A method for the co-enrichment of tungsten and rutile by flotation

Abstract

The application discloses a method for co-enriching tungsten ore and rutile, and belongs to the technical field of ore dressing. The method comprises the following steps: crushing, grinding, removing iron and removing sulfur from a tungsten-titanium associated ore in sequence to obtain a desulfurized tailing ore slurry; after pH adjustment, metal ion-hydroxamic acid complex is used as a collector to perform tungsten-titanium mixed flotation on the desulfurized tailing ore slurry to obtain a tungsten-titanium mixed concentrate; after removing a reagent, fatty acid is used as a collector and aluminum sulfate is used as an inhibitor to perform tungsten ore flotation on the tungsten-titanium mixed concentrate, and the flotation concentrate is a tungsten concentrate, and the flotation tailings are a titanium concentrate. The method can realize efficient separation and recovery of tungsten ore and rutile in the tungsten-titanium associated ore, and truly realizes the synergistic extraction of tungsten and titanium resources.

Description

Technical Field

[0001] This invention relates to a method for processing tungsten-titanium associated minerals, and particularly to a method for flotation co-enrichment and separation of tungsten ore and rutile in a tungsten-rutile associated system, belonging to the field of mineral processing technology. Background Technology

[0002] Titanium is an ideal structural material with excellent properties such as low specific gravity, high strength, and corrosion resistance. It is widely used in aerospace, aviation, and shipbuilding technologies. Especially in recent years, the rapid development of the aerospace industry has led to a continuous rise in titanium prices. Titanium carbides not only have high melting points but also high hardness, making them the main component in the manufacture of tungsten-titanium cemented carbides. Titanium compounds, such as titanium dioxide, also have a wide range of applications. Titanium dioxide, used in the pigment industry, is the most widely produced and used component in the titanium industry. Industrially pure TiO2 or natural TiO2 rutile is also an indispensable raw material for the manufacture of welding electrodes.

[0003] With the continuous advancement of China's national defense and military modernization, the consumption of high-end titanium materials has grown rapidly, and the apparent consumption of titanium concentrate has increased year by year, reaching a significant 9.34 million tons in 2020. In fact, titanium is not rare; it ranks seventh in abundance in the Earth's crust, accounting for 0.45% of the total, far exceeding many common metals. However, due to the complex associated components of titanium, outdated beneficiation processes, low recovery rates, and high production costs, subsequent metallurgical and material processing stages have long been unable to produce large quantities of titanium, thus classifying it as a "rare" metal. In other words, mining titanium ore as a single valuable metal is too costly, resulting in low production profits. Therefore, it is necessary to consider the comprehensive utilization of polymetallic associated minerals and the multi-component perspective. Thus, developing beneficiation processes and methods for associated rutile is meaningful.

[0004] Geochemical studies of tungsten have demonstrated that sulfur (F) is an essential transport mineralizer in the formation of tungsten deposits. High F content in magma is crucial for tungsten enrichment and mineralization. It lowers the melt solidus line, viscosity, and density, which is beneficial for increasing the degree of crystallization differentiation in the magma. This allows for the enrichment and mineralization of highly incompatible tungsten elements during magmatic evolution and later hydrothermal stages. In fact, recent studies have shown that F is equally important for the migration and enrichment of titanium. Research has shown that F-rich solutions primarily enrich titanium through K₂TiF₆ complexes, ultimately crystallizing and precipitating under certain stable pressure conditions of the ore-forming fluids. Therefore, when tungsten ore-forming materials originate from titanium-rich source rocks, the affinity of tungsten (W) and titanium (Ti) for F during hydrothermal migration will eventually lead to the formation of associated tungsten and titanium minerals, with titanium primarily occurring in the form of rutile. Therefore, some tungsten mines contain stable titanium resources in the form of rutile. Taking the Xingluokeng tungsten mine in Ninghua, Fujian as an example, the average grade of WO3 in the raw ore is about 0.20-0.23%, and the grade of TiO2 is 0.7-0.9%. At present, there is still no specific technology for the development of such resources. Summary of the Invention

