Beneficiation recovery method of calcium-magnesium-containing gangue type molybdenum bismuth sulfur polymetallic ore

Abstract

The application provides a beneficiation recovery method of a calcium-magnesium gangue type molybdenum-bismuth-sulfur multi-metal ore, which comprises the following steps: firstly, recovering molybdenum and part of bismuth with good floatability, then recovering the remaining bismuth with poor floatability and sulfur, and finally, through molybdenum-bismuth separation and bismuth-sulfur separation, obtaining final molybdenum, bismuth and sulfur concentrates respectively. The beneficiation process scheme of molybdenum-bismuth partial preferential mixed flotation-residual bismuth and sulfur flotation-molybdenum-bismuth separation-bismuth-sulfur separation is adopted, and through the measures of reagent B11+F9 combination collection-foaming recovery of molybdenum and part of bismuth with good floatability, CD-N1 inhibition of calcium-magnesium argillaceous gangue minerals and the like, the interference of calcium-magnesium argillaceous gangue on the enrichment and separation process of molybdenum-bismuth-sulfur is reduced, the beneficiation process is strengthened in stages, and the beneficiation recovery efficiency and indexes of molybdenum, bismuth and sulfur are improved. The method effectively solves the problem of efficient recovery of the calcium-magnesium gangue type molybdenum-bismuth-sulfur multi-metal ore, has simple and reliable process, efficient reagent system, and provides a new effective method for the recovery of similar molybdenum-bismuth-sulfur resources.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ore dressing, and in particular to a beneficiation recovery method for a calcium-magnesium gangue type molybdenum-bismuth-sulfur polymetallic ore. BACKGROUND

[0002] The calcium-magnesium gangue type molybdenum-bismuth-sulfur polymetallic ore is a molybdenum-bismuth-sulfur resource containing a certain amount of calcite, dolomite, calcium-aluminum garnet, tremolite, actinolite, diopside and other calcium-magnesium carbonate or silicate minerals in the ore. The existing beneficiation recovery technology is mainly flotation method. When applied to this type of ore, the calcium-magnesium gangue is prone to mudification after grinding, and Ca 2+ , Mg 2+ and other metal cations are continuously dissolved and released in the ore pulp. On the one hand, these metal cations consume molybdenum-bismuth flotation reagents, and on the other hand, they cover the surface of molybdenum-bismuth minerals through electrostatic action, affecting the flotation effect, and at the same time, they have a dispersing effect on the ore pulp, causing the ore pulp to be sticky, not easy to settle, and the middling circulating amount to be large, which greatly affects the molybdenum-bismuth-sulfur flotation process, resulting in poor molybdenum-bismuth-sulfur beneficiation indicators.

[0003] The current flotation process for this type of molybdenum-bismuth-sulfur resource mainly includes two methods: “molybdenum-bismuth-sulfur mixed flotation-molybdenum-bismuth-sulfur separation” and “molybdenum-bismuth and other floatable-molybdenum-bismuth separation-tailings flotation sulfur”. For example, the invention patent (application number CN 202310854562.1) discloses a beneficiation method for efficient recovery of low-grade molybdenum-bismuth-sulfur polymetallic ore flotation, which first grinds and classifies the raw ore to form an ore pulp, adds flotation reagents for sulfide ore full-flotation roughing, flotation cleaning, full-flotation scavenging, flotation scavenging cleaning, grinding, and full-flotation cleaning reselection. The full-flotation concentrate can obtain molybdenum concentrate, bismuth concentrate, copper concentrate and sulfur concentrate products through separation. The invention patent (application number CN 202111460430.8) discloses an efficient non-toxic molybdenum-bismuth-sulfur recovery method, step one: sulfide ore full-flotation mixed concentrate is subjected to molybdenum-bismuth-sulfur separation, step two: lime, kerosene, and sulfur suppression reagent are added to the ore sample of step one, and water glass is added for molybdenum-bismuth-sulfur separation to obtain molybdenum-bismuth mixed concentrate, and the tailings are sulfur concentrate, step three: the molybdenum-bismuth mixed concentrate obtained in step two is subjected to molybdenum-bismuth separation, and the scum is molybdenum concentrate, and the tailings are bismuth concentrate. However, in the two methods of “molybdenum-bismuth-sulfur mixed flotation-molybdenum-bismuth-sulfur separation” and “molybdenum-bismuth and other floatable-molybdenum-bismuth separation-tailings flotation sulfur”, the former needs to add strong collectors, and calcium-magnesium gangue is easy to be entrained and float, and the separation of molybdenum-bismuth-sulfur is difficult and costly, and the latter needs to use selective collectors, and the metal recovery rate is relatively low.

[0004] In recent years, some researchers have adopted the scheme of "raw ore coarse grinding-intermediate ore concentrated regrinding-molybdenum bismuth sulfur gradient strengthening separation" to strengthen the recovery of difficult-to-float molybdenum bismuth sulfur minerals. For example, the invention patent (application number CN 202211174476.8) discloses a beneficiation method for gradient strengthening flotation and efficient recovery of low-grade molybdenum bismuth sulfur polymetallic ore. However, this scheme does not have corresponding measures for calcium and magnesium gangue, so it is not completely suitable for the recovery of calcium and magnesium gangue type molybdenum bismuth sulfur resources.

