Beneficiation method for recovering bismuth resource from polymetallic ore concentrate tailings

Abstract

The invention relates to the technical field of mineral resource recycling and reusing, in particular to a beneficiation method for recycling bismuth resources from polymetallic ore concentrate tailings, which comprises the following steps: obtaining the polymetallic ore concentrate tailings containing bismuth and bismuthite inhibitor sodium sulfide; concentrating the tailings to discharge sodium sulfide, diluting, and then adding a reagent removal agent and a sulfur removal agent for activating treatment to finish the procedures of concentration reagent removal and surface de-intercalation; and roughing, concentration and scavenging are conducted, and bismuth concentrate is obtained. According to the beneficiation method, the surface of the bismuthite subjected to reagent removal treatment can be effectively repaired and optimized, so that the hydrophobic floatability of the bismuthite is recovered and enhanced; meanwhile, the accurate selection and dosage control of the gangue inhibitor ensure that other impurities are effectively inhibited while the bismuth is activated and floated, and the grade of bismuth concentrate is guaranteed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of tailings recycling, and in particular to a beneficiation method for recycling bismuth resources from multi-metal ore dressing tailings. BACKGROUND

[0002] Bismuth is a kind of scattered metal resources with important strategic value, and its application range covers medicine, electronics, metallurgy, chemical industry, semiconductor and nuclear industry and other traditional fields and emerging high-tech industries. In recent years, the demand for bismuth materials in the electronic information, high temperature superconducting, radiation protection, advanced ceramics and other industries has been increasing, and the single type of bismuth resources in China has been consumed too fast, and has gradually faced the situation of supply shortage.

[0003] The reserves of associated bismuth resources in China are relatively rich, especially in tungsten, tin, molybdenum, lead, zinc and other multi-metal deposits, and the comprehensive recovery potential is huge. However, the grade of bismuth in such ores is generally low, and the mineral composition is complex, and in addition to sulfides, the main associated minerals include galena (PbS), antimony (Sb2S3), chalcopyrite (CuFeS2) and the like.

[0004] The main technical bottlenecks for recovering low-grade bismuth from multi-metal tailings are as follows: 1. The extremely fine mineral dissemination size is the core problem. The bismuth minerals in the tailings are often closely associated with other minerals and intertwined together, and the existing conventional grinding process is difficult to fully dissociate them, resulting in that the valuable metals cannot be effectively exposed and enriched.

[0005] 2. A large amount of sodium sulfide is usually used as an inhibitor in the previous beneficiation separation stage (for example, for separating molybdenum or copper), and these residual strong inhibitors will have a strong inhibitory effect on the subsequent bismuth minerals, so that their surfaces lose floatability, thus being "poisoned" and deactivated, and it is difficult to be captured and recovered in the subsequent flotation process. SUMMARY

[0006] Therefore, it is necessary to provide a beneficiation method for recovering bismuth resources from multi-metal ore dressing tailings, to solve the problem of difficult recovery of existing low-grade associated bismuth resources.

[0007] The present application adopts the following technical scheme: The present application provides a beneficiation method for recovering bismuth resources from multi-metal ore dressing tailings, comprising the following steps: obtaining multi-metal ore dressing tailings, the tailings containing sodium sulfide and bismuth elements, and the concentration being 2-10%; concentrating the concentration of the tailings to 40-60% to obtain a slurry from which sodium sulfide is discharged; diluting the slurry; adding a de-drugging agent and a sulfur removal agent for activation treatment; performing roughing, cleaning and scavenging treatment to obtain bismuth concentrate.

[0008] In some embodiments, the bismuth content in the raw ore of the polymetallic ore is less than 0.05%, the bismuth content in the tailings is 2-5%, and the bismuth grade in the bismuth concentrate is 15-25%.

[0009] In some embodiments, the sulfur removal agent is at least one selected from hydrogen peroxide, sodium hypochlorite, and dilute hydrochloric acid, and the amount is 2000-4000 g / t.

[0010] In some embodiments, the drug removal agent is at least one selected from activated carbon and hot activated sodium persulfate, and the amount is 3000-5000 g / t.