[0005] To address the shortcomings of existing methods for the comprehensive development of tungsten ore associated with rutile, this invention aims to provide a method for the flotation co-enrichment of tungsten ore and rutile. This method is based on extensive research by the inventors, which demonstrates similar flotation behavior of tungsten minerals and rutile in a metal ion-hydroxyoxime acid complex flotation reagent system. Therefore, the idea of ​​preliminary co-enrichment of tungsten minerals and rutile is proposed. After de-reagent treatment, the mixed concentrate is easily separated from the tungsten minerals using a fatty acid flotation reagent system. The rutile enters the tailings to become titanium concentrate, while the tungsten minerals enter the concentrate as tungsten concentrate. This achieves efficient separation and recovery of tungsten minerals and rutile in tungsten-titanium co-existing ores, truly realizing the synergistic extraction of tungsten and titanium resources.

[0006] To achieve the above-mentioned technical objectives, this invention provides a method for the co-enrichment of tungsten ore and rutile through flotation. The method involves sequentially crushing, grinding, removing iron, and desulfurizing the associated tungsten-titanium ore to obtain a desulfurized tailings slurry. After pH adjustment, the desulfurized tailings slurry is subjected to mixed flotation of tungsten and titanium using a metal ion-hydroxyoxime complex as a collector to obtain a mixed tungsten-titanium concentrate. After de-reagent treatment, the mixed tungsten-titanium concentrate is used for tungsten ore flotation using fatty acids as a collector and aluminum sulfate as a depressant. The flotation concentrate is tungsten concentrate, and the flotation tailings are titanium concentrate.

[0007] The technical solution of this invention is based on the mineral composition and occurrence state of tungsten-titanium associated minerals (the main metallic minerals are scheelite, wolframite, and rutile, while the gangue minerals are mainly feldspar, quartz, muscovite, biotite, and sericite, followed by fluorite, chlorite, and apatite). The key lies in using a metal ion-hydroxyxamic acid complex as a co-collector for tungsten minerals and rutile. Without the need for other gangue mineral inhibitors, it can simultaneously and efficiently enrich tungsten minerals and rutile, recovering them as a mixed concentrate. After the de-chemical treatment, fatty acids are used as collectors, which have good selectivity for tungsten minerals but almost no collecting effect on rutile. At the same time, aluminum sulfate is used as an inhibitor, which not only inhibits the flotation of rutile but also activates silicate minerals such as feldspar, quartz, and mica. This allows tungsten minerals and some silicate gangues to enter the tungsten concentrate. The silicate minerals in the tungsten concentrate are easily separated using existing known technologies, while rutile is retained in the tailings and recovered as titanium concentrate, ultimately achieving comprehensive recovery of tungsten and titanium.

[0008] As a preferred embodiment, the concentration of the desulfurization tailings slurry is controlled at 40–50 wt%, and the pH is adjusted to 9.5–10.0. Adjusting the pH to 9.5–10.0 facilitates the participation of some hydroxide ions in coordination, which improves the collection capacity and selectivity of metal ion-hydroxyoxime acid complexes. Sodium carbonate can be used as a pH adjuster.

[0009] As a preferred embodiment, the metal ion-hydroxyoxime acid complex is formed by coordination of a hydrooxime acid ligand with a metal ion; the metal ion is Fe. 3+ Fe 2+ Pb 2+ Cu 2+ Zn 2+ Mn 2+ Ni 2+ and Ca 2+ At least one of the following; the hydroxamic acid ligands are salicylic acid, benzoic acid, naphthyl hydroxamic acid, and C6-C6 hydroxyxamic acid. 12 At least one alkyl hydroxyoxime acid. A further preferred metal ion is Fe. 3+ Fe 2+ or Pb 2+ C6~C 12The alkyl group in the alkyl hydroxamic acid can be a straight-chain alkyl group or a branched alkyl group. As a preferred embodiment, the coordination molar ratio of the metal ion to the hydroxamic acid ligand is 1:(1–16); a further preferred molar ratio is 1:(1–8). Based on the surface state density analysis of scheelite (CaWO4), wolframite ((Fe,Mn)WO4), and rutile (TiO2), the metal ion-hydroxamic acid collector, with the metal group as the polar group, can interact with the active oxygen atoms (O 2p orbitals) on the surface of wolframite and rutile, thereby achieving simultaneous collection of wolframite and rutile.

