Beneficiation method for intensively recovering tungsten and fluorite in sulphide ore flotation tailings

Abstract

The invention discloses a beneficiation method for intensively recovering tungsten and fluorite in sulphide ore flotation tailings, which comprises the following steps: aiming at the sulphide ore flotation tailings with high pyrrhotite content, before scheelite and wolframite flotation, intensively floating and recovering pyrrhotite which is difficult to float, reducing the sulfur content in floating tungsten feed to be about 0.05 percent, and recovering the tungsten and fluorite in the sulphide ore flotation tailings; the influence of sulfide minerals on the tungsten flotation process is eliminated, the obtained tungsten concentrate continues to be subjected to flotation, and in the flotation process, the flotation process aims at sulfide ore flotation tailings which are fine in fluorite dissemination particle size, low in flotation feeding fluorite dissociation degree, high in content of calcium gangue minerals, silicate minerals, mica and the like and extremely complex in gangue components. Fluorite minerals subjected to monomer dissociation are subjected to selective trapping and selective inhibition recovery, fluorite intergrowth minerals are subjected to reinforced flotation, selective ore grinding and reinforced gangue mineral inhibition separation, and tungsten concentrate and fluorite concentrate with high grade and high recovery rate can be obtained.

Description

Technical Field

[0001] The invention belongs to the technical field of mineral processing and flotation, and in particular relates to a mineral processing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings. Background Art

[0002] Sulfide ore flotation tailings from a large concentrator in Hunan 3 The content is about 0.40%, S content is 0.3-0.5%, CaF 2 Content 16-22%, CaCO 3 The content is 5-25%. The on-site process of preferential tungsten flotation-fluorite flotation recovery is adopted. The flotation tungsten sorting process is one rough, two fine and two sweeping to obtain tungsten concentrate WO 3 Grade ≥30%, WO 3 The recovery rate is about 73%; the fluorite flotation separation process is one coarse six fine one sweep, and the fluorite concentrate CaF 2 Grade 87%, CaF 2 The recovery rate is about 65%.

[0003] The above main process has the following problems: (1) Since the sulfide ore flotation tailings contain high levels of pyrrhotite (S ≥ 0.3%), it is easy to be enriched in the tungsten concentrate during the tungsten ore flotation process, resulting in the sulfur content (≥ 8%) in the tungsten concentrate seriously exceeding the standard, affecting the grade and sales of tungsten concentrate. Pyrrhotite and scheelite in the ore pulp compete strongly for the adsorption of tungsten collectors, resulting in increased flotation agent consumption, a significant increase in the cost per ton of ore dressing, and affecting WO 3 Recovery rate.

[0004] (2) The tailings contain a large amount of calcite, and the Ca contained in its crystal lattice is 2+ The active sites are the same as those of scheelite and fluorite, and the three have surface mutual conversion behavior in the solution, which leads to the convergence of the physical and chemical properties of the mineral surface and similar floatability. In addition, in the geological mineralization process, the three minerals are closely associated, making flotation separation extremely difficult.

[0005] (3) Fluorite minerals in tailings have coarse-grained structures, fine-grained structures and micro-grained structures, with particle sizes ranging from 0.03 to 0.30 mm. Some of them are disseminated in the basement composed of garnet, quartz, feldspar, mica and calcite. In the densely disseminated areas, the volume content of fluorite is usually between 30% and 50%, while that of sparsely disseminated areas is usually below 30%. Moreover, as the density of disseminated areas decreases, the dispersion of fluorite increases, and most of the particle sizes tend to become finer, and some parts are even less than 5%, transitioning to scattered disseminated areas. The above situation leads to large differences in the dissociation degree of fluorite monomers in the tailings. The one-stage grinding process used on site cannot achieve the monomer dissociation of fine-crystalline and microcrystalline fluorite, and it is difficult to obtain high-quality fluorite concentrate products. If the second-stage pre-selection fine grinding is added, although the monomer dissociation degree of fine-crystalline and microcrystalline fluorite can be improved, it is easy to cause over-crushing and mudification of coarse-crystalline fluorite and brittle and easily over-grinded minerals such as scheelite and calcite, which will deteriorate the flotation indicators of tungsten ore and fluorite, and increase the grinding cost, which is not conducive to energy saving and consumption reduction, cost reduction and efficiency improvement of the concentrator.