[0011] In some embodiments, the concentration of the diluted ore slurry is 8-15%.

[0012] In some embodiments, the roughing process respectively adds water glass 4000-8000 g / t, lime 3000-4000 g / t, butyl xanthate 150-200 g / t, and 2# oil 50-70 g / t.

[0013] In some embodiments, the cleaning is six times, and the amount of water glass and lime decreases with the increase of the cleaning times. Preferably, the reagents added in the cleaning I process are: water glass 3000 g / t, and lime 1500 g / t; the reagents added in the cleaning II process are: water glass 1500 g / t, and lime 750 g / t; the reagents added in the cleaning III process are: water glass 1000 g / t, and lime 500 g / t; the reagents added in the cleaning IV process are: water glass 750 g / t, and lime 375 g / t; the reagents added in the cleaning V process are: water glass 500 g / t, and lime 250 g / t; and the reagents added in the cleaning VI process are: water glass 250 g / t, and lime 125 g / t.

[0014] In some embodiments, the scavenging includes scavenging I and scavenging II, and the reagents added in the scavenging I process are: butyl xanthate 50 g / t, and 2# oil 20 g / t; and the reagents added in the scavenging II process are: butyl xanthate 50 g / t.

[0015] The application also provides a bismuthinite activation and beneficiation method, which comprises the following steps: preparing a bismuthinite ore slurry; adding a drug removal agent and a sulfur removal agent for activation treatment, wherein the sulfur removal agent is at least one selected from hydrogen peroxide, sodium hypochlorite, and dilute hydrochloric acid, and the drug removal agent is at least one selected from activated carbon and hot activated sodium persulfate; and performing roughing and cleaning to obtain a bismuth concentrate.

[0016] Compared with the prior art, the core technical advantages and beneficial effects of the application are that: The present application aims to solve the problem of low-grade bismuth resource recovery. By concentrating and discharging sodium sulfide from the tailings, and then adding a de-drugging agent and a sulfur removal agent for activation treatment after dilution, the following synergistic effects are achieved: 1. The "pre-de-drugging and deep activation" bismuthinite recovery process is innovatively developed. In the traditional process, bismuthinite is deeply inhibited by sodium sulfide, a strong inhibitor, and is lost in the tailings. Instead of directly performing conventional re-flotation on this part of the tailings, the present application first removes excess sodium sulfide in the liquid phase by concentration, and then introduces a special "de-drugging agent" process, which aims to completely remove the thin film of sodium sulfide firmly adsorbed on the surface of bismuthinite minerals and release its "inhibited" state. This pretreatment step lays a solid foundation for subsequent efficient activation, which is equivalent to "cleaning the battlefield" for the subsequent action of reagents. It is a key process breakthrough for specific inhibition environment, which is significantly different from the simple process of directly adding an activator.

[0017] 2. A targeted and highly efficient reagent system is constructed. Instead of relying on a single activator, the present application designs a complete reagent addition scheme. First, after successfully removing the surface inhibitor, a special "bismuth activator" is used to restore the natural floatability of bismuthinite. This activator may have the special function of repairing the mineral surface or forming an oleophilic film. Second, on the basis of activation, gangue inhibitors (lime and water glass) are used in combination to reduce the impact of impurity minerals on concentrate grade. Finally, a combination of collectors (butyl xanthate) and frothing agents (No. 2 oil) is used to achieve selective enrichment of bismuthinite. By using a progressive and synergistic reagent scheme of "inhibiting gangue-activating target-collecting and floating", the high selectivity and high recovery rate of bismuth minerals in complex tailings systems are ensured.

