A beneficiation method of tungsten-tin copper-containing molybdenum bismuth polymetallic ore

Abstract

The application discloses a beneficiation method of tungsten-tin copper-molybdenum bismuth polymetallic ore, which comprises the following steps: (1) grinding and gravity separation of the ore: after one-stage grinding, the content of the particle size of 0.075 mm in the grinding fineness is 25-35%, the grinding slurry is subjected to gravity separation to obtain gravity separation concentrate and gravity separation tailings; (2) screening and grading of the gravity separation concentrate; grinding of the coarse particle size slurry on the screen, mixing of the grinding product with the fine particle size slurry under the screen to obtain mixed slurry; (3) sulfide ore mixed flotation of the mixed slurry to obtain mixed flotation concentrate and mixed flotation tailings; recovery of molybdenum, copper, bismuth and sulfur from the mixed flotation concentrate; and recovery of tungsten and tin from the mixed flotation tailings. The beneficiation method realizes efficient and economic recovery of tungsten, tin, copper, molybdenum and bismuth, provides a new way and thought for recovery and utilization of the tungsten-tin copper-molybdenum bismuth polymetallic ore, reduces the beneficiation cost, improves the beneficiation efficiency and effect, and is green and environment-friendly.

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metal beneficiation technology, specifically to a beneficiation method for efficient and comprehensive recovery of tungsten-tin-containing copper-molybdenum-bismuth polymetallic ores. Background Technology

[0002] Tungsten-tin polymetallic ores containing copper, molybdenum, and bismuth, in addition to the main valuable elements tungsten and tin, can also recover valuable elements such as copper, molybdenum, bismuth, and sulfur. The ores have high economic value, but due to the variety of minerals and the low content of valuable elements, it is difficult to achieve economical and efficient comprehensive recovery of each valuable element.

[0003] Currently, mining companies typically use a flotation-gravity separation-magnetic separation process for this type of ore. This involves crushing the raw ore and then grinding it into fine powder to separate the target minerals such as tungsten, tin, molybdenum, and bismuth. Flotation is then used to prioritize the recovery of sulfide minerals such as copper, molybdenum, and bismuth. The tailings from the flotation are then subjected to gravity separation to recover tungsten and tin to obtain a tungsten-tin mixed concentrate. Finally, strong magnetic separation is used to separate the tungsten concentrate and tin concentrate. After research, the inventors found that the above process has the following defects and shortcomings: (1) The flotation of sulfide minerals such as copper, molybdenum, and bismuth usually requires a grinding fineness of -0.075mm particle size content of not less than 60%, or even more than 80%. Grinding the raw ore to this fineness in one go not only consumes a lot of grinding energy, but also causes serious over-grinding and mud formation of some fragile and easily ground minerals. For example, fine mud-grade tungsten-tin minerals are prone to heterogeneous agglomeration and capping, resulting in homogenization with gangue minerals, making recovery extremely difficult, resulting in low gravity separation recovery rate and serious loss of valuable minerals; (2) The feed volume of the beneficiation operation is large, the beneficiation efficiency is low, the processing capacity of the beneficiation plant is seriously limited, and the beneficiation economic and technical indicators are poor.

[0004] Therefore, it is urgent to design and develop a new economical and efficient mineral processing and recovery method based on the physicochemical properties of each mineral, and to achieve efficient comprehensive recovery of tungsten, tin, copper, molybdenum, bismuth and sulfur, so as to realize the high-level comprehensive utilization of such mineral resources and significantly improve the overall economic benefits of enterprises. Summary of the Invention

[0005] This invention provides a beneficiation method for tungsten-tin copper-molybdenum-bismuth polymetallic ores with advantages such as high grade of tungsten and tin concentrates, good recovery index, high comprehensive utilization rate of associated elements, and significant economic benefits. This method aims to solve the technical problems of low tungsten and tin beneficiation recovery rate, high energy consumption of grinding and flotation operations, and low comprehensive resource utilization rate in existing beneficiation technologies for tungsten-tin copper-molybdenum-bismuth polymetallic ores.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0007] A beneficiation method for a tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore includes the following steps:

[0008] (1) The tungsten-tin copper-molybdenum-bismuth polymetallic ore is subjected to a first-stage grinding and gravity separation to obtain gravity concentrate and gravity tailings; after the tungsten-tin copper-molybdenum-bismuth polymetallic ore is ground into a first-stage rod mill, the content of the particle size with a grinding fineness of -0.075mm is 25% to 35%.

