Mud-resistant and low-temperature-resistant collecting agent for recovering tungsten molybdenum oxide ore from molybdenite flotation tailings and preparation and application of mud-resistant and low-temperature-resistant collecting agent

Abstract

The invention discloses a mud-resistant and low-temperature-resistant collecting agent for recovering molybdenum tungsten oxide ore from molybdenite flotation tailings, preparation and application, and relates to the molybdenite flotation separation technology, and the collecting agent is formed by compounding 10-15% by mass of monobasic fatty alcohol, 30-50% by mass of sodium oleate, 10-15% by mass of polyoxyethylene ether and 20-50% by mass of hydroximic acid. During flotation, molybdenite raw ore is ground until-0.074 mm accounts for 80%, flotation is carried out, molybdenite rough concentrate and tailings are obtained, a regulator and a collecting agent are sequentially added into the obtained tailings, stirring is carried out for 10-30 minutes, then one-time roughing, one-time scavenging and two-time heating concentration are carried out, and tungsten concentrate is obtained. Compared with a single sodium oleate collecting agent, the collecting agent has the advantages that the molybdenum recovery rate and the tungsten recovery rate can be increased by more than 23% and 19% respectively, and the combined collecting agent is simple in composition, wide in agent source, easy to operate, free of desliming during flotation and particularly suitable for flotation application of low-grade high-mud-content molybdenum tungsten oxide ore.

Description

Technical Field

[0001] This invention belongs to the field of molybdenite flotation separation technology, specifically, it relates to a mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings, its preparation and application. Background Technology

[0002] Molybdenum (Mo) and tungsten (W) are important strategic metal resources, widely used in aerospace, electronics, metallurgy, chemical industry, and military industry. Low-grade, highly weathered oxidized molybdenum-tungsten ore is a typical complex and difficult-to-process mineral resource with huge reserves. This type of mineral resource has poor endowment and is characterized by being "poor, fine-grained, and complex." To ensure the secure supply of molybdenum and tungsten resources in my country, it is urgent to develop efficient recovery technologies for highly weathered oxidized molybdenum-tungsten ore resources to achieve the rational utilization of these valuable resources.

[0003] Currently, the process for recovering molybdenum and tungsten oxide ores commonly employs a method of preferential flotation of sulfide ores followed by flotation of oxide ores. However, traditional collectors face significant challenges: fatty acids (such as sodium oleate) exhibit poor low-temperature solubility and weak selectivity, easily capturing calcium-bearing gangue; high-efficiency chelating agents (such as the GY series) are costly and unsuitable for low-grade ores; and compounded agents show poor adaptability to high-mud-content ores (>15%), resulting in large fluctuations in recovery rates. These problems severely restrict the efficient recovery of molybdenum and tungsten oxide from secondary resources such as molybdenite flotation tailings, necessitating the development of a new, low-cost, low-temperature resistant, and mud-resistant high-efficiency collector and supporting process. Summary of the Invention

[0004] The technical problem to be solved by this invention is to overcome the shortcomings of the prior art and provide a mud-resistant and low-temperature resistant collector for recovering molybdenum-tungsten oxide ore from molybdenite flotation tailings, its preparation and application. By rationally compounding different types of collectors, this invention can not only effectively improve the flotation recovery rate of molybdenum-tungsten ore, but also significantly improve the selectivity in the flotation process. Especially when processing low-grade, high-muddy molybdenum-tungsten ore, it can overcome the shortcomings of traditional single collectors and improve the overall flotation efficiency.

[0005] To solve the above-mentioned technical problems, the basic concept of the technical solution adopted by the present invention is as follows:

[0006] In one aspect, this invention provides a collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings. The collector is composed of a compound of monohydric fatty alcohol, sodium oleate, polyoxyethylene ether, and hydroxamic acid, specifically, the collector is composed of the following components in the indicated mass percentages: 10%–15% monohydric fatty alcohol;

[0007] Sodium oleate 30%–50%;

[0008] Polyoxyethylene ether 10%–15%;

[0009] Hydroxyxamic acid 20%–50%.

[0010] The monohydric fatty alcohol is selected from one or any combination of n-butanol, isobutanol, n-hexanol, n-octanol, and isooctanol.

[0011] The polyoxyethylene ether is one or any combination of fatty alcohol polyoxyethylene ether JFC-5, fatty alcohol polyoxyethylene ether MOA-9, fatty alcohol polyoxyethylene ether MOA-15, isotridecyl alcohol polyoxyethylene ether E-1310, and isotridecyl alcohol polyoxyethylene ether E-1308.

