetic tailings removal-flotation desulfurization method for high-sulfur, low-grade manganese carbonate ore according to claim 4, characterized in that, In S3, the flotation separation adopts a flotation process of one roughing, one scavenging, and two cleaning steps.

10. The dry magnetic tailings removal-flotation desulfurization method for high-sulfur, low-grade manganese carbonate ore according to claim 4, characterized in that, Based on the weight of the manganese crude concentrate, the amount of the composite collector is 100~500 g / t, and the amount of the frother is 40 g / t.

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