Step separation and recovery process for sulfur-oxygen mixed type antimony oxide ore

Abstract

The invention relates to a sulfur-oxygen mixed type antimony oxide ore cascade separation and recovery process. According to the process disclosed by the invention, a cascade separation process of grading jigging, coarse grinding reselection, regrinding flotation and centrifugal reselection is adopted, so that antimony oxide particles can be collected early, stage grinding and stage grading are realized, and overgrinding argillization of antimony oxide caused by first-stage grinding in a traditional crushing and grinding process is reduced. And flotation only aims at fully dissociated fine-grain antimony sulfide, the dosage of chemicals is small, the process is simple, the energy consumption and the chemical cost are remarkably reduced, and the comprehensive economic benefits are prominent.

Description

Technical Field

[0001] This invention belongs to the field of mineral processing technology, specifically relating to a cascade separation and recovery process for sulfur-oxygen mixed antimony oxide ore. Background Technology

[0002] Antimony, as an important strategic metal, plays an irreplaceable role in flame retardants, batteries, ceramics, and the defense industry. Antimony ore is mainly divided into antimony sulfide ore and antimony oxide ore. However, antimony oxide ore with mixed sulfur and oxide content presents a significant challenge in beneficiation due to the coexistence of sulfides and oxides, uneven particle size distribution, and severe interference from gangue minerals such as quartz and calcite.

[0003] Currently, the main beneficiation processes for antimony oxide include gravity separation and flotation.

[0004] Gravity separation is a traditional method that utilizes the density difference between antimony oxide and gangue minerals for separation. It typically employs equipment such as jigs and shaking tables to separate the crushed raw ore, while spiral sluices and vibrating cone concentrators are used to recover fine-grained materials. Patent CN 106391296 B discloses a gravity separation method for fine-grained antimony oxide ore. In this method, antimony tailings or ground antimony oxide ore are first screened with a vibrating screen to remove coarse particles, then a hydrocyclone is used to remove slime, and finally, the material flows by gravity into a vibrating cone concentrator for a single separation to obtain antimony concentrate and final tailings. However, because antimony minerals are brittle and prone to over-grinding and sliming, the desliming process results in a significant loss of fine-grained antimony.

[0005] The flotation process includes two routes: sulfide flotation and direct flotation. Sulfide flotation first sulfides the surface of antimony oxide with reagents such as sodium sulfide, and then uses xanthate collectors for flotation. However, the process conditions of sulfide flotation are difficult to control, and the stability of the sulfide film is poor. Direct flotation uses special collectors such as fatty acids and hydroxamic acids to directly float antimony oxide. Patent CN103223377 A discloses a flotation separation method for low-grade antimony oxide ore. Under the condition that the grinding fineness is 70% to 90% of -0.074 mm, 2500 g / t to 4000 g / t of sodium carbonate and water glass combined modifier, 300 g / t to 500 g / t of copper sulfate or lead nitrate as antimony oxide activator, and 800 g / t to 1200 g / t of combined collector composed of carboxyl, oxime, and sulfonic acid groups are added to the ore pulp to achieve flotation separation of antimony oxide and gangue minerals. However, due to the very similar properties of antimony oxide and quartz, direct flotation has poor selectivity, complex reagent formulations, weak adaptability to complex ores, and unstable industrial application effects of new high-efficiency collectors.

[0006] In existing technologies, most beneficiation methods for antimony oxide ore employ a "one-size-fits-all" approach of crushing and grinding followed by direct separation. This results in the over-grinding and mudding of coarse antimony oxide particles, reducing the efficiency of gravity separation and flotation recovery. Furthermore, the flotation process for fine antimony oxide particles involves complex reagent formulations, poor reagent selection, and lacks industrial production examples. Therefore, developing a synergistic process that integrates early recovery of coarse particles, sulfur-oxygen separation, and fine particle re-separation is of great significance for improving the resource utilization rate of sulfur-oxygen mixed antimony oxide ore. Summary of the Invention

[0007] This invention provides a cascade separation and recovery process for sulfur-oxygen mixed antimony oxide ore, which includes the following steps: Step (1): Raw ore crushing and jigging The sulfur-oxygen mixed antimony oxide ore is crushed to -15~-25mm and then separated into three particle sizes by a vibrating screen: coarse particle size +10mm, medium particle size 5~7-10~12mm, and fine particle size -5~7mm. The three-stage particle size separation products are fed into jigs with corresponding parameters: coarse particle jigs use a stroke of 12-15mm and a stroke rate of 180-220 times / min; medium particle jigs use a stroke of 8-10mm and a stroke rate of 220-250 times / min; and fine particle jigs use a stroke of 5-7mm and a stroke rate of 250-300 times / min. The three-stage jigging concentrate is combined into a coarse-grained antimony oxide-antimony sulfide mixed concentrate, with an Sb grade ≥40% and a recovery rate of ≥35% of the original ore. The jigging tailings are then processed in the next step. Step (2): Jigging tailings coarse grinding and gravity separation The jigging tailings obtained in the previous step are coarsely ground to control the particle size of the grinding product to be -0.074mm, accounting for 15-30%. The coarsely ground product is screened and classified by a vibrating screen, with a particle size of 150-74 microns. The oversize material is fed into a spiral chute for roughing, and the chute concentrate is fed into a coarse sand shaking table for cleaning, with a stroke rate of 240-280 times / min and a stroke of 15-25 mm. The undersize material is fed into a fine mud shaking table for cleaning, with a stroke rate of 280-320 times / min and a stroke of 8-16 mm. The concentrates from the two shaking tables are combined to form a coarsely ground antimony oxide concentrate with an Sb grade ≥20% and a recovery rate of ≥20% from the original ore. The tailings from the sluice box and the tailings from the two particle size shaking tables are combined into coarse grinding and gravity separation tailings, which then proceed to the next step of processing. Step (3): Gravity separation tailings regrinding and flotation The tailings obtained from the coarse grinding and gravity separation process in the previous step are then regrinded to control the particle size of the grinding product to be -0.074mm, accounting for 60-75%. The regrinding pulp concentration is adjusted to 20-40%, and the pH is adjusted to 7-8. Lead nitrate or a combination of lead nitrate and copper sulfate activator is added sequentially, with a total dosage of 50-300 g / t and a lead nitrate to copper sulfate mass ratio of 1-3:1. A combination of pentyl xanthate and ethyl thiocyanate collector is added, with a total dosage of 150-400 g / t and a pentyl xanthate to ethyl thiocyanate mass ratio of 1-3:1. Pine oil (a frother) is added at a dosage of 20-100 g / t. The flotation process consists of 1-2 roughing stages, 1-3 cleaning stages, and 1-3 scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade ≥30% and a recovery rate of ≥17% from the original ore. The flotation tailings proceed to the next step of processing. Step (4): Centrifugation re-selection of flotation tailings Adjust the concentration of the flotation tailings slurry obtained in the previous step to 15-30%, and centrifuge it using a centrifuge with a centrifugal force of 50-150g, with a washing water volume of 4-10 ml. 3 / h, to obtain centrifuged crude concentrate; The centrifuge tailings are the final tailings. The centrifuged coarse concentrate is then finely separated by a fine mud shaking table with a stroke rate of 280-320 times / min and a stroke of 8-16mm to obtain a re-selected concentrate with an Sb grade of ≥15% and a recovery rate of ≥3% of the original ore.

[0008] In some embodiments of the present invention, the jigging concentrate, coarse grinding gravity concentrate, flotation concentrate and reconcentration concentrate obtained in steps (1) to (4) are combined into a total concentrate with an Sb grade ≥30% and a recovery rate ≥75%, for example, an Sb grade of 30~40% and a recovery rate of 75~90%.

[0009] In some embodiments of the present invention, the oxidation rate of the sulfur-oxygen mixed antimony oxide ore before sorting is ≥50%, for example, 50~80%, such as 51~75%.

[0010] In some embodiments of the present invention, the sulfur-oxygen mixed antimony oxide ore before sorting contains 1% to 3% Sb by mass percentage, for example 1.5% to 2.5%.

[0011] In some embodiments of the present invention, the sulfur-oxygen mixed antimony oxide ore before sorting contains 75% to 90% SiO2 by mass percentage, for example 80% to 88%, such as 85% to 87%.

[0012] In some embodiments of the present invention, the sulfur-oxygen mixed antimony oxide ore before sorting contains 3% to 8% Al2O3 by mass percentage, for example, 3.5% to 7.5%.

[0013] In some embodiments of the present invention, in step (1), the oxidation rate of the sulfur-oxygen mixed antimony oxide ore before sorting is ≥50%, and it contains 1%~3% Sb, 75%~90% SiO2, 0.5%~5% CaO, and 3%~8% Al2O3 by mass percentage.