[0012] The hydroxamic acid is selected from one or any combination of benzohydroxyxamic acid, phenoxyethylene hydroxamic acid, octyl hydroxamic acid, and salicylic acid.

[0013] Furthermore, the collector is composed of the following components in weight percentage: 12%–13% monohydric fatty alcohol;

[0014] Sodium oleate 40%–45%;

[0015] Polyoxyethylene ether 12%–14%;

[0016] Hydroxyxamic acid 30%–35%.

[0017] Another aspect of the present invention provides a method for preparing the above-mentioned collector: weigh each component according to the specified ratio, first heat the monohydric fatty alcohol to 60°C to 70°C, add sodium oleate and polyoxyethylene ether in sequence under uniform stirring, and finally add hydroxamic acid, and continue stirring for more than 1 hour until the mixture is uniform, and the product is obtained.

[0018] In another aspect, the present invention provides the application of the above-mentioned collector: applying the above-mentioned collector to the flotation of molybdenum oxide tungsten ore recovered from molybdenite flotation tailings, wherein the flotation steps include:

[0019] (a) Molybdenite flotation: Grind the raw molybdenite ore to a particle size of -0.074 mm or higher (over 80%), adjust the pulp concentration to 30%-35%, add 1500-3000 g / t of water glass as a gangue inhibitor, and stir for 3 minutes; add sodium carbonate or sodium hydroxide to adjust the pH to 8.0-10.0, and stir for 3 minutes; add 800-1200 g / t of kerosene as a collector, and stir for 3 minutes; add 30-80 g / t of methyl isobutyl methanol as a frother, and stir for 3 minutes; use a flotation process of one roughing and two scavenging stages to obtain molybdenite rough concentrate and tailings;

[0020] (b) Flotation of molybdenum oxide tungsten ore: The tailings do not need to be deslimed and are directly subjected to flotation; first, add 800-1500 g / t of gangue inhibitor and stir for 3 minutes; add sodium carbonate or sodium hydroxide to adjust the pH to 8.0-10.0 and stir for 3 minutes; add 200-800 g / t of collector and stir for 10-30 minutes; then perform one roughing, one to two scavenging, and two to three heating cleaning to obtain molybdenum oxide tungsten concentrate.

[0021] Furthermore, the gangue inhibitor is water glass.

[0022] Furthermore, the amount of additional harvesting agent added during the sweeping process is 20-30% of that used in the roughing process.

[0023] Furthermore, the selection process is a heated selection process, with a selection temperature of 60℃-90℃.

[0024] This preparation method is simple, requiring only sequential mixing and stirring, with mild operating conditions, low energy consumption, and all raw materials are readily available and cost-controllable. The flotation method eliminates the need for pre-desliming, directly adjusting and flotating the tailings, simplifying the process, reducing energy consumption and costs, and making it particularly suitable for large-scale industrial applications.

[0025] By adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art.

[0026] This invention features a scientifically formulated and environmentally friendly collector. Hydroxime acid is the core chelating collector component, exhibiting high selectivity for molybdenum oxide and tungsten oxide minerals. A monohydric fatty alcohol acts as a co-solvent and dispersant, effectively improving the applicability of the composite reagent system (especially sodium oleate) in low-temperature slurries. Polyoxyethylene ether, as a highly efficient surfactant, optimizes foam structure, enhances stability, and reduces slime interference, making it suitable for tailings flotation with high fine slime content. The synergistic effect of these components overcomes the industrial technical bottleneck of poor selectivity and low recovery rates in traditional collectors used for flotation of high-slime, low-temperature, and low-grade tailings. Compared to a single sodium oleate collector, this collector can increase molybdenum and tungsten recovery rates by more than 23 and 19 percentage points, respectively. This combined collector has a simple composition, a wide range of reagent sources, is easy to operate, and requires no desliming during flotation, making it particularly suitable for flotation applications of low-grade, high-slime molybdenum oxide and tungsten oxide ores. The flotation process is simple, easy to control, and requires no desliming, significantly reducing production costs and making it ideal for large-scale industrial applications.

[0027] The collector and flotation method of this invention are significantly different from traditional single fatty acid collectors and high-priced chelating agents, and have significant advantages such as high efficiency, strong adaptability and energy saving.