[0005] Therefore, it is necessary to design an improved beneficiation and recovery method for calcium and magnesium gangue type molybdenum bismuth sulfur polymetallic ore to solve the above problems. SUMMARY

[0006] The purpose of the present application is to provide a beneficiation and recovery method for calcium and magnesium gangue type molybdenum bismuth sulfur polymetallic ore, which adopts the beneficiation process of molybdenum bismuth partial preferential mixed flotation-residual bismuth and sulfur flotation-molybdenum bismuth separation-bismuth sulfur separation, and through the measures of reagent B11+F9 combination collection-foaming to recover molybdenum and part of bismuth, CD-N1 to inhibit calcium and magnesium argillaceous gangue minerals, etc., to reduce the interference of calcium and magnesium argillaceous gangue on the enrichment and separation process of molybdenum bismuth sulfur, to strengthen the beneficiation process in stages, and to improve the beneficiation and recovery efficiency and index of molybdenum, bismuth and sulfur.

[0007] To achieve the above-mentioned purpose of the application, the present application provides a beneficiation and recovery method for calcium and magnesium gangue type molybdenum bismuth sulfur polymetallic ore, comprising the following steps:

[0008] S1, crushing and grinding the raw ore to obtain a grinding product with a fineness of less than 0.074mm, the content of the grinding product being 78% to 83% of the total mass, and adding water to the grinding product to obtain a pulp with a concentration of 30% to 35%;

[0009] S2, adding molybdenum bismuth collector B11 and frother F9 to the pulp obtained in step S1 to perform molybdenum bismuth partial preferential mixed flotation, and obtaining molybdenum bismuth mixed rough concentrate and molybdenum bismuth flotation tailings;

[0010] S3, performing two closed-circuit pre-concentration processes on the molybdenum bismuth mixed rough concentrate of step S2 to obtain molybdenum bismuth mixed concentrate, and adding argillaceous gangue inhibitor CD-N1 in the two closed-circuit pre-concentration processes; performing molybdenum bismuth separation flotation on the molybdenum bismuth mixed concentrate to obtain molybdenum concentrate and first bismuth concentrate;

[0011] S4, adding argillaceous gangue inhibitor CD-N1, activator, collector and frother F9 in sequence to the molybdenum bismuth flotation tailings of step S2 to perform flotation roughing of residual bismuth and sulfur, and obtaining bismuth sulfur rough concentrate and bismuth sulfur flotation tailings;

[0012] S5, the bismuth-sulfur rough concentrate of step S4 is subjected to two closed-circuit pre-concentration to obtain a bismuth-sulfur mixed concentrate, a slime inhibitor CD-N1 is added in the two closed-circuit pre-concentration processes; the bismuth-sulfur mixed concentrate is subjected to bismuth-sulfur separation flotation to obtain a second bismuth concentrate and a sulfur concentrate;

[0013] S6, the bismuth-sulfur flotation tailings of step S4 are subjected to three closed-circuit scavenging to obtain a final tailings, the middlings obtained in the three scavenging processes are returned to the previous process in turn.

[0014] As a further improvement of the present application, the components of the molybdenum-bismuth collector B11 include 40-50% mineral oil, 30-40% diesel oil, 10-20% O-isopropyl-N-ethyl thiocarbamate and 10-20% polyoxypropylene ether by mass percentage; the frother F9 includes 50-70% triethoxy butyl ether, 20-30% methyl isobutyl carbinol and 20-40% camphor oil by mass percentage; the slime inhibitor CD-N1 includes 40-50% hydroxyethyl cellulose, 10-30% locust bean gum and 20-30% lactic acid by mass percentage.

[0015] As a further improvement of the present application, in step S2, the addition amount of the molybdenum-bismuth collector B11 is 80-120 g / t, and the addition amount of the frother F9 is 20-40 g / t.

[0016] As a further improvement of the present application, in step S3, the middlings produced by the first closed-circuit pre-concentration are returned to the molybdenum-bismuth partial preferential mixing flotation of step S2, the middlings produced by the second closed-circuit pre-concentration are returned to the first closed-circuit pre-concentration, the addition amount of the slime inhibitor CD-N1 in the first closed-circuit pre-concentration is 40-60 g / t, and the addition amount of the slime inhibitor CD-N1 in the second closed-circuit pre-concentration is 10-30 g / t; activated carbon is added for scrubbing and removing the medicine during the molybdenum-bismuth separation flotation, and sodium sulfide or sodium hydrosulfide is selected as the bismuth inhibitor.

[0017] As a further improvement of the present application, in step S4, the addition amount of the slime inhibitor CD-N1 is 180-220 g / t, the activator is copper sulfate, the addition amount is 130-170 g / t, the collector is butyl xanthate and ethylthiourea, the addition amounts are 80-120 g / t and 10-30 g / t respectively, and the addition amount of the frother F9 is 10-20 g / t.

