A beneficiation and separation method for black tungsten-molybdenum-bismuth-rubidium-beryllium polymetallic ore

Abstract

This invention discloses a beneficiation and separation method for a polymetallic ore of wolframite, molybdenum, bismuth, rubidium, beryllium, and zinc, relating to the field of metal ore beneficiation and separation. The method includes grinding the raw ore, followed by asynchronous preferential flotation and separation of molybdenum and bismuth, mixed flotation and separation of zinc and sulfur, and asynchronous activation flotation of wolframite and tungsten minerals, ultimately obtaining various concentrate products and rubidium-beryllium enrichments. Based on the differences in mineral floatability, the most difficult-to-float molybdenum and bismuth are first suppressed, followed by activation flotation of zinc and sulfur, achieving orderly separation of sulfide ores. Furthermore, a combination of sodium silicate and acidified water glass is used as a depressant to selectively and strongly suppress scheelite and calcium-bearing gangue under weakly alkaline conditions, thus preferentially floating wolframite. Subsequently, scheelite is activated for flotation, achieving efficient and clean separation of both. This method solves the problem in existing technologies of lacking directional enrichment guidance in the beneficiation process, which is detrimental to subsequent comprehensive recovery.

Description

Technical Field

[0001] This invention relates to metal ore beneficiation and separation technology, specifically to a beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc. Background Technology

[0002] Polymetallic associated deposits containing wolframite, molybdenum, bismuth, rubidium, beryllium, zinc, and sulfur have extremely high economic value. However, these deposits are characterized by a wide variety of minerals, complex intergrowth relationships, low grades, and close association, making separation extremely difficult. Existing technologies typically employ full flotation or gravity-flotation combined processes, but these generally suffer from problems such as lengthy processes, high reagent consumption, severe interference between valuable minerals, high cross-contamination in concentrates, and, in particular, incomplete separation of tungsten minerals from calcium-bearing gangue and sulfide minerals.

[0003] Chinese invention patent CN116637716B discloses a beneficiation method for polymetallic ores, which adopts a framework of mixed flotation of sulfide ores and tailings tungsten beneficiation. However, when processing ores containing ferruginous wolframite and scheelite, rich in easily floatable silicate gangue and residual sulfide ores, the mixed flotation products of sulfide ores are complex, making subsequent separation of molybdenum, bismuth, zinc, and sulfur difficult and inefficient. The recovery of tungsten minerals often uses mixed flotation or gravity separation of wolframite and scheelite. When the floatability of the two differs greatly and gangue is easily floatable, the selectivity is poor, and it is difficult to balance concentrate grade and recovery rate. For rare metals such as rubidium and beryllium dispersed in silicates such as mica and feldspar in isomorphous form, there is a lack of directional enrichment guidance in the beneficiation process, which is not conducive to subsequent comprehensive recovery. Summary of the Invention

[0004] The purpose of this invention is to provide a beneficiation and separation method for black tungsten-molybdenum-bismuth-rubidium-beryllium-zinc polymetallic ores, in order to solve the problem that the existing technology lacks directional enrichment guidance in the beneficiation process, which is not conducive to subsequent comprehensive recovery.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a beneficiation and separation method for black tungsten-molybdenum-bismuth-rubidium-beryllium polymetallic ore, comprising the following steps:

[0006] S1. The raw ore is crushed and ground until the minerals are liberated;

[0007] S2. Asynchronous preferential flotation of sulfide ore: Sulfide ore flotation inhibitor and collector are added to the slurry after grinding, and molybdenum-bismuth mixed flotation is carried out to obtain molybdenum-bismuth mixed concentrate and flotation tailings. The molybdenum-bismuth mixed concentrate is then subjected to molybdenum-bismuth separation flotation to obtain molybdenum concentrate and bismuth concentrate, respectively.

[0008] S3. Add zinc mineral activator and collector to the first flotation tailings to carry out zinc-sulfur mixed flotation to obtain zinc-sulfur mixed concentrate and flotation tailings II. Then, carry out zinc-sulfur separation flotation on the zinc-sulfur mixed concentrate to obtain zinc concentrate and sulfur concentrate respectively.

[0009] S4. Asynchronous activation flotation of black and white tungsten minerals: The flotation tailings II are thickened and dewatered, sodium silicate and acidified water glass are added as a combined inhibitor, and after stirring and adjusting the slurry, a black tungsten collector is added for roughing of black tungsten to obtain black tungsten rough concentrate and tailings III. The black tungsten rough concentrate is then finely selected to obtain black tungsten concentrate.

