A method of floating rhodochrosite

Abstract

This invention belongs to the field of manganese ore flotation, specifically disclosing a novel flotation method for rhodochrosite. The method involves pre-oxidizing the surface of rhodochrosite with an oxidant, followed by flotation using a flotation reagent containing sulfur-nitrogen-hydroxyoxime acid collectors to obtain rhodochrosite concentrate. This invention enhances the surface reactivity of rhodochrosite by oxidizing it, thereby strengthening the interaction between rhodochrosite and sulfur-nitrogen-hydroxyoxime acid collectors, achieving highly efficient flotation separation and enrichment of rhodochrosite. Compared with existing rhodochrosite flotation processes, the oxidation flotation method uses lower collector dosages, exhibits better selectivity, and has promising prospects for industrial application.

Description

Technical Field

[0001] This invention belongs to the field of mineral flotation technology, specifically relating to the flotation of rhodochrosite. Background Technology

[0002] Rhodochrosite is a major manganese resource in my country, but its grade is generally low, requiring beneficiation and enrichment. Coarser-grained rhodochrosite is mainly enriched and utilized through washing, gravity separation, and strong magnetic separation, while fine-grained rhodochrosite is primarily recovered through flotation. However, the main metal ions on the surface of rhodochrosite are Mn and Mg. 2+ The reactivity of rhodochrosite is relatively low, requiring the use of collectors with strong hydrophobic properties such as oleic acid, oxidized paraffin soap, and tal oil for flotation. However, these collectors with strong hydrophobic properties have poor selectivity for common gangue minerals in rhodochrosite, such as calcium and magnesium, which severely restricts the selective flotation separation of rhodochrosite.

[0003] In addition, to address the issue of low flotation activity in rhodochrosite, the industry has also reported on some long-chain hydroxamic acid collectors, such as octadecyl hydroxamic acid (Feng Zhou, Chunjie Yan, Hongquan Wang, et al. Flotation behavior of four C18 hydroxamic acids as collectors of rhodochrosite. Minerals Engineering 78(2015)15-20) and octyl hydroxamic acid (Song Zou, Xin Ma, Shuai Wang, et al. Flotation of rhodochrosite fines induced by octyl hydroxamicacid as hydrophobic agglomerates. Powder Technology 392(2021)108-115). These long-chain hydroxamic acids have strong collecting ability, but they also face problems such as poor selectivity and strong foaming ability. Although using short-chain hydroxamic acid collectors such as hexyl hydroxamic acid and benzohydroxamic acid can reduce the flotation capacity of gangue, it will also reduce the flotation capacity of rhodochrosite and affect the flotation recovery rate.

[0004] Therefore, for rhodochrosite, the flotation methods in the industry are still difficult to balance flotation activity and flotation selectivity, and the flotation effect is difficult to meet the needs of industrial applications. Summary of the Invention

[0005] To address the difficulty in balancing flotation selectivity and flotation activity in existing rhodochrosite flotation methods, the primary objective of this invention is to provide a flotation method for rhodochrosite that aims to improve the flotation recovery rate and flotation selectivity of rhodochrosite.

[0006] The second objective of this invention is to provide a flotation reagent for use in the flotation of rhodochrosite.

[0007] A flotation method for rhodochrosite involves pre-treating the surface of the rhodochrosite with an oxidant, followed by flotation in a flotation reagent containing a sulfur-nitrogen-hydroxyoxime acid collector as described in Formula 1, to obtain rhodochrosite concentrate.

[0008]

[0009] In Equation I, M 1 It can be sodium, potassium, ammonium, or hydrogen; M 2 Sodium, potassium, or ammonium; R 1 For C2~C 16 Hydrocarbon group or oxygen-containing hydrocarbon group; n is 1-4.

[0010] The present invention shows that pre-treatment of rhodochrosite with surface oxidation followed by flotation using the collector of Formula 1 can achieve synergy, significantly improve the flotation activity of rhodochrosite, improve the flotation recovery rate, and also help improve the flotation selectivity with gangue such as calcium and magnesium.

[0011] In this invention, the combination of pre-surface oxidation and the collector of Formula 1 is key to synergistically improving the activity of rhodochrosite and enhancing flotation selectivity. The study also found that further control of the oxidant, oxidation conditions, and flotation conditions during surface oxidation helps to further enhance the synergistic effect of the process.

