Beneficiation method for efficiently separating molybdenum, bismuth and sulfur bulk concentrate

Abstract

The invention discloses a beneficiation method for efficiently separating molybdenum, bismuth and sulfur bulk concentrate, and relates to the technical field of beneficiation. The molybdenum-bismuth-sulfur bulk concentrate is subjected to flotation desiliconization, and the closed-loop process of one-time roughing, two-time concentration and one-time scavenging is adopted; selective re-grinding and re-selecting: re-grinding the materials through a moxa sand mill; flotation is carried out, water glass and ammonium dibutyl dithiophosphate are added, and concentrate and tailings are obtained; desiliconizing and roughing the concentrate again, and recovering tailings; strong shearing, inflating and efficient stirring are performed for reagent removal; a zinc sulfate and sodium sulfite combined inhibitor with the mass ratio being 2: 1 is adopted, gradient decreasing adding is conducted, and molybdenum-bismuth bulk concentrate and sulfur concentrate are separated through roughing, three-time concentration and two-time scavenging; molybdenum and bismuth are subjected to flotation separation, and then molybdenum concentrate and bismuth concentrate are obtained through four-stage concentration and two-time scavenging; waste water is classified and directionally circulated, highly toxic beneficiation reagents easy to raise dust are thoroughly abandoned, mineral dissociation is strengthened, the separation efficiency is improved, the content of gangue SiO2 in concentrate is reduced, and the grade and the recovery rate of the concentrate are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of molybdenum-bismuth-sulfur mixed ore beneficiation, and specifically to a beneficiation method for efficient separation of molybdenum, bismuth, and sulfur mixed concentrates. Background Art

[0002] Commonly, metal ores are currently obtained by bulk flotation of sulfide ores to obtain molybdenum-bismuth-sulfur mixed concentrates, and then high-concentration sulfur concentrates, molybdenum concentrates, and bismuth concentrates are separately separated from the molybdenum-bismuth-sulfur mixed concentrates. The separation first uses flotation separation, and then molybdenum is separated from bismuth and sulfur by flotation to obtain molybdenum concentrates. The tailings are then concentrated and subjected to bismuth-sulfur flotation separation to obtain bismuth concentrates and sulfur concentrates. Among them, for the molybdenum separation from bismuth and sulfur by flotation operation: sodium sulfide, water glass, and kerosene are added for flotation to obtain molybdenum concentrates; for the bismuth-sulfur flotation separation operation: the tailings from the molybdenum separation from bismuth and sulfur by flotation are first concentrated, and then activated carbon, lime, sodium cyanide, and ethyl thionocarbamate are added for pulp conditioning and flotation to obtain bismuth concentrates and sulfur concentrates respectively.

[0003] Main disadvantages of the prior art:

[0004] 1) Poor concentrate quality. The Mo grade in molybdenum concentrates is only 40 - 45%, and the SiO2 content is 10 - 12%. The Bi grade in bismuth concentrates is 20 - 25%, and the SiO2 content is 10 - 12%. The main reasons are insufficient monomer dissociation of molybdenum and bismuth minerals, more associated minerals with SiO2, and poor selectivity of reagents.

[0005] 2) Large reagent consumption, high cost, and strong toxicity. The consumption of sodium sulfide, activated carbon, and water glass is large (total consumption > 150000 g / t), and the reagent cost is very high. The use of sodium cyanide (a highly toxic reagent) and lime and activated carbon that are prone to dusting poses safety and environmental protection risks.

[0006] 3) Low beneficiation efficiency. The recoveries of molybdenum and bismuth are low (Mo recovery rate is 80 - 85%, Bi recovery rate is 75 - 80%). Due to serious mutual inclusion, the Bi content in molybdenum concentrates is ≥1.0%, the Mo content in bismuth concentrates is ≥1.5%, and at the same time, a considerable part of molybdenum and bismuth is also lost in sulfur concentrates.

[0007] 4) Difficult treatment of beneficiation wastewater. The COD of beneficiation wastewater is as high as 3000 - 4000 mg / L, the sedimentation rate is slow, and the non-reuse of wastewater leads to high external treatment costs.

[0008] The root cause analysis is as follows: There is no targeted silicon removal, the mineral intergrowth and encapsulation are serious, and there is a lack of effective pretreatment method for drug removal, relying on excessive reagents to inhibit impurities; the grinding fineness is insufficient, and the mineral dissociation is not sufficient; the wastewater is not recycled, the reagent utilization rate is low, and the wastewater disposal is difficult. Therefore, we provide a beneficiation method for efficient separation of molybdenum, bismuth, and sulfur mixed concentrates to solve the above problems. Summary of the Invention

[0009] The present invention aims to design a beneficiation method for the efficient separation of molybdenum-bismuth-sulfur mixed concentrate, which is both green and environmentally friendly, efficient and low-consumption. Through a technical chain of flotation desilication and selective regrinding pre-concentration - high-shear aeration high-efficiency stirring for drug removal - green and high-efficiency reagent substitution and stepwise addition - wastewater recycling, highly toxic and easily dust-raising beneficiation reagents are completely abandoned, mineral dissociation is strengthened, separation efficiency is improved, the gangue SiO2 content in the concentrate is reduced, the concentrate grade and recovery rate are increased, and the efficient separation of molybdenum-bismuth-sulfur mixed concentrate is achieved. To solve the above technical problems, the present invention provides the following technical solutions:

[0010] A beneficiation method for the efficient separation of molybdenum, bismuth, and sulfur mixed concentrate, comprising the following steps:

[0011] Using the molybdenum-bismuth-sulfur mixed concentrate obtained by the bulk flotation of sulfide ore as the test raw material, wherein the Mo grade is 1.0%, the Bi grade is 3.5%, the S grade is 35%, the gangue SiO2 grade is 12%, and the fineness is 85 - 90% of -200 mesh. The molybdenum-bismuth-sulfur mixed concentrate is processed in the following procedures in sequence:

[0012] Step 1, perform flotation desilication on the molybdenum-bismuth-sulfur mixed concentrate, adopting a closed-circuit process of one roughing, two cleanings, and one scavenging;

[0013] Desilication roughing: Grind the molybdenum-bismuth-sulfur mixed concentrate to a fineness of -200 mesh, with a proportion of 85 - 90%; perform desilication roughing by adding 2000 - 3000 g / t of water glass to obtain a rough concentrate and a rough tailing;

[0014] The rough concentrate is subjected to two cleanings and then concentrated to obtain overflow water and molybdenum-bismuth-sulfur mixed concentrate; the two cleanings are respectively: adding 1000 - 2000 g / t of water glass for the first desilication cleaning; adding 500 - 1000 g / t of water glass for the second desilication cleaning;

[0015] The rough tailing is subjected to one scavenging, and 5 - 10 g / t of butylamine black drug is added during scavenging;

[0016] Step 2, selective regrinding and re-selection: The scavenging tailing of flotation desilication is re-ground by an Aisha mill to -325 mesh, with a proportion of 90 - 95%; then re-floated, adding 500 - 1000 g / t of water glass and 5 - 10 g / t of butylamine black drug to obtain the concentrate and tailing after regrinding and re-selection; the concentrate after regrinding and re-selection is subjected to desilication roughing again, and the tailing is siliceous gangue minerals;

[0017] Step 3, high-shear aeration high-efficiency stirring for drug removal: Concentrate the molybdenum-bismuth-sulfur mixed concentrate after desilication to a concentration of 60 - 65%, add 3000 - 5000 g / t of modified kerosene, and the modified kerosene is prepared by mixing diesel and kerosene according to a mass ratio of (2:8) - (3:7); Stir with a high-shear aeration stirring tank for 30 min, with a stirring speed of 40 - 50 r / min and an air inflow rate of 0.1 - 0.12 m3 / (m2·min);

[0018] Step 4, molybdenum-bismuth and sulfur flotation separation: Dilute to a concentration of 30-35%, and use a combination inhibitor of zinc sulfate and sodium sulfite with a mass ratio of 2:1, adding in a stepwise decreasing manner; for roughing, add zinc sulfate 4000-6000 g / t + sodium sulfite 2000-3000 g / t, and gradually reduce it to zinc sulfate 120-200 g / t + sodium sulfite 60-100 g / t for three-stage cleaning; add butylamine black drug for two-stage scavenging to separate molybdenum-bismuth mixed concentrate and sulfur concentrate;

[0019] Step 5, molybdenum-bismuth flotation separation: Use sodium sulfide to inhibit bismuth minerals, and use modified kerosene to collect molybdenum minerals; then through four-stage cleaning, add sodium sulfide 15000-20000 g / t to 500-1000 g / t in a stepwise decreasing manner to separate molybdenum concentrate; and obtain bismuth concentrate through two-stage scavenging;

[0020] Step 6, wastewater hierarchical directional recycling: The desiliconization tailings wastewater is recycled to the desiliconization operation, the overflow water of molybdenum-bismuth-sulfur mixed concentrate is recycled to the dilution water for molybdenum-bismuth and sulfur separation, the sulfur concentrate wastewater is recycled to the makeup water for molybdenum-bismuth and sulfur separation, and the molybdenum-bismuth concentrate wastewater is recycled to the makeup water for molybdenum-bismuth separation. Overall effect: The dosage of reagents is reduced by 30-46%, and the COD of the tail water is reduced to below 800 mg / L, greatly reducing the environmental protection pressure of wastewater treatment.

[0021] (1) The quality and technical indicators of the concentrate are significantly improved

[0022] The Mo grade of molybdenum concentrate reaches 45-50% and contains SiO2 ≤ 6%; the Bi grade of bismuth concentrate reaches 28-32% and contains SiO2 ≤ 6%; the S grade of sulfur concentrate is 40-45%; the recovery rates of molybdenum and bismuth are respectively increased to 90-93% and 85-88%.

[0023] (2) Green and environmental protection

[0024] Completely abandon sodium cyanide, lime, and activated carbon, significantly reducing the safety and environmental protection risks, reducing the dust of reagent preparation by more than 90%, and reducing the COD of the tail water by 80%.

[0025] (3) Low consumption and high efficiency

[0026] The total dosage of sodium sulfide is reduced to within 32000 g / t (reducing by ≥ 46% compared with the sodium sulfide dosage of 60000 g / t in the traditional process), and the wastewater recycling rate is ≥ 90%.

[0027] In a further technical solution, in Step 2, the Aisha mill uses ceramic balls with a diameter of 1-5 mm as the grinding medium.

[0028] In a further technical solution, in the molybdenum-bismuth and sulfur flotation separation in Step 4, the sulfur grade of the obtained sulfur concentrate is 40-45%.

[0029] In a further technical solution, in the strong shear aeration high-efficiency stirring and drug removal in step 3, the mass ratio of diesel to kerosene in the modified kerosene is 3:7.

[0030] In a further technical solution, in the molybdenum-bismuth and sulfur flotation separation in step 4, the three-stage cleaning operations are as follows:

[0031] For the first sulfur concentrate cleaning, add (400 - 800) g / t of zinc sulfate and (200 - 400) g / t of sodium sulfite;

[0032] For the second sulfur concentrate cleaning, add (200 - 400) g / t of zinc sulfate and (100 - 200) g / t of sodium sulfite;

[0033] For the third sulfur concentrate cleaning, add (120 - 200) g / t of zinc sulfate and (60 - 100) g / t of sodium sulfite.

[0034] In a further technical solution, in the molybdenum-bismuth and sulfur flotation separation in step 4, the two-stage scavenging operations are as follows: For the first sulfur scavenging, add 10 - 20 g / t of butylamine black drug, and pump the scavenged concentrate pulp back to the rough selection in the molybdenum-bismuth and sulfur flotation separation;

[0035] For the second sulfur scavenging, add 5 - 10 g / t of butylamine black drug, and pump the scavenged concentrate pulp back to the first sulfur scavenging; the tailings of the molybdenum-bismuth and sulfur flotation separation are the sulfur concentrate.