[0018] As a further improvement of the present application, in step S5, middlings produced by the first closed-circuit pre-concentration are returned to the remaining bismuth and sulfur flotation roughing of step S4, middlings produced by the second closed-circuit pre-concentration are returned to the first closed-circuit pre-concentration, the addition amount of the slime inhibitor CD-N1 in the first closed-circuit pre-concentration is 80-120 g / t, and the addition amount of the slime inhibitor CD-N1 in the second closed-circuit pre-concentration is 40-60 g / t; and activated carbon is added for scrubbing and removing the drug during the bismuth-sulfur separation flotation, and a combination of lime and sodium humate is selected as the sulfur inhibitor.

[0019] As a further improvement of the present application, in step S6, 50-100 g / t of the slime inhibitor CD-N1, 30-50 g / t of butyl xanthate, and 2-7 g / t of the frother F9 are added to the middlings of the three closed-circuit scavenging, the middlings of the first closed-circuit scavenging are returned to the remaining bismuth and sulfur flotation roughing of step S4, and the middlings of the second and third closed-circuit scavenging are returned to the last scavenging in turn.

[0020] As a further improvement of the present application, the process of the molybdenum-bismuth separation flotation is one of a combination of one roughing, three, four, five, and six cleanings, and two, three, and four scavengings, the amount of the activated carbon is 100-500 g / t, the amount of sodium sulfide is 200-8000 g / t, or the amount of sodium hydrosulfide is 100-6000 g / t.

[0021] As a further improvement of the present application, the process of the bismuth-sulfur separation flotation is one of a combination of one roughing, two, three, four, and five cleanings, and two, three, and four scavengings, the amount of the activated carbon is 100-500 g / t, the amount of lime is 500-10000 g / t, and the amount of sodium humate is 20-300 g / t.

[0022] As a further improvement of the present application, in step S1, the grade of the raw ore is: Mo grade 0.05%-0.15%, Bi grade 0.05%-0.2%, and S grade 0.5%-4.5%; the content of calcite is 2%-8%, the content of dolomite is 0.5%-5%, the content of calcium-aluminum garnet is 10%-25%, the content of tremolite is 1%-10%, the content of actinolite is 1%-10%, and the content of diopside is 1%-10%.

[0023] The present application has the following beneficial effects:

[0024] 1. The application provides a kind of calcium magnesium gangue type molybdenum bismuth sulfur multi-metal ore recovery method, based on the commonness of molybdenum, bismuth, sulfur mineral floatability, individuality reasonable design beneficiation process, preferentially recover molybdenum and part of good bismuth, then recover the rest of bismuth and sulfur, finally through molybdenum bismuth separation, bismuth sulfur separation, respectively get the final molybdenum, bismuth, sulfur concentrate.The new beneficiation process scheme of the application effectively solves the interference of the part of bismuth mineral with large difference in floatability on molybdenum bismuth, bismuth sulfur recovery and separation, maximizes the avoidance of the problems of difficult separation of molybdenum bismuth and poor index in the process of "molybdenum bismuth sulfur mixed flotation-molybdenum bismuth sulfur separation", and the problem of low metal recovery rate in the process of "molybdenum bismuth etc. floatable-molybdenum bismuth separation-tailings flotation sulfur". Through the stage of strengthening beneficiation process, the recovery efficiency and index of molybdenum, bismuth and sulfur are improved, and the problem of efficient recovery and utilization of calcium magnesium gangue type molybdenum bismuth sulfur multi-metal ore is solved.

[0025] 2. The application adopts the beneficiation process of molybdenum bismuth partial preferential mixed flotation-residual bismuth and sulfur flotation-molybdenum bismuth separation-bismuth sulfur separation, and recovers molybdenum and part of bismuth with good floatability through the combination of reagent B11+F9, and through the reasonable selection of the collector system, effectively avoids the entrainment of calcium magnesium argillaceous gangue, realizes the rapid and efficient recovery of molybdenum bismuth, and provides good molybdenum bismuth mixed concentrate conditions for molybdenum bismuth separation flotation. At the same time, on the basis of using strong collector, reagent CD-N1 is used as high-efficiency calcium magnesium gangue inhibitor, which effectively reduces the interference of calcium magnesium argillaceous gangue on bismuth sulfur mineral flotation and concentration process, and provides conditions for full and efficient recovery of bismuth and sulfur.

[0026] 3. The application recovers molybdenum, bismuth and sulfur by reasonable segmentation, and cooperates with the reagent independently developed, which plays the role of efficient collection of metal minerals and effective regulation of calcium magnesium argillaceous gangue, so that the cost of reagent is low, the separation difficulty of molybdenum bismuth and bismuth sulfur is small, the mineral circulation amount in main process is small, and the process flow is stable. The method effectively solves the problem of efficient recovery of calcium magnesium gangue type molybdenum bismuth sulfur multi-metal ore, and has the advantages of simple and reliable process, efficient reagent system, and provides a new effective method for the recovery of similar molybdenum bismuth sulfur resources. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The flowchart of the beneficiation recovery method of calcium magnesium gangue type molybdenum bismuth sulfur multi-metal ore of the application. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical scheme and advantages of the application clearer, the application will be described in detail below with reference to the drawings and specific examples.

[0029] It should be noted that, in order not to obscure the present application with unnecessary details, only the structures and / or processing steps closely related to the present application are shown in the drawings, and other details not closely related to the present application are omitted.

[0030] In addition, it should be noted that the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed or inherent to such a process, method, article or device.