[0010] S5. Add calcium mineral activator to the tailings three, stir, add collector to carry out roughing of scheelite, and obtain scheelite rough concentrate and tailings four. The scheelite rough concentrate is heated and then finely selected to obtain scheelite concentrate.

[0011] S6. Tailings recovery: After adjusting the pH of the tailings slurry, a fatty acid collector is added to recover beryllium minerals by flotation, resulting in beryllium concentrate and final tailings. The final tailings are retained as a rubidium-rich carrier mineral concentrate for subsequent extraction.

[0012] Furthermore, in step S2, the sulfide ore flotation inhibitor is sodium sulfide, sodium sulfite, and sodium thiosulfate, and the collector is kerosene, diesel oil, xanthate, and thiocyanate.

[0013] Furthermore, in step S2, the molybdenum-bismuth separation flotation uses Knox reagent and sodium cyanide as inhibitors for bismuth minerals, and sodium mercaptoacetate and mercaptoethanol as auxiliary inhibitors for molybdenum minerals.

[0014] Furthermore, in step S3, the zinc mineral activator is copper sulfate, and the collector is a combination of butyl xanthate and ethyl thiocyanate.

[0015] Furthermore, in step S4, the mass ratio of sodium silicate to acidified water glass is within 1:0.5 and 1:2, the modulus of the acidified water glass is within 2.0 to 2.8, the acidification pH value is within 4 to 6, and the total amount of combined inhibitor added is 800 to 1500 g / t of raw ore.

[0016] Furthermore, before the roughing of wolframite in step S4, the pH value of the pulp is adjusted to within 8.0 to 9.5. The wolframite collector is benzylarsonic acid, toluenearsonic acid, salicylhydroxyxamic acid and benzoylhydroxyxamic acid, and the wolframite collector is used in conjunction with oxidized paraffin soap.

[0017] Furthermore, in step S5, the calcium mineral activator is a mixed solution of sodium carbonate and a small amount of water glass, or sodium carbonate used alone, and the collector is oleic acid, sodium oleate, and 731 oxidized paraffin soap.

[0018] Furthermore, the heating and refining process in step S5 is the Petrov process, which involves concentrating the crude scheelite concentrate, adding water glass, heating it to 80 to 95°C, and stirring it for 30 to 60 minutes. Then, it is diluted and floated at room temperature to obtain the scheelite concentrate.

[0019] Furthermore, the fatty acid collector is oxidized paraffin soap, and the addition amount is 400 to 800 g / t.

[0020] Compared with existing technologies, the present invention provides a beneficiation and separation method for a polymetallic ore of tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc. By relying on the differences in mineral floatability, the most difficult-to-suppress molybdenum and bismuth are first suppressed during flotation, and then zinc and sulfur are activated for flotation, thus achieving orderly separation of sulfide ores. Furthermore, by using a combination of sodium silicate and acidified water glass as inhibitors, scheelite and calcium-bearing gangue are selectively and strongly suppressed under weakly alkaline conditions, thereby preferentially floating tungsten. Subsequently, scheelite is activated for flotation, achieving efficient and clean separation of the two. This solves the problem in existing technologies of lacking directional enrichment guidance in the beneficiation process, which is not conducive to subsequent comprehensive recovery. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this invention. For those skilled in the art, other drawings can be obtained based on these drawings.

[0022] Figure 1 A flowchart of the separation method provided in an embodiment of the present invention. Detailed Implementation

[0023] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings.

[0024] As attached Figure 1 As shown:

[0025] Example 1:

[0026] This invention provides a beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc, comprising grinding the raw ore and then sequentially performing asynchronous preferential flotation and separation of molybdenum and bismuth, mixed flotation and separation of zinc and sulfur, and asynchronous activation flotation of black and white tungsten minerals [first black tungsten, then white tungsten], ultimately obtaining a variety of concentrate products and rubidium-beryllium enrichments;

[0027] For example, a complex polymetallic ore has the following main chemical components: WO3, Mo, Bi, Zn, S, Rb2O and BeO. Its mineral composition is mainly composed of wolframite, scheelite, molybdenite, bismuthite, sphalerite, pyrite and rubidium- and beryllium-containing silicate gangues (such as mica and feldspar). The ratio of wolframite to scheelite in the raw ore is about 6:4.