[0036] In a further technical solution, in step 5, the four-stage cleaning operations respectively include:

[0037] For the first molybdenum-bismuth concentrate cleaning, add (4000 - 6000) g / t of sodium sulfide; pump the tailings pulp of the first cleaning back to the rough selection of molybdenum-bismuth separation;

[0038] For the second molybdenum-bismuth concentrate cleaning, add (4000 - 6000) g / t of sodium sulfide and (500 - 1000) g / t of modified kerosene;

[0039] For the third molybdenum-bismuth concentrate cleaning, add (1000 - 2000) g / t of sodium sulfide;

[0040] For the fourth molybdenum-bismuth concentrate cleaning, add (4000 - 6000) g / t of sodium sulfide and (500 - 1000) g / t of modified kerosene;

[0041] The concentrate of the fourth cleaning obtains the molybdenum concentrate, and the tailings pulp of each cleaning stage needs to be pumped back to the previous stage for re-cleaning;

[0042] The two-stage scavenging operations respectively include:

[0043] For the first molybdenum-bismuth scavenging, add 10 - 20 g / t of butylamine black drug; pump the scavenged concentrate pulp back to the rough selection of molybdenum-bismuth separation;

[0044] For the second scavenging of molybdenum and bismuth, add 5 - 10 g / t of butyl xanthate; the pulp of the second scavenging concentrate is pumped back to the first scavenging of molybdenum and bismuth.

[0045] Using the molybdenum-bismuth-sulfur mixed concentrate obtained from the bulk flotation of the sulfide ore as the test raw material, where the Mo grade is 1.0%, the Bi grade is 3.5%, the S grade is 35%, the gangue SiO2 grade is 12%, and the fineness is 85 - 90% passing through 200 mesh. The molybdenum-bismuth-sulfur mixed concentrate is processed in the following procedures successively: In a further technical solution, the high-shear aeration stirring tank includes a stirring cylinder, and an aeration component is installed at the bottom of the stirring cylinder; a cover is installed at the top of the stirring cylinder, and a reduction motor is installed on the top of the cover; the output end of the reduction motor is installed downward with a stirring rod, and a stirring blade is installed at the end of the stirring rod;

[0046] The stirring cylinder includes a stirring chamber, an overflow return chamber, and a bottom collection chamber. The aeration component is installed in the bottom collection chamber, and a stirring blade is installed on the aeration component; the top of the stirring chamber is not higher than the height of the cover;

[0047] Fixing plates are installed on the inner wall of the stirring chamber, and pulp passing holes are opened on the fixing plates; a fan blade plate that can rotate up and down is suitable for being installed on the stirring rod;

[0048] The aeration component includes an aeration element, a bottom pipe, and a gas release pipe. The aeration element is located outside the high-shear aeration stirring tank and is connected to the gas release pipe through the bottom pipe. Multiple groups of gas release pipes are arranged evenly in a circumferential direction in the bottom collection chamber.

[0049] In a further technical solution, an inner cavity is opened in the stirring rod, and the length of the inner cavity is lower than the length of the stirring rod; a central column is installed in the inner cavity, an upper collar and a lower collar are installed on the central column, and the lower collar is fixedly installed on the central column; a hinge joint is arranged outside the lower collar, a first articulated rod is correspondingly installed at the hinge joint, and a fan blade plate is installed at the end of the first articulated rod; a second articulated rod is installed on the upper collar, the top of the second articulated rod is hinged to the upper collar, and the bottom is hinged to the rod body of the first articulated rod;

[0050] The upper collar is slidably connected to the central column, a protective shell is installed on the upper section of the central column, and the upper section of the protective shell is a soft sleeve; an airbag is installed in the protective shell, and a top support plate is integrally installed at the top of the airbag, and the top support plate passes through the soft sleeve and is connected to the airbag.

[0051] In a further technical solution, a suction cup is movably installed at the top of the inner wall of the stirring chamber. A liquid suction pipe is arranged in the suction cup, and the top extends to the outside of the cover and is installed with a liquid suction pump; a sleeve is arranged at the top of the top support plate, and the sleeve is fixedly connected to the suction cup.

[0052] Compared with the prior art, the following beneficial effects are achieved:

[0053] (1) Flotation desilication - regrinding and re - separation combined process

[0054] The molybdenum - bismuth - sulfur mixed concentrate is preferentially subjected to flotation desilication, and then selectively reground to a fineness of 90 - 95% passing 325 mesh, followed by another flotation. This not only ensures the efficient removal of SiO2 but also enhances the effective recovery of molybdenum and bismuth in the insufficiently dissociated part.

[0055] (2) High - efficiency shearing and aeration stirring drug removal method

[0056] Use a high - efficiency stirring tank with strong shearing force for stirring, with a stirring speed of 40 - 50 r / min. During the stirring process, fresh air with a flow rate of 0.1 - 0.12 m 3 / ㎡·min is uniformly introduced. By adding modified kerosene, the "overflow" caused by the generation of bubbles during the aeration process is prevented (the molybdenum - bismuth - sulfur mixed concentrate is obtained by bulk flotation of sulfide ores, and the raw material contains pine oil foaming agent components), and the drug removal effect of mechanical friction and oxidation is enhanced.

[0057] (3) Research and development of green environmental protection reagents and hierarchical directional recycling of wastewater

[0058] Using the high - efficiency shearing and aeration stirring drug removal method to replace the activated carbon drug removal not only improves the working environment but also reduces the labor intensity of workers. Using a combination inhibitor of zinc sulfate + sodium sulfite to replace sodium cyanide to inhibit pyrite enhances the intrinsic safety and environmental protection level.

[0059] Modified kerosene formula: Diesel and kerosene are mixed in a mass ratio of 2:8 - 3:7 to enhance the selective collection performance.