[0012] Preferably, the oxidant is at least one of hypochlorous acid and its salts, hydrogen peroxide, and persulfate.

[0013] Further preferably, the oxidant is hypochlorite, and even more preferably, at least one selected from sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and bleaching powder. This invention has found that the preferred hypochlorite as an oxidant helps to synergize with the subsequent Formula 1, further improving the flotation selectivity and recovery rate of rhodochrosite.

[0014] In this invention, further controlling the content of the oxidant during the oxidation stage helps to synergistically improve the flotation recovery and selectivity of rhodochrosite. Preferably, based on the weight of the rhodochrosite, the dosage of the oxidant is 50-5000 g / t, more preferably 200-2000 g / t.

[0015] In this invention, the surface oxidation temperature is not particularly required, for example it can be 5 to 100°C, preferably 15 to 80°C; considering the convenience of process operation, the temperature is, for example, 20 to 60°C.

[0016] Preferably, the oxidation time is less than or equal to 30 min, more preferably 1 to 20 min, and even more preferably 5 to 15 min.

[0017] In this invention, in Formula I, R 1 For C2~C 16 Alkyl or oxygen-containing alkane group; preferably C4-C5. 10 The alkane group; more preferably butyl, isobutyl, pentyl, isopentyl or n-hexyl;

[0018] Preferably, n is 2.

[0019] The present invention also found that, under the surface oxidation-Form 1 flotation, further combined control of the amount of flotation collector and pH can further synergistically improve the flotation selectivity and recovery rate of rhodochrosite.

[0020] Preferably, the pH of the pulp during flotation is 6.0–11.0; more preferably 7.0–10.0; even more preferably 8.0–10.0; and most preferably 8.0–9.0. This invention demonstrates that, under the surface oxidation-Form 1 flotation, further control at the preferred pH can further synergistically improve the flotation recovery rate.

[0021] Preferably, based on the weight of the rhodochrosite, the dosage of the sulfur-nitrogen-hydroxyoxime acid collector is 100–6000 g / t, more preferably 200–4000 g / t. For example, the concentration of the Formula 1 collector in the flotation pulp is preferably greater than or equal to 0.3 × 10⁻⁶ g / t. -4 M. Considering the treatment effect and cost, the concentration of the Formula 1 collector in the flotation pulp is further preferably 0.4 to 1 × 10⁻⁶. -4 M.

[0022] In the flotation reagents described in this invention, other flotation auxiliary components, such as frothers, pH adjusters, or dispersants, can be selectively added as needed. These flotation auxiliary components are known in the industry, and their content can be controlled as needed based on existing flotation theories.

[0023] A preferred embodiment of the present invention includes the following steps:

[0024] Step (1): Rhodochrosite ore is crushed and mixed to obtain slurry;

[0025] Step (2): Add hypochlorite and flotation reagents to the slurry described in step (1) for flotation and collect the flotation concentrate; other flotation reagents, in addition to sulfur-nitrogen-hydroxyoxime collectors as shown in Formula I, may include frothers, pH adjusters or dispersants.

[0026] The present invention also provides a combined flotation reagent for rhodochrosite, comprising an oxidant and a collector of formula 1.

[0027] The present invention has found that the combined use of the oxidant and Formula 1 helps to synergistically improve the flotation effect of rhodochrosite, thereby improving flotation selectivity and recovery rate.

[0028] Preferably, the combined flotation reagent may also include at least one of a frother, a pH adjuster, and a dispersant.

[0029] In this invention, each component of the combined flotation reagent can exist independently before use.

[0030] Compared with the prior art, the advantages of the present invention are:

[0031] 1. The rhodochrosite flotation recovery method provided by this invention has the characteristics of high recovery rate and good selectivity. This invention uses an oxidant, such as hypochlorite, to oxidize the surface of rhodochrosite, thereby reducing the Mn content on the surface of the rhodochrosite. 2+ It can be oxidized to a higher valence state, increasing the reactivity of rhodochrosite surface, strengthening the binding with sulfur-nitrogen-hydroxyoxime acid collectors, enhancing the hydrophobicity of rhodochrosite surface, and achieving flotation recovery.