[0006] Chinese patent document CN 202111494659.3 discloses a beneficiation method for polymetallic associated fluorite ore using fractional flotation-step suppression. At the front end of fluorite flotation, fluorite with relatively good endowment and fluorite with relatively poor endowment are separated and flotated to obtain high-grade fluorite concentrate and low-grade fluorite concentrate respectively. Although this process improves the fluorite flotation efficiency to a certain extent, it has poor calcium suppression effect for high-calcite floating sulfur tailings, especially when CaCO 3 :CaF 2 When the value is ≥1, the calcite content in the fluorite concentrate will increase significantly, affecting the CaF 2 In actual production, it is difficult to obtain qualified high-quality fluorite concentrate products stably. In addition, although the high-gradient strong magnetic separation of the flotation foam can remove some magnetic gangue and intergrowth that interfere with subsequent selection operations, the yield of strong magnetic tailings is high at this time, and CaF 2 The grade is low, and the subsequent classification and regrinding energy consumption cost is high; at the same time, low-grade fluorite is fed into the flotation feed CaF 2 The low grade results in the low grade and poor grade of the produced low-grade fluorite concentrate, which can only be sold or used in the form of blending, which is not conducive to the rationalization of the company's economic benefits.

[0007] Therefore, for the sulfide ore flotation tailings with high pyrrhotite content (S≥0.3%), fine fluorite embedded particle size, low flotation feed fluorite dissociation degree, high content of calcium gangue minerals, silicate minerals and mica, and extremely complex gangue components, it is urgent to invent a new economical, efficient, green and environmentally friendly mineral processing technology to break through the shackles and bottlenecks of current mineral processing technology and realize the efficient and economical comprehensive utilization of mineral resources for this type of mining enterprises. Summary of the invention

[0008] In order to overcome the problems in the prior art, the present invention provides a mineral processing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings, which significantly improves the comprehensive utilization rate of mineral resources such as tungsten and fluorite.

[0009] In order to solve the above technical problems, the technical solution proposed by the present invention is: The present invention provides a ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings, comprising the following steps: S1. Add flotation agent A to the sulfide ore flotation tailings, stir thoroughly, and then perform pyrrhotite enhanced flotation roughing to obtain enhanced flotation tailings.

[0010] S2. Add flotation agent B to the enhanced flotation tailings and stir them thoroughly, then carry out black and white tungsten mixed flotation roughing to obtain black and white tungsten mixed rough concentrate and flotation tungsten roughing tailings.

[0011] S3, adding the black and white tungsten mixed rough concentrate obtained in step S2 to flotation reagent C for at least one concentration to obtain tungsten concentrate.

[0012] S4, adding flotation reagent D to the rough tungsten flotation tailings obtained in step S2 for at least one scavenging to obtain tungsten flotation tailings.

[0013] S5, adding flotation agent E to the floating tungsten tailings obtained in step S4, stirring the mixture sufficiently, and then performing rough flotation of fluorite to obtain rough fluorite concentrate and rough fluorite tailings.

[0014] S6. After adding reagents to the fluorite rougher tailings obtained in step S5 for scavenging, the scavenging concentrate and the first-stage flotation tailings are obtained. The fluorite rougher concentrate is further refined for at least 3 times to obtain fluorite concentrate and refined middlings. The fluorite concentrate is subjected to strong magnetic separation to remove impurities, and the non-magnetic product is a first-stage high-quality fluorite concentrate.

[0015] S7, the scavenged concentrate obtained in step S6, the selected middlings obtained by secondary selection of the fluorite coarse concentrate, and the magnetic products obtained by strong magnetic separation and impurity removal of the fluorite concentrate are classified through a cyclone to obtain classified overflow slurry.

[0016] S8, after concentrating the classified overflow pulp obtained in step S7, adding reagents and stirring sufficiently, performing second-stage flotation roughing of fluorite to obtain second-stage fluorite rough concentrate.

[0017] S9, beneficiating the second-stage fluorite coarse concentrate obtained in step S8 at least three times to obtain a second-stage fluorite concentrate.