[0060] Wastewater hierarchical directional recycling technology for mineral processing: The wastewater from different concentrates is recycled to the corresponding flotation operations, which not only does not affect the mineral processing technical indicators but also saves mineral processing reagents and reduces the pressure of wastewater treatment. Brief description of the drawings

[0061] Figure 1 It is a process flow schematic diagram of the separation process of the present invention;

[0062] Figure 2 It is a front view of the high - efficiency shearing and aeration stirring tank of the present invention;

[0063] Figure 3 It is a front - view sectional view of the high - efficiency shearing and aeration stirring tank of the present invention (air - bag inflation);

[0064] Figure 4 It is Figure 3 An enlarged view of part A;

[0065] Figure 5 It is Figure 3 An enlarged view of part B;

[0066] Figure 6Front view cross-sectional view of the strong shear aeration stirring tank of the present invention (the airbag is not inflated).

[0067] In the figure:

[0068] 1. Strong shear aeration stirring tank; 11. Stirring cylinder; 12. Cover; 2. Reduction motor;

[0069] 3. Stirring rod; 31. Central column; 32. Upper collar; 33. Lower collar; 34. First articulated rod; 35. Second articulated rod; 36. Protective shell; 37. Soft sleeve; 38. Airbag; 39. Top support plate; 391. Sleeve;

[0070] 4. Stirring blade; 5. Fixed plate;

[0071] 6. Inflation assembly; 61. Aeration element; 62. Bottom pipeline; 63. Deflation pipeline;

[0072] 7. Fan blade plate; 8. Suction cup; 81. Liquid suction pipe; 82. Liquid suction pump;

[0073] 100. Stirring cavity; 200. Overflow return cavity; 300. Bottom collection cavity; Detailed implementation mode

[0074] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0075] Embodiment 1

[0076] Please refer to Figure 1 , a technical solution provided by the present invention:

[0077] Raw materials: A certain mine obtained a molybdenum-bismuth-sulfur mixed concentrate through full flotation of molybdenum-bismuth-sulfur, with a grade of 1.0% molybdenum, 3.5% bismuth, 35% sulfur, 12% silicon dioxide, and a fineness of -200 mesh accounting for 85%, that is, the fineness is less than 200 mesh. It is processed in sequence according to the processes of desilication flotation - selective regrinding and reseparation - concentration, strong shear aeration stirring and de-drugging - molybdenum-bismuth and sulfur flotation separation - molybdenum-bismuth flotation separation.

[0078] (1) Desilication flotation: 2500 g / t of water glass for roughing, 1500 g / t for the first concentrate, 800 g / t for the second concentrate, and 8 g / t of butylamine black drug for scavenging. In this step, the first concentrate corresponds to the first concentrate of desilication flotation, that is, the first rough selection in desilication flotation; the second concentrate in this step corresponds to the second concentrate of desilication flotation, that is, the second rough selection in desilication flotation;

[0079] (2) Selective regrinding and re-selection: The ilmenite is ground in an iron sand mill to -325 mesh accounting for 92%, that is, the particles smaller than 325 mesh account for more than 92%. After grinding, 800 g / t of sodium silicate and 6 g / t of butylamine black drug are added for the first flotation. The concentrate of this flotation is returned to the desilication roughing operation, and the tailings of the flotation are the final tailings of desilication.

[0080] (3) Thickening, strong shear aeration and stirring for drug removal: It is thickened to a concentration of 65%, 5000 g / t of modified kerosene is added, and then it enters the strong shear aeration and stirring for 30 minutes. The stirring speed is 45 r / min, and fresh air with a flow rate of 0.12 m 3 / ㎡·min is evenly introduced during the stirring process.

[0081] (4) Flotation separation of molybdenum-bismuth and sulfur: 5000 g / t of zinc sulfate + 2500 g / t of sodium sulfite are added in the roughing, 600 g / t of zinc sulfate + 300 g / t of sulfurous acid in the first cleaning, 300 g / t of zinc sulfate + 150 g / t of sodium sulfite in the second cleaning, 200 g / t of sulfuric acid + 100 g / t of sodium sulfite in the third cleaning, 12 g / t of butylamine black drug in the first scavenging, and 7 g / t of butylamine black drug in the second scavenging. In this step, the first cleaning is the first cleaning in the flotation separation of molybdenum-bismuth and sulfur; similarly, the second cleaning is the second cleaning in the flotation separation of molybdenum-bismuth and sulfur; the third cleaning is the third cleaning in the flotation separation of molybdenum-bismuth and sulfur; the first scavenging is the first scavenging in the flotation separation of molybdenum-bismuth and sulfur; the second scavenging is the second scavenging in the flotation separation of molybdenum-bismuth and sulfur;

[0082] (5) Flotation separation of molybdenum-bismuth: 20000 g / t of sodium sulfide and 2000 g / t of modified kerosene are added in the roughing, 4000 g / t of sodium sulfide in the first cleaning, 2000 g / t of sodium sulfide + 1000 g / t of modified kerosene in the second cleaning, 1000 g / t of sodium sulfide in the third cleaning, 600 g / t of sodium sulfide + 300 g / t of modified kerosene in the fourth cleaning, 15 g / t of butylamine black drug in the first scavenging, and 6 g / t of butylamine black drug in the second scavenging. In this step, the first cleaning is the first cleaning in the flotation separation of molybdenum-bismuth; similarly, the second cleaning is the second cleaning in the flotation separation of molybdenum-bismuth; the third cleaning is the third cleaning in the flotation separation of molybdenum-bismuth; the fourth cleaning is the fourth cleaning in the flotation separation of molybdenum-bismuth; the first scavenging is the first scavenging in the flotation separation of molybdenum-bismuth; the second scavenging is the second scavenging in the flotation separation of molybdenum-bismuth;

[0083] (6) Implementation and application results: The recovery rate of molybdenum concentrate is 92.6%, containing 48.5% molybdenum, 0.3% bismuth, and 5.2% silicon dioxide; the recovery rate of bismuth concentrate is 87.3%, containing 30.1% bismuth, 0.4% molybdenum, and 5.5% silicon dioxide; the sulfur concentrate contains 42.8% sulfur. The COD of the beneficiation wastewater is reduced to 750 mg / L, and the consumption of sodium sulfide is reduced by 46%.