[0014] In some embodiments of the present invention, in step (1), the oxidation rate of the sulfur-oxygen mixed antimony oxide ore before sorting is 51-75%, and it contains 1.5%-2.5% Sb, 80%-88% SiO2, 1.5%-5% CaO, 3.5%-7.5% Al2O3 by mass percentage, with the remainder being impurities such as Fe2O3 and / or MgO.

[0015] In some embodiments of the present invention, in step (1), the oxidation rate of the sulfur-oxygen mixed antimony oxide ore before sorting is 55-65%, and it contains 1.5%-2.5% Sb, 80%-88% SiO2, 3%-5% CaO, 4%-6% Al2O3 by mass percentage, with the remainder being impurities such as Fe2O3 and / or MgO.

[0016] In some embodiments of the present invention, in step (1), the sulfur-oxygen mixed antimony oxide ore is crushed to -15~-25mm and divided into three particle sizes by a vibrating screen: +10~12mm, medium particle size 5~7-10~12mm, and fine particle size -5~7mm.

[0017] In some embodiments of the present invention, in step (1), the tertiary jigging concentrate is combined into a coarse-grained antimony oxide-antimony sulfide mixed concentrate, wherein Sb is 41-50%, for example 42-48%.

[0018] In some embodiments of the present invention, in step (1), the three-stage jigging concentrate is combined into a coarse-grained antimony oxide-antimony sulfide mixed concentrate, wherein the recovery rate of the original ore is 35-40%, for example 36-38%.

[0019] In some embodiments of the present invention, in step (2), the coarse grinding is performed using a rod mill.

[0020] In some embodiments of the present invention, in step (2), the coarse grinding controls the particle size of the ground product to be -0.074 mm, accounting for 20-25%, for example 21-24%.

[0021] In some embodiments of the present invention, in step (2), the coarsely ground product is graded into particles of 140-80 micrometers, for example 130-70 micrometers.

[0022] In some embodiments of the present invention, in step (2), the material on the screen is fed into a spiral chute for roughing, and the concentrate from the chute is fed into a coarse sand shaking table for fine selection, with a stroke of 250-270 times / minute and a stroke of 18-24mm.

[0023] In some embodiments of the present invention, in step (2), the screened material is fed into a fine mud shaking table for selection, with a stroke of 290-310 times / minute and a stroke of 10-14mm.

[0024] In some embodiments of the present invention, in step (2), the two particle size shaker concentrates are combined into a coarsely ground antimony oxide concentrate with an Sb grade of 20-30%, for example 22-28%. The recovery rate of the original ore is 20-30%.

[0025] In some embodiments of the present invention, in step (2), the two particle size shaker concentrates are combined into coarsely ground antimony oxide concentrate, with a recovery rate of 20-30% of the original ore, for example 22-28%.

[0026] In some embodiments of the present invention, in step (3), the gravity separation tailings are fed into a ball mill or a rod mill for regrinding.

[0027] In some embodiments of the present invention, in step (3), the tailings obtained from the previous coarse grinding and gravity separation are regrinded to control the particle size of the grinding product to be -0.074mm, accounting for 65~70%, for example 66~68%.

[0028] In some embodiments of the present invention, in step (3), the concentration of the regrinding slurry is adjusted to 20-40%, the pH is adjusted to 7-8, and lead nitrate or lead nitrate + copper sulfate combination activator is added in sequence, with a total amount of 50-300 g / t and the mass ratio of lead nitrate to copper sulfate is 1-3:1. Amyl xanthate + ethyl thiocyanate combination collector is added in sequence, with a total amount of 150-400 g / t and the mass ratio of amyl xanthate to ethyl thiocyanate is 1-3:1. 20-100 g / t of pine oil frother is added to carry out 1-2 roughing, 1-3 cleaning and 1-3 scavenging.

[0029] In some embodiments of the present invention, in step (3), the flotation concentrate is antimony sulfide concentrate with an Sb grade of 30-50%, for example, an Sb grade of 31-48%.

[0030] In some embodiments of the present invention, in step (3), the flotation concentrate is antimony sulfide concentrate, and the recovery rate of the original ore is 18-30%, for example 20-28%.

[0031] In some embodiments of the present invention, in step (4), the concentration of the flotation tailings slurry is adjusted to 15-30% and then centrifuged, for example, 15-25%.

[0032] In some embodiments of the present invention, a vertical centrifuge is used in step (4) with a centrifugal force of 50-150g and a rinsing water volume of 4-10 m³. 3 / h.

[0033] In some embodiments of the present invention, in step (4), the coarse concentrate from the centrifuge is selected by a fine mud shaking table with a stroke of 280-320 times / min and a stroke of 8-16mm.

[0034] In some embodiments of the present invention, in step (4), the grade of the concentrate is further selected to be 15-20%, for example 16-18%.

[0035] In some embodiments of the present invention, in step (4), the recovery rate of the raw ore in the re-selected concentrate is 3-8%, for example 4-6%.

[0036] In some embodiments of the present invention, the sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process includes the following steps: Step (1'): Raw ore crushing and jigging The sulfur-oxygen mixed antimony oxide ore is crushed to -20mm and then separated into three particle sizes by a vibrating screen: coarse particle size +10~12mm, medium particle size 5~7-10~12mm, and fine particle size -5~7mm. In step (1') above, the oxidation rate of the sulfur-oxygen mixed antimony oxide ore is ≥50%, and it contains 1%~3% Sb, 75%~90% SiO2, 0.5%~5% CaO, and 3%~8% Al2O3 by mass percentage; The three-stage particle size separation products are fed into jigs with corresponding parameters: coarse particle jigs use a stroke of 12-15mm and a stroke rate of 180-220 times / min; medium particle jigs use a stroke of 8-10mm and a stroke rate of 220-250 times / min; and fine particle jigs use a stroke of 5-7mm and a stroke rate of 250-300 times / min. The three-stage jigging concentrate is combined into a coarse-grained antimony oxide-antimony sulfide mixed concentrate, with an Sb grade ≥40% and a recovery rate of ≥35% of the original ore. The jigging tailings are then processed in the next step. Step (2'): Jigging tailings coarse grinding and gravity separation The jigging tailings obtained in the previous step are fed into a rod mill for coarse grinding, and the particle size of the grinding product is controlled to be -0.074mm, accounting for 15-30%. The coarsely ground product is screened and classified by a vibrating screen, with a particle size of 150~74 microns. The oversize material is fed into a spiral chute for roughing, and the chute concentrate is fed into a coarse sand shaking table for cleaning, with a stroke rate of 240~280 times / min and a stroke of 15~25mm. The undersize material is fed into a fine mud shaking table for cleaning, with a stroke rate of 280~320 times / min and a stroke of 8~16mm. The concentrates from the two shaking tables are combined to form a coarsely ground antimony oxide concentrate with an Sb grade ≥20% and a recovery rate of ≥20% from the original ore. The tailings from the sluice box and the tailings from the two particle size shaking tables are combined into coarse grinding and gravity separation tailings, and the resulting coarse grinding and gravity separation tailings are then processed in the next step. Step (3'): Gravity separation tailings regrinding and flotation The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a ball mill or rod mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 60-75%, so that the antimony sulfide minerals in the ore are fully liberated. The regrinding pulp concentration is adjusted to 25-35%, and the pH is adjusted to 7-8. Lead nitrate or a combination of lead nitrate and copper sulfate activator is added sequentially, with a total dosage of 50-300 g / t and a lead nitrate to copper sulfate mass ratio of 1-3:1. A combination of pentyl xanthate and ethyl thiocyanate collector is added, with a total dosage of 150-400 g / t and a pentyl xanthate to ethyl thiocyanate mass ratio of 1-3:1. Pine oil (a frother) is added at a dosage of 20-100 g / t. The flotation process consists of 1-2 roughing stages, 1-3 cleaning stages, and 1-3 scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade ≥30% and a recovery rate of ≥17% from the original ore. The flotation tailings proceed to the next step of processing. Step (4'): Centrifugation and re-selection of flotation tailings Adjust the concentration of the flotation tailings slurry obtained in the previous step to 15-30%, and feed it into a vertical centrifuge with a centrifugal force of 50-150g and a washing water volume of 4-10 ml. 3 / h is used for roughing to obtain centrifuged rough concentrate; The centrifuge tailings are the final tailings. The centrifuge rough concentrate is then finely separated by a fine mud shaking table with a stroke rate of 280-320 times / min and a stroke of 8-16mm to obtain a re-selected concentrate with an Sb grade of ≥15% and a recovery rate of ≥3% of the original ore.

[0037] The jigging concentrate, coarse grinding gravity concentrate, flotation concentrate, and reconcentration concentrate obtained in steps (1') to (4') are combined into a total concentrate with an Sb grade of ≥30% and a recovery rate of ≥75%.