[0028] The specific embodiments of the present invention will now be described in further detail with reference to the accompanying drawings. Attached Figure Description

[0029] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments and descriptions of the invention are used to explain the invention, but do not constitute an undue limitation of the invention. Obviously, the drawings described below are merely some embodiments, and those skilled in the art can obtain other drawings based on these drawings without creative effort. In the drawings:

[0030] Figure 1 This is a comparison chart showing the improvement in recovery rate of different types of monohydric alcohol tetrameric collectors compared to sodium oleate alone.

[0031] Figure 2 This is a comparison chart of the collection effects of a quaternary combined collector and sodium oleate under low-temperature conditions.

[0032] Figure 3 This is a comparison chart of the capture effects of different polyoxyethylene ethers;

[0033] Figure 4 This is a comparison chart of the harvesting effects of different types of hydroxyxamic acid.

[0034] It should be noted that these accompanying drawings and textual descriptions are not intended to limit the scope of the invention in any way, but rather to illustrate the concept of the invention to those skilled in the art by referring to specific embodiments. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be clearly and completely described below with reference to the accompanying drawings. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

[0036] Example 1: Preparation of the collector

[0037] To prepare a quaternary collector, the following raw materials were weighed according to their mass percentages: 12% monohydric fatty alcohol, 43% sodium oleate, 13% polyoxyethylene ether E-1310, and 32% benzoic acid. The monohydric fatty alcohol was heated to 60℃~70℃, and sodium oleate and polyoxyethylene ether E-1310 were added sequentially under stirring. Finally, benzoic acid was added, and the mixture was stirred continuously for 1 hour to ensure thorough mixing, thus obtaining the molybdenum oxide tungsten ore collector.

[0038] The flotation test used tailings from a molybdenum mine (original ore grade: molybdenum 0.166%, tungsten 0.141%) as the sample. The pulp concentration was adjusted to 30%, and 1200 g / t of water glass was added as a depressant. After stirring, the pH was adjusted to 9.0 using sodium carbonate. Then, the collector prepared above was added, with a total dosage of 300 g / t, and the pulp was prepared at a stirring speed of 1900 r / min. The flotation performance was compared between different types of monohydric fatty alcohols (such as n-octanol, isooctanol, etc.) and those using sodium oleate as a single collector. The flotation results for different collector schemes are shown in Table 1 and appendix. Figure 1 .

[0039] Table 1: Comparison of Flotation Results for Different Collector Schemes

[0040] Collector program Total usage (g / t) Mo recovery rate (%) <![CDATA[WO3 Recovery Rate (%)]]> Mo grade (%) <![CDATA[WO3 grade (%)]]> Sodium oleate (comparative example) 800 42.1 68.5 1.5 4.1 n-Butanol combination 300 62.3 84.7 2.1 5.0 Isobutanol combination 300 63.1 85.2 2.2 5.1 hexanol combination 300 64.5 86.3 2.3 5.2 Octyl alcohol combination 300 65.7 87.9 2.4 5.4 Isooctyl alcohol combination 300 65.1 87.2 2.4 5.3

[0041] Conclusion: The combination of C8 alcohols (n-octanol and isooctanol) yields the best results. Taking the n-octanol combination as an example, the recovery rates of Mo and WO3 in the crude concentrate reached 65.7% and 87.9%, respectively, both of which are higher than those of sodium oleate alone; moreover, the WO3 grade in the concentrate increased from 4.1% to 5.4%. This demonstrates that the quaternary combined collectors significantly reduce the dosage (by 62.5%) while possessing the dual advantages of high recovery rate and high selectivity.

[0042] Example 2: Low-temperature adaptability verification of the collector

[0043] To verify the stability and flotation effectiveness of the collector under low-temperature pulp conditions, the following comparative experiment was conducted. This example used a fixed combination collector composed of n-octanol, sodium oleate, polyoxyethylene ether E-1310, and benzohydroxyxamic acid in a mass percentage ratio of 12%:43%:13%:32%, with a total dosage of 350 g / t. The test sample was the same as in Example 1, taken from the same molybdenum-tungsten ore flotation tailings. An ice-water bath was used to precisely control the pulp temperature at 10±1 ℃ to simulate industrial conditions in a cold environment. The flotation process was consistent with Example 1, and the remaining reagent formulation and operating parameters were also the same. This experiment allows for a systematic evaluation of the collector's performance under low-temperature conditions. The low-temperature flotation results are shown in Table 2 and Appendix. Figure 2 .