[0084] Example 2

[0085] Referring to the solution in Reference Example 1, raw materials: A certain mine obtained a molybdenum-bismuth-sulfur mixed concentrate through full flotation of molybdenum-bismuth-sulfur. The grade was 1.0% molybdenum, 3.5% bismuth, 35% sulfur, 12% silicon dioxide, and the fineness of -200 mesh accounted for 85%. It was processed in sequence according to the procedures of desilication flotation - selective regrinding and reseparation - concentration, strong shear aeration and agitation for drug removal - molybdenum-bismuth and sulfur flotation separation - molybdenum-bismuth flotation separation.

[0086] (1) Desilication flotation: 3000 g / t of water glass for roughing, 2000 g / t for the first cleaning, 1000 g / t for the second cleaning, and 10 g / t of butylamine black drug for scavenging.

[0087] (2) Selective regrinding and reseparation: Grind with an Aisha mill to 95% passing -325 mesh. After grinding, add 1000 g / t of water glass and 10 g / t of butylamine black drug for primary flotation. The concentrate of this flotation is returned to the roughing operation of desilication, and the tailings of the flotation are the final tailings of desilication.

[0088] (3) Concentration, strong shear aeration and agitation for drug removal: Concentrate to 65% concentration, add 5000 g / t of modified kerosene, then enter strong shear aeration and agitation for 30 minutes. The agitation speed is 50 r / min. During the agitation process, fresh air with a flow rate of 0.12 m 3 / ㎡·min is evenly introduced.

[0089] (4) Molybdenum-bismuth and sulfur flotation separation: 6000 g / t of zinc sulfate + 3000 g / t of sodium sulfite for roughing, 800 g / t of zinc sulfate + 400 g / t of sulfurous acid for the first cleaning, 400 g / t of zinc sulfate + 200 g / t of sodium sulfite for the second cleaning, 200 g / t of sulfuric acid + 100 g / t of sodium sulfite for the third cleaning, 20 g / t of butylamine black drug for the first scavenging, and 10 g / t of butylamine black drug for the second scavenging.

[0090] (5) Molybdenum-bismuth separation: 20000 g / t of sodium sulfide + 2000 g / t of modified kerosene for roughing, 6000 g / t of sodium sulfide for the first cleaning, 3000 g / t of sodium sulfide + 1000 g / t of modified kerosene for the second cleaning, 2000 g / t of sodium sulfide for the third cleaning, 1000 g / t of sodium sulfide + 400 g / t of modified kerosene for the fourth cleaning, 20 g / t of butylamine black drug for the first scavenging, and 10 g / t of butylamine black drug for the second scavenging.

[0091] (6) Implementation and application results: The recovery rate of molybdenum concentrate was 91.8%, containing 49.3% molybdenum, 0.28% bismuth, and 4.8% silicon dioxide; the recovery rate of bismuth concentrate was 87.8%, containing 31.2% bismuth, 0.33% molybdenum, and 5.1% silicon dioxide; the sulfur concentrate contained 44.5% sulfur.

[0092] Example 3

[0093] Referring to the solution in Reference Example 1, raw materials: A certain mine obtained a molybdenum-bismuth-sulfur mixed concentrate through full flotation of molybdenum-bismuth-sulfur. The grade was 1.0% molybdenum, 3.5% bismuth, 35% sulfur, 12% silicon dioxide, and the fineness of -200 mesh accounted for 85%. It was processed in sequence according to the procedures of desilication flotation - selective regrinding and reseparation - thickening, strong shear aeration and stirring for drug removal - molybdenum-bismuth and sulfur flotation separation - molybdenum-bismuth flotation separation.

[0094] (1) Desilication flotation: The dosage of water glass in roughing was 2400 g / t, 1600 g / t in the first concentrate, 800 g / t in the second concentrate, and 8 g / t of dibutyl dithiophosphate in scavenging.

[0095] (2) Selective regrinding and reseparation: Grind with an Isa mill to -325 mesh accounting for 93%. After grinding, add 800 g / t of water glass and 6 g / t of dibutyl dithiophosphate for primary flotation. The concentrate of this flotation is returned to the roughing operation of desilication, and the tailings of the flotation are the final tailings of desilication.

[0096] (3) Thickening, strong shear aeration and stirring for drug removal: Concentrate to a concentration of 63%, add 4000 g / t of modified kerosene, and then enter strong shear aeration and stirring for 30 minutes. The stirring speed is 48 r / min. During the stirring process, fresh air with a flow rate of 0.11 m 3 / ㎡·min is evenly introduced.

[0097] (4) Molybdenum-bismuth and sulfur flotation separation: Add 5200 g / t of zinc sulfate + 2600 g / t of sodium sulfite in roughing, 700 g / t of zinc sulfate + 350 g / t of sulfurous acid in the first concentrate, 300 g / t of zinc sulfate + 150 g / t of sodium sulfite in the second concentrate, 180 g / t of sulfuric acid + 90 g / t of sodium sulfite in the third concentrate, 16 g / t of dibutyl dithiophosphate in the first scavenging, and 7 g / t of dibutyl dithiophosphate in the second scavenging.

[0098] (5) Molybdenum-bismuth separation: Add 16000 g / t of sodium sulfide and 1600 g / t of modified kerosene in roughing, 5000 g / t of sodium sulfide in the first concentrate, 2500 g / t of sodium sulfide + 800 g / t of modified kerosene in the second concentrate, 1600 g / t of sodium sulfide in the third concentrate, 700 g / t of sodium sulfide + 300 g / t of modified kerosene in the fourth concentrate, 15 g / t of dibutyl dithiophosphate in the first scavenging, and 6 g / t of dibutyl dithiophosphate in the second scavenging.