[0010] As a preferred embodiment, the tungsten-titanium mixed flotation includes at least one roughing stage, two or more cleaning stages, and two or more scavenging stages. As a more preferred embodiment, the reagent regime for the roughing stage (relative to the reagents added to the tungsten-titanium associated ore) is as follows: the amount of metal ion-hydroxyoxime acid complex is 300–800 g / t, and No. 2 oil is used as a frother at a dosage of 30–50 g / t. As a more preferred embodiment, the cleaning stage is a blank cleaning. As a more preferred embodiment, the reagent regime for the scavenging stage is as follows: the dosage of No. 2 oil is 10–20 g / t. With the optimized tungsten-titanium mixed flotation reagent regime, the resulting tungsten-titanium mixed flotation concentrate contains WO3 ≥ 15% and TiO2 ≥ 25%.

[0011] As a preferred embodiment, the desiccant treatment process is as follows: the pH of the tungsten-titanium mixed concentrate is adjusted to 10.0–11.5 with caustic soda, stirred for at least 15 minutes, and then concentrated for desiccant removal. The desiccant treatment mainly employs the addition of caustic soda, and the OH- produced by the caustic soda... - Competition with hydroxamic acids for the binding of metal ions disrupts the adsorption structure of metal ion-hydroxamic acid complexes on the mineral surface, thereby achieving desorption of flotation reagents. After concentration, the slurry of the de-removed tungsten-titanium mixed concentrate contains metal ions in the supernatant that form metal hydroxyl complexes (such as Pb(OH)3). - Hydroxyxamic acid exists in the form of hydroxyxamic acid molecules, while hydroxyxamic acid exists in the form of hydroxyxamic acid molecules. Further optimization involves returning the supernatant obtained after concentration to the original tungsten-titanium mixed flotation process, which can significantly reduce the amount of reagents used in the original process. After de-reagent treatment, the slurry of the tungsten-titanium mixed concentrate, after concentration, should have a mass percentage of 40-45%.

[0012] As a preferred embodiment, the fatty acid includes at least one selected from sodium oleate, linoleic acid, linolenic acid, ricinoleic acid, talc oil, palmitic acid, naphthenic acid, and 731 oxidized paraffin soap. The preferred fatty acid collector exhibits good selective collection of tungsten minerals, but weaker collection ability for rutile.

[0013] As a preferred embodiment, the tungsten ore flotation includes one roughing stage and two to three scavenging stages. As a more preferred embodiment, the reagent regime for the roughing stage (relative to the reagents added to the tungsten-titanium mixed concentrate) is as follows: fatty acid dosage is 50–120 g / t, and aluminum sulfate dosage is 600–1800 g / t. As a more preferred embodiment, the pH of the pulp system is maintained stable between 8.5 and 9.8 during the roughing process. As a more preferred embodiment, the reagent regime for the scavenging stage is as follows: fatty acid dosage is 20–60 g / t. In the separation process of the tungsten-titanium mixed concentrate, fatty acids are used as collectors. Fatty acids can coordinate with the metal active sites on the surface of tungsten minerals through their carboxyl groups, forming a collector bilayer or oleic acid-metal ion precipitation, thus giving fatty acids a strong collecting ability for tungsten minerals. Simultaneously, aluminum sulfate (Al2(SO4)3) is used as a rutile inhibitor. After adding aluminum sulfate, the pH of the slurry should be stabilized between 8.5 and 9.8. Under a weakly alkaline environment (8.5–9.8), Al... 3+ In solution, it mainly exists as Al(OH)4 - It exists in the form of Ti-OH, and its reactivity allows it to react with Al. 3+ The hydrolyzed components react to form Ti-O-Al rings that mask the Ti and hydrolyzed components on the rutile surface, making the surface strongly hydrophilic and thus inhibiting the flotation of rutile; while Al 3+ The specific adsorption on the surfaces of chlorite and plagioclase can alter the surface potential of silicate minerals, activating feldspar, quartz, and chlorite, thus allowing them to enter the tungsten concentrate. Furthermore, the titanium-material separation process in the tungsten-titanium mixed concentrate includes one roughing and two to three scavenging processes. Because fatty acids have strong collecting ability but poor selectivity, adding too much fatty acid at once can result in a high rutile grade in the froth product due to high fatty acid concentration. Therefore, the collector in the tungsten-titanium separation process is added using a starvation method: the collector is added in small amounts multiple times to the roughing and scavenging processes, and the froth product from each scavenging process is combined with the froth product from the roughing process to form the tungsten concentrate.