[0028] Explanation of the meanings of the above English abbreviations:

[0029] WO3 represents tungsten trioxide;

[0030] Mo represents molybdenum;

[0031] Bi represents bismuth;

[0032] Zn stands for zinc;

[0033] S represents sulfur;

[0034] Rb₂O represents rubidium oxide;

[0035] BeO represents beryllium oxide;

[0036] g / t represents grams per ton of raw ore;

[0037] The specific steps for mineral processing and separation using the method of this invention are as follows:

[0038] S1. Grinding: After crushing, the raw ore is ground until the minerals are basically liberated, and the grinding fineness is such that particles smaller than 0.074 mm account for 75%;

[0039] S2, asynchronous preferential flotation and separation of molybdenum and bismuth;

[0040] Add lime to the slurry after grinding to adjust the pH to 9;

[0041] Sodium sulfide [800 g / t] was added as an inhibitor, kerosene [50 g / t] as a collector, and methyl isobutyl methanol [MIBC, 20 g / t] as a frother. Roughing and scavenging were carried out to obtain molybdenum-bismuth mixed concentrate and tailings.

[0042] Molybdenum-bismuth mixed concentrate was separated and floated. Knox reagent [300 g / t] was added to suppress bismuthite, and molybdenite was floated. After fine cleaning, molybdenum concentrate [containing 48.2% molybdenum, recovery rate 89.5%] and bismuth concentrate [containing 18.6% bismuth, recovery rate 82.1%] were obtained.

[0043] S3, Zinc-Sulfur Mixed Flotation and Separation:

[0044] Copper sulfate [200g / t] was added to tailings one to activate sphalerite, and then butyl xanthate and ethyl thiocyanate [total 120g / t] were added as a combined collector. The mixture was then floated to obtain zinc-sulfur concentrate and tailings two.

[0045] Lime (approximately 2000 g / t) was added to the zinc-sulfur mixed concentrate to suppress pyrite, and sphalerite was floated to obtain zinc concentrate (containing 52.5% zinc, with a recovery rate of 88.3%) and sulfur concentrate (containing 48.8% sulfur), respectively.

[0046] S4, asynchronous activated flotation of wolframite:

[0047] The tailings ore 2 is thickened to remove residual chemicals and fine mud;

[0048] Add the combined inhibitor: 600g / t of sodium silicate and 400g / t of acidified water glass with a modulus of 2.4, stir and adjust the slurry to stabilize the pH of the slurry at 9.0;

[0049] Add benzylarsic acid [150 g / t], a selective collector for wolframite, and oxidized paraffin soap [80 g / t], an auxiliary collector, and carry out a roughing, scavenging, and cleaning flotation process to obtain wolframite concentrate [containing 68.5% tungsten trioxide, with a recovery rate of 86.2% of the wolframite in the original ore].

[0050] S5, Scheelite Activated Flotation:

[0051] Add sodium carbonate (1500g / t) to the tailings 3 from step S4 (i.e., wolframite flotation tailings) to adjust and activate the surface of scheelite;

[0052] Add sodium oleate collector [120g / t] to carry out roughing and scavenging of scheelite to obtain scheelite rough concentrate;

[0053] The scheelite rough concentrate was refined using the Petrov process with heating: after concentration, water glass [5 kg / t] was added, heated to 85°C and stirred for 40 minutes, then diluted and refined at room temperature to finally obtain scheelite concentrate [containing 72.1% tungsten trioxide, with a recovery rate of 81.5% of the scheelite in the original ore];

[0054] S6. Rubidium and Beryllium Concentrate Treatment: The tailings ore produced in step S5 mainly consists of silicate minerals such as quartz, mica, and feldspar. Rubidium oxide [Rb2O] is enriched to 0.12% and beryllium oxide [BeO] is enriched to 0.08%. The recovery rate of rubidium and beryllium in the original ore exceeds 85%. This product can be used as a high-quality raw material for the comprehensive recovery of rubidium and beryllium.

[0055] Working principle:

[0056] Firstly, asynchronous preferential flotation of sulfide minerals is based on differential dissociation of natural floatability and inhibition sensitivity. Its principle is based on the active utilization of the differences in surface properties and reagent response of four major sulfide minerals: molybdenite, bismuthite, sphalerite, and pyrite.

[0057] Among them, molybdenite [MoS2] has natural hydrophobicity and excellent floatability, while bismuthite [Bi2S3] is second best. However, they are extremely sensitive to common sulfide inhibitors [such as sodium sulfide and cyanide]. If zinc-sulfur mixed flotation is carried out first, the activator [copper sulfate] and strong collector used are very likely to produce non-selective adsorption or activation on the surface of molybdenum-bismuth minerals, resulting in a sharp increase in the amount of inhibitor used and a deterioration in the separation effect during subsequent molybdenum-bismuth separation.