[0032] 2. The collector used in the rhodochrosite flotation recovery method provided by this invention is a short-chain sulfur-nitrogen-hydroxyoxime acid, which has weak collecting ability for gangue minerals such as calcium and magnesium. The rhodochrosite flotation recovery method of this invention provides a new approach for the highly selective flotation separation of rhodochrosite.

[0033] 3. The rhodochrosite flotation recovery method provided by this invention has the advantages of simple process and high flotation efficiency. Using the sulfur-nitrogen-hydroxyxamic acid shown in Formula I as the collector, a high rhodochrosite flotation recovery rate can be obtained even at low dosage. Furthermore, the new flotation method can achieve rhodochrosite flotation recovery without changing the existing industrial production process equipment and procedures.

[0034] Specific Implementation Cases

[0035] Numerous specific details are set forth in the following description to provide a full understanding of the invention. However, the invention can be practiced in many other ways different from those described herein, and similar modifications can be made by those skilled in the art without departing from the spirit of the invention. Therefore, the invention is not limited to the specific embodiments disclosed below.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0037] The concentrations of the oxidant in the surface oxidation stage below refer to its initial concentration.

[0038] Comparative Example 1: Potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate flotation of rhodochrosite

[0039] The concentration of potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate is 0.4 × 10⁻⁶. -4 The slurry concentration was 1.0 × 10⁻⁶ mol / L, the slurry pH was 8.0, and the foaming agent methyl isobutyl methanol (MIBC) concentration was 1.0 × 10⁻⁶. -4 At a concentration of mol / L, rhodochrosite with a particle size of 0.037–0.074 mm was floated for 3 minutes, and the recovery rate of rhodochrosite was 42.1%.

[0040] Example 1: Flotation of rhodochrosite using sodium hypochlorite and potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate

[0041] 3.0×10 at 25℃ -4 Rhodochrosite particles with a diameter of 0.037–0.074 mm were treated with sodium hypochlorite (mol / L) for 5 min (surface oxidation), followed by treatment with 0.4 × 10⁻⁶ mol / L sodium hypochlorite. -4 Flotation was performed using potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate at a concentration of mol / L, with a pulp pH of 8.0 and a frother concentration of 1.0 × 10⁻⁶ mol / L. -4 At a concentration of mol / L, after flotation for 3 minutes, the recovery rate of rhodochrosite was 86.7%.

[0042] Example 2: Flotation of rhodochrosite using sodium hypochlorite and potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate

[0043] Compared with Example 1, the main difference is that the surface oxidation time is 10 minutes, and the specific operation is as follows:

[0044] 3.0×10 at 25℃ -4 Rhodochrosite particles with a diameter of 0.037–0.074 mm were treated with sodium hypochlorite (oxidant) for 10 min, followed by treatment with 0.4 × 10⁻⁶ mol / L sodium hypochlorite (oxidant). -4 Flotation was performed using potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate at a concentration of mol / L, with a pulp pH of 8.0 and a frother concentration of 1.0 × 10⁻⁶ mol / L. -4 At a concentration of mol / L, and after flotation for 3 minutes, the recovery rate of rhodochrosite was 89.8%.

[0045] Example 3: Flotation of rhodochrosite using sodium hypochlorite and potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate

[0046] Compared with Example 1, the main difference is that the surface oxidation time is 15 minutes, and the specific operation is as follows:

[0047] 3.0×10 at 25℃ -4 Rhodochrosite particles with a diameter of 0.037–0.074 mm were treated with sodium hypochlorite at a concentration of 0.4 × 10⁻⁶ mol / L for 15 min, and then treated with 0.4 × 10⁻⁶ mol / L sodium hypochlorite. -4 Flotation was performed using potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate at a concentration of mol / L, with a pulp pH of 8.0 and a frother concentration of 1.0 × 10⁻⁶ mol / L. -4 At a concentration of mol / L, after flotation for 3 minutes, the recovery rate of rhodochrosite was 89.0%.

[0048] As can be seen from the above, compared with the direct flotation method using only collectors, the sodium hypochlorite pre-oxidation-flotation method of the present invention has a high flotation recovery rate for rhodochrosite, indicating that the sodium hypochlorite oxidation method can effectively improve the flotation recovery of rhodochrosite.