[0014] The iron removal and desulfurization processes of this invention are conventional tungsten ore pretreatment processes in the prior art.

[0015] Compared with existing technologies, the beneficial technical effects of the present invention are as follows:

[0016] This invention utilizes a metal-hydroxyoxime acid complex flotation reagent system to achieve preliminary co-enrichment of tungsten minerals and rutile in tungsten-titanium co-existing ores. After de-reagent treatment, a fatty acid collector and an aluminum sulfate flotation reagent system are used to efficiently separate and recover tungsten and titanium separately as concentrates. Furthermore, the return of the supernatant after de-reagent concentration significantly reduces the amount of reagents used in the tungsten-titanium mixed flotation section. Titanium recovery can reach approximately 67%, while the WO3 recovery rate in the tungsten concentrate can reach approximately 75%. Compared to current technologies, this approach avoids the impact of large amounts of rutile entering the tungsten concentrate on its grade and separates rutile concentrate products, achieving comprehensive resource recovery from tungsten-titanium co-existing ores.

[0017] The technical solution of this invention provides a simple and cost-effective beneficiation method for tungsten-titanium symbiotic ores, which is suitable for various tungsten-titanium symbiotic ores and is conducive to large-scale promotion and use. Attached Figure Description

[0018] Figure 1 This is a process flow diagram of the present invention.

[0019] Figure 2 The process flow diagram of the existing waterless glass process in Example 1 is shown for comparison.

[0020] Figure 3 This is a process flow diagram for Example 1. Detailed Implementation

[0021] The following embodiments are intended to further illustrate the present invention, but are not intended to limit the scope of protection of the claims of the present invention.

[0022] Comparative Example 1 (Compared with Example 1)

[0023] 0.125 mol of lead nitrate was added to 1 L of 1.0 mol / L benzohydroxyxamic acid solution under stirring, and the reaction was carried out for 3 min to obtain the metal ion complex collector.

[0024] For the Xingluokeng tungsten mine, the raw ore with a fineness of 74% was obtained after two-stage closed-circuit grinding. The raw ore was then subjected to a 3000Gs weak magnetic separator to remove magnetite. The iron tailings were then fed into a desulfurization flotation process. In the desulfurization stage, 100g / t copper sulfate was used as an activator, 80g / t butyl xanthate and 40g / t ethyl thiocyanate were used as collectors, and 30g / t No. 2 oil was used as a frother. The sulfide ore was separated through a coarsening and scavenging process.

[0025] Adopting such Figure 2The anhydrous glass process flow shown involves adjusting the pH of desulfurization tailings to 9.7 with sodium carbonate, adding 600 g / t of metal ion complex collector, aerating and stirring for 5 minutes to achieve pH 8.5, and using 30 g / t of No. 2 oil as a frother for roughing. Two scavenging processes are performed with only 15 g / t and 10 g / t of No. 2 oil frother added respectively. Salt-treated water glass is added as a cleaning inhibitor (Al2(SO4)3 and water glass in a 1:2 ratio). After three cleaning processes (inhibitor dosages of 100, 50, and 50 g / t respectively), a final concentrate with a WO3 grade of 30.44% and a TiO2 grade of 32.32% is obtained, with a WO3 recovery rate of 79.5% and an overall TiO2 recovery rate of 27.85%.