[0038] Beneficial effects The process of this invention adopts a stepped separation flow of "grading and jigging - coarse grinding and gravity separation - regrinding and flotation - centrifugal re-separation", realizing the early and efficient collection of antimony oxide particles and staged grinding and separation, reducing the over-grinding and mudding of antimony oxide caused by the single-stage grinding process in traditional crushing and grinding. Flotation is only for fully liberated fine-grained antimony sulfide, requiring small reagent dosages and a simple process, significantly reducing energy consumption and reagent costs, resulting in outstanding overall economic benefits. The specific beneficial effects of this invention are reflected in: (1) By crushing and classifying the raw ore into three particle sizes of +10mm, 5-10mm and -5mm, the coarse minerals can be recovered quickly and early, reducing resource loss from the source. The recovery rate of coarse mixed concentrate is over 35%, significantly improving the overall utilization efficiency of resources.

[0039] (2) Separation of sulfur and oxygen minerals in stages: a step-by-step separation method of “coarse grinding and gravity separation for priority recovery of antimony oxide + regrinding and flotation for recovery of antimony sulfide” is adopted. The coarse grinding controls the proportion of -0.074mm to 15-30% to reduce over-grinding. Antimony oxide concentrate with a grade of ≥20% is obtained by combining spiral chute and coarse and fine mud shaking table. The amount of regrinding and flotation is reduced by coarse grinding and gravity separation. Regrinding to -0.074mm accounts for 60-75% to ensure the dissociation of antimony sulfide, thereby achieving efficient separation of sulfur and oxygen minerals and keeping the total concentrate grade stable at over 30%.

[0040] (3) For the fine antimony oxide particles in the flotation tailings, a vertical centrifuge is used to enhance the recovery, which makes up for the shortcomings of the traditional shaking table in the recovery of fine tailings. Then, the fine mud shaking table is used to select a re-selected concentrate with a grade of ≥15%, and the fine particle recovery rate is increased to more than 5%, thus realizing the deep recovery of resources.

[0041] (4) It has strong adaptability and wide application range. The process is designed for sulfur-oxygen mixed antimony oxide ore with oxidation rate ≥50%, Sb content 1%-3% and high silicon (SiO2 75%-90%). It can adapt to complex intercalation characteristics and wide particle size distribution, providing a reliable technical solution for the efficient recovery of similar ores. It has high practicality and promotion value.

[0042] The differences between the process of this invention and the prior art include at least the following: The process of this invention adopts a stepped grinding and beneficiation approach of "coarse grinding and gravity separation to recover antimony oxide + regrinding and flotation to recover antimony sulfide", which realizes the stage separation of sulfur and oxygen minerals, and the product grade of each stage is high, avoiding the low grade caused by sulfur and oxygen co-concentration in existing processes. The process of this invention introduces a vertical centrifuge to treat fine-particle tailings, using centrifugal force to enhance the recovery of fine-particle antimony oxide, which is different from the inefficient methods of recovering fine particles that rely on flotation or traditional shaking tables in the prior art.

[0043] The reagent system used in the entire process of this invention is simple, contains no highly toxic reagents, and conforms to the trend of green mineral processing. Attached Figure Description

[0044] Figure 1 This is a process flow diagram of the cascade separation and recovery of sulfur-oxygen mixed antimony oxide ore in the embodiments. Detailed Implementation

[0045] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0046] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0047] Example 1 The sulfur-oxygen mixed antimony oxide ore used in this embodiment comes from an antimony mine in Hunan Province. Its main chemical composition (mass percentage) is: Sb 2.15% (of which antimony sulfide accounts for 42%, ore oxidation rate 58%), SiO2 85.3%, CaO 2.7%, Al2O3 5.2%, and the remainder is impurities such as Fe2O3 and MgO. The antimony sulfide in the ore is mainly stibnite, and the antimony oxide mineral composition is complex, mainly composed of stibnite, antimony travertine, and stibnite, with a small amount of red stibnite and antimony calcium stone. The antimony mineral particle size distribution ranges from -2mm to +0.005mm, of which antimony minerals with a particle size of -0.037mm account for ≥20% by mass percentage. The gangue minerals are mainly quartz, with a small amount of calcite and kaolinite. In this embodiment, an antimony concentrate with an Sb grade of 32.7% and a recovery rate of 86.8% is separated and recovered. The specific separation and recovery process includes the following steps: (1) The raw ore is crushed to -20mm by a jaw crusher and classified by a double-layer vibrating screen (10mm upper screen and 5mm lower screen) to obtain three particle sizes, which are then fed into a jig for separation. The jig parameters for the coarse particle size (+10mm) are: stroke 14mm, stroke 200 times / min, and slurry concentration 35%; the jig parameters for the medium particle size (5-10mm) are: stroke 9mm, stroke 230 times / min, and slurry concentration 30%; and the jig parameters for the fine particle size (-5mm) are: stroke 6mm, stroke 280 times / min, and slurry concentration 25%. After merging the three-stage jig concentrates, a coarse-grained antimony oxide-antimony sulfide mixed concentrate is obtained with an Sb grade of 42.3% and a recovery rate of 36.5% from the raw ore. The jig tailings are then merged and proceeded to the next step of processing.

[0048] (2) The jigging tailings obtained in the previous step were coarsely ground using a rod mill. The particle size of the ground product was controlled to be -0.074 mm, accounting for 22%, to avoid over-grinding and mud formation. The coarsely ground product was screened by a 150-mesh (106 μm) vibrating screen to obtain oversize (+106 μm, yield 65%) and undersize (-106 μm, yield 35%). The oversize was fed into a spiral sluice for roughing (14° inclination, 20% slurry concentration), and the sluice concentrate was fed into a coarse sand shaking table for cleaning (260 strokes / min, 20 mm stroke). The undersize (-106 μm) was directly fed into a fine mud shaking table for cleaning (300 strokes / min, 12 mm stroke). The two sizes of shaking table concentrates were combined into coarsely ground antimony oxide concentrate with an Sb grade of 21.5% and a recovery rate of 21.2% from the original ore. The sluice tailings and shaking table tailings were combined into coarsely ground gravity separation tailings for further processing.

[0049] (3) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a rod mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 68%, to ensure the liberation of antimony sulfide minerals. The regrinding pulp concentration is adjusted to 30%, and the pH is adjusted to 7.5 with sodium carbonate. Activator (lead nitrate + copper sulfate, with a mass ratio of lead nitrate to copper sulfate of 2:1, total dosage 150g / t), collector (pentyl xanthate + ethyl thiocyanate, with a mass ratio of pentyl xanthate to ethyl thiocyanate of 2:1, total dosage 250g / t), and frother (pine oil 50g / t) are added in sequence. The flotation process consists of one roughing, two cleaning, and two scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 41.8% and a recovery rate of 24.6% from the original ore. The flotation tailings are then processed in the next step.

[0050] (4) The concentration of the flotation tailings slurry is adjusted to 20%, and then fed into a vertical centrifuge with a centrifugal force of 100g and a washing water volume of 6m³ / h to obtain centrifuged rough concentrate. The centrifuged rough concentrate is then fed into a fine mud shaking table for further cleaning (300 strokes / min, 12mm stroke) to obtain a re-selected concentrate with an Sb grade of 16.2% and a recovery rate of 5.5% for the original ore.

[0051] The concentrates from steps (1) to (4) are combined to obtain an antimony concentrate with an Sb grade of 32.7% and a recovery rate of 86.8% from the original ore.

[0052] Comparative Example 1: The raw materials, methods, and steps used in this comparative example are the same as in Example 1, except that: (1) After the raw ore is crushed to -20mm by a jaw crusher, it is divided into coarse (+10mm) and fine (-10mm) particles by a 10mm sieve, with the jigging parameters of each particle size remaining unchanged. After merging the secondary jigging concentrates, a coarse antimony oxide-antimony sulfide mixed concentrate is obtained, with an Sb grade of 36.6% and a recovery rate of 28.7% from the raw ore. (2) The jigging tailings obtained in the previous step were coarsely ground using a rod mill with other parameters unchanged. The Sb grade of the coarsely ground antimony oxide concentrate was 22.8%, and the recovery rate of the original ore was 22.6%. (3) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a rod mill for regrinding. Other parameters remain unchanged. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 37.5% and a recovery rate of 25.8% from the original ore. (4) With other parameters remaining unchanged, the Sb grade of the re-concentrated concentrate is 16.8%, and the recovery rate of the original ore is 4.4%. (5) Combine the concentrates from steps (1) to (4) to obtain an antimony concentrate with an Sb grade of 28.4% and a recovery rate of 81.5% from the original ore.