[0018] 3. Green recovery of high-value elements from extremely low-grade waste resources is achieved, creating a new model of circular economy. The raw material treated by the present application is "waste" tailings produced after the beneficiation of raw ore with a bismuth content of only 0.05%. The tailings are "secondary ore" with a bismuth content of 2-5%. Not only does it activate the dormant strategic metal resources and expand the supply sources of bismuth metal, but it also significantly reduces the environmental risks and land occupation caused by tailings storage, perfectly fitting the development concept of "waste-free mine" and green mining. It provides a new technical paradigm and circular economy path for the comprehensive utilization of similar low-grade and difficult-to-treat mineral resources. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 The process flow diagram for recovering bismuth concentrate from molybdenum concentrate tailings. DETAILED DESCRIPTION

[0020] One of the technical concepts of the present application is to provide a bismuthinite activation and beneficiation method, comprising the following steps: preparing a bismuthinite slurry; adding a de-drugging agent and a sulfur removal agent for activation treatment, the de-drugging agent being selected from at least one of hydrogen peroxide, sodium hypochlorite and dilute hydrochloric acid, and the sulfur removal agent being selected from at least one of activated carbon and hot activated sodium persulfate; and obtaining a bismuth concentrate through roughing and cleaning.

[0021] Based on the above principle, the second technical concept of the present application is to provide a beneficiation method for recovering a cleaned bismuth concentrate from a molybdenum cleaning tailing, comprising the following steps: S1, the concentration of the molybdenum cleaning tailing slurry is concentrated from 2-10% to 40-60%, and a large amount of residual sodium sulfide in the slurry is discharged.

[0022] S2, the slurry is diluted with clean water to a concentration of 8-15% to dilute the concentration of sodium sulfide on the surface of the mineral, and a diluted slurry is obtained.

[0023] S3, the diluted slurry is sequentially added with a sulfur removal agent (any one or several of hydrogen peroxide, sodium hypochlorite and dilute hydrochloric acid, in an amount of 2000-4000 g / t) and a de-drugging agent (any one or several of activated carbon and hot activated sodium persulfate, in an amount of 3000-5000 g / t), and is fully stirred.

[0024] S4, the slurry after step S3 is subjected to a test process of one roughing, two scavenging and six cleaning, and the roughing section uses the following reagents: lime 4000 g / t, water glass 4000 g / t, butyl xanthate 200 g / t and 2# oil 70 g / t. The test process and the reagent dosage are as shown in Figure 1 .

[0025] The present application will be further described in detail below with reference to specific examples, so that those skilled in the art can more clearly understand the present application. The following examples are only used to illustrate the present application, but not to limit the scope of the present application. Based on the specific examples in the present application, all other examples obtained by those skilled in the art without creative labor are within the scope of protection of the present application. In the examples of the present application, all raw material components are commercially available products well known to those skilled in the art, unless otherwise specified; in the examples of the present application, the technical means used are conventional means well known to those skilled in the art, unless otherwise specified.

[0026] Example 1 As Figure 1 shown, the present example provides a beneficiation method for recovering a bismuth concentrate from a molybdenum cleaning section tailing, comprising the following steps: S1, obtaining a bismuth-containing molybdenum cleaning section tailing.

[0027] A polymetallic ore in Hunan: Mo grade of raw ore is 0.05%, using the process of molybdenum-bismuth mixed flotation and molybdenum-bismuth separation, a large amount of sodium sulfide is added as bismuth inhibitor during molybdenum-bismuth separation. Bi content in raw ore is about 0.03~0.04%, which is enriched in molybdenum rough concentrate synchronously with molybdenum, after molybdenum-bismuth separation, lime is added as flocculant to obtain molybdenum concentrate section tailings (hereinafter referred to as: feed ore). Bi content in tailings is about 3~5%, main gangue mineral components in feed ore sample are CaCO3, SiO2, secondary components are Al2O3, MgO.

[0028] S2, concentrated to remove sodium sulfide.

[0029] The molybdenum concentrate section tailings containing bismuth are concentrated from 2% to 50% to remove a large amount of residual sodium sulfide in the slurry, and the concentrated slurry is obtained.

[0030] S3, dilution with water.

[0031] Add clean water to the concentrated slurry and dilute it to a slurry concentration of 10% to dilute the sodium sulfide concentration on the surface of the mineral.

[0032] S4, deep activation.

[0033] Add sulfur removal agent (dilute hydrochloric acid 3000g / t) and drug removal agent (activated carbon 3000g / t) to the diluted slurry in sequence and mix thoroughly.

[0034] S5, once roughing, twice scavenging and six times cleaning of the deep activated slurry to recover bismuth concentrate.