[0026] As shown in Table 1, the system using metal ion complexes as the sole collector achieves a good overall WO3 recovery rate of 79.5%, but the overall recovery of rutile is very poor, with a recovery rate of only 27.85%, and it ends up in the tungsten concentrate. Selling it under these conditions means that the titanium resources contained within it cannot be valued, and they will accumulate in large quantities in the slag phase during tungsten smelting, resulting in a serious waste of resources.

[0027] Table 1 shows the flotation test results in Comparison Example 1.

[0028]

[0029] Example 1

[0030] 0.125 mol of lead nitrate was added to 1 L of 1.0 mol / L benzohydroxyxamic acid solution under stirring, and the reaction was carried out for 3 min to obtain the metal ion complex collector.

[0031] Using this process to process the Xingluokeng tungsten mine, the raw ore is first obtained by two-stage closed-circuit grinding with a fineness of 74%. The raw ore is then subjected to a 3000Gs weak magnetic separator to remove magnetite. The iron tailings enter the desulfurization flotation process. In the desulfurization stage, 100g / t copper sulfate is used as an activator, 80g / t butyl xanthate and 40g / t ethyl thiocyanate are used as collectors, and 30g / t No. 2 oil is used as a frother. The sulfide ore is separated through a coarsening and scavenging process.

[0032] Adopting such Figure 3The process flow shown involves adjusting the pH of desulfurization tailings to 9.7 with sodium carbonate, adding 600 g / t of metal ion complex collector, aerating and stirring for 5 min to bring the pH to 8.5, and using 30 g / t of No. 2 oil as a frother for roughing. Two scavenging processes are performed with only 15 g / t and 10 g / t of No. 2 oil frother added respectively. No inhibitors are added for cleaning. After three blank cleaning processes, a mixed concentrate with 16.94% WO3 and 29.14% TiO2 is obtained. 300 g / t of NaOH is added to the mixed concentrate to bring the pH to 11.2, and the mixture is stirred at 300 rpm for 15 min. The concentrated slurry then enters the tungsten-titanium separation process.

[0033] like Figure 3 As shown, 1600 g / t of aluminum sulfate was added to the slurry as a rutile inhibitor. After stirring and adjusting the slurry, 100 g / t of sodium oleate was added as a collector, and flotation was carried out at pH 9.8 to obtain a rougher froth product. 25 g / t and 20 g / t of sodium oleate were added to the first and second scavenging processes, respectively, and flotation was carried out. The froth products obtained from the scavenging and the rougher froth products were combined as tungsten concentrate, and the tailings after scavenging were titanium concentrate.

[0034] As shown in Table 2, the new method for processing the Xingluokeng tungsten ore, without adding inhibitors in the tungsten-titanium mixed flotation section, allows for the natural enrichment of tungsten and titanium. The resulting mixed concentrate has WO3 and TiO2 grades of 16.94% and 29.14%, respectively. Although the WO3 grade is relatively low, the recovery rates of both tungsten and titanium are significantly improved, reaching 86.37% and 48.88%, respectively. In the subsequent tungsten-titanium separation process, tungsten and titanium are efficiently separated to obtain two products. The yields of tungsten concentrate and titanium concentrate are comparable, so the grades of WO3 and TiO2 after tungsten-titanium separation are nearly doubled. Ultimately, a tungsten concentrate with a WO3 grade of 30.99% and a WO3 recovery rate of 84% and a titanium concentrate with a TiO2 grade of 47.54% and a TiO2 recovery rate of 37.36% are obtained. The recovery rates of both tungsten and titanium are significantly improved, and the tungsten-titanium separation process effectively separates the two products, truly achieving the comprehensive utilization of both tungsten and titanium resources.

[0035] Table 2 Results of the Flotation Closed-Circuit Test in Example 1

[0036]

[0037] Comparative Example 2 (Compared with Example 1)

[0038] 0.125 mol of lead nitrate was added to 1 L of 1.0 mol / L benzohydroxyxamic acid solution under stirring, and the reaction was carried out for 3 min to obtain the metal ion complex collector.