[0053] Example 2 The sulfur-oxygen mixed antimony oxide ore used in this embodiment comes from an antimony mine in Hunan Province. Its main chemical composition (mass percentage) is: Sb 1.92% (of which antimony sulfide accounts for 21%, and the ore oxidation rate is 79%), SiO2 84.8%, CaO 2.9%, Al2O3 6.3%, and the remainder is impurities such as Fe2O3 and MgO. The antimony sulfide in the ore is mainly stibnite, and the composition of antimony oxide minerals is complex, mainly consisting of calcium stibite, stibnite, a small amount of antimony ochre, stibnite, and antimony oxide, etc. The antimony mineral particle size distribution ranges from -2mm to +0.005mm, of which antimony minerals with a particle size of -0.037mm account for ≥30% by mass percentage. The gangue minerals are mainly quartz and kaolinite. In this embodiment, an antimony concentrate with an Sb grade of 30.8% and a recovery rate of 76.1% is separated and recovered. The specific separation and recovery process includes the following steps: (1) The raw ore is crushed to -16mm by a jaw crusher and classified by a double-layer vibrating screen (11mm upper screen and 5mm lower screen) to obtain three particle sizes, which are then fed into a jig for separation. The jig parameters for the coarse particle size (+11mm) are: stroke 13mm, stroke 215 times / min, and slurry concentration 33%; the jig parameters for the medium particle size (5-11mm) are: stroke 9mm, stroke 225 times / min, and slurry concentration 30%; and the jig parameters for the fine particle size (-5mm) are: stroke 6mm, stroke 295 times / min, and slurry concentration 27%. After merging the three-stage jig concentrates, a coarse-grained antimony oxide-antimony sulfide mixed concentrate is obtained with an Sb grade of 40.5% and a recovery rate of 35.1% from the raw ore. The jig tailings are then merged and proceeded to the next step of processing.

[0054] (2) The jigging tailings obtained in the previous step are coarsely ground using a rod mill. The particle size of the ground product is controlled to be -0.074mm, accounting for 25%, to avoid over-grinding and mud formation. The coarsely ground product is screened by a 150-mesh (corresponding to 106μm) vibrating screen to obtain oversize (+106μm, yield 64%) and undersize (-106μm, yield 36%). The oversize is fed into a spiral chute for roughing (inclination angle 14°, slurry concentration 20%), and the chute concentrate is fed into a coarse sand shaking table for cleaning (stroke 265 times / min, stroke 21mm). The undersize (-106μm) is directly fed into a fine mud shaking table for cleaning (stroke 305 times / min, stroke 13mm). The concentrates from the two shaking tables were combined into a coarse-grind antimony oxide concentrate with an Sb grade of 21.5% and a recovery rate of 20.2% from the original ore. The tailings from the sluice box were combined with the tailings from the two shaking tables into a coarse-grind gravity separation tailings, which will proceed to the next step of processing.

[0055] (3) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a rod mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 71%, to ensure the liberation of antimony sulfide minerals. The regrinding pulp concentration is adjusted to 30%, and the pH is adjusted to 7.4 with sodium carbonate. Activator (lead nitrate + copper sulfate, with a mass ratio of lead nitrate to copper sulfate of 2:1, total dosage 180g / t), collector (pentyl xanthate + ethyl thiocyanate, with a mass ratio of pentyl xanthate to ethyl thiocyanate of 1.5:1, total dosage 260g / t), and frother (pine oil 55g / t) are added in sequence. The flotation process consists of one roughing, two cleaning, and two scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 31.5% and a recovery rate of 17.4% from the original ore. The flotation tailings are then processed in the next step.

[0056] (4) The concentration of the flotation tailings slurry is adjusted to 23% and fed into a vertical centrifuge with a centrifugal force of 80g and a washing water volume of 6m³ / h to obtain centrifuged rough concentrate. The centrifuged rough concentrate is fed into a fine mud shaking table for cleaning (305 strokes / min, 13mm stroke) to obtain a re-selected concentrate with an Sb grade of 15.0% and a recovery rate of 3.4% of the original ore.

[0057] The concentrates from steps (1) to (4) are combined to obtain an antimony concentrate with an Sb grade of 30.8% and a recovery rate of 76.1% from the original ore.

[0058] Comparative Example 2: The raw materials and methods used in this comparative example are the same as in Example 2, except that: (1) The jigging tailings obtained in step (1) are directly fed into a rod mill for fine grinding. Other parameters remain unchanged. The two-stage grinding and beneficiation process is changed to a single-stage grinding and beneficiation process. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 32.6% and a recovery rate of 28.5% from the original ore. (2) With other parameters of the re-selection process unchanged, the Sb grade of the re-selected concentrate from the flotation tailings is 15.4%, and the recovery rate of the original ore is 5.3%; (3) Combine the concentrates from steps (1) to (4) to obtain an antimony concentrate with an Sb grade of 31.5% and a recovery rate of 68.9% from the original ore.

[0059] Example 3 The sulfur-oxygen mixed antimony oxide ore used in this embodiment comes from an antimony mine in Guizhou Province. Its main chemical composition (mass percentage) is: Sb 2.24% (of which antimony sulfide accounts for 32%, and the ore oxidation rate is 68%), SiO2 87.2%, CaO 4.2%, Al2O3 5.6%, and the remainder is impurities such as Fe2O3 and MgO. The antimony sulfide in the ore is mainly stibnite, and the antimony oxide is mainly stibnite and yellow stibnite. The antimony mineral particle size distribution ranges from -1.5 mm to +0.010 mm, of which the antimony mineral with a particle size of -0.037 mm accounts for ≥22% by mass percentage. The gangue minerals are mainly quartz and a small amount of kaolinite. In this embodiment, an antimony concentrate with an Sb grade of 31.7% and a recovery rate of 80.8% is separated and recovered. The specific separation and recovery process includes the following steps: The raw ore is crushed to -20mm by a jaw crusher and then classified by a double-layer vibrating screen (10mm upper screen, 5mm lower screen) to obtain three particle sizes, which are then fed into a jig for separation. The jig parameters for the coarse particle size (+10mm) are: stroke 14mm, stroke rate 205 times / min, slurry concentration 35%; for the medium particle size (5-10mm), stroke rate 9mm, stroke rate 220 times / min, slurry concentration 32%; and for the fine particle size (-5mm), stroke rate 6mm, stroke rate 285 times / min, slurry concentration 28%. The three-stage jig concentrates are combined to obtain a coarse-grained antimony oxide-antimony sulfide mixed concentrate with an Sb grade of 41.5% and a recovery rate of 35.8% from the raw ore. The jig tailings are then combined and proceed to the next step of processing.

[0060] (2) The jigging tailings obtained in the previous step were coarsely ground using a rod mill. The particle size of the ground product was controlled to be -0.074 mm, accounting for 23%, to avoid over-grinding and mud formation. The coarsely ground product was screened by a 160-mesh (96 μm) vibrating screen to obtain oversize (+96 μm, yield 66%) and undersize (-96 μm, yield 34%). The oversize was fed into a spiral sluice for roughing (14° inclination, 20% slurry concentration), and the sluice concentrate was fed into a coarse sand shaking table for cleaning (260 strokes / min, 20 mm stroke). The undersize (-96 μm) was directly fed into a fine mud shaking table for cleaning (300 strokes / min, 12 mm stroke). The two sizes of shaking table concentrates were combined into coarsely ground antimony oxide concentrate with an Sb grade of 22.3% and a recovery rate of 21.5% from the original ore. The sluice tailings and shaking table tailings were combined into coarsely ground gravity separation tailings for further processing.

[0061] (3) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a ball mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 72%, to ensure the liberation of antimony sulfide minerals. The regrinding pulp concentration is adjusted to 32%, and the pH is adjusted to 7.6 with sodium carbonate. Activator (lead nitrate + copper sulfate, with a mass ratio of lead nitrate to copper sulfate of 2:1, total dosage 250g / t), collector (pentyl xanthate + ethyl thiocyanate, with a mass ratio of pentyl xanthate to ethyl thiocyanate of 2:1, total dosage 350g / t), and frother (pine oil 70g / t) are added in sequence. The flotation process consists of 2 roughing, 2 cleaning, and 3 scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 32.6% and a recovery rate of 18.7% from the original ore. The flotation tailings are then processed in the next step.

[0062] (4) The concentration of the flotation tailings slurry is adjusted to 28%, and then fed into a vertical centrifuge with a centrifugal force of 140g and a washing water volume of 8m³ / h to obtain centrifuged rough concentrate. The centrifuged rough concentrate is then fed into a fine mud shaking table for further cleaning (300 strokes / min, 12mm stroke) to obtain a re-selected concentrate with an Sb grade of 15.9% and a recovery rate of 4.8% for the original ore.

[0063] The concentrates from steps (1) to (4) are combined to obtain an antimony concentrate with an Sb grade of 31.7% and a recovery rate of 80.8% from the original ore.

[0064] Comparative Example 3: The raw materials and methods used in this comparative example are the same as in Example 3, except that: (1) The jigging tailings obtained in step (1) are directly fed into a ball mill for fine grinding. Other parameters remain unchanged. The two-stage grinding and beneficiation process is changed to a single-stage grinding and beneficiation process. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 34.3% and a recovery rate of 30.1% from the original ore. (2) With other parameters of the re-selection process unchanged, the Sb grade of the re-selected concentrate from the flotation tailings is 16.0%, and the recovery rate of the original ore is 6.5%; (3) Combine the concentrates from each step to obtain an antimony concentrate with an Sb grade of 31.9% and a recovery rate of 72.4% from the original ore.