[0099] (6) Implementation application results: The finally flotation desilication tailing wastewater is recycled for supplementing water in the flotation desilication operation; the concentrated overflow water of the molybdenum-bismuth-sulfur mixed concentrate after desilication is recycled for supplementing water in the initial pulp of the molybdenum-bismuth and sulfur flotation separation; the sulfur concentrate wastewater is recycled for supplementing water in the molybdenum-bismuth and sulfur flotation separation; the molybdenum and bismuth concentrate wastewater is recycled for supplementing water in the molybdenum-bismuth flotation separation. The fresh water consumption of the whole process is reduced by 75%, the total consumption of sodium sulfide is reduced by 50%, and the tail water COD is 680 mg / L. At the same time, the recovery rate of molybdenum concentrate is 90.5%, containing 48.3% molybdenum, 0.31% bismuth, and 5.6% silicon dioxide; the recovery rate of bismuth concentrate is 86.4%, containing 30.7% bismuth, 0.31% molybdenum, and 5.9% silicon dioxide; the sulfur concentrate contains 43.1% sulfur.

[0100] The above three groups of examples show that this separation and beneficiation method can achieve a molybdenum concentrate with a Mo grade of 45 - 50% and SiO2 content ≤ 6%; a bismuth concentrate with a Bi grade of 28 - 32% and SiO2 content ≤ 6%; a sulfur concentrate with an S grade of 40 - 45%; and the recovery rates of molybdenum and bismuth are respectively increased to 90 - 93% and 85 - 88%.

[0101] Completely abandon sodium cyanide, lime, and activated carbon, significantly reduce the safety and environmental protection risks, reduce the dust of reagent preparation by more than 90%, and reduce the tail water COD by 80%.

[0102] The total dosage of sodium sulfide is reduced to within 32000 g / t, and the wastewater reuse rate ≥ 90%.

[0103] The present invention preferentially performs flotation desilication on the molybdenum-bismuth-sulfur mixed concentrate, then selectively re-grinds it to a fineness of -325 mesh accounting for 90 - 95%, and then performs flotation again, which not only ensures the efficient removal of SiO2 but also strengthens the effective recovery of molybdenum and bismuth with insufficient dissociation.

[0104] Example 4

[0105] As Figures 2 - 6 shown, it is another implementation scheme of the present invention. Based on the separation and beneficiation method of Example 1, it specifically includes a strong shear aeration stirring tank. The strong shear aeration stirring tank 1 includes a stirring cylinder 11, and an aeration component 6 is installed at the bottom of the stirring cylinder 11; a cover 12 is installed at the top of the stirring cylinder 11, and a reduction motor 2 is installed at the top of the cover 12; the output end of the reduction motor 2 is installed downward with a stirring rod 3, and a stirring blade 4 is installed at the end of the stirring rod 3;

[0106] The stirring cylinder 11 includes a stirring chamber 100, an overflow return chamber 200, and a bottom receiving chamber 300. The aeration component 6 is installed in the bottom receiving chamber 300, and a stirring blade 4 is installed on the aeration component 6; the top of the stirring chamber 100 is not higher than the height of the cover 12; the aeration component realizes pumping gas into the stirring cylinder to achieve a fresh air pumping flow rate of 0.12 m 3 / ㎡·min in step 3.

[0107] A fixing plate 5 is installed on the inner wall of the stirring chamber 100, and slurry passing holes are formed in the fixing plate 5; a fan blade plate 7 that rotates up and down is suitable to be installed on the stirring rod 3;

[0108] The gas charging assembly 6 includes an aeration element 61, a bottom pipeline 62 and an air release pipeline 63. The aeration element 61 is located outside the high-shear gas charging and stirring barrel 1, and is connected to the air release pipeline 63 through the bottom pipeline 62. Multiple groups of the air release pipelines 63 are arranged in a circumferential and uniform manner in the bottom receiving cavity 300. The aeration element is preferably an electric air pump, which pumps external air into it, and a filter plate is arranged on the air release pipeline to prevent the continuous entry of pulp. And it is required that the pumped gas pressure is relatively large to achieve the air flow pumping.

[0109] As Figures 3 - 6 shown, an inner cavity is formed in the stirring rod 3, and the length of the inner cavity is lower than that of the stirring rod 3; a central column 31 is installed in the inner cavity, an upper collar 32 and a lower collar 33 are installed on the central column 31, and the lower collar 33 is fixedly installed on the central column 31; a hinge joint is arranged outside the lower collar 33, and a first hinge rod 34 is correspondingly installed at the hinge joint. A fan blade plate 7 is installed at the end of the first hinge rod 34; a second hinge rod 35 is installed on the upper collar 32. The top end of the second hinge rod 35 is hinged to the upper collar 32, and the bottom is hinged to the rod body of the first hinge rod 34;

[0110] The upper collar 32 is slidably connected to the central column 31. A protective shell 36 is installed on the upper section of the central column 31, and the upper section of the protective shell 36 is a soft sleeve 37; an airbag 38 is installed in the protective shell 36, and a top support plate 39 is integrally installed at the top of the airbag 38. The top support plate 39 passes through the soft sleeve 37 and is connected to the airbag 38. By opening holes in the airbag or the top support plate and pumping gas, synchronous upward and downward extension is realized. The top drives the suction cup to lift through the extended support top support plate. When reaching the upper limit position, there is a gap between the suction cup and the stirring chamber. When rotating at a high speed, the generated bubbles will overflow from the stirring chamber and flow back to the bottom receiving cavity at the bottom through the lateral overflow return cavity. After stirring again like this, stop pumping gas, and in the stable state, the upper layer of liquid is discharged through the suction cup; a cavity is provided in the center of the suction cup, and is respectively connected to a liquid suction pump through pipelines at the top. The pipeline is provided with branch pipes connected to electromagnetic exhaust valves; the central column in the middle of the stirring rod passes through the airbag, so the airbag does not rotate synchronously with the stirring. Therefore, it is necessary to strengthen the surface treatment by abutting one side of the upper collar with the airbag. The upper collar rotates synchronously with the stirring rod through the first hinge rod and the second hinge rod and the lower collar. When the electromagnetic exhaust valve is opened, the gas in the airbag flows out and the whole shrinks, so that the airbag retracts into the protective shell. As Figure 6 shown, the suction cup is downwardly clamped to seal the upper part of the stirring chamber, the electromagnetic exhaust valve is closed, and the liquid suction pump sucks and adsorbs the liquid for liquid discharge.