[0049] Comparative Example 2: Potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate flotation of rhodochrosite

[0050] Rhodochrosite with a particle size of 0.037–0.074 mm was added to a certain concentration of potassium N-[(3-hydroxyoxime)-propyl]-N-hexyl dithiocarbamate. The mixture was stirred at a certain temperature for a period of time. Then, it was stirred for 2 minutes with a certain concentration of potassium N-[(3-hydroxyoxime)-propyl]-N-hexyl dithiocarbamate (HAHD) and a certain pH value of the slurry (see Table 1). Finally, a foaming agent, methyl isobutyl methanol (MIBC, concentration 1.0 × 10⁻⁶), was added. -4 The flotation recovery rate of rhodochrosite (mol / L) for 3 minutes is shown in Table 1.

[0051] Table 1. Results of flotation experiments on rhodochrosite using potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate (HAHD)

[0052]

[0053] Comparative Example 3: Flotation of Rhodochrosite using Sodium Hypochlorite and Benzyl Hydroxamic Acid

[0054] Compared with Example 2, the main difference is that benzohydroxyxamic acid is used instead of the HAHD, specifically:

[0055] 3.0×10 at 25℃ -4 Rhodochrosite particles with a diameter of 0.037–0.074 mm were treated with sodium hypochlorite at a concentration of 0.4 × 10⁻⁶ mol / L for 10 min. -4The slurry concentration was 1.0 × 10⁻⁶ mol / L, the slurry pH was 8.0, and the foaming agent methyl isobutyl methanol (MIBC) concentration was 1.0 × 10⁻⁶. -4 At a concentration of mol / L, rhodochrosite with a particle size of 0.037–0.074 mm was floated for 3 minutes, and the recovery rate of rhodochrosite was 11.7%.

[0056] Comparative Example 4: Flotation of Rhodochrosite using Sodium Hypochlorite and Hexyl Hydroxamic Acid

[0057] Compared with Example 2, the main difference is that hexyl hydroxamic acid is used instead of HAHD, specifically:

[0058] 3.0×10 at 25℃ -4 Rhodochrosite particles with a diameter of 0.037–0.074 mm were treated with sodium hypochlorite at a concentration of 0.4 × 10⁻⁶ mol / L for 10 min. -4 The slurry concentration was 1.0 × 10⁻⁶ mol / L, the slurry pH was 8.0, and the foaming agent methyl isobutyl methanol (MIBC) concentration was 1.0 × 10⁻⁶. -4 At a concentration of mol / L, the recovery rate of rhodochrosite was 22.3% after 3 minutes of flotation for particles with a diameter of 0.037–0.074 mm.

[0059] Comparative Example 5: Flotation of calcite with sodium hypochlorite and potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyldithiocarbamate

[0060] 3.0×10 at 25℃ -4 Calcite particles with a diameter of 0.037–0.074 mm were treated with sodium hypochlorite at a concentration of mol / L for 10 min. The calcite particles with a diameter of 0.037–0.074 mm were then added to a solution of potassium N-[(3-hydroxyoxime)-propyl]-N-hexyl dithiocarbamate (HAHD) at a specific concentration and stirred at a certain temperature for a period of time. Then, the solution was stirred for 2 minutes at a specific concentration of HAHD and a specific pH value of the slurry. Finally, a foaming agent, methyl isobutyl methanol (MIBC) at a concentration of 1.0 × 10⁻⁶ mol / L, was added. -4 The flotation recovery rate of calcite (mol / L) was obtained by flotation for 3 minutes. The results are shown in Table 2.

[0061] Table 2. Results of sodium hypochlorite (NaClO) oxidation flotation of calcite (25℃, NaClO oxidation time 10 min, NaClO 3.0×10⁻⁶). -4 mol / L)

[0062]

[0063] Example 5: Flotation of rhodochrosite using sodium hypochlorite and potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate

[0064] Rhodochrosite with a particle size of 0.037–0.074 mm was added to sodium hypochlorite of a certain concentration and stirred at a certain temperature for a period of time. Then, it was stirred for 2 minutes with potassium N-[(3-hydroxyoxime acid)-propyl]-N-n-hexyl dithiocarbamate (HAHD) of a certain concentration and a certain pH value of the slurry. Finally, methyl isobutyl methanol (MIBC, concentration 1.0 × 10⁻⁶) was added as a foaming agent. -4 The flotation recovery of rhodochrosite (mol / L) for 3 minutes is shown in Tables 3 and 4.