[0031] Please refer to Figure 1 The method for recovering a calcium-magnesium gangue type molybdenum-bismuth sulfur polymetallic ore shown includes the following steps:

[0032] S1, crushing and grinding the raw ore to obtain a grinding product with a fineness of less than 0.074 mm, the content of the grinding product being 78% to 83% of the total mass, and adding water to the grinding product to obtain a pulp with a concentration of 30% to 35%; wherein the grade of the raw ore is: Mo grade 0.05% to 0.15%, Bi grade 0.05% to 0.2%, S grade 0.5% to 4.5%; the content of calcite is 2% to 8%, the content of dolomite is 0.5% to 5%, the content of calcium-aluminum garnet is 10% to 25%, the content of tremolite is 1% to 10%, the content of actinolite is 1% to 10%, and the content of diopside is 1% to 10%;

[0033] S2, adding a molybdenum-bismuth collector B11 and a frother F9 to the pulp obtained in step S1 to perform molybdenum-bismuth partial preferential mixed flotation to obtain a molybdenum-bismuth mixed rough concentrate and a molybdenum-bismuth flotation tailings; wherein the addition amount of the molybdenum-bismuth collector B11 is 80 to 120 g / t, and the addition amount of the frother F9 is 20 to 40 g / t;

[0034] S3, performing two closed-circuit pre-concentration on the molybdenum-bismuth mixed rough concentrate of step S2 to obtain a molybdenum-bismuth mixed concentrate, and adding a slime depressant CD-N1 in the two closed-circuit pre-concentration processes; performing molybdenum-bismuth separation flotation on the molybdenum-bismuth mixed concentrate to obtain a molybdenum concentrate and a first bismuth concentrate;

[0035] S4, adding a slime depressant CD-N1, an activator, a collector and a frother F9 to the molybdenum-bismuth flotation tailings of step S2 in sequence to perform rough flotation of the remaining bismuth and sulfur to obtain a bismuth-sulfur rough concentrate and a bismuth-sulfur flotation tailings;

[0036] S5, performing two closed-circuit pre-concentration on the bismuth-sulfur rough concentrate of step S4 to obtain a bismuth-sulfur mixed concentrate, and adding a slime depressant CD-N1 in the two closed-circuit pre-concentration processes; performing bismuth-sulfur separation flotation on the bismuth-sulfur mixed concentrate to obtain a second bismuth concentrate and a sulfur concentrate;

[0037] S6, the bismuth sulfide flotation tailings of step S4 are subjected to three closed-circuit scavenging to obtain a final tailings, and the middlings obtained in the three scavenging processes are returned to the previous process in turn.

[0038] In particular, the method is based on the common floatability of molybdenum, bismuth and sulfur minerals, and the beneficiation process is reasonably designed according to the individual characteristics, molybdenum and part of bismuth with good floatability are preferentially recovered, the remaining bismuth and sulfur with poor floatability are recovered, and finally molybdenum, bismuth and sulfur concentrates are obtained through molybdenum-bismuth separation and bismuth-sulfur separation. The new beneficiation process scheme effectively solves the interference of bismuth minerals with large differences in floatability on molybdenum-bismuth and bismuth-sulfur recovery and separation, maximizes the problems of difficult molybdenum-bismuth-sulfur separation and poor indicators in the prior art "molybdenum-bismuth-sulfur mixed flotation-molybdenum-bismuth-sulfur separation" process, and the low metal recovery rate in the "molybdenum-bismuth floatable-molybdenum-bismuth separation-tailings flotation sulfur" process. Through the stage-by-stage strengthening of the beneficiation process, the molybdenum, bismuth and sulfur beneficiation recovery efficiency and indicators are improved, and the efficient recovery and utilization problem of calcium and magnesium-containing gangue type molybdenum-bismuth-sulfur polymetallic ore is solved.

[0039] Specifically, the components of the molybdenum-bismuth collector B11 include 40-50% mineral oil, 30-40% diesel oil, 10-20% O-isopropyl-N-ethyl thiocarbamate and 10-20% polyoxypropylene ether by mass percentage; the molybdenum-bismuth collector system has good recovery of molybdenum and bismuth with high floatability through the synergistic cooperation of the components. The foaming agent F9 includes 50-70% triethoxybutyl ether, 20-30% methyl isobutyl carbinol and 20-40% camphor oil by mass percentage, and the foaming agent has the advantages of strong foaming capacity, good selectivity and stable foam layer through the synergistic cooperation of the components. The slime inhibitor CD-N1 includes 40-50% hydroxyethyl cellulose, 10-30% locust bean gum and 20-30% lactic acid by mass percentage, wherein the hydroxyethyl cellulose has small molecular weight, good selectivity and weak inhibition ability to metal ore, so that the dosage of the slime inhibitor CD-N1 can be adjusted in a large range, the locust bean gum and lactic acid can adjust the foam state and reduce the viscosity of the foam, so that the gangue components are shed in the secondary enrichment process, and the influence of the gangue on the metal ore recovery rate is reduced.