[0111] A suction cup 8 is movably installed at the top of the inner wall of the stirring chamber 100. A liquid suction pipe 81 is arranged inside the suction cup 8, and the top of the liquid suction pipe extends to the outside of the cover 12 and is equipped with a liquid suction pump 82; a sleeve 391 is arranged at the top of the top support plate 39, and the sleeve 391 is adapted to movably abut against the suction cup 8.

[0112] A constraint chamber is arranged at the top of the suction cup and is connected to a liquid suction pump at the top of the cover through a pipeline, and the liquid suction pump is used to suck the liquid on the surface of the pulp.

[0113] The core objective of high-efficiency stirring and drug removal with strong shear and aeration is to remove the residual pine oil. Pine oil is a foaming agent. For the molybdenum-bismuth-sulfur mixed concentrate from the bulk flotation of sulfide ores, the raw materials contain residual pine oil components. The high rotation speed of the strong shear stirring barrel generates intense mechanical friction, which destroys the adsorption state of pine oil on the mineral surface, makes it peel off from the mineral surface and disperse into the pulp. After air is filled, oxygen reacts with pine oil through an oxidation reaction, partially degrading its molecular structure and reducing its foaming ability; at the same time, the bubbles carry pine oil to float to the surface of the pulp, and after forming a foam layer, it is removed. Thus, the problems of low drug removal efficiency and large dust pollution in the traditional process are solved.

[0114] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, in any aspect, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, it is intended to embrace all changes falling within the meaning and scope of the equivalent elements of the claims in the present invention.

[0115] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative manner of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A beneficiation method for efficient separation of molybdenum, bismuth and sulfur mixed concentrate, characterized in that, It includes the following steps: Step 1: Flotation desilication of the molybdenum-bismuth-sulfur mixed concentrate is carried out, adopting a closed-circuit process of one roughing, two cleanings, and one scavenging; Coarse desilication: Grind the molybdenum-bismuth-sulfur mixed concentrate to a fineness of -200 mesh, accounting for 85 - 90%; Add 2000 - 3000 g / t of water glass for coarse desilication to obtain a rough concentrate and a rough tailing; The rough concentrate is subjected to two cleanings and then concentrated to obtain overflow water and a molybdenum-bismuth-sulfur mixed concentrate; The two cleanings are respectively: Add 1000 - 2000 g / t of water glass for the first desilication cleaning; Add 500 - 1000 g / t of water glass for the second desilication cleaning; The rough tailing is subjected to one scavenging, and 5 - 10 g / t of butylamine black medicine is added during scavenging; Step 2: Selective regrinding and reseparation: The scavenging tailing of flotation desilication is reground by an Aisha mill to -325 mesh, accounting for 90 - 95%; Then reflotate, add 500 - 1000 g / t of water glass and 5 - 10 g / t of butylamine black medicine to obtain the concentrate and tailing after regrinding and reseparation; The concentrate after regrinding and reseparation is returned to the coarse desilication again, and the tailing is siliceous gangue minerals; Step 3: Strong-shear aeration and high-efficiency stirring for drug removal: Concentrate the molybdenum-bismuth-sulfur mixed concentrate after desilication to a concentration of 60 - 65%, add 3000 - 5000 g / t of modified kerosene, and the modified kerosene is prepared by mixing diesel and kerosene in a mass ratio of (2:8) - (3:7); Stir with a strong-shear aeration stirring tank (1) for 30 min, with a stirring speed of 40 - 50 r / min and an aeration rate of 0.1 - 0.12 m3 / (m2·min); Step 4: Flotation separation of molybdenum-bismuth and sulfur: Dilute to a concentration of 30 - 35%, adopt a combination inhibitor of zinc sulfate and sodium sulfite with a mass ratio of 2:1, and add it in a stepwise decreasing manner; Add 4000 - 6000 g / t of zinc sulfate + 2000 - 3000 g / t of sodium sulfite for roughing, and gradually reduce it to 120 - 200 g / t of zinc sulfate + 60 - 100 g / t of sodium sulfite for three cleanings, and add butylamine black medicine for two scavengings to separate a molybdenum-bismuth mixed concentrate and a sulfur concentrate; Step 5: Flotation separation of molybdenum and bismuth: Use sodium sulfide to inhibit bismuth minerals and modified kerosene to collect molybdenum minerals; Then through four cleanings, add sodium sulfide from 15000 - 20000 g / t to 500 - 1000 g / t in a stepwise decreasing manner to separate molybdenum concentrate; And obtain bismuth concentrate through two scavengings; Step 6: Hierarchical and directional recycling of wastewater: The wastewater from desilication tailings is recycled for desilication operations, the overflow water of molybdenum-bismuth-sulfur mixed concentrate is recycled for dilution water in the separation of molybdenum-bismuth and sulfur, the wastewater of sulfur concentrate is recycled for makeup water in the separation of molybdenum-bismuth and sulfur, and the wastewater of molybdenum-bismuth concentrate is recycled for makeup water in the separation of molybdenum and bismuth.

2. A beneficiation method for efficient separation of a mixed concentrate of molybdenum, bismuth and sulfur according to claim 1, characterized in that, In Step 2, the Aisha mill uses ceramic balls with a diameter of 1 - 5 mm as grinding media.

3. A beneficiation method for efficient separation of molybdenum, bismuth, and sulfur mixed concentrate according to claim 1, characterized in that, In the flotation separation of molybdenum-bismuth and sulfur in Step 4, the sulfur grade of the obtained sulfur concentrate is 40 - 45%.