[0039] Using this process to process the Xingluokeng tungsten mine, the raw ore is first obtained by two-stage closed-circuit grinding with a fineness of 74%. The raw ore is then subjected to a 3000Gs weak magnetic separator to remove magnetite. The iron tailings enter the desulfurization flotation process. In the desulfurization stage, 100g / t copper sulfate is used as an activator, 80g / t butyl xanthate and 40g / t ethyl thiocyanate are used as collectors, and 30g / t No. 2 oil is used as a frother. The sulfide ore is separated through a coarsening and scavenging process.

[0040] The experimental procedure of Comparative Example 2 was exactly the same as that of Example 1, except that the tungsten-titanium mixed flotation was exactly the same as in Example 1. However, in Comparative Example 2, the "small amount, multiple times" starvation method was not used for tungsten-titanium separation. Instead, all 145 g / t of sodium oleate was added to the roughing phase of the tungsten-titanium separation, while no reagent was added to the blank phase of the tungsten-titanium separation. The remaining experimental conditions were completely consistent with those of Example 1.

[0041] The experimental results are shown in Table 3. In Comparative Example 2, the recovery rates of tungsten and titanium during the mixed flotation were still relatively high, consistent with Example 1. However, due to the high concentration of sodium oleate during the roughing stage of the tungsten-titanium separation operation, a large amount of rutile was non-selectively entrained, resulting in an increased TiO2 grade in the tungsten concentrate and a lower TiO2 grade in the titanium concentrate. While this had little impact on the grade and recovery rate of the tungsten concentrate, the final titanium concentrate had a TiO2 grade of only 34.54% and a recovery rate of only 26.05%, indicating that a large amount of rutile was entrained in the tungsten concentrate. Compared to Example 1, the separation efficiency was significantly reduced.

[0042] Table 3 Results of the flotation closed-circuit test in Comparative Example 2

[0043]

[0044] Example 2

[0045] 0.25 mol of lead nitrate was added to 1 L of a 1.0 mol / L salicylic acid hydroxamic acid solution under stirring, and the reaction was carried out for 3 min to obtain the metal ion complex collector.

[0046] This process was used to process a scheelite and rutile symbiotic ore in Jiangxi Province. First, the ore was ground in two closed-circuit mills to obtain a fineness of 77%. The ore was then subjected to a 1500Gs weak magnetic separator to remove magnetite. The iron tailings were then fed into a desulfurization flotation process. In the desulfurization stage, 60g / t copper sulfate was used as an activator, 80g / t butyl xanthate was used as a collector, and 50g / t No. 2 oil was used as a frother. The sulfide ore was separated through a coarsening and scavenging process.

[0047] The desulfurization tailings were adjusted to pH 10.0 with sodium carbonate, and 800 g / t of metal ion complex collector was added. After aeration and stirring for 5 min, the pH reached 8.4. 30 g / t of No. 2 oil was used as a frother for roughing. Two scavenging processes were performed, with only 10 g / t and 5 g / t of No. 2 oil frother added respectively. No inhibitors were added for cleaning. After three blank cleaning processes, a mixed concentrate with 15.76% WO3 and 29.07% TiO2 was obtained. 330 g / t of NaOH was added to the mixed concentrate to bring the pH to 11.3, and the mixture was stirred at 350 rpm for 20 min. The concentrated slurry then entered the tungsten-titanium separation process.

[0048] The tungsten-titanium separation process begins by adding 1500 g / t aluminum sulfate as a depressant to the slurry. After stirring and conditioning, 120 g / t of 731 oxidized paraffin soap is added as a collector, and flotation is performed at pH 10.0 to obtain a rougher froth product. Then, 30 g / t and 20 g / t sodium oleate are added to the first and second scavenging processes, respectively, for further flotation. The froth products obtained from the scavenging and rougher froth processes are combined to form the tungsten concentrate, and the tailings after scavenging become the titanium concentrate.