[0035] In this step, the roughing process adds the following reagents: water glass 8000g / t, lime 4000g / t, butyl xanthate 200g / t, 2# oil 70g / t, and the treatment time is 4min.

[0036] The reagents added in the scavenging I process are: butyl xanthate 50g / t, 2# oil 20g / t, and the treatment time is 4min.

[0037] The reagents added in the scavenging II process are: butyl xanthate 50g / t, and the treatment time is 2min.

[0038] The reagents added in the cleaning I process are: water glass 3000g / t, lime 1500g / t, and the treatment time is 3min.

[0039] The reagents added in the cleaning II process are: water glass 1500g / t, lime 750g / t, and the treatment time is 2.5min.

[0040] The reagents added in the cleaning III process are: water glass 1000g / t, lime 500g / t, and the treatment time is 2min.

[0041] The reagent added in the process of the fine selection IV is: water glass 750 g / t, lime 375 g / t, and the processing time is 2 min.

[0042] The reagent added in the process of the fine selection V is: water glass 500 g / t, lime 250 g / t, and the processing time is 2 min.

[0043] The reagent added in the process of the fine selection VI is: water glass 250 g / t, lime 125 g / t, and the processing time is 2 min.

[0044] It is tested that the yield of bismuth concentrate obtained in the embodiment is 14.30%, the Bi grade is 22.01%, and the recovery rate is 81.21%.

[0045] Embodiment 2 The embodiment provides a beneficiation method for recovering bismuth concentrate from tailings of a molybdenum beneficiation section, and the steps thereof are basically the same as those of embodiment 1, and the only difference is that in the step S4 of deep activation, the desulfurizing agent is replaced by hydrogen peroxide.

[0046] It is tested that the yield of bismuth concentrate obtained in the test example is 14.79%, the Bi grade is 21.82%, and the recovery rate is 81.49%.

[0047] Embodiment 3 The embodiment provides a beneficiation method for recovering bismuth concentrate from tailings of a molybdenum beneficiation section, and the steps thereof are basically the same as those of embodiment 1, and the only difference is that in the step S4 of deep activation, the desulfurizing agent is replaced by sodium hypochlorite.

[0048] It is tested that the yield of bismuth concentrate obtained in the test example is 15.37%, the Bi grade is 20.47%, and the recovery rate is 81.93%.

[0049] Embodiment 4 The embodiment provides a beneficiation method for recovering bismuth concentrate from tailings of a molybdenum beneficiation section, and the steps thereof are basically the same as those of embodiment 1, and the only difference is that in the step S4 of deep activation, the desulfurizing agent is replaced by sodium hypochlorite hot-activated sodium persulfate (Na2S2O8).

[0050] It is tested that the yield of bismuth concentrate obtained in the test example is 16.37%, the Bi grade is 19.58%, and the recovery rate is 82.91%.

[0051] Comparative Example 1 The comparative example provides a beneficiation method for recovering bismuth concentrate from tailings of a molybdenum beneficiation section, and the steps thereof are basically the same as those of embodiment 1, and the only difference is that the step S2 of concentrating and removing sodium sulfide is not performed.

[0052] It is tested that the yield of bismuth concentrate obtained in the test example is 19.58%, the Bi grade is 8.24%, and the recovery rate is 43.84%.

[0053] Comparative Example 2 The present comparative example provides a beneficiation method for recovering bismuth concentrate from molybdenum beneficiation section tailings, the steps of which are basically the same as those of Example 1, the only difference being that no desorption agent is added in the deep activation step S4.

[0054] After testing, the test example obtained a bismuth concentrate yield of 33.76%, a Bi grade of 7.36%, and a recovery rate of 63.67%.

[0055] Comparative Example 3 The present comparative example provides a beneficiation method for recovering bismuth concentrate from molybdenum beneficiation section tailings, the steps of which are basically the same as those of Example 1, the only difference being that no desulfurizing agent is added in the deep activation step S4.

[0056] After testing, the test example obtained a bismuth concentrate yield of 33.76%, a Bi grade of 7.36%, and a recovery rate of 63.67%.