[0044] Table 2: Comparison of Low-Temperature Flotation Results

[0045] Types of collectors Pulp temperature (°C) <![CDATA[WO3 Recovery Rate (%)]]> Mo recovery rate (%) <![CDATA[WO3 grade (%)]]> Mo grade (%) Sodium oleate (comparative example) 10 48.7 45.2 3.8 1.6 The quaternary compound of the present invention 10 83.5 61.8 5.2 2.3

[0046] Conclusion: At a low temperature of 10℃, the flotation performance of traditional sodium oleate deteriorates sharply, with WO3 recovery dropping by approximately 20 percentage points compared to room temperature. In contrast, the collector of this invention maintains stable performance, with tungsten oxide recovery remaining at a high level of 83.5% and a rough concentrate grade of 5.2%. This fully demonstrates the excellent low-temperature adaptability of the collector of this invention, solving the technical problem of poor performance of conventional collectors in winter.

[0047] Example 3: Screening Test for Polyoxyethylene Ethers

[0048] To screen the optimal type of polyoxyethylene ether (PEE) for optimizing the foam performance and flotation selectivity of the collector, a comparative experiment was conducted in this embodiment under the condition of fixing other key parameters. The test ore sample was the same as in Example 1. The fixed parameters were: collector ratio (n-octanol:sodium oleate:PEE:benzyl hydroxamic acid = 12% : 43% : 13% : 32%), total dosage 300 g / t, pulp pH 9.0 (adjusted with sodium carbonate), and pulp concentration 30%. The flotation process was exactly the same as in Example 1. By systematically comparing the flotation indicators of different types of PEEs, such as JFC-5, MOA-9, MOA-15, E-1310, and E-1308, in this compound system, the optimal type that can significantly improve the foam state and enhance selectivity can be screened. The test results of different types of PEEs are shown in Table 3 and Appendix. Figure 3 .

[0049] Table 3: Flotation Results of Polyoxyethylene Ether Types

[0050] Polyoxyethylene ether type <![CDATA[WO3 Recovery Rate (%)]]> Mo recovery rate (%) <![CDATA[WO3 grade (%)]]> Mo grade (%) Foam lifespan (seconds) JFC-5 80.3 58.5 4.9 2.1 115 MOA-9 84.9 63.2 5.3 2.4 170 MOA-15 79.6 67.8 4.7 2.0 125 E-1310 87.9 65.7 5.4 2.5 183 E-1308 84.2 62.6 5.2 2.3 165

[0051] Conclusion: E-1310 performed best in this system, achieving peak values ​​for both WO3 recovery (87.9%) and concentrate grade (5.4%), with good foam stability. Its performance is significantly superior to other types of polyoxyethylene ethers, such as MOA-15.

[0052] Example 4: Screening test for hydroxamic acid species

[0053] To verify the influence of different types of hydroxamic acids on the flotation indicators of molybdenum-tungsten oxide ore and to screen out the most suitable type of hydroxamic acid, a comparative experiment was designed in this embodiment. The same ore sample as in Example 1 was used in the experiment. The following parameters were fixed: the collector ratio was n-octanol: sodium oleate: polyoxyethylene ether E-1310: hydroxamic acid = 12%: 43%: 13%: 32%, with a total dosage of 300 g / t; the pulp pH was adjusted with sodium carbonate and kept constant at 9.0; and the pulp concentration was 30%. The flotation process was completely consistent with Example 1. By systematically comparing the recovery rate and grade of molybdenum and tungsten rough concentrate under this compound system with different hydroxamic acids such as benzoyl hydroxamic acid, phenoxyethylene hydroxamic acid, octyl hydroxamic acid, and salicylic acid, the type of hydroxamic acid with the best comprehensive performance can be scientifically screened. The experimental results of different types of hydroxamic acids are shown in Table 4 and appendix. Figure 4 .

[0054] Table 4: Flotation Results of Hydroxyxamic Acid Species Test

[0055] Hydroxyxamic acid type <![CDATA[WO3 Recovery Rate (%)]]> Mo recovery rate (%) <![CDATA[WO3 grade (%)]]> Mo grade (%) Benzylhydroxamic acid 87.9 65.7 5.4 2.5 Phenoxyethylene hydroxamic acid 86.5 64.3 5.2 2.3 Octyl hydroxamic acid 85.2 63.0 5.1 2.2 salicyl hydroxamic acid 83.8 61.2 5.6 2.0

[0056] Conclusion: All four hydroxamic acids exhibited good collection performance. Benzyl hydroxamic acid achieved the highest WO3 and Mo recoveries while maintaining high selectivity, demonstrating the best overall performance. Phenoxyethylene hydroxamic acid showed similar collection performance to benzoyl hydroxamic acid, with WO3 and Mo recoveries reaching 86.5% and 64.3%, respectively, but its selectivity was slightly lower than that of benzoyl hydroxamic acid. Salicylic acid showed the best selectivity but a relatively low recovery rate; octyl hydroxamic acid had both moderate recovery and selectivity. This experiment further demonstrates the rationality of using benzoyl hydroxamic acid in the formulation and indicates that phenoxyethylene hydroxamic acid can be an effective alternative.