[0009] (2) The gravity concentrate is screened and classified to obtain undersize fine slurry and oversize coarse slurry; the oversize coarse slurry is ground and the grinding product is mixed with the undersize fine slurry to obtain a mixed slurry.

[0010] (3) The mixed slurry is subjected to mixed flotation of sulfide minerals to obtain mixed flotation concentrate and mixed flotation tailings; the mixed flotation concentrate is subjected to molybdenum, copper, bismuth metal and sulfur recovery; the mixed flotation tailings are subjected to tungsten and tin metal recovery.

[0011] The design concept of the above technical solution is to perform a coarse grinding on the raw tungsten-tin-copper-molybdenum-bismuth polymetallic ore, relying on the crushing and grinding action generated by "line contact" to crush the ore. The grinding process is selective, significantly reducing the over-crushing of tungsten and tin minerals caused by over-grinding. Under the condition that the content of the -0.075mm particle size is 25% to 35% after coarse grinding, a single gravity separation and tailings removal can achieve a high-efficiency enrichment ratio of 12 to 23 times for minerals such as tungsten, tin, copper, molybdenum, bismuth, and sulfur, and preferentially remove low-grade coarse-grained tailings with a yield of ≥90%, which greatly improves the flotation grade of sulfide ore while significantly reducing the investment and production energy consumption costs of beneficiation equipment such as flotation machines and shaking tables. The concentrate is then pre-classified and regrinded, which on the one hand solves the problem of... This technology solves the problem of high energy consumption per ton of grinding caused by the fine grinding of all raw ore in existing technologies. On the other hand, it also effectively avoids the problem of over-grinding and mud formation of tungsten and tin minerals due to excessive fine grinding, resulting in loss in tailings, low gravity separation recovery rate, and serious loss of valuable minerals. At the same time, this technology adopts a pre-classification-regrinding and re-concentration process for gravity separation concentrate after gravity separation. Considering the complex intergrowth relationship and uneven particle size of the minerals in the raw ore, this technology effectively reduces the amount of regrinding work and efficiently fine grinds the intergrowth minerals in the coarse-grained product after classification, improving their individual liberation degree while avoiding the over-grinding problem of tungsten and tin minerals with good liberation degree in the fine-grained product due to excessively long single fine grinding.

[0012] As a further preferred embodiment of the above technical solution, in step (2), the fineness of the undersize fine slurry is -0.075mm, and the fineness of the oversize coarse slurry after grinding is -0.075mm.

[0013] As a further preferred embodiment of the above technical solution, step (3) involves the following operations for recovering molybdenum, copper, bismuth and sulfur from the mixed flotation concentrate: performing molybdenum-suppressing, copper-bismuth-sulfur flotation on the mixed flotation concentrate to obtain molybdenum concentrate and copper-bismuth-sulfur mixed concentrate; performing copper-bismuth-sulfur flotation on the copper-bismuth-sulfur mixed concentrate to obtain sulfur concentrate and copper-bismuth mixed concentrate; and performing flotation separation on the copper-bismuth mixed concentrate to obtain copper concentrate and bismuth concentrate.

[0014] As a further preferred embodiment of the above technical solution, when performing copper-bismuth-sulfur mixed concentrate flotation for copper-bismuth and sulfur suppression, a pyrite inhibitor is added to the flotation system; the pyrite inhibitor comprises the following components in parts by weight: 50-75 parts sodium dimethyl dithiocarbamate, 10-15 parts pyrogallol and 10-15 parts polyacrylic acid. This preferred solution abandons the traditional method of using cyanide for sulfur suppression. Instead, it employs a novel and highly efficient combination inhibitor of sodium dimethyl dithiocarbamate, pyrogallic acid, and propylene carboxylic acid to suppress pyrite. The adsorption of polypropylene carboxylic acid masks the surface active potential of pyrite. Then, sodium dimethyl dithiocarbamate, a heavy metal ion chelating agent, is adsorbed onto the pyrite surface to form a hydrophilic dithiocarbamate, and pyrogallic acid forms a slightly water-soluble hydrophilic complex on the pyrite surface. This further expands the hydrophobic difference between pyrite and molybdenum-bismuth minerals, achieving highly efficient separation of molybdenum-bismuth and sulfur. This solution has advantages such as being environmentally friendly and having good copper-bismuth and sulfur separation performance.