[0058] Therefore, in a weakly alkaline environment, only a low amount of selective inhibitor (such as sodium sulfide) and a medium-strength collector (such as kerosene) are added to create a mild flotation environment. Under this environment, molybdenite and bismuthite, which have the best floatability and some tolerance to inhibitors, can be preferentially and selectively captured and floated, while sphalerite and pyrite are effectively suppressed and remain in the pulp. The molybdenum and bismuth minerals are recovered first, and tailings are obtained.

[0059] After obtaining tailings, copper sulfate is added to selectively activate the surface of sphalerite, making its floatability significantly higher than that of pyrite. Then, xanthate collectors can be used to achieve efficient separation of zinc and sulfur. Asynchronous processing avoids the cross-interference of reagents when multiple sulfide minerals coexist, thereby improving the efficiency of subsequent sorting and the purity of concentrate.

[0060] Secondly, the asynchronous activation flotation of black and white tungsten minerals is based on the precise control and sequential desuppression of surface chemical properties;

[0061] Sodium silicate or water glass alone strongly inhibits calcium-containing minerals, but also has a strong inhibitory effect on wolframite. However, a synergistic effect is achieved by combining sodium silicate with acidified water glass under weakly alkaline conditions (pH 8.0-9.5). The acidified water glass (modulus 2.0-2.8, pH 4-6) provides a large amount of silica sol and HSiO. 2- Ions, and then their interaction with Ca in the slurry 2+ Mg 2+ Ions and Ca on the surface of scheelite 2+ Strong adsorption or reaction occurs at the site, forming a hydrophilic calcium magnesium silicate hydration film, which inhibits calcium-containing minerals;

[0062] Furthermore, the combined inhibitors with a reasonable ratio exhibit weak adsorption on the surface of wolframite, and the weakly alkaline environment is conducive to the characteristic adsorption of wolframite collectors (such as arsonic acid and hydroxamic acid), thereby establishing a selective chemical barrier against calcium-containing minerals in the slurry.

[0063] In the specific environment created by the aforementioned combined inhibitors, the addition of a collector with high selectivity for wolframite (such as benzylarsonic acid) allows the collector to react with Fe on the surface of wolframite. 2+ / Mn 2+ The site forms a stable chelate, which makes it hydrophobic and floats, while the scheelite and calcium gangue, which are strongly inhibited, cannot float, thus achieving preferential and efficient separation of wolframite;

[0064] Furthermore, in the third tailings after wolframite flotation, the surface of scheelite is still covered by inhibitors, at which point sodium carbonate [Na2CO3] is added;

[0065] The functions of sodium carbonate mentioned above are as follows:

[0066] I. Providing CO3 2-Ions compete with silicate inhibitors adsorbed on the surface of scheelite for adsorption or desorption.

[0067] II. Adjust the pH to a slightly alkaline state to create the optimal working environment for fatty acid collectors;

[0068] III. CO3 2- Ions can react with Ca on the surface of scheelite 2+ Its function is to clean and activate its surface to a certain extent;

[0069] Furthermore, the activated scheelite can be effectively collected by fatty acid collectors (such as sodium oleate), and then the classic "Petrov process" (heated beneficiation) is used to further remove the small amount of silicate gangue, thereby obtaining high-grade scheelite concentrate and avoiding the problem of mutual interference between the two tungsten minerals in the flotation cell.

[0070] Finally, the control and passive enrichment of rare metals are as follows:

[0071] For rubidium and beryllium, which are present in aluminosilicate minerals such as mica and feldspar in an isomorphous form, the reagent system design throughout the flotation process should always avoid using reagents that can activate or collect silicate gangue (such as cationic collectors and certain strong activators). Whether it is lime and sodium sulfide in the sulfide mineral flotation stage or combined depressants and sodium carbonate in the tungsten flotation stage, they all exhibit inhibitory and neutral effects on silicate minerals.

[0072] The gangue minerals such as mica and feldspar, which serve as carriers for rubidium and beryllium, never obtained the hydrophobic conditions necessary for flotation. As a result, they were naturally and passively retained in the tailings of each flotation stage and eventually all accumulated in the fourth tailings.

[0073] As valuable independent minerals [molybdenum, bismuth, zinc, sulfur, wolframite, scheelite] are effectively extracted and removed step by step, the amount of tailings 4 is greatly reduced. Among them, the grades of rubidium and beryllium are physically enriched several times compared with the original ore, forming a high-quality raw material that can be used for subsequent metallurgical extraction [such as leaching].