[0049] As shown in Table 4, the method of processing the tungsten ore in Jiangxi Province ultimately yielded a tungsten concentrate containing 27.89% WO3 with a recovery rate of 80.26%, and a titanium concentrate containing 48.94% TiO2 with a recovery rate of 38.94%. The recovery rates of both tungsten and titanium were relatively high. Furthermore, the two products were separated through tungsten-titanium separation operations, thus truly realizing the comprehensive utilization of both tungsten and titanium resources.

[0050] Table 4 Results of Flotation Closed-Circuit Test in Example 2

[0051]

Claims

1. A method for co-enrichment of tungsten ore and rutile by flotation, characterized in that: The tungsten-titanium associated ore is sequentially crushed, ground, deferroalved, and desulfurized to obtain a desulfurized tailings slurry. After adjusting the pH of the desulfurized tailings slurry to 9.5-10.0, a metal ion-hydroxyxamic acid complex is used as a collector for tungsten-titanium mixed flotation to obtain a tungsten-titanium mixed concentrate. This tungsten-titanium mixed concentrate is then detreated and subjected to tungsten ore flotation using fatty acids as a collector and aluminum sulfate as a depressant. The flotation concentrate is tungsten concentrate, and the flotation tailings are titanium concentrate. The metal ion-hydroxyxamic acid complex is formed by the coordination of a hydroxyxamic acid ligand with a metal ion; the metal ion is Fe. 3+ Fe 2+ Pb 2+ Cu 2+ Zn 2 + Mn 2+ Ni 2+ and Ca 2+ At least one of the following; the hydroxamic acid ligand is salicylic acid, benzoic acid, naphthyl hydroxamic acid, and C6-C6 hydroxyxamic acid. 12 At least one of the alkyl hydroxamic acids.

2. The method for co-enrichment of tungsten ore and rutile by flotation according to claim 1, characterized in that: The concentration of the desulfurization tailings slurry is controlled at 40~50wt%.

3. The method for co-enrichment of tungsten ore and rutile by flotation according to claim 1, characterized in that: The coordination molar ratio of the metal ion to the hydroxamic acid ligand is 1:(1~16).

4. The method for co-enrichment of tungsten ore and rutile by flotation according to claim 1 or 3, characterized in that: The tungsten-titanium mixed flotation includes at least one roughing stage, two or more cleaning stages, and two or more scavenging stages.

5. The method for co-enrichment of tungsten ore and rutile by flotation according to claim 4, characterized in that: The reagent system for the roughing process is as follows: the amount of metal ion-hydroxamic acid complex is 300~800 g / t, and No. 2 oil is used as a foaming agent, with the amount of No. 2 oil being 30~50 g / t. The selected selections are blank selections; The reagent system for the scavenging process is as follows: the dosage of No. 2 oil is 10~20 g / t.

6. The method for co-enrichment of tungsten ore and rutile by flotation according to claim 1, characterized in that: The de-drug treatment process is as follows: the pH of the tungsten-titanium mixed concentrate is adjusted to 10.0~11.5 with caustic soda, stirred for more than 15 minutes, and then concentrated for de-drug treatment.

7. The method for co-enrichment of tungsten ore and rutile by flotation according to claim 1, characterized in that: The fatty acids include at least one of sodium oleate, linoleic acid, linolenic acid, ricinoleic acid, tal oil, palmitic acid, naphthenic acid, and 731 oxidized paraffin soap.

8. A method for co-enrichment of tungsten ore and rutile by flotation according to claim 1 or 7, characterized in that: The tungsten ore flotation includes one roughing stage and two to three scavenging stages.

9. The method for co-enrichment of tungsten ore and rutile by flotation according to claim 8, characterized in that: The reagent system for the roughing process is as follows: the amount of fatty acids used is 50~120g / t, and the amount of aluminum sulfate used is 600~1800g / t; During the roughing process, the pH of the pulp system remained stable between 8.5 and 9.8; The reagent system for the scavenging process is as follows: the amount of fatty acids used is 20~60g / t.

Images