[0040] The present application adopts a beneficiation process of molybdenum bismuth partial preferential bulk flotation-residual bismuth and sulfur flotation-molybdenum bismuth separation-bismuth sulfur separation, and through the combined collection of reagent B11+F9 and foaming recovery, part of the bismuth with good floatability is recovered, through the reasonable selection of the collector system, the entrainment of calcium magnesium argillaceous gangue is effectively avoided, the rapid and efficient recovery of molybdenum bismuth is realized, and good molybdenum bismuth mixed concentrate conditions are provided for molybdenum bismuth separation flotation. At the same time, on the basis of using a strong collector, reagent CD-N1 is used as a high-efficiency calcium magnesium gangue inhibitor, which effectively reduces the interference of calcium magnesium argillaceous gangue on the flotation and cleaning process of bismuth sulfur minerals, and provides conditions for the full and efficient recovery of bismuth sulfur.

[0041] In step S3, the middlings produced by the first closed-circuit pre-concentration are returned to the molybdenum bismuth partial preferential bulk flotation of step S2, and the middlings produced by the second closed-circuit pre-concentration are returned to the first closed-circuit pre-concentration. The addition amount of the middlings slime inhibitor CD-N1 in the first closed-circuit pre-concentration is 40-60 g / t, and the addition amount of the middlings slime inhibitor CD-N1 in the second closed-circuit pre-concentration is 10-30 g / t. Active carbon is added for scrubbing and removing the reagent during molybdenum bismuth separation flotation, and sodium sulfide or sodium hydrosulfide is selected as a bismuth inhibitor. The process of molybdenum bismuth separation flotation is one of the combinations of one roughing, three, four, five, six cleaning, and two, three, four scavenging. The amount of active carbon is 100-500 g / t, the amount of sodium sulfide is 200-8000 g / t, or the amount of sodium hydrosulfide is 100-6000 g / t.

[0042] In step S4, the addition amount of the slime inhibitor CD-N1 is 180-220 g / t, the activation agent is copper sulfate, the addition amount is 130-170 g / t, the collector is butyl xanthate and ethion, the addition amounts are 80-120 g / t and 10-30 g / t respectively, and the addition amount of the foaming agent F9 is 10-20 g / t.

[0043] In step S5, the middlings produced by the first closed-circuit pre-concentration are returned to the roughing of the residual bismuth and sulfur flotation of step S4, and the middlings produced by the second closed-circuit pre-concentration are returned to the first closed-circuit pre-concentration. The addition amount of the middlings slime inhibitor CD-N1 in the first closed-circuit pre-concentration is 80-120 g / t, and the addition amount of the middlings slime inhibitor CD-N1 in the second closed-circuit pre-concentration is 40-60 g / t. Active carbon is added for scrubbing and removing the reagent during bismuth sulfur separation flotation, and lime and sodium humate are selected as a sulfur inhibitor. The process of bismuth sulfur separation flotation is one of the combinations of one roughing, two, three, four, five cleaning, and two, three, four scavenging. The amount of active carbon is 100-500 g / t, the amount of lime is 500-10000 g / t, and the amount of sodium humate is 20-300 g / t.

[0044] In step S6, 50-100 g / t of slime depressant CD-N1, 30-50 g / t of butyl xanthate and 2-7 g / t of frother F9 are added in the three times of closed-circuit sweeping, the middlings of the first closed-circuit sweeping are returned to the remaining bismuth and sulfur flotation roughing of step S4, and the middlings of the second and third closed-circuit sweepings are returned to the previous sweepings in turn.

[0045] The present application has the advantages that the process for reasonably segmenting and recovering molybdenum, bismuth and sulfur is combined with the independently developed reagent, the reagent has the functions of efficiently collecting metal ores and effectively regulating calcium and magnesium argillaceous gangue, the use cost of the reagent is low, the separation difficulty of molybdenum and bismuth and bismuth and sulfur is small, the circulating amount of middlings in the main process is small, and the process has strong stability. The method effectively solves the problem of efficient recovery of calcium and magnesium gangue type molybdenum, bismuth and sulfur multi-metal ore, has simple and reliable process, efficient reagent system, and provides a new effective method for recovery of similar molybdenum, bismuth and sulfur resources.

[0046] Embodiment 1

[0047] The present embodiment provides a beneficiation and recovery method for calcium and magnesium gangue type molybdenum, bismuth and sulfur multi-metal ore, including the following steps:

[0048] S1, crushing the raw ore to-2mm, then using a Φ240*90mm conical ball mill to grind the crushed ore, to obtain a grinding product with a fineness of less than 0.074mm, accounting for 80% of the total mass, and adding water to the grinding product to a pulp concentration of 30%; wherein the grade of the raw ore is: Mo grade 0.092%, Bi grade 0.053%, S grade 2.03%; the content of calcite is 5%, the content of dolomite is 3%, the content of calcium-aluminum garnet is 15%, the content of tremolite is 5%, the content of actinolite is 5%, and the content of diopside is 5%;

[0049] S2, adding 100 g / t of molybdenum and bismuth collector B11 and 30 g / t of frother F9 to the pulp obtained in step S1 to perform molybdenum and bismuth partial preferential mixed flotation, to obtain molybdenum and bismuth mixed rough concentrate and molybdenum and bismuth flotation tailings;