[0074] Finally, a fatty acid collector is added for flotation recovery of beryllium minerals to obtain beryllium concentrate and final tailings. The final tailings are retained as a rubidium-rich carrier mineral concentrate for subsequent extraction.

[0075] The foregoing has only described certain exemplary embodiments of the present invention by way of illustration. Undoubtedly, those skilled in the art can modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the foregoing drawings and descriptions are illustrative in nature and should not be construed as limiting the scope of protection of the claims of the present invention.

Claims

1. A beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc, characterized in that: Includes the following steps: S1. The raw ore is crushed and ground until the minerals are liberated; S2. Asynchronous preferential flotation of sulfide ore: Sulfide ore flotation inhibitor and collector are added to the slurry after grinding, and molybdenum-bismuth mixed flotation is carried out to obtain molybdenum-bismuth mixed concentrate and flotation tailings. The molybdenum-bismuth mixed concentrate is then subjected to molybdenum-bismuth separation flotation to obtain molybdenum concentrate and bismuth concentrate, respectively. S3. Add zinc mineral activator and collector to the first flotation tailings to carry out zinc-sulfur mixed flotation to obtain zinc-sulfur mixed concentrate and flotation tailings II. Then, carry out zinc-sulfur separation flotation on the zinc-sulfur mixed concentrate to obtain zinc concentrate and sulfur concentrate respectively. S4. Asynchronous activation flotation of black and white tungsten minerals: The flotation tailings II are thickened and dewatered, sodium silicate and acidified water glass are added as a combined inhibitor, and after stirring and adjusting the slurry, a black tungsten collector is added for roughing of black tungsten to obtain black tungsten rough concentrate and tailings III. The black tungsten rough concentrate is then finely selected to obtain black tungsten concentrate. S5. Add calcium mineral activator to the tailings three, stir, add collector to carry out roughing of scheelite, and obtain scheelite rough concentrate and tailings four. The scheelite rough concentrate is heated and then finely selected to obtain scheelite concentrate. S6. Tailings recovery: After adjusting the pH of the tailings slurry, a fatty acid collector is added to recover beryllium minerals by flotation, resulting in beryllium concentrate and final tailings. The final tailings are retained as a rubidium-rich carrier mineral concentrate for subsequent extraction.

2. The beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc according to claim 1, characterized in that: In step S2, the sulfide ore flotation inhibitors are sodium sulfide, sodium sulfite, and sodium thiosulfate, and the collectors are kerosene, diesel oil, xanthate, and thiocyanate.

3. The beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc according to claim 1, characterized in that: In step S2, the molybdenum-bismuth separation flotation uses Knox reagent and sodium cyanide as inhibitors for bismuth minerals, and sodium mercaptoacetate and mercaptoethanol as auxiliary inhibitors for molybdenum minerals.

4. The beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc according to claim 1, characterized in that: In step S3, the zinc mineral activator is copper sulfate, and the collector is a combination of butyl xanthate and ethyl thiocyanate.

5. The beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc according to claim 1, characterized in that: In step S4, the mass ratio of sodium silicate to acidified water glass is within 1:0.5 and 1:2, the modulus of the acidified water glass is within 2.0 to 2.8, the acidification pH value is within 4 to 6, and the total amount of combined inhibitor added is 800 to 1500 g / t of raw ore.

6. The beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc according to claim 1, characterized in that: Before roughing of wolframite in step S4, the pH value of the pulp is adjusted to within 8.0 to 9.

5. The wolframite collector is benzylarsonic acid, toluenearsonic acid, salicylhydroxyxamic acid and benzoylhydroxyxamic acid, and the wolframite collector is used in conjunction with oxidized paraffin soap.

7. The beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc according to claim 5, characterized in that: In step S5, the calcium mineral activator is a mixed solution of sodium carbonate and a small amount of water glass, or sodium carbonate used alone, and the collector is oleic acid, sodium oleate, and 731 oxidized paraffin soap.

8. The beneficiation and separation method for a polymetallic ore of tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc according to claim 1, characterized in that: In step S5, the heating and refining process is the Petrov process, which involves concentrating the crude scheelite concentrate, adding water glass, heating it to 80 to 95°C, and stirring it for 30 to 60 minutes. Then, it is diluted and floated at room temperature to obtain the scheelite concentrate.

9. The beneficiation and separation method for a polymetallic ore of black tungsten, molybdenum, bismuth, rubidium, beryllium, and zinc according to claim 1, characterized in that: The fatty acid collector is oxidized paraffin soap, and the addition amount is 400 to 800 g / t.

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