[0065] Example 4 The sulfur-oxygen mixed antimony oxide ore used in this embodiment comes from an antimony mine in Yunnan Province. Its main chemical composition (mass percentage) is: Sb 1.97% (of which antimony sulfide accounts for 35%, and the ore oxidation rate is 65%), SiO2 81.9%, CaO 1.5%, Al2O3 7.5%, and the remainder is impurities such as Fe2O3 and MgO. The antimony sulfide in the ore is mainly stibnite, and the antimony oxide is mainly anthracite. The antimony mineral particle size distribution ranges from -1.0 mm to +0.003 mm, of which the antimony mineral with a particle size of -0.037 mm accounts for ≥18% by mass percentage. The gangue mineral is mainly quartz. In this embodiment, an antimony concentrate with an Sb grade of 32.5% and a recovery rate of 83.3% is separated and recovered. The specific separation and recovery process includes the following steps: (1) The raw ore is crushed to -15mm by a jaw crusher and classified by a double-layer vibrating screen (12mm upper screen and 5mm lower screen) to obtain three particle sizes, which are then fed into a jig for separation. The jig parameters for the coarse particle size (+12mm) are: stroke 12mm, stroke 220 times / min, and slurry concentration 32%; the jig parameters for the medium particle size (5-12mm) are: stroke 9mm, stroke 235 times / min, and slurry concentration 28%; and the jig parameters for the fine particle size (-5mm) are: stroke 6mm, stroke 300 times / min, and slurry concentration 25%. After merging the three-stage jig concentrates, a coarse-grained antimony oxide-antimony sulfide mixed concentrate is obtained with an Sb grade of 42.8% and a recovery rate of 36.5% from the raw ore. The jig tailings are then merged and proceeded to the next step of processing.

[0066] (2) The jigging tailings obtained in the previous step were coarsely ground using a rod mill. The particle size of the ground product was controlled to be -0.074mm, accounting for 26%, to avoid over-grinding and mud formation. The coarsely ground product was screened by a 140-mesh (corresponding to 106μm) vibrating screen to obtain oversize (+106μm, yield 60%) and undersize (-106μm, yield 40%). The oversize was fed into a spiral sluice for roughing (13° inclination, 18% slurry concentration), and the sluice concentrate was fed into a coarse sand shaking table for cleaning (265 strokes / min, 21mm stroke). The undersize (-106μm) was directly fed into a fine mud shaking table for cleaning (305 strokes / min, 14mm stroke). The two sizes of shaking table concentrates were combined into coarsely ground antimony oxide concentrate with an Sb grade of 22.7% and a recovery rate of 23.1% from the original ore. The sluice tailings and shaking table tailings were combined into coarsely ground gravity separation tailings for further processing.

[0067] (3) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a rod mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 66%, to ensure the liberation of antimony sulfide minerals. The regrinding pulp concentration is adjusted to 27%, and the pH is adjusted to 7.0 with sodium carbonate. Activator (lead nitrate, total dosage 80g / t), collector (pentyl xanthate + ethyl thiocyanate, the mass ratio of pentyl xanthate to ethyl thiocyanate is 2:1, total dosage 180g / t), and frother (pine oil 30g / t) are added in sequence. The flotation process consists of one roughing, two cleaning, and one scavenging. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 33.2% and a recovery rate of 19.2% from the original ore. The flotation tailings are then processed in the next step.

[0068] (4) The concentration of the flotation tailings slurry is adjusted to 22% and fed into a vertical centrifuge with a centrifugal force of 100g and a washing water volume of 6m³ / h to obtain centrifuged rough concentrate. The centrifuged rough concentrate is fed into a fine mud shaking table for cleaning (305 strokes / min, 14mm stroke) to obtain a re-selected concentrate with an Sb grade of 16.8% and a recovery rate of 4.5% of the original ore.

[0069] The concentrates from steps (1) to (4) are combined to obtain an antimony concentrate with an Sb grade of 32.5% and a recovery rate of 83.3% from the original ore.

[0070] Comparative Example 4: The raw materials, methods, and steps used in this comparative example are the same as in Example 4, except that: (1) The jigging tailings obtained in step (1) are coarsely ground in a rod mill. The particle size of the rod mill grinding product is controlled to be -0.074mm, accounting for 45%, while other parameters remain unchanged. The Sb grade of the coarsely ground antimony oxide concentrate is 14.6%, and the recovery rate of the raw ore is 21.8%. (2) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a rod mill for regrinding. Other parameters remain unchanged. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 31.8% and a recovery rate of 16.5% from the original ore. (3) With other parameters remaining unchanged in the flotation tailings re-selection process, the Sb grade of the re-selected concentrate is 17.4%, and the recovery rate of the original ore is 6.8%; (4) Combine the concentrates from each step to obtain an antimony concentrate with an Sb grade of 27.5% and a recovery rate of 81.6% from the original ore.

[0071] Example 5 The sulfur-oxygen mixed antimony oxide ore used in this embodiment comes from an antimony mine in Guangxi. Its main chemical composition (mass percentage) is: Sb 1.28% (of which antimony sulfide accounts for 25%, and the ore oxidation rate is 75%), SiO2 88.9%, CaO 1.5%, Al2O3 7.5%, and the remainder is impurities such as Fe2O3 and MgO. The antimony sulfide in the ore is mainly stibnite, and the antimony oxide is mainly stibnite, antimony travertine, and yellow antimony travertine. The antimony mineral particle size distribution ranges from -3.5mm to +0.005mm, of which antimony minerals with a particle size of -0.037mm account for ≥15% by mass percentage. The gangue minerals are mainly quartz and calcite. In this embodiment, an antimony concentrate with an Sb grade of 30.3% and a recovery rate of 77.4% is separated and recovered. The specific separation and recovery process includes the following steps: (1) The raw ore is crushed to -25mm by a jaw crusher and classified by a double-layer vibrating screen (11mm upper screen and 6mm lower screen) to obtain three particle sizes, which are then fed into a jig for separation. The jig parameters for the coarse particle size (+11mm) are: stroke 15mm, stroke 195 times / min, and slurry concentration 35%; the jig parameters for the medium particle size (6-11mm) are: stroke 10mm, stroke 230 times / min, and slurry concentration 32%; and the jig parameters for the fine particle size (-6mm) are: stroke 7mm, stroke 260 times / min, and slurry concentration 29%. After merging the three-stage jig concentrates, a coarse-grained antimony oxide-antimony sulfide mixed concentrate is obtained with an Sb grade of 40.8% and a recovery rate of 35.6% from the raw ore. The jig tailings are then merged and proceeded to the next step of processing.

[0072] (2) The jigging tailings obtained in the previous step were coarsely ground using a rod mill. The particle size of the ground product was controlled to be -0.074mm, accounting for 21%, to avoid over-grinding and mud formation. The coarsely ground product was screened by a 200-mesh (corresponding to 74μm) vibrating screen to obtain oversize (+74μm, yield 79%) and undersize (-74μm, yield 21%). The oversize was fed into a spiral sluice for roughing (15° inclination, 22% slurry concentration), and the sluice concentrate was fed into a coarse sand shaking table for cleaning (270 strokes / min, 24mm stroke). The undersize (-74μm) was directly fed into a fine mud shaking table for cleaning (315 strokes / min, 15mm stroke). The two sizes of shaking table concentrates were combined into coarsely ground antimony oxide concentrate with an Sb grade of 20.2% and a recovery rate of 20.9% from the original ore. The sluice tailings and shaking table tailings were combined into coarsely ground gravity separation tailings for further processing.

[0073] (3) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a rod mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 67%, to ensure the liberation of antimony sulfide minerals. The regrinding pulp concentration is adjusted to 33%, and the pH is adjusted to 7.9 with sodium carbonate. Activator (lead nitrate + copper sulfate, with a mass ratio of lead nitrate to copper sulfate of 3:1 and a total dosage of 300g / t), collector (pentyl xanthate + ethyl thiocyanate, with a mass ratio of pentyl xanthate to ethyl thiocyanate of 3:1 and a total dosage of 400g / t), and frother (pine oil 100g / t) are added in sequence. The flotation process consists of 2 roughing stages, 3 cleaning stages, and 3 scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 35.2% and a recovery rate of 17.1% from the original ore. The flotation tailings are then processed in the next step.

[0074] (4) The concentration of the flotation tailings slurry is adjusted to 26% and fed into a vertical centrifuge with a centrifugal force of 110g and a washing water volume of 8m³ / h to obtain centrifuged rough concentrate. The centrifuged rough concentrate is fed into a fine mud shaking table for further cleaning (315 strokes / min, 15mm stroke) to obtain a re-selected concentrate with an Sb grade of 15.1% and a recovery rate of 3.8% for the original ore.