[0050] S3, performing two times of closed-circuit pre-concentration on the molybdenum and bismuth mixed rough concentrate of step S2 to obtain molybdenum and bismuth mixed concentrate, the middlings of the first closed-circuit pre-concentration are returned to the molybdenum and bismuth partial preferential mixed flotation of step S2, the middlings of the second closed-circuit pre-concentration are returned to the first closed-circuit pre-concentration, the addition amount of slime depressant CD-N1 in the first closed-circuit pre-concentration is 50 g / t, and the addition amount of slime depressant CD-N1 in the second closed-circuit pre-concentration is 20 g / t;

[0051] The molybdenum-bismuth mixed concentrate is subjected to molybdenum-bismuth separation flotation, a one-roughing-three-cleaning-three-scavenging process is selected, 300 g / t of activated carbon is added for scrubbing and removing the drug, 5000 g / t of sodium sulfide is selected as a bismuth inhibitor, and a molybdenum concentrate and a first bismuth concentrate are obtained;

[0052] S4, the molybdenum-bismuth flotation tailings of step S2 are subjected to remaining bismuth and sulfur flotation roughing by sequentially adding 200 g / t of a slime inhibitor CD-N1, 150 g / t of an activator copper sulfate, a collector (100 g / t of butyl xanthate + 20 g / t of ethyl thiourea), and 15 g / t of a frother F9, to obtain a bismuth-sulfur rough concentrate and a bismuth-sulfur flotation tailings;

[0053] S5, the bismuth-sulfur rough concentrate of step S4 is subjected to two closed-circuit pre-cleaning to obtain a bismuth-sulfur mixed concentrate, and the slime inhibitor CD-N1 is added in both closed-circuit pre-cleaning processes; the middlings produced in the first closed-circuit pre-cleaning are returned to the remaining bismuth and sulfur flotation roughing of step S4, and the middlings produced in the second closed-circuit pre-cleaning are returned to the first closed-circuit pre-cleaning; the addition amount of the slime inhibitor CD-N1 in the first closed-circuit pre-cleaning is 100 g / t, and the addition amount of the slime inhibitor CD-N1 in the second closed-circuit pre-cleaning is 50 g / t;

[0054] The bismuth-sulfur mixed concentrate is subjected to bismuth-sulfur separation flotation, a one-roughing-two-cleaning-three-scavenging process is selected, 300 g / t of activated carbon is added for scrubbing and removing the drug, 6000 g / t of lime and 150 g / t of sodium humate are selected as a sulfur inhibitor, a second bismuth concentrate and a sulfur concentrate are obtained, and the second bismuth concentrate is combined with the first bismuth concentrate of step S3 to obtain a bismuth concentrate;

[0055] S6, the bismuth-sulfur flotation tailings of step S4 are subjected to three closed-circuit scavenging to obtain a final tailings, 80 g / t of the slime inhibitor CD-N1, 40 g / t of butyl xanthate, and 5 g / t of the frother F9 are added in the three closed-circuit scavenging processes; the middlings of the first closed-circuit scavenging are returned to the remaining bismuth and sulfur flotation roughing of step S4, and the middlings of the second closed-circuit scavenging and the third closed-circuit scavenging are returned to the previous scavenging processes in turn.

[0056] The components of the molybdenum-bismuth collector B11 used in the embodiment include, by mass percentage, 45% of mineral oil, 35% of diesel oil, 10% of O-isopropyl-N-ethyl thiocarbamate, and 10% of polyoxypropylene ether; the frother F9 includes, by mass percentage, 60% of triethoxy butyl ether, 25% of methyl isobutyl carbinol, and 15% of camphor oil; and the slime inhibitor CD-N1 includes, by mass percentage, 50% of hydroxyethyl cellulose, 20% of locust bean gum, and 30% of lactic acid.

[0057] The grades and recovery rates of each ore obtained in Example 1 are detected, and the obtained results are shown in the following table.

[0058] Table 1 experimental data obtained by example 1

[0059]

[0060] As can be seen from Table 1, the molybdenum concentrate, bismuth concentrate and sulfur concentrate obtained by the recovery method of the present embodiment have high grade and high recovery rate, and the metal content in the tailings is low, which shows that the present method improves the recovery efficiency and index of molybdenum, bismuth and sulfur beneficiation by strengthening the beneficiation process in stages, and solves the problem of efficient recovery and utilization of calcium and magnesium containing gangue type molybdenum bismuth sulfur polymetallic ore.

[0061] Comparative example 1

[0062] Comparative example 1 provides a beneficiation and recovery method for calcium and magnesium containing gangue type molybdenum bismuth sulfur polymetallic ore, which is different from example 1 in that a conventional "molybdenum bismuth sulfur mixed flotation-molybdenum bismuth sulfur separation" flotation process is used, and the experimental data obtained is shown in the following table.

[0063] Table 2 experimental data obtained by comparative example 1

[0064]

[0065] As can be seen from Table 2, the recovery rate of molybdenum, bismuth and sulfur is low when the conventional "molybdenum bismuth sulfur mixed flotation-molybdenum bismuth sulfur separation" flotation process is used for metal recovery.