[0057] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-described technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings, characterized in that, Includes the following components by mass percentage: Monohydric fatty alcohols: 10-15%; Sodium oleate: 30-50%; Polyoxyethylene ether: 10-15%; Hydroxyxamic acid: 20-50%.

2. The mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings according to claim 1, characterized in that: The monohydric fatty alcohol is selected from one or any combination of n-butanol, isobutanol, n-hexanol, n-octanol, and isooctanol; The polyoxyethylene ether is one or any combination of fatty alcohol polyoxyethylene ether JFC-5, fatty alcohol polyoxyethylene ether MOA-9, fatty alcohol polyoxyethylene ether MOA-15, isotridecyl alcohol polyoxyethylene ether E-1310, and isotridecyl alcohol polyoxyethylene ether E-1308. The hydroxamic acid is selected from one or any combination of benzohydroxyxamic acid, phenoxyethylene hydroxamic acid, octyl hydroxamic acid, and salicylic acid.

3. The mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings according to claim 1, characterized in that, The collector consists of the following components by mass percentage: Monohydric fatty alcohols 12%–13%; Sodium oleate 40%–45%; Polyoxyethylene ether 12%–14%; Hydroxyxamic acid 30%–35%.

4. The method for preparing the collector according to any one of claims 1-3, characterized in that, Weigh each component according to the specified ratio, heat the monohydric fatty alcohol to 60℃-70℃, add sodium oleate and stir, then add polyoxyethylene ether and stir, and finally add hydroxamic acid and stir for 1 hour. Stir until uniform to obtain the collector.

5. An application of a mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings, characterized in that, The collector prepared according to claim 4 was used for the flotation of molybdenite flotation tailings at a low temperature of 10°C.

6. The application of the mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings according to claim 5, characterized in that, Flotation specifically includes the following steps: Step (a) Molybdenite flotation: Grind the raw molybdenite ore to a particle size of -0.074 mm or more (80%), adjust the pulp to a pulp concentration of 30% to 35%, add reagents, and use a flotation process of one roughing and two scavenging steps to obtain molybdenite rough concentrate and tailings. The tailings obtained in step (b) do not need to be deslimed. After adding a collector, they can be directly subjected to flotation, including one roughing, one to two scavenging, and two to three heating cleaning processes, to obtain molybdenum oxide tungsten concentrate.

7. The application of the mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings according to claim 6, characterized in that: In step (a), the reagent addition process is as follows: add 1500-3000 g / t of gangue inhibitor, stir for 3 minutes at a stirring speed of 1900 r / min; add sodium carbonate or sodium hydroxide to adjust the pH to 8.0-10.0, stir for 3 minutes at a stirring speed of 1900 r / min; add 800-1200 g / t of kerosene as a collector, stir for 3 minutes at a stirring speed of 1900 r / min; add 30-80 g / t of methyl isobutyl methanol as a foaming agent, stir for 3 minutes at a stirring speed of 1900 r / min.

8. The application of the mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings according to claim 6, characterized in that: In step (b), the agent addition process is as follows: add 800-1500 g / t of gangue inhibitor, stir for 3 minutes at a stirring speed of 1900 r / min; add sodium carbonate or sodium hydroxide to adjust the pH to 8.0-10.0, stir for 3 minutes at a stirring speed of 1900 r / min; add 200-800 g / t of the collector prepared according to claim 4, stir for 10-30 minutes at a stirring speed of 1900 r / min.

9. The application of a mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings according to claim 7 or 8, characterized in that, The gangue inhibitor is water glass.

10. The application of the mud-resistant and low-temperature-resistant collector for recovering molybdenum oxide tungsten ore from molybdenite flotation tailings according to claim 6, characterized in that, In step (b), the amount of supplementary harvesting agent added during the sweeping process is 20-30% of the amount added during the roughing process, and the fine selection is a heated fine selection process with a fine selection temperature of 60℃-90℃.

Images