[0075] The concentrates from steps (1) to (4) are combined to obtain an antimony concentrate with an Sb grade of 30.3% and a recovery rate of 77.4% from the original ore.

[0076] Comparative Example 5: The raw materials, methods, and steps of this comparative example are the same as those of Example 5, except that: (1) The flotation tailings are directly fed into the fine mud shaking table for separation without being roughed by centrifuge. Other parameters remain unchanged. The concentrate is then separated, with an Sb grade of 9.8% and a recovery rate of 1.4% from the original ore. (2) The concentrates from each step are combined to obtain an antimony concentrate with an Sb grade of 29.2% and a recovery rate of 74.6% from the original ore.

[0077] Example 6 The sulfur-oxygen mixed antimony oxide ore used in this embodiment comes from an antimony mine in Shaanxi Province. Its main chemical composition (mass percentage) is: Sb 1.67% (of which antimony sulfide accounts for 28%, and the ore oxidation rate is 72%), SiO2 85.5%, CaO 4.3%, Al2O3 5.9%, and the remainder is impurities such as Fe2O3 and MgO. The antimony sulfide in the ore is mainly stibnite, and the antimony oxide is mainly yellow antimony tannin. The antimony mineral particle size distribution ranges from -3.5 mm to +0.010 mm, of which the antimony mineral with a particle size of -0.037 mm accounts for ≥20% by mass percentage. The gangue minerals are mainly quartz and a small amount of calcite. In this embodiment, an antimony concentrate with an Sb grade of 32.9% and a recovery rate of 79.5% is separated and recovered. The specific separation and recovery process includes the following steps: (1) The raw ore is crushed to -24mm by a jaw crusher and classified by a double-layer vibrating screen (12mm upper screen and 5mm lower screen) to obtain three particle sizes, which are then fed into a jig for separation. The jig parameters for the coarse particle size (+12mm) are: stroke 13mm, stroke 185 times / min, and slurry concentration 31%; the jig parameters for the medium particle size (5-12mm) are: stroke 8mm, stroke 245 times / min, and slurry concentration 29%; and the jig parameters for the fine particle size (-5mm) are: stroke 5mm, stroke 275 times / min, and slurry concentration 26%. After merging the three-stage jig concentrates, a coarse-grained antimony oxide-antimony sulfide mixed concentrate is obtained with an Sb grade of 40.7% and a recovery rate of 35.2% from the raw ore. The jig tailings are then merged and proceeded to the next step of processing.

[0078] (2) The jigging tailings obtained in the previous step are coarsely ground using a rod mill. The particle size of the ground product is controlled to be -0.074mm, accounting for 28%, to avoid over-grinding and mud formation. The coarsely ground product is screened by a 100-mesh (corresponding to 150μm) vibrating screen to obtain oversize (+150μm, yield 59%) and undersize (-150μm, yield 41%). The oversize is fed into a spiral chute for roughing (inclination angle 13.8°, slurry concentration 19%), and the chute concentrate is fed into a coarse sand shaking table for cleaning (stroke 255 times / min, stroke 18mm). The undersize (-115μm) is directly fed into a fine mud shaking table for cleaning (stroke 295 times / min, stroke 10mm). The two particle size shaking table concentrates were combined into coarse-ground antimony oxide concentrate with an Sb grade of 24.1% and a recovery rate of 20.8% from the original ore. The sluice box tailings and shaking table tailings were combined into coarse-ground gravity separation tailings for further processing.

[0079] (3) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a ball mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 68%, to ensure the liberation of antimony sulfide minerals. The regrinding pulp concentration is adjusted to 29%, and the pH is adjusted to 7.3 with sodium carbonate. Activator (lead nitrate + copper sulfate, with a mass ratio of lead nitrate to copper sulfate of 2.5:1 and a total dosage of 250g / t), collector (pentyl xanthate + ethyl thiocyanate, with a mass ratio of pentyl xanthate to ethyl thiocyanate of 2.5:1 and a total dosage of 280g / t), and frother (pine oil 60g / t) are added in sequence. The flotation process consists of one roughing, two cleaning, and two scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 35.9% and a recovery rate of 17.3% from the original ore. The flotation tailings are then processed in the next step.

[0080] (4) The concentration of the flotation tailings slurry is adjusted to 20% and fed into a vertical centrifuge with a centrifugal force of 90g and a washing water volume of 5.5m³ / h to obtain centrifuged rough concentrate. The centrifuged rough concentrate is fed into a fine mud shaking table for cleaning (295 strokes / min, 10mm stroke) to obtain a re-selected concentrate with an Sb grade of 15.4% and a recovery rate of 6.2% of the original ore.

[0081] The concentrates from steps (1) to (4) are combined to obtain an antimony concentrate with an Sb grade of 32.9% and a recovery rate of 79.5% from the original ore.

[0082] Comparative Example 6: The raw materials, methods, and steps of this comparative example are the same as those of Example 6, except that: (1) The jigging tailings obtained in step (1) are coarsely ground using a rod mill. The grinding fineness is kept constant. The coarsely ground product is fed directly into a spiral chute for roughing and a shaking table for cleaning without classification. Other parameters remain unchanged. The Sb grade of the coarsely ground antimony oxide concentrate is 22.7%, and the recovery rate of the original ore is 15.5%. (2) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a ball mill for regrinding. Other parameters remain unchanged. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 36.6% and a recovery rate of 17.9% from the original ore. (3) With other parameters remaining unchanged in the flotation tailings re-selection process, the Sb grade of the re-selected concentrate is 15.8%, and the recovery rate of the original ore is 6.0%; (4) Combine the concentrates from each step to obtain an antimony concentrate with an Sb grade of 32.2% and a recovery rate of 74.6% from the original ore.

[0083] Example 7 The sulfur-oxygen mixed antimony oxide ore used in this embodiment comes from an antimony mine in Guizhou Province. Its main chemical composition (mass percentage) is: Sb 2.41% (of which antimony sulfide accounts for 42%, ore oxidation rate 58%), SiO2 86.7%, CaO 3.8%, Al2O3 5.6%, and the remainder is impurities such as Fe2O3 and MgO. The antimony sulfide in the ore is mainly stibnite, and the antimony oxide is mainly stibnite, antimony travertine, and yellow antimony travertine. The antimony mineral particle size distribution ranges from -3.2 mm to +0.005 mm, of which antimony minerals with a particle size of -0.037 mm account for ≥28% by mass percentage. The gangue minerals are mainly quartz and a small amount of calcite. In this embodiment, an antimony concentrate with an Sb grade of 37.8% and a recovery rate of 87.3% is separated and recovered. The specific separation and recovery process includes the following steps: (1) The raw ore is crushed to -22mm by a jaw crusher and classified by a double-layer vibrating screen (11mm upper screen and 5mm lower screen) to obtain three particle sizes, which are then fed into a jig for separation. The jig parameters for the coarse particle size (+11mm) are: stroke 15mm, stroke 210 times / min, and slurry concentration 34%; the jig parameters for the medium particle size (5-11mm) are: stroke 10mm, stroke 225 times / min, and slurry concentration 31%; and the jig parameters for the fine particle size (-5mm) are: stroke 7mm, stroke 270 times / min, and slurry concentration 27%. After merging the three-stage jig concentrates, a coarse-grained antimony oxide-antimony sulfide mixed concentrate is obtained with an Sb grade of 44.1% and a recovery rate of 37.6% from the raw ore. The jig tailings are then merged and proceeded to the next step of processing.

[0084] (2) The jigging tailings obtained in the previous step were coarsely ground using a rod mill. The particle size of the ground product was controlled to be -0.074 mm, accounting for 24%, to avoid over-grinding and mud formation. The coarsely ground product was screened by a 200-mesh (74 μm) vibrating screen to obtain oversize (+74 μm, yield 76%) and undersize (-74 μm, yield 24%). The oversize was fed into a spiral sluice for roughing (angle 14.5°, slurry concentration 21%), and the sluice concentrate was fed into a coarse sand shaking table for cleaning (stroke 270 times / min, stroke 22 mm). The undersize (-88 μm) was directly fed into a fine mud shaking table for cleaning (stroke 310 times / min, stroke 13 mm). The two particle size shaking table concentrates were combined into coarsely ground antimony oxide concentrate with an Sb grade of 27.3% and a recovery rate of 21.2% from the original ore. The sluice tailings and shaking table tailings were combined into coarsely ground gravity separation tailings for the next step of processing.

[0085] (3) The tailings obtained from the previous coarse grinding and gravity separation are fed into a rod mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 70%, to ensure the liberation of antimony sulfide minerals.