[0066] Comparative example 2

[0067] Comparative example 2 provides a beneficiation and recovery method for calcium and magnesium containing gangue type molybdenum bismuth sulfur polymetallic ore, which is different from example 1 in that no slime inhibitor CD-N1 is added in steps S3, S4, S5 and S6, and the rest is substantially the same as example 1, which will not be described here. The experimental data obtained by comparative example 2 is shown in the following table.

[0068] Table 3 experimental data obtained by comparative example 2

[0069]

[0070] As can be seen from Table 3, when no slime inhibitor CD-N1 is added, the calcium and magnesium argillaceous gangue disturbs the preferential mixed flotation of molybdenum and bismuth, the flotation of bismuth and sulfur minerals and the concentration process, resulting in low recovery rate and concentrate grade of molybdenum, bismuth and sulfur.

[0071] Comparative example 3

[0072] Comparative Example 3 provides a beneficiation recovery method of a calcium-magnesium gangue type molybdenum bismuth sulfur multi-metal ore, which is different from Example 1 in that in step S2, a conventional collector kerosene is used instead of molybdenum bismuth collector B11, and the rest is substantially the same as Example 1, which will not be repeated here. The experimental data obtained in Comparative Example 3 is shown in the following table.

[0073] Table 4 Experimental data obtained in Comparative Example 3

[0074]

[0075] Comparative Example 4

[0076] Comparative Example 4 provides a beneficiation recovery method of a calcium-magnesium gangue type molybdenum bismuth sulfur multi-metal ore, which is different from Example 1 in that in step S2, a conventional frother 2 # oil (pine oil) is used instead of frother F9, and the rest is substantially the same as Example 1, which will not be repeated here. The experimental data obtained in Comparative Example 4 is shown in the following table.

[0077] Table 5 Experimental data obtained in Comparative Example 4

[0078]

[0079] From Tables 4-5, it can be seen that using conventional collector kerosene or conventional frother 2 # oil mainly affects the separation and recovery of molybdenum bismuth, and the grade and recovery rate of molybdenum concentrate and bismuth concentrate decrease, mainly because the selectivity of kerosene and 2# oil decreases, resulting in high mutual inclusion of metals, thereby affecting the grade and recovery rate of the concentrate.

[0080] In summary, the application provides a beneficiation recovery method of calcium-magnesium gangue type molybdenum bismuth sulfur polymetallic ore, based on the commonness of floatability of molybdenum, bismuth and sulfur minerals, the beneficiation process is reasonably designed according to the individuality, molybdenum and part of bismuth with good floatability are preferentially recovered, the remaining bismuth and sulfur with poor floatability are recovered, and finally the final molybdenum, bismuth and sulfur concentrates are obtained through molybdenum-bismuth separation and bismuth-sulfur separation; the beneficiation process scheme of molybdenum-bismuth partial preferential mixed flotation-remaining bismuth and sulfur flotation-molybdenum-bismuth separation-bismuth-sulfur separation effectively solves the interference of the difference in floatability of part of bismuth minerals on molybdenum-bismuth and bismuth-sulfur recovery and separation, maximally avoids the problems of difficult molybdenum-bismuth-sulfur separation and poor indicators in the prior art process of "molybdenum-bismuth-sulfur mixed flotation-molybdenum-bismuth-sulfur separation", and the problem of low metal recovery rate in the process of "molybdenum-bismuth floatable-molybdenum-bismuth separation-tailings flotation sulfur", through the stage-strengthened beneficiation process, the molybdenum, bismuth and sulfur beneficiation recovery efficiency and indicators are improved, and the efficient recovery and utilization problem of calcium-magnesium gangue type molybdenum bismuth sulfur polymetallic ore is solved. The application reduces the interference of calcium-magnesium argillaceous gangue minerals on molybdenum-bismuth-sulfur enrichment and separation process through the measures of reagent B11+F9 combination collection-foaming recovery of molybdenum and part of bismuth with good floatability, and CD-N1 inhibition of calcium-magnesium argillaceous gangue minerals, the stage-strengthened beneficiation process is improved, and the molybdenum, bismuth and sulfur beneficiation recovery efficiency and indicators are improved. The method effectively solves the problem of efficient recovery of calcium-magnesium gangue type molybdenum bismuth sulfur polymetallic ore, the process is simple and reliable, the reagent system is efficient, and a new effective method is provided for the recovery of similar molybdenum bismuth sulfur resources.

[0081] The above examples are only used to illustrate the technical solutions of the application and not to limit the application. Although the application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the application can be modified or replaced by equivalents without departing from the spirit and scope of the application.