[0065] Table 3 Effect of NaClO dosage and oxidation temperature on the flotation recovery of rhodochrosite (oxidation temperature 25℃, C NaClO 1.0×10 -4 mol / L, C HAHD 0.4×10 -4 mol / L)

[0066]

[0067] As shown in Table 3, pre-oxidation treatment, combined with controlled oxidation conditions (e.g., controlling the initial concentration of the oxidant to be greater than or equal to 2 × 10⁻⁶), effectively addresses the challenges of oxidation. -4 M, at a temperature of 25–40℃, can further improve the synergistic effect of the oxidation process and subsequent sulfur-nitrogen-hydroxyoxime acid collectors; especially when the temperature is 25–35℃, the concentration of the oxidant is controlled at 2.5–3.5 × 10⁻⁶. -4 M; or a temperature of 35–45℃ and an oxidant concentration controlled at 1.5–2.5 × 10⁻⁶. -4 M can achieve better synergistic effects.

[0068] Table 4. Results of flotation experiments on rhodochrosite using potassium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate (HAHD)

[0069] (NaClO concentration: 3.0 × 10⁻⁶) -4 (mol / L, oxidation time 10 min at 25℃)

[0070]

[0071] As shown in Table 4, under the surface oxidation-sulfur nitrogen-hydroxyoxime collector, further controlling the pH of the flotation stage at 7-10, preferably at 8-9, and controlling the flotation reagent dosage at greater than or equal to 0.3 × 10⁻⁶, is beneficial. -4 M is preferably 0.4 to 1×10 -4 Under M, better synergistic effects can be achieved.

[0072] The above experimental results show that, compared with the direct flotation method using only collectors, the pre-oxidation-flotation method combining the oxidant and sulfur-nitrogen-hydroxamic acid of this invention achieves a higher flotation recovery rate for rhodochrosite, indicating that the oxidation method can effectively improve the flotation recovery of rhodochrosite. However, the flotation recovery rates of oxidized rhodochrosite using traditional benzyl hydroxamic acid and hexyl hydroxamic acid are not ideal, indicating that the difunctional collector sulfur-nitrogen-hydroxamic acid used in this invention has a stronger metal complexing ability and can achieve the flotation recovery of oxidized rhodochrosite. Furthermore, the pre-oxidation-flotation method of this invention has a weaker collecting ability for calcite, indicating that the method of this invention has good selectivity.

[0073] Example 6: Flotation of rhodochrosite using sodium hypochlorite and sodium N-[(3-hydroxyoxime)-propyl]-N-n-butyldithiocarbamate

[0074] 3.0×10 at 25℃ -4 Rhodochrosite particles with a diameter of 0.037–0.074 mm were treated with sodium hypochlorite at a concentration of 0.4 × 10⁻⁶ mol / L for 10 min, and then treated with 0.4 × 10⁻⁶ mol / L sodium hypochlorite. -4 Flotation was performed using sodium N-[(3-hydroxyoxime)-propyl]-N-n-butyldithiocarbamate at a concentration of mol / L, with a pulp pH of 8.5 and a frother concentration of 1.0 × 10⁻⁶ mol / L. -4 At a concentration of mol / L, after flotation for 3 minutes, the recovery rate of rhodochrosite was 81.2%.

[0075] Example 7: Flotation of rhodochrosite using potassium hypochlorite and sodium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate

[0076] 3.0×10 at 25℃ -4 Rhodochrosite particles with a diameter of 0.037–0.074 mm were treated with 0.4 × 10⁻⁶ mol / L potassium hypochlorite for 10 min, followed by treatment with 0.4 × 10⁻⁶ mol / L potassium hypochlorite. -4 Flotation was performed using sodium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate at a concentration of mol / L, with a pulp pH of 8.5 and a frother concentration of 1.0 × 10⁻⁶ mol / L. -4 At a concentration of mol / L, after flotation for 3 minutes, the recovery rate of rhodochrosite was 90.2%.