[0015] As a further preferred embodiment of the above technical solution, when performing copper-bismuth-sulfur mixed concentrate flotation for copper-bismuth and sulfur suppression, at least one of sulfur-nitrogen collectors, ester collectors, and CYA collectors is used as the collector. The CYA collector comprises the following components in parts by weight: 40 parts of O-isopropyl-N-methylthiocarbamate, 30 parts of diesel oil, and 30 parts of MIBC; the modifier is one or a combination of mercapto compounds, sodium cyanurate, acetone cyanohydrin, activated carbon, carboxymethyl cellulose, sodium sulfite, water glass, zinc sulfate, and lime.

[0016] As a further preferred embodiment of the above technical solution, when performing flotation separation on the copper-bismuth mixed concentrate, a combined inhibitor is added to the flotation system. The combined inhibitor includes sodium sulfite and carboxymethyl cellulose, and the weight ratio of sodium sulfite to carboxymethyl cellulose in the combined inhibitor is (3-5):1.

[0017] As a further preferred embodiment of the above technical solution, when performing flotation separation on the copper-bismuth mixed concentrate, at least one of xanthate collectors, sulfur-nitrogen collectors, ester collectors, and CYA collectors is used as the collector. The CYA collector comprises the following components in parts by weight: 40 parts of O-isopropyl-N-methylthiocarbamate, 30 parts of diesel oil, and 30 parts of MIBC; at least one of BK205, MIBC, and terpineol is used as the frother; and at least one of carboxymethyl cellulose, sodium sulfide, sodium sulfite, humic acid, mercapto compounds, water glass, zinc sulfate, lime, and lead nitrate is used as the modifier.

[0018] As a further preferred embodiment of the above technical solution, in step (3), the mixed flotation tailings are subjected to strong magnetic separation to obtain tungsten concentrate and strong magnetic tailings, and the strong magnetic tailings are subjected to gravity separation to obtain tin concentrate, tin middlings and gravity separation tailings A; and the tin middlings are subjected to gravity separation to obtain tin secondary concentrate and gravity separation tailings B.

[0019] As a further preferred embodiment of the above technical solution, when performing strong magnetic separation on the mixed flotation tailings, the number of strong magnetic separations is 1 to 3 times, the number of scavenging separations is 1 to 3 times, and the magnetic field strength is 0.5T to 2.0T.

[0020] As a further preferred embodiment of the above technical solution, in step (3), when the mixed ore is subjected to sulfide ore flotation, non-polar hydrocarbon oil is used as a collector, at least one of BK205, MIBC and terpineol is used as a foaming agent, and at least one of phosphoroxane, mercapto compounds, sodium sulfide, water glass, sodium hexametaphosphate and lime is used as an inhibitor.

[0021] As a further preferred embodiment of the above technical solution, when the mixed ore is subjected to sulfide ore flotation, the number of flotation and cleaning cycles is 1 to 3 times, and the number of scavenging cycles is 1 to 3 times.

[0022] Compared with the prior art, the advantages of the present invention are as follows:

[0023] The mineral processing method of this invention employs a combination of flotation, gravity, and magnetic processes based on the characteristics of the target mineral to achieve efficient and economical recovery of tungsten, tin, copper, molybdenum, bismuth, and sulfur. This provides a new approach and strategy for the recovery and utilization of such polymetallic ores containing tungsten, tin, copper, molybdenum, and bismuth. It solves the problem of high energy consumption per ton of grinding caused by the excessive fine grinding of the raw ore in existing technologies. It avoids the over-grinding and mudding of tungsten and tin minerals due to excessive fine grinding, resulting in loss in tailings, low gravity separation recovery rates, and severe loss of valuable minerals. Addressing the complex intergrowth relationships and uneven particle size distribution of the minerals in the raw ore, this method effectively reduces the amount of regrinding required. It efficiently fine grinds the intergrowth minerals in the coarse-grained product after classification, improving their individual liberation degree while avoiding over-grinding of the well-liberated tungsten and tin minerals in the fine-grained product due to prolonged single-cycle fine grinding. Furthermore, this invention is environmentally friendly and has good copper-bismuth and sulfur separation indicators. The mineral processing method of this invention comprehensively recovers tungsten, tin, molybdenum, bismuth, and sulfur from tungsten-tin-copper-molybdenum-bismuth polymetallic ores, achieving the following recovery results: tungsten concentrate grade WO3 ≥ 60%, recovery rate WO3 ≥ 90%; tin concentrate grade Sn ≥ 65%, recovery rate Sn ≥ 80%; tin secondary concentrate grade ≥ 10%, recovery rate Sn ≥ 5%; copper concentrate grade Cu ≥ 30%, recovery rate Cu ≥ 40%; molybdenum concentrate grade Mo ≥ 45%, recovery rate Mo ≥ 30%; bismuth concentrate grade Bi ≥ 25%, recovery rate Bi ≥ 30%; and sulfur concentrate grade ≥ 46.5%, recovery rate S ≥ 30%. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0025] Figure 1 The process flow diagram is shown for the beneficiation method of tungsten-tin copper-molybdenum-bismuth polymetallic ore in Example 1. Detailed Implementation

[0026] The present invention will be further described in detail below with reference to specific embodiments.

[0027] Example 1

[0028] The beneficiation method for tungsten-tin-copper-molybdenum-bismuth polymetallic ore in this embodiment yields 0.42% WO3, 0.237% Sn, 0.52% sulfur, 0.071% bismuth, 0.015% molybdenum, and 0.026% copper in the processed ore. The ore contains a complex mineral composition. Tungsten minerals are primarily wolframite, with WO3 accounting for 91.9% of its content, and trace amounts of scheelite are also present. Tin minerals are mainly cassiterite, with Sn accounting for 94.9% of its content, and occasional scattered distributions of sterlingite. Bismuth minerals are present in low amounts, including native bismuth, bismuthite, basaltite, and bismuth sulfide. Other metal sulfides are mainly pyrite, followed by molybdenite, chalcopyrite, and pyrrhotite, with occasional marcasite, covellite, and sphalerite. Gangue minerals are predominantly quartz and topaz, followed by small amounts of mica (including muscovite, phlogopite, and sericite) and montmorillonite.

[0029] The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore in this embodiment is as follows: Figure 1 As shown, the specific steps include:

[0030] (1) Tungsten-tin copper-molybdenum-bismuth polymetallic ore was subjected to a first-stage rod mill to obtain a rod mill slurry with a grinding fineness of -0.075mm and a particle size content of 26%.

[0031] (2) The rod mill slurry was subjected to gravity separation using a spiral concentrator to obtain gravity concentrate and gravity tailings. The yield of gravity concentrate was 4.00%, of which the grades of WO3, Sn, Cu, Mo, Bi and S were 9.76%, 5.25%, 0.45%, 0.19%, 1.01% and 6.69%, respectively. The recovery rates of WO3, Sn, Cu, Mo, Bi and S were 92.95%, 88.61%, 69.23%, 50.67%, 56.90% and 51.46%, respectively. The yield of gravity tailings was 96.00%, and the gravity tailings were discharged into the tailings pond.

[0032] (3) The gravity concentrate is screened and classified to obtain undersize fine slurry (fineness of -0.075mm) and oversize coarse slurry.

[0033] (4) Grind the coarse slurry on the screen to obtain a two-stage grinding slurry, wherein the content of the grinding fineness of -0.075mm particles accounts for 50%.

[0034] (5) The two-stage grinding slurry is mixed with the undersize fine slurry to obtain a mixed slurry. The content of particles with a fineness of -0.075mm in the mixed slurry accounts for 60%.