Claims

1. A beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore, characterized in that, Includes the following steps: S1. The raw ore is crushed and ground to obtain a grinding product with a fineness of less than 0.074 mm accounting for 78% to 83% of the total mass. Water is added to the grinding product to make the slurry concentration 30% to 35%. S2. Add molybdenum-bismuth collector B11 and frother F9 to the slurry obtained in step S1, and carry out partial preferential mixing flotation of molybdenum-bismuth to obtain molybdenum-bismuth mixed rough concentrate and molybdenum-bismuth flotation tailings. S3. The molybdenum-bismuth mixed rough concentrate from step S2 is subjected to two closed-circuit pre-selection processes to obtain a molybdenum-bismuth mixed concentrate. The slime inhibitor CD-N1 is added in both closed-circuit pre-selection processes. The molybdenum-bismuth mixed concentrate is then subjected to molybdenum-bismuth separation flotation to obtain a molybdenum concentrate and a first bismuth concentrate. S4. The molybdenum-bismuth flotation tailings from step S2 are subjected to roughing flotation of the remaining bismuth and sulfur by adding slime inhibitor CD-N1, activator, collector and frother F9 in sequence to obtain bismuth-sulfur rough concentrate and bismuth-sulfur flotation tailings. S5. The bismuth-sulfur rough concentrate obtained in step S4 is subjected to two closed-circuit pre-selection processes to obtain a bismuth-sulfur mixed concentrate. The slime inhibitor CD-N1 is added in both closed-circuit pre-selection processes. The bismuth-sulfur mixed concentrate is then subjected to bismuth-sulfur separation flotation to obtain a second bismuth concentrate and a sulfur concentrate. S6. The bismuth-sulfur flotation tailings from step S4 are subjected to three closed-circuit scavenging processes to obtain the final tailings. The middlings obtained from the three scavenging processes are returned to the previous process in sequence. The molybdenum bismuth collector B11 comprises, by weight percentage, 40%–50% mineral oil, 30%–40% diesel oil, 10%–20% O-isopropyl-N-ethyl thiocarbamate, and 10%–20% polyoxypropylene ether; the foaming agent F9 comprises, by weight percentage, 50%–70% triethoxybutyl ether, 20%–30% methyl isobutyl methanol, and 20%–40% camphor oil; and the sludge inhibitor CD-N1 comprises, by weight percentage, 40%–50% hydroxyethyl cellulose, 10%–30% locust bean gum, and 20%–30% lactic acid.

2. The beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore according to claim 1, characterized in that, In step S2, the amount of molybdenum bismuth collector B11 added is 80~120 g / t, and the amount of foaming agent F9 added is 20~40 g / t.

3. The beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore according to claim 1, characterized in that, In step S3, the middlings produced in the first closed-circuit pre-selection are returned to the molybdenum-bismuth fraction in step S2 for preferential mixing and flotation. The middlings produced in the second closed-circuit pre-selection are returned to the first closed-circuit pre-selection. The amount of slime inhibitor CD-N1 added in the first closed-circuit pre-selection is 40~60 g / t, and the amount of slime inhibitor CD-N1 added in the second closed-circuit pre-selection is 10~30 g / t. Activated carbon is added for scrubbing and descaling during the molybdenum-bismuth separation flotation, and sodium sulfide or sodium hydrosulfide is selected as the bismuth inhibitor.

4. The beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore according to claim 1, characterized in that, In step S4, the amount of the slime inhibitor CD-N1 added is 180~220 g / t, the activator is copper sulfate added at an amount of 130~170 g / t, the collector is butyl xanthate and ethyl thiocyanate added at amounts of 80~120 g / t and 10~30 g / t respectively, and the amount of the frother F9 added is 10~20 g / t.

5. The beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore according to claim 1, characterized in that, In step S5, the middlings produced in the first closed-circuit pre-selection are returned to the remaining bismuth and sulfur flotation roughing in step S4, and the middlings produced in the second closed-circuit pre-selection are returned to the first closed-circuit pre-selection. The amount of slime inhibitor CD-N1 added in the first closed-circuit pre-selection is 80~120 g / t, and the amount of slime inhibitor CD-N1 added in the second closed-circuit pre-selection is 40~60 g / t. Activated carbon is added for scrubbing and decanting during the bismuth-sulfur separation flotation, and lime and sodium humate are selected as a combination of sulfur inhibitors.

6. The beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore according to claim 1, characterized in that, In step S6, 50-100 g / t of slime inhibitor CD-N1, 30-50 g / t of butyl xanthate, and 2-7 g / t of frother F9 are added to each of the three closed-circuit scavenging processes. The middlings from the first closed-circuit scavenging process are returned to the flotation roughing process for the remaining bismuth and sulfur in step S4. The middlings from the second and third closed-circuit scavenging processes are returned to the previous scavenging process in turn.

7. The beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore according to claim 3, characterized in that, The process for separating and flotating molybdenum and bismuth is a combination of one of the following: roughing, three, four, five, and six cleaning, two, three, and four scavenging. The amount of activated carbon used is 100-500 g / t, and the amount of sodium sulfide used is 200-8000 g / t, or the amount of sodium hydrosulfide used is 100-6000 g / t.

8. The beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore according to claim 5, characterized in that, The bismuth-sulfur separation flotation process is a combination of one of the following five stages: roughing, cleaning, scavenging, and finishing. The amount of activated carbon used is 100-500 g / t, the amount of lime used is 500-10000 g / t, and the amount of sodium humate used is 20-300 g / t.

9. The beneficiation and recovery method for calcium-magnesium gangue-type molybdenum-bismuth-sulfur polymetallic ore according to claim 1, characterized in that, In step S1, the grade of the raw ore is: Mo grade 0.05%~0.15%, Bi grade 0.05%~0.2%, S grade 0.5%~4.5%; calcite content is 2%~8%, dolomite content is 0.5%~5%, grossular content is 10%~25%, tremolite content is 1%~10%, actinolite content is 1%~10%, and diopside content is 1%~10%.

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