[0077] Example 8: Flotation of rhodochrosite using hydrogen peroxide and sodium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate

[0078] 2.0×10 at 40℃ -4 Rhodochrosite particles with a diameter of 0.037–0.074 mm were treated with 0.4 × 10⁻⁶ mol / L H₂O₂ for 10 min, then treated with 0.4 × 10⁻⁶ mol / L H₂O₂. -4Flotation was performed using sodium N-[(3-hydroxyoxime)-propyl]-N-n-hexyl dithiocarbamate at a concentration of mol / L, with a pulp pH of 8.0 and a frother concentration of 1.0 × 10⁻⁶ mol / L. -4 At a concentration of mol / L, after flotation for 3 minutes, the recovery rate of rhodochrosite was 65.8%.

[0079] In summary, the rhodochrosite pre-oxidation flotation recovery method provided by this invention is green and efficient. Compared with traditional rhodochrosite flotation methods, the method of this invention has the advantages of high flotation recovery rate and good selectivity. Therefore, the flotation method provided by this invention can replace the traditional rhodochrosite flotation method, realizing green and efficient flotation recovery of rhodochrosite, and has significant economic and environmental benefits.

Claims

1. A flotation method for rhodochrosite, characterized in that, Rhodochrosite is first surface-oxidized with an oxidant, and then floated in a flotation reagent containing the sulfur-nitrogen-hydroxyoxime acid collector described in Formula 1 to obtain rhodochrosite concentrate. Formula I In formula I, M 1 is sodium, potassium, ammonium or hydrogen; M 2 is sodium, potassium or ammonium; R 1 is a C2-C 16 hydrocarbon radical or an oxygen-containing hydrocarbon radical; and n is 1-4.

2. The flotation method for rhodochrosite as described in claim 1, characterized in that, The oxidant is at least one of hypochlorous acid and its salts, hydrogen peroxide, and persulfate.

3. The flotation method for rhodochrosite as described in claim 2, characterized in that, The oxidant is hypochlorite; it is at least one of sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and bleaching powder.

4. The flotation method for rhodochrosite as described in claim 1, characterized in that, Based on the weight of the rhodochrosite, the dosage of the oxidant is 50~5000 g / t.

5. The flotation method for rhodochrosite as described in claim 4, characterized in that, Based on the weight of the rhodochrosite, the dosage of the oxidant is 200~2000 g / t.

6. The flotation method for rhodochrosite as described in claim 1, characterized in that, The surface oxidation temperature is 5~100℃.

7. The flotation method for rhodochrosite as described in claim 6, characterized in that, The surface oxidation temperature is 15~80℃.

8. The flotation method for rhodochrosite as described in claim 1, characterized in that, The oxidation time is less than or equal to 30 min.

9. The flotation method for rhodochrosite as described in claim 8, characterized in that, The oxidation time is 1~20 min.

10. The flotation method for rhodochrosite as described in claim 9, characterized in that, The oxidation time is 5~15 min.

11. The flotation method for rhodochrosite as described in claim 1, characterized in that, In Formula I, R 1 For C2~C 16 Alkyl groups or oxygen-containing alkane groups.

12. The flotation method for rhodochrosite as described in claim 11, characterized in that, In Formula I, R 1 C4~C 10 alkane group.

13. The flotation method for rhodochrosite as described in claim 12, characterized in that, In Formula I, R 1 It is butyl, isobutyl, pentyl, isopentyl, or n-hexyl.

14. The flotation method for rhodochrosite as described in claim 1, characterized in that, In Equation I, n is 2.

15. The flotation method for rhodochrosite as described in claim 1, characterized in that, The pH of the pulp during flotation is 6.0~11.

0.

16. The flotation method for rhodochrosite as described in claim 15, characterized in that, The pH of the pulp during flotation is 7.0~10.

0.

17. The flotation method for rhodochrosite as described in claim 16, characterized in that, The pH of the pulp during flotation is 8.0~9.

0.

18. The flotation method for rhodochrosite as described in any one of claims 1 to 17, characterized in that, Based on the weight of the rhodochrosite, the dosage of the sulfur-nitrogen-hydroxyoxime collector is 100~6000 g / t.

19. The flotation method for rhodochrosite as described in claim 18, characterized in that, Based on the weight of the rhodochrosite, the dosage of the sulfur-nitrogen-hydroxyoxime collector is 200~4000 g / t.

20. A combined flotation reagent for rhodochrosite, characterized in that, Includes the oxidant and the collector of formula I as described in any one of claims 1 to 19; It also contains at least one of foaming agents, pH adjusters, and dispersants.

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