[0035] (6) The mixed slurry was subjected to sulfide ore co-flotation (the process flow consisted of one roughing, one cleaning, and one scavenging; 10 g / t of a new high-efficiency sulfide ore collector CYA was added during the roughing; 7 g / t of copper sulfate activator and 3 g / t of collector CYA were added during the scavenging; blank cleaning was used for the cleaning), to obtain flotation concentrate and flotation tailings. The yield of flotation concentrate was 0.472%, and the grades of WO3, Sn, Cu, Mo, Bi, and S were 0.94%, 0.47%, 3.10%, 1.27%, 6.74%, and 44.14%, respectively. The recoveries of WO3, Sn, Cu, Mo, Bi, and S were 1.06%, 0.94%, and 56%, respectively. The yields of the mixed flotation tailings were 3.528%, with WO3, Sn, Cu, Mo, Bi, and S grades of 10.94%, 5.89%, 0.095%, 0.046%, 0.243%, and 1.68%, respectively. The recoveries of WO3, Sn, Cu, Mo, Bi, and S were 91.90%, 87.67%, 12.95%, 10.70%, 12.09%, and 11.40%, respectively.

[0036] (7) The mixed flotation tailings were subjected to strong magnetic separation using a ZH-560 industrial strong magnetic separator (the process flow consists of one roughing, one scavenging and one cleaning, with the middlings from the cleaning and the scavenging concentrate returned to the roughing operation section) to obtain strong magnetic concentrate (wolfonate concentrate) and strong magnetic tailings. The yield of the strong magnetic concentrate was 0.63%, the WO3 grade was 60.27%, and the WO3 recovery rate was 90.41%. The yield of the strong magnetic tailings was 2.898%, the Sn grade was 7.07%, and the Sn recovery rate was 86.48%.

[0037] (8) The strong magnetic tailings were subjected to gravity separation using a shaking table to obtain tin concentrate, tin middlings and gravity separation tailings A. The yield of tin concentrate was 0.29%, the Sn grade was 66.02% and the Sn recovery rate was 80.78%. The yield of tin middlings was 0.45%, the Sn grade was 2.49% and the Sn recovery rate was 4.73%. The yield of gravity separation tailings A was 2.158%, and the WO3 and Sn grades were 0.214% and 0.106%, respectively.

[0038] (9) The tin ore is subjected to gravity separation to obtain tin secondary concentrate and gravity separation tailings B. The yield of tin secondary concentrate is 0.10%, the Sn grade is 8.19%, the Sn recovery rate is 3.46%, and the yield of gravity separation tailings B is 0.35%, the Sn grade is 0.86%.

[0039] (10) After regrinding the mixed flotation concentrate from step (6) to a fineness of -0.075mm with a particle size of 97.17%, prioritize the flotation of molybdenum, copper, bismuth, and sulfur (the process includes one roughing, one scavenging, and three cleaning processes; the middlings from the cleaning process are returned sequentially, and the scavenging concentrate is returned to the roughing process; in the roughing process, 35g / t of sodium sulfide inhibitor, 1.03g / t of kerosene collector, and 2g / t of frother are added). # Oil 0.16 g / t; the amount of sodium sulfide inhibitor added in the first to third cleaning processes were 2.96 g / t, 1.18 g / t, and 0.59 g / t, respectively; mercapto compound 10 g / t per cleaning; kerosene collector 0.34 g / t and foaming agent 2 g / t were added during scavenging. # The oil yield was 0.16 g / t, and the concentrate consisted of molybdenum concentrate and copper-bismuth-sulfur mixed concentrate. The molybdenum concentrate yield was 0.01%, the Mo grade was 45.24%, and the Mo recovery rate was 30.16%. The copper-bismuth-sulfur mixed concentrate yield was 0.462%, and the Cu, Mo, Bi, and S grades were 3.16%, 0.318%, 6.88%, and 44.33%, respectively. The Cu, Mo, Bi, and S recoveries were 56.22%, 9.80%, 44.75%, and 39.38%, respectively.

[0040] (11) The copper-bismuth-sulfur mixed concentrate is subjected to copper-bismuth flotation and sulfur suppression (the process includes one roughing and two cleaning processes, with middlings returned sequentially; during the roughing process, 14.2 g / t of calcium oxide, 14 g / t of activated carbon, 7.96 g / t of new high-efficiency pyrite inhibitor CYT-12, 1.18 g / t of collector CYA, and 2 g / t of frother are added). # The oil content was 0.33 g / t. The amount of inhibitor CYT-12 added in the first and second beneficiations was 2.96 g / t and 1.18 g / t, respectively. A mixed concentrate of sulfur concentrate and copper-bismuth concentrate was obtained. The yield of sulfur concentrate was 0.34%, the sulfur grade was 46.55%, and the sulfur recovery rate was 30.44%. The yield of copper-bismuth concentrate was 0.122%, the Cu and Bi grades were 11.01% and 24.54%, respectively, and the Cu and Bi recoveries were 51.64% and 42.16%, respectively.