4. A beneficiation method for efficient separation of molybdenum, bismuth, and sulfur mixed concentrate according to claim 1, characterized in that, In the strong-shear aeration and high-efficiency stirring for drug removal in Step 3, the mass ratio of diesel to kerosene in the modified kerosene is 3:

7.

5. The beneficiation method for efficient separation of molybdenum, bismuth and sulfur mixed concentrate according to claim 1, characterized in that, In the flotation separation of molybdenum-bismuth and sulfur in Step 4, the three cleanings are respectively: For the first sulfur separation concentrate, add (400 - 800) g / t of zinc sulfate and (200 - 400) g / t of sodium sulfite; For the second sulfur separation concentrate, add (200 - 400) g / t of zinc sulfate and (100 - 200) g / t of sodium sulfite; For the third sulfur separation concentrate, add (120 - 200) g / t of zinc sulfate and (60 - 100) g / t of sodium sulfite.

6. A beneficiation method for efficient separation of molybdenum, bismuth, and sulfur mixed concentrate according to claim 1, characterized in that In the molybdenum-bismuth and sulfur flotation separation in step 4, for the two scavenging operations, in the first sulfur scavenging, add 10 - 20 g / t of butylamine black medicine, and the pulp of the first scavenging concentrate is pumped back to the rough selection in the molybdenum-bismuth and sulfur flotation separation; In the second sulfur scavenging, add 5 - 10 g / t of butylamine black medicine, and the pulp of the second scavenging concentrate is pumped back to the first sulfur scavenging; the tailings of the molybdenum-bismuth and sulfur separation are the sulfur concentrate.

7. The beneficiation method for efficient separation of molybdenum, bismuth and sulfur mixed concentrate according to claim 1, characterized in that, In step 5, the four-stage cleaning respectively includes: For the first molybdenum-bismuth concentrate, add (4000 - 6000) g / t of sodium sulfide; the pulp of the first concentrate tailings is pumped back to the rough selection of molybdenum-bismuth separation; For the second molybdenum-bismuth concentrate, add (4000 - 6000) g / t of sodium sulfide and (500 - 1000) g / t of modified kerosene; For the third molybdenum-bismuth concentrate, add (1000 - 2000) g / t of sodium sulfide; For the fourth molybdenum-bismuth concentrate, add (4000 - 6000) g / t of sodium sulfide and (500 - 1000) g / t of modified kerosene; The concentrate of the fourth cleaning obtains the molybdenum concentrate, and the pulp of the tailings of each stage of cleaning needs to be pumped back to the previous stage for further cleaning; The two scavenging operations respectively include: For the first molybdenum-bismuth scavenging, add 10 - 20 g / t of butylamine black medicine; the pulp of the first scavenging concentrate is pumped back to the rough selection of molybdenum-bismuth separation; For the second molybdenum-bismuth scavenging, add 5 - 10 g / t of butylamine black medicine; the pulp of the second scavenging concentrate is pumped back to the first molybdenum-bismuth scavenging.

8. The beneficiation method for efficient separation of molybdenum, bismuth and sulfur mixed concentrate according to claim 1, wherein, The strong shear aeration stirring tank (1) includes a stirring cylinder (11), and an aeration assembly (6) is installed at the bottom of the stirring cylinder (11); a cover (12) is installed at the top of the stirring cylinder (11), and a reduction motor (2) is installed at the top of the cover (12); the output end of the reduction motor (2) is installed with a stirring rod (3) downward, and a stirring blade (4) is installed at the end of the stirring rod (3); a discharge port is arranged at the bottom of the stirring cylinder (11); The stirring cylinder (11) includes a stirring chamber (100), an overflow return chamber (200) and a bottom collecting chamber (300), the aeration assembly (6) is installed in the bottom collecting chamber (300), and a stirring blade (4) is installed on the aeration assembly (6); the top of the stirring chamber (100) is not higher than the height of the cover (12); A fixing plate (5) is installed on the inner wall of the stirring chamber (100), and a pulp passing hole is opened on the fixing plate (5); a fan blade plate (7) that can rotate up and down is suitable for being installed on the stirring rod (3); The aeration assembly (6) includes an aeration element (61), a bottom pipeline (62) and a gas release pipeline (63), the aeration element (61) is located outside the strong shear aeration stirring tank (1), and is connected to the gas release pipeline (63) through the bottom pipeline (62), and multiple groups of the gas release pipelines (63) are arranged in a circumferential direction evenly in the bottom collecting chamber (300).

9. A beneficiation method for efficient separation of molybdenum, bismuth and sulfur mixed concentrate according to claim 1, characterized in that, A built-in cavity is formed inside the stirring rod (3), and the length of the built-in cavity is lower than that of the stirring rod (3); a central column (31) is installed in the built-in cavity, an upper collar (32) and a lower collar (33) are installed on the central column (31), and the lower collar (33) is fixedly installed on the central column (31); a hinge joint is arranged outside the lower collar (33), a first hinge rod (34) is correspondingly installed at the hinge joint, and a fan blade plate (7) is installed at the end of the first hinge rod (34); a second hinge rod (35) is installed on the upper collar (32), the top end of the second hinge rod (35) is hinged to the upper collar (32), and the bottom end is hinged to the rod body of the first hinge rod (34). The upper collar (32) is slidably connected to the central column (31), a protective shell (36) is installed on the upper section of the central column (31), and the upper section of the protective shell (36) is a soft sleeve (37); an airbag (38) is installed in the protective shell (36), and a top support plate (39) is integrally installed at the top of the airbag (38), and the top support plate (39) passes through the soft sleeve (37) and is connected to the airbag (38).

10. The beneficiation method for efficient separation of molybdenum, bismuth and sulfur mixed concentrate according to claim 1, characterized in that, A suction cup (8) is movably installed at the top of the inner wall of the stirring cavity (100), a liquid suction pipe (81) is arranged inside the suction cup (8), and the top extends to the outside of the cover (12) and is installed with a liquid suction pump (82). A sleeve (391) is arranged at the top of the top support plate (39), and the sleeve (391) is fixedly connected to the suction cup (8).

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