[0086] The regrinding pulp concentration was adjusted to 31%, and the pH was adjusted to 7.8 with sodium carbonate. Then, activator (lead nitrate + copper sulfate, lead nitrate to copper sulfate mass ratio 3:1, total dosage 280 g / t), collector (pentyl xanthate + ethyl thiocyanate, pentyl xanthate to ethyl thiocyanate mass ratio 3:1, total dosage 380 g / t), and frother (pine oil 90 g / t) were added sequentially. The flotation process consisted of two roughing stages, three cleaning stages, and two scavenging stages. The flotation concentrate was antimony sulfide concentrate with an Sb grade of 42.7% and a recovery rate of 24.8% from the original ore. The flotation tailings proceeded to the next stage of processing.

[0087] (4) The concentration of the flotation tailings slurry is adjusted to 25% and fed into a vertical centrifuge with a centrifugal force of 120g and a washing water volume of 8m³ / h to obtain centrifuged rough concentrate. The centrifuged rough concentrate is fed into a fine mud shaking table for cleaning (310 strokes / min, 13mm stroke) to obtain a re-selected concentrate with an Sb grade of 17.6% and a recovery rate of 3.7% of the original ore.

[0088] The concentrates from steps (1) to (4) are combined to obtain an antimony concentrate with an Sb grade of 37.8% and a recovery rate of 87.3% from the original ore.

[0089] Comparative Example 7: The raw materials, methods, and steps of this comparative example are the same as in Example 7, except that: (1) The jigging tailings obtained in step (1) are coarsely ground using a rod mill. The grinding fineness is kept constant. The coarsely ground product is fed directly into a spiral chute for roughing and a shaking table for cleaning without classification. Other parameters remain unchanged. The Sb grade of the coarsely ground antimony oxide concentrate is 26.6%, and the recovery rate of the original ore is 14.4%. (2) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a rod mill for regrinding. Other parameters remain unchanged. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 40.2% and a recovery rate of 25.8% from the original ore. (3) With other parameters remaining unchanged in the flotation tailings re-selection process, the Sb grade of the re-selected concentrate is 17.7%, and the recovery rate of the original ore is 4.0%; (4) Combine the concentrates from each step to obtain an antimony concentrate with an Sb grade of 35.1% and a recovery rate of 81.8% from the original ore.

[0090] Example 8 The sulfur-oxygen mixed antimony oxide ore used in this embodiment comes from an antimony mine in Hunan Province. Its main chemical composition (mass percentage) is: Sb 2.38% (of which antimony sulfide accounts for 49%, and the ore oxidation rate is 51%), SiO2 83.2%, CaO 4.1%, Al2O3 4.5%, and the remainder is impurities such as Fe2O3 and MgO. The antimony sulfide in the ore is mainly stibnite, and the antimony oxide is mainly stibnite and yellow stibnite. The antimony mineral particle size distribution ranges from -3mm to +0.003mm, of which the antimony mineral with a particle size of -0.037mm accounts for ≥16% by mass percentage. The gangue minerals are mainly quartz and a small amount of kaolinite. In this embodiment, an antimony concentrate with an Sb grade of 39.6% and a recovery rate of 89.6% is separated and recovered. The specific separation and recovery process includes the following steps: (1) The raw ore is crushed to -18mm by a jaw crusher and classified by a double-layer vibrating screen (10mm upper screen and 5mm lower screen) to obtain three particle sizes, which are then fed into a jig for separation. The jig parameters for the coarse particle size (+10mm) are: stroke 13mm, stroke 190 times / min, and slurry concentration 33%; the jig parameters for the medium particle size (5-10mm) are: stroke 8mm, stroke 240 times / min, and slurry concentration 29%; and the jig parameters for the fine particle size (-5mm) are: stroke 5mm, stroke 290 times / min, and slurry concentration 26%. After merging the three-stage jig concentrates, a coarse-grained antimony oxide-antimony sulfide mixed concentrate is obtained with an Sb grade of 45.2% and a recovery rate of 38.2% from the raw ore. The jig tailings are then merged and proceeded to the next step of processing.

[0091] (2) The jigging tailings obtained in the previous step are coarsely ground using a rod mill. The particle size of the ground product is controlled to be -0.074mm, accounting for 20%, to avoid over-grinding and mud formation. The coarsely ground product is screened by a 120-mesh (125μm) vibrating screen to obtain oversize (+125μm, yield 62%) and undersize (-125μm, yield 38%). The oversize is fed into a spiral chute for roughing (angle 13.5°, slurry concentration 19%), and the chute concentrate is fed into a coarse sand shaking table for cleaning (stroke 250 times / min, stroke 19mm). The undersize (-125μm) is directly fed into a fine mud shaking table for cleaning (stroke 290 times / min, stroke 11mm). The two particle size shaking table concentrates were combined into coarse-ground antimony oxide concentrate with an Sb grade of 24.2% and a recovery rate of 25.8% from the original ore. The sluice box tailings and shaking table tailings were combined into coarse-ground gravity separation tailings for further processing.

[0092] (3) The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a ball mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 65%, to ensure the liberation of antimony sulfide minerals. The regrinding pulp concentration is adjusted to 28%, and the pH is adjusted to 7.2 with sodium carbonate. Activator (lead nitrate + copper sulfate, with a mass ratio of lead nitrate to copper sulfate of 1:1 and a total dosage of 120g / t), collector (pentyl xanthate + ethyl thiocyanate, with a mass ratio of pentyl xanthate to ethyl thiocyanate of 1:1 and a total dosage of 220g / t), and frother (pine oil 40g / t) are added in sequence. The flotation process consists of one roughing, one cleaning, and two scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade of 43.3% and a recovery rate of 22.5% from the original ore. The flotation tailings are then processed in the next step.

[0093] (4) The concentration of the flotation tailings slurry is adjusted to 18%, and then fed into a vertical centrifuge with a centrifugal force of 80g and a washing water volume of 5m³ / h to obtain centrifuged rough concentrate. The centrifuged rough concentrate is then fed into a fine mud shaking table for further cleaning (290 strokes / min, 11mm stroke) to obtain a re-selected concentrate with an Sb grade of 18.9% and a recovery rate of 3.1% from the original ore.

[0094] The concentrates from steps (1) to (4) are combined to obtain an antimony concentrate with an Sb grade of 39.6% and a recovery rate of 89.6% from the original ore.

[0095] As can be seen from the results of the above embodiments and comparative examples, the recovery process of the present invention, through a stepped separation process of "grading and jigging - coarse grinding and gravity separation - regrinding and flotation - centrifugal re-separation," addresses the differences in particle size and sulfur and oxygen mineral properties in sulfur-oxygen mixed-type antimony oxide ores. Under the condition that the oxidation rate of the raw ore is ≥50%, it achieves early recovery of coarse particles, separation of sulfur and oxygen, and re-separation of fine particles, with a total antimony recovery rate of over 75% and an antimony concentrate grade of over 30%, significantly superior to the total antimony recovery rate and grade in existing technologies. Therefore, the process of the present invention has a certain degree of efficiency and feasibility for antimony recovery from sulfur-oxygen mixed-type antimony oxide ores.

[0096] The exemplary embodiments of the present invention have been described above. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A cascade separation and recovery process for sulfur-oxygen mixed-type antimony oxide ore, characterized in that, Includes the following steps: Step (1): Raw ore crushing and jigging The sulfur-oxygen mixed antimony oxide ore is crushed to -15~-25mm and then separated into three particle sizes by a vibrating screen: coarse particle size +10 mm, medium particle size 5~7-10~12mm, and fine particle size -5~7mm. The three-stage particle size separation products are fed into jigs with corresponding parameters: coarse particle jigs use a stroke of 12-15mm and a stroke rate of 180-220 times / min; medium particle jigs use a stroke of 8-10mm and a stroke rate of 220-250 times / min; and fine particle jigs use a stroke of 5-7mm and a stroke rate of 250-300 times / min. The three-stage jigging concentrate is combined into a coarse-grained antimony oxide-antimony sulfide mixed concentrate, with an Sb grade ≥40% and a recovery rate of ≥35% of the original ore. The jigging tailings are then processed in the next step. Step (2): Jigging tailings coarse grinding and gravity separation The jigging tailings obtained in the previous step are coarsely ground to control the particle size of the grinding product to be -0.074mm, accounting for 15-30%. The coarsely ground product is screened and classified by a vibrating screen, with a particle size of 150-74 microns. The oversize material is fed into a spiral chute for roughing, and the chute concentrate is fed into a coarse sand shaking table for cleaning, with a stroke rate of 240-280 times / min and a stroke of 15-25 mm. The undersize material is fed into a fine mud shaking table for cleaning, with a stroke rate of 280-320 times / min and a stroke of 8-16 mm. The concentrates from the two shaking tables are combined to form a coarsely ground antimony oxide concentrate with an Sb grade ≥20% and a recovery rate of ≥20% from the original ore. The tailings from the sluice box and the tailings from the two particle size shaking tables are combined into coarse grinding and gravity separation tailings, which then proceed to the next step of processing. Step (3): Gravity separation tailings regrinding and flotation The tailings obtained from the coarse grinding and gravity separation process in the previous step are then regrinded to control the particle size of the grinding product to be -0.074mm, accounting for 60-75%. The regrinding pulp concentration is adjusted to 20-40%, and the pH is adjusted to 7-8. Lead nitrate or a combination of lead nitrate and copper sulfate activator is added sequentially, with a total dosage of 50-300 g / t and a lead nitrate to copper sulfate mass ratio of 1-3:

1. A combination of pentyl xanthate and ethyl thiocyanate collector is added, with a total dosage of 150-400 g / t and a pentyl xanthate to ethyl thiocyanate mass ratio of 1-3:

1. Pine oil (a frother) is added at a dosage of 20-100 g / t. The flotation process consists of 1-2 roughing stages, 1-3 cleaning stages, and 1-3 scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade ≥30% and a recovery rate of ≥17% from the original ore. The flotation tailings proceed to the next step of processing. Step (4): Centrifugation re-selection of flotation tailings Adjust the concentration of the flotation tailings slurry obtained in the previous step to 15-30%, and centrifuge it using a centrifuge with a centrifugal force of 50-150g, with a washing water volume of 4-10 ml. 3 / h, to obtain centrifuged crude concentrate; The centrifuge tailings are the final tailings. The centrifuged coarse concentrate is then finely separated by a fine mud shaking table with a stroke rate of 280-320 times / min and a stroke of 8-16mm to obtain a re-selected concentrate with an Sb grade of ≥15% and a recovery rate of ≥3% of the original ore.

2. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to claim 1, characterized in that, Before sorting, the sulfur-oxygen mixed-type antimony oxide ore described above meets at least one of the following conditions: (a) Oxidation rate ≥ 50%; (b) Contains 1% to 3% Sb by mass; (c) Contains 75%~90% SiO2 by mass percentage; (d) Contains 3%~8% Al2O3 by mass percentage.

3. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to claim 1 or 2, characterized in that, In step (1), the oxidation rate of the sulfur-oxygen mixed antimony oxide ore before sorting is ≥50%, and it contains Sb 1%~3%, SiO2 75%~90%, CaO 0.5%~5%, and Al2O3 3%~8% by mass percentage; Preferably, in step (1), the oxidation rate of the sulfur-oxygen mixed antimony oxide ore before sorting is 51-75%, and it contains 1.5%-2.5% Sb, 80%-88% SiO2, 1.5%-5% CaO, 3.5%-7.5% Al2O3 by mass percentage, with the remainder being Fe2O3 and / or MgO.

4. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to any one of claims 1-3, characterized in that, In step (1), the sulfur-oxygen mixed antimony oxide ore is crushed to -15~-25mm and then divided into three particle sizes by a vibrating screen: +10~12mm, medium particle size 5~7-10~12mm, and fine particle size -5~7mm.

5. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to any one of claims 1-4, characterized in that, In step (2), the coarse grinding is performed using a rod mill; Preferably, in step (2), the particle size of the coarse grinding product is controlled to be -0.074 mm, accounting for 20-25%; Preferably, in step (2), the particle size of the coarsely ground product is 140-80 micrometers.

6. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to any one of claims 1-5, characterized in that, In step (2), the material on the screen is fed into the spiral chute for roughing, and the concentrate from the chute is fed into the coarse sand shaking table for fine selection, with a stroke of 250-270 times / min and a stroke of 18-24mm. Preferably, in step (2), the screened material is fed into a fine mud shaking table for selection, with a stroke of 290-310 times / minute and a stroke of 10-14mm.

7. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to any one of claims 1-6, characterized in that, In step (3), the gravity separation tailings are fed into a ball mill or rod mill for regrinding; Preferably, in step (3), the tailings obtained from the coarse grinding and gravity separation in the previous step are regrinded to control the particle size of the grinding product to be -0.074mm, accounting for 65-70%; Preferably, in step (3), the concentration of the regrinding slurry is adjusted to 20-40%, the pH is adjusted to 7-8, and lead nitrate or lead nitrate + copper sulfate combination activator is added in sequence, with a total dosage of 50-300g / t and the mass ratio of lead nitrate to copper sulfate is 1-3:

1. Amyl xanthate + ethyl thiocyanate combination collector is added in total, with a total dosage of 150-400g / t and the mass ratio of amyl xanthate to ethyl thiocyanate is 1-3:

1. 20-100g / t of pine oil frother is added for 1-2 roughing, 1-3 cleaning and 1-3 scavenging.

8. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to any one of claims 1-7, characterized in that, In step (4), the concentration of the flotation tailings slurry is adjusted to 15-30% before centrifugation.

9. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to any one of claims 1-8, characterized in that, In step (4), a vertical centrifuge is used with a centrifugal force of 50-150g and a rinsing water volume of 4-10 m³. 3 / h; Preferably, in step (4), the coarse concentrate from the centrifuge is further refined by a fine mud shaking table with a stroke rate of 280-320 times / minute and a stroke of 8-16mm.

10. The sulfur-oxygen mixed-type antimony oxide ore cascade separation and recovery process according to any one of claims 1-9, characterized in that, Includes the following steps: Step (1'): Raw ore crushing and jigging The sulfur-oxygen mixed antimony oxide ore is crushed to -20mm and then separated into three particle sizes by a vibrating screen: coarse particle size +10~12mm, medium particle size 5~7-10~12mm, and fine particle size -5~7mm. In step (1') above, the oxidation rate of the sulfur-oxygen mixed antimony oxide ore is ≥50%, and it contains 1%~3% Sb, 75%~90% SiO2, 0.5%~5% CaO, and 3%~8% Al2O3 by mass percentage; The three-stage particle size separation products are fed into jigs with corresponding parameters: coarse particle jigs use a stroke of 12-15mm and a stroke rate of 180-220 times / min; medium particle jigs use a stroke of 8-10mm and a stroke rate of 220-250 times / min; and fine particle jigs use a stroke of 5-7mm and a stroke rate of 250-300 times / min. The three-stage jigging concentrate is combined into a coarse-grained antimony oxide-antimony sulfide mixed concentrate, with an Sb grade ≥40% and a recovery rate of ≥35% of the original ore. The jigging tailings are then processed in the next step. Step (2'): Jigging tailings coarse grinding and gravity separation The jigging tailings obtained in the previous step are fed into a rod mill for coarse grinding, and the particle size of the grinding product is controlled to be -0.074mm, accounting for 15-30%. The coarsely ground product is screened and classified by a vibrating screen, with a particle size of 150~74 microns. The oversize material is fed into a spiral chute for roughing, and the chute concentrate is fed into a coarse sand shaking table for cleaning, with a stroke rate of 240~280 times / min and a stroke of 15~25mm. The undersize material is fed into a fine mud shaking table for cleaning, with a stroke rate of 280~320 times / min and a stroke of 8~16mm. The concentrates from the two shaking tables are combined to form a coarsely ground antimony oxide concentrate with an Sb grade ≥20% and a recovery rate of ≥20% from the original ore. The tailings from the sluice box and the tailings from the two particle size shaking tables are combined into coarse grinding and gravity separation tailings, and the resulting coarse grinding and gravity separation tailings are then processed in the next step. Step (3'): Gravity separation tailings regrinding and flotation The tailings obtained from the coarse grinding and gravity separation in the previous step are fed into a ball mill or rod mill for regrinding. The particle size of the grinding product is controlled to be -0.074mm, accounting for 60-75%, so that the antimony sulfide minerals in the ore are fully liberated. The regrinding pulp concentration is adjusted to 25-35%, and the pH is adjusted to 7-8. Lead nitrate or a combination of lead nitrate and copper sulfate activator is added sequentially, with a total dosage of 50-300 g / t and a lead nitrate to copper sulfate mass ratio of 1-3:

1. A combination of pentyl xanthate and ethyl thiocyanate collector is added, with a total dosage of 150-400 g / t and a pentyl xanthate to ethyl thiocyanate mass ratio of 1-3:

1. Pine oil (a frother) is added at a dosage of 20-100 g / t. The flotation process consists of 1-2 roughing stages, 1-3 cleaning stages, and 1-3 scavenging stages. The flotation concentrate is antimony sulfide concentrate with an Sb grade ≥30% and a recovery rate of ≥17% from the original ore. The flotation tailings proceed to the next step of processing. Step (4'): Centrifugation and re-selection of flotation tailings Adjust the concentration of the flotation tailings slurry obtained in the previous step to 15-30%, and feed it into a vertical centrifuge with a centrifugal force of 50-150g and a washing water volume of 4-10 ml. 3 / h is used for roughing to obtain centrifuged rough concentrate; The centrifuge tailings are the final tailings. The centrifuge rough concentrate is then finely separated by a fine mud shaking table with a stroke rate of 280-320 times / min and a stroke of 8-16mm to obtain a re-selected concentrate with an Sb grade of ≥15% and a recovery rate of ≥3% of the original ore.

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