[0041] (12) The copper-bismuth mixed concentrate is subjected to copper flotation and bismuth suppression separation (the process includes one roughing and two cleaning processes, with the middlings from the cleaning process returned sequentially; the inhibitor CY-2 is used in the roughing, first cleaning, and second cleaning processes). # Using 5.15 g / t, 1.45 g / t, and 1.05 g / t respectively, copper concentrate and bismuth concentrate were obtained. The yield of copper concentrate was 0.034%, the grade of Cu was 30.85%, and the recovery rate of Cu was 40.34%. The yield of bismuth concentrate was 0.088%, the grade of Bi was 25.45%, and the recovery rate of Bi was 31.54%.

[0042] Comparative Example 1

[0043] The beneficiation method for tungsten-tin-copper-molybdenum-bismuth polymetallic ore in this comparative example uses the same raw ore as in Example 1, employing a conventional flotation-gravity-magnetic separation process for flotation recovery. Specifically, it includes the following steps:

[0044] (1) Tungsten-tin copper-molybdenum-bismuth polymetallic ore was subjected to a first-stage rod milling to obtain a rod milling slurry with a grinding fineness of -0.075mm particle size of 50%.

[0045] (2) The rod mill slurry was subjected to sulfide ore mixed flotation (the process flow is one roughing, four cleaning, and one scavenging process; the roughing process adds a combination collector of butyl xanthate + ethyl thiocyanate 20 + 10 g / t; the scavenging process adds an activator of copper sulfate 100 g / t; the collector is butyl xanthate + ethyl thiocyanate 10 + 5 g / t; the cleaning process uses water glass + aluminum sulfate as the depressant; the first cleaning process uses water glass + aluminum sulfate 200 + 40 g / t; the second cleaning process uses water glass + aluminum sulfate 100 + 20 g / t; the third cleaning process uses water glass + aluminum sulfate 50 + 10 g / t; and the fourth cleaning process uses water glass + aluminum sulfate 50 + 10 g / t) to obtain a mixed flotation concentrate (yield 1.54%, WO3, Sn, Cu, Mo, Bi, and S grades 1.42%). The grades of WO3, Sn, Cu, Mo, Bi, and S were 1.27%, 0.68%, 0.38%, 1.92%, and 16.04%, with recoveries of WO3, Sn, Cu, Mo, Bi, and S of 5.21%, 8.25%, 40.21%, 38.59%, 41.56%, and 47.50%, respectively. The mixed flotation tailings had a yield of 98.46%, with grades of WO3, Sn, Cu, Mo, Bi, and S of 0.40%, 0.22%, 0.016%, 0.009%, 0.042%, and 0.28%, and recoveries of WO3, Sn, Cu, Mo, Bi, and S of 94.79%, 91.75%, 59.79%, 61.41%, 58.44%, and 52.50%, respectively.

[0046] (3) After regrinding the mixed flotation concentrate to a fineness of -0.075mm with a particle size of 96.83%, prioritize the flotation of molybdenum, copper, bismuth, and sulfur (the process flow is one roughing, one scavenging, and four cleaning processes; the roughing process adds 45g / t of sodium sulfide inhibitor, 4.00g / t of kerosene collector, and 2g / t of frother). # Oil 0.40 g / t, sodium sulfide inhibitor added in the first to fourth cleaning processes is 8.87 g / t, 3.48 g / t, 1.52 g / t and 0.86 g / t respectively, mercapto compound dosage in the first to fourth cleaning processes is 10 g / t per cleaning, middlings are returned sequentially in the cleaning process, kerosene collector 1 g / t and frother 2 g / t are added in the scavenging process. #Oil 0.30 g / t, scavenged concentrate returned to roughing operation), to obtain molybdenum concentrate (yield 0.010%, Mo grade 32.45%, Mo recovery 21.63%) and copper-bismuth-sulfur mixed concentrate (yield 1.53%, Cu, Mo, Bi, S grades 0.68%, 0.166%, 1.93%, 15.95%, Cu, Mo, Bi, S recoveries 40.13%, 16.95%, 41.48%, 46.92%).