[0057] Statistical table of mineral test results of the above examples Among them, the Bi grade is obtained by testing, and the yield and recovery rate calculation formula is: Yield = product weight / raw ore weight 100%; Recovery rate = (product grade product yield) / raw ore grade 100.

[0058] As can be seen from the above table: As can be seen from Comparative Examples 1 to 3, canceling the concentration sodium sulfide operation step, canceling the desorption agent and the desulfurizing agent addition, has a greater impact on the recovery of bismuth from tailings, and the recovery rate is greatly reduced, and at the same time, qualified bismuth concentrate cannot be obtained.

[0059] It is necessary to point out here that the above examples are only limited to further elaboration and explanation of the technical solutions of the present application, and are not further limited to the technical solutions of the present application. The method of the present application is only a preferred embodiment, and is not used to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A mineral processing method for recovering bismuth resources from tailings of polymetallic ores, characterized in that, Includes the following steps: Obtain fine tailings from polymetallic mineral deposits, wherein the tailings contain bismuth and sodium sulfide at a concentration of 2-10%. The tailings are concentrated to a concentration of 40-60% to obtain a slurry containing sodium sulfide. The slurry was diluted with water, and desulphurizing and de-chemical agents were added for activation treatment. After roughing, cleaning and scavenging processes, bismuth concentrate is obtained.

2. The mineral processing method for recovering bismuth resources from polymetallic ore tailings according to claim 1, characterized in that, The tailings contain 2-5% bismuth, and the bismuth concentrate contains 15-25% bismuth.

3. The beneficiation method for recovering bismuth resources from polymetallic ore tailings according to claim 1 or 2, characterized in that, The desulfurizing agent is selected from at least one of hydrogen peroxide, sodium hypochlorite, and dilute hydrochloric acid, and the dosage is 2000~4000 g / t; and / or The desiccant is selected from at least one of activated carbon and thermally activated sodium persulfate, and the dosage is 3000~5000g / t.

4. The mineral processing method for recovering bismuth resources from polymetallic ore tailings according to claim 3, characterized in that, The concentration of the diluted slurry is 8-15%.

5. The beneficiation method for recovering bismuth resources from polymetallic ore tailings according to claim 4, characterized in that, The roughing process involves adding 4000-8000 g / t of water glass, 3000-4000 g / t of lime, 150-200 g / t of butyl xanthate, and 50-70 g / t of No. 2 oil.

6. The mineral processing method for recovering bismuth resources from polymetallic ore tailings according to claim 5, characterized in that, The selection process involves six rounds of selection, with the amount of water glass and lime decreasing as the number of selection rounds increases.

7. The beneficiation method for recovering bismuth resources from polymetallic ore tailings according to claim 6, characterized in that, The reagents added in the Selected Process I are: 3000g / t of water glass and 1500g / t of lime; The reagents added in the Selected II process are: 1500g / t of water glass and 750g / t of lime; The reagents added in the Selected III process are: 1000g / t of water glass and 500g / t of lime; The reagents added to the IV process are: 750g / t of water glass and 375g / t of lime. The selected reagents added to the V process are: 500g / t of water glass and 250g / t of lime; The chemicals added to the VI process are: 250g / t of water glass and 125g / t of lime.

8. The beneficiation method for recovering bismuth resources from polymetallic ore tailings according to claim 5, characterized in that, The scavenging process includes scavenging I and scavenging II. The reagents added in scavenging I are: 50g / t of butyl xanthate and 20g / t of No. 2 oil; the reagents added in scavenging II are: 50g / t of butyl xanthate.

9. The beneficiation method for recovering bismuth resources from polymetallic ore tailings according to claim 1 or 2, characterized in that, The bismuth content in the raw polymetallic ore is less than 0.05%.

10. A method for activating and beneficiating bismuthinite, characterized in that, The process includes the following steps: preparing bismuth ore slurry; adding a desulfurizing agent and a desulfurizing agent for activation treatment, wherein the desulfurizing agent is selected from at least one of hydrogen peroxide, sodium hypochlorite, and dilute hydrochloric acid, and the desulfurizing agent is selected from at least one of activated carbon and thermally activated sodium persulfate; and obtaining bismuth concentrate through roughing and cleaning.

Images