[0047] (4) The copper-bismuth-sulfur mixed concentrate is subjected to preferential copper flotation and bismuth-sulfur suppression (the process flow is one roughing and four cleaning processes; the roughing process adds 50 g / t of calcium oxide and 20 g / t of activated carbon, 20.5 g / t of the new high-efficiency pyrite inhibitor CYT-12, and 30 g / t of sodium sulfite, and collector Z). 200 The amount of calcium oxide and sodium sulfite added during the first to fourth beneficiation processes was 10.33 + 10.33 g / t, 5.02 + 5.02 g / t, and 2.15 + 2.15 g / t, respectively (mid-ore was returned in sequence after beneficiation). This yielded a general concentrate (yield of 0.02%, Cu grade of 15.12%, Cu recovery of 11.63%) and a bismuth-sulfur mixed concentrate (yield of 1.51%, Bi and S grades of 1.95% and 15.86%, respectively, Bi and S recovery rates of 41.48% and 46.05%, respectively).

[0048] (5) The bismuth-sulfur mixed concentrate is subjected to bismuth-sulfur separation (the process flow is one roughing, one scavenging, and three cleaning processes; the roughing process adds 40 g / t of sodium carbonate as a modifier, 5.16 g / t of pyrite inhibitor CYT-12, 2.52 g / t of collector ethyl xanthate, and 2 g / t of frother). # Oil 0.20g / t, scavenging agent ethyl xanthate 0.52g / t, foaming agent 2 # The oil was 0.10 g / t. Blank cleaning was used for the first to third cleanings, and the ore was returned sequentially from the cleanings. Bismuth concentrate (yield of 0.12%, Bi grade of 17.01%, Bi recovery rate of 28.76%) and bismuth-sulfur separation tailings (yield of 1.39%, Bi and S grades of 0.65% and 15.06% respectively, Bi and S recovery rates of 12.73% and 40.25% respectively) were obtained.

[0049] (6) The bismuth-sulfur separation tailings are subjected to flotation (the process adopts a one-roughing-three-cleansing method, with copper sulfate 3.25 g / t as the roughing activator, pentyl xanthate 1.23 g / t as the collector, and frother 2...). # Oil 0.10g / t, blank cleaning was used for the first to third cleanings, and the middle ore was returned sequentially in the cleaning process, to obtain sulfur concentrate (yield of 0.52%, S grade of 35.53%, S recovery rate of 35.53%).

[0050] (7) The mixed tailings from step (2) are subjected to shaking table gravity separation of tungsten and tin to obtain tungsten-tin mixed concentrate (yield 0.92%, WO3 and Sn grades 30.27% and 15.45% respectively, WO3 and Sn recovery rates 69.95% and 65.37% respectively).

[0051] (8) The tungsten-tin mixed concentrate was separated by strong magnetic separation using a ZH-560 industrial strong magnetic separator with a magnetic field strength of 1.5T. Tungsten concentrate (strong magnetic concentrate, yield 0.53%, WO3 grade 50.27%, WO3 recovery rate 66.92%) and tin concentrate (strong magnetic tailings, yield 0.39%, Sn grade 34.92%, Sn recovery rate 62.64%) were obtained.

[0052] The above description is merely a preferred embodiment of the present invention, and the scope of protection of the present invention is not limited to the above embodiments. For those skilled in the art, improvements and modifications obtained without departing from the inventive concept should also be considered within the scope of protection of the present invention.

Claims

1. A beneficiation method for a tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore, characterized in that, Includes the following steps: (1) The tungsten-tin copper-molybdenum-bismuth polymetallic ore is subjected to a first-stage grinding and gravity separation to obtain gravity concentrate and gravity tailings; after the first-stage grinding, the content of the tungsten-tin copper-molybdenum-bismuth polymetallic ore with a grinding fineness of -0.075mm is 25% to 35%. (2) The gravity concentrate is screened and classified to obtain undersize fine slurry and oversize coarse slurry; the oversize coarse slurry is subjected to two-stage grinding, and the product of the two-stage grinding is mixed with the undersize fine slurry to obtain a mixed slurry. (3) The mixed slurry is subjected to mixed flotation of sulfide minerals to obtain mixed flotation concentrate and mixed flotation tailings; the mixed flotation concentrate is subjected to molybdenum, copper, bismuth metal and sulfur recovery; the mixed flotation tailings are subjected to tungsten and tin metal recovery.

2. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to claim 1, characterized in that, In step (2), the fineness of the undersize fine slurry is -0.075 mm, and the fineness of the oversize coarse slurry after two-stage grinding is -0.075 mm.

3. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to claim 1, characterized in that, In step (3), the recovery of molybdenum, copper, bismuth metals and sulfur from the mixed flotation concentrate includes the following operations: the mixed flotation concentrate is subjected to molybdenum-suppressed copper-bismuth-sulfur flotation to obtain molybdenum concentrate and copper-bismuth-sulfur mixed concentrate; the copper-bismuth-sulfur mixed concentrate is subjected to copper-bismuth-suppressed sulfur flotation to obtain sulfur concentrate and copper-bismuth mixed concentrate; the copper-bismuth mixed concentrate is subjected to flotation separation to obtain copper concentrate and bismuth concentrate.

4. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to claim 3, characterized in that, When performing copper-bismuth-sulfur mixed concentrate flotation for copper-bismuth and sulfur suppression, pyrite inhibitor is added to the flotation system; the pyrite inhibitor comprises the following components in parts by weight: 60-70 parts sodium dimethyl dithiocarbamate, 25-30 parts pyrogallol and 5-10 parts polyacrylic acid.

5. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to claim 3, characterized in that, When performing copper-bismuth-sulfur mixed concentrate flotation for copper-bismuth and sulfur suppression, the collector includes CYA collector, which comprises the following components in parts by weight: 40 parts O-isopropyl-N-methylthiocarbamate, 30 parts diesel oil, and 30 parts MIBC; the modifier is one or a combination of mercapto compounds, sodium cyanate, acetone cyanohydrin, activated carbon, carboxymethyl cellulose, sodium sulfite, water glass, zinc sulfate, and lime.

6. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to claim 3, characterized in that, When performing flotation separation on the copper-bismuth mixed concentrate, a combined inhibitor is added to the flotation system. The combined inhibitor includes sodium sulfite and carboxymethyl cellulose, and the weight ratio of sodium sulfite to carboxymethyl cellulose in the combined inhibitor is (3-5):

1.

7. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to claim 3, characterized in that, When performing flotation separation on the copper-bismuth mixed concentrate, at least one of xanthate collectors, sulfur-nitrogen collectors, ester collectors, and CYA collectors is used as the collector. The CYA collector comprises the following components in parts by weight: 40 parts of O-isopropyl-N-methylthiocarbamate, 30 parts of diesel oil, and 30 parts of MIBC. At least one of BK205, MIBC, and terpineol is used as the frother, and at least one of carboxymethyl cellulose, sodium sulfide, sodium sulfite, humic acid, mercapto compounds, water glass, zinc sulfate, lime, and lead nitrate is used as the modifier.

8. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to any one of claims 1-6, characterized in that, In step (3), the recovery of tungsten and tin metals from the mixed flotation tailings includes the following operations: the mixed flotation tailings are subjected to strong magnetic separation to obtain black tungsten concentrate and strong magnetic tailings; the strong magnetic tailings are subjected to gravity separation to obtain tin concentrate, tin middlings and gravity separation tailings A; and the tin middlings are subjected to gravity separation to obtain tin secondary concentrate and gravity separation tailings B.

9. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to claim 7, characterized in that, When performing high-gradient magnetic separation on the mixed flotation tailings, the number of times the strong magnetic separation is selected is 1 to 3 times, the number of times the scavenging is 1 to 3 times, and the magnetic field strength is 0.5T to 2.0T.

10. The beneficiation method for tungsten-tin-containing copper-molybdenum-bismuth polymetallic ore according to any one of claims 1-6, characterized in that, In step (3), when the mixed ore is subjected to sulfide flotation, non-polar hydrocarbon oil is used as a collector, at least one of BK205, MIBC and terpineol is used as a foaming agent, and at least one of phosphoroxane, mercapto compounds, sodium sulfide, water glass, sodium hexametaphosphate and lime is used as an inhibitor.

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