[0018] In the present invention, for the flotation tailings of sulfide ores with high pyrrhotite content, the pyrrhotite which is difficult to float is firstly subjected to enhanced flotation recovery before the flotation of black and white tungsten, so as to reduce the sulfur content in the flotation tungsten feed to about 0.05%. Since the influence of sulfide minerals on the flotation process of tungsten is eliminated, the sulfur content in the obtained tungsten concentrate is reduced from 5-10% to ≤1%, and WO 3 The recovery rate increased from about 73% to about 82%, and the recovery rate of tungsten concentrate was greatly improved. For the flotation tailings of sulfide ores with fine fluorite distribution, low fluorite dissociation degree of flotation feed, high content of calcium gangue minerals, silicate minerals and mica, and extremely complex gangue components, the fluorite minerals that have been dissociated from the monomers are selectively captured and selectively suppressed for recovery, and the fluorite conjoined minerals are enhanced by flotation, selective grinding and enhanced suppression and separation of gangue minerals. The first-grade fluorite concentrate grade CaF 2 ≥97%, recovery rate CaF 2 ≥60%, second stage fluorite concentrate grade ≥93%, recovery rate CaF 2 ≥25%, fluorite comprehensive concentrate grade ≥95%, recovery rate CaF 2 ≥85%. In the prior art, conventional fluorite flotation methods are used to treat this type of tailings, and the grade of the obtained fluorite concentrate is only 87%, and the recovery rate is only about 65%.

[0019] As an optional embodiment, in the method provided by the present invention, in step S1, after the pyrrhotite enhanced flotation roughing, a pyrrhotite rough concentrate is obtained, and after the pyrrhotite rough concentrate is subjected to 1-3 times of concentrating, a pyrrhotite concentrate and a concentrating middling are obtained, and the concentrating middling is sequentially returned to the previous flotation operation.

[0020] As an optional implementation, in the method provided by the present invention, in step S3, after concentration, concentrated middlings are obtained, and the concentrated middlings are sequentially returned to the previous flotation operation.

[0021] As an optional implementation, in the method provided by the present invention, in step S4, scanned and selected ore is obtained after scanning, and the scanned and selected ore is sequentially returned to the previous flotation operation.

[0022] As an optional embodiment, in the method provided by the present invention, in step S7, classified sand is also obtained after classification, and the classified sand slurry is ground to obtain fine-ground slurry, so that the dissociation degree of fluorite monomer in the fine-ground slurry is ≥80%, and the fine-ground slurry is returned to the classification operation to form a closed-loop process.

[0023] As an optional embodiment, in the method provided by the present invention, in step S1, the flotation agent A contains an activator, and the activator is selected from two or more of ammonium fluorosilicate, ammonium persulfate, oxalic acid, sulfuric acid, copper sulfate, and ammonium chloride.

[0024] For the flotation tailings of sulfide ores with high pyrrhotite content, the composite pyrrhotite high-efficiency activator YH is used for deep activation and cleaning. Through the preparation of the above activator, Fe(OH) generated on the surface of pyrrhotite minerals due to severe oxidation can be removed. 3 , FeO(OH) hydrophilic layer, and eliminate Ca in the slurry by complexation 2+ The deterioration effect of Cu 2+ It provides favorable conditions for the formation of active sites on the surface of pyrrhotite, thereby significantly improving the floatability of pyrrhotite.

[0025] As an optional embodiment, in the method provided by the present invention, in step S1, the flotation reagent A is prepared from an activator, isopentyl xanthate and butyl ammonium black medicine in a mass ratio of 300-350:10-12:10-12.

[0026] As an optional embodiment, in the method provided by the present invention, the flotation reagent B contains a composite tungsten ore collector, and the composite tungsten ore collector is composed of salicylic acid, styrenephosphonic acid and benzoic acid.

[0027] The present invention adopts a composite tungsten ore collector for roughing and collecting, which is composed of salicylic acid, styrene phosphonic acid and benzoic acid hydroxamic acid, so that it has good selectivity and strong collecting ability for wolframite and scheelite, greatly improving WO 3 Recovery rate.

[0028] As an optional embodiment, in the method provided by the present invention, in step S3, the flotation reagent B is composed of sodium carbonate, salinized water glass, lead nitrate, a composite tungsten ore collector and 2# oil.

[0029] 2 of the present invention # Oil is a commonly used and effective foaming agent in the mineral processing industry and is a common commercially available substance.

[0030] As an optional embodiment, in the method provided by the present invention, in step S3, the flotation reagent C is salinized water glass, and the salinized water glass is Al 2 (SO) 4 It is prepared with water glass in a mass ratio of 1:10-1:2.

[0031] In the present invention, salted water glass is added to the black and white tungsten mixed rough concentrate to inhibit calcium-containing gangue and realize the flotation process of black and white tungsten.

[0032] As an optional embodiment, in the method provided by the present invention, in step S4, the flotation reagent D is composed of a composite tungsten ore collector and 2 #The composite tungsten ore collector is composed of salicylic acid, styrene phosphonic acid and benzoic acid.

[0033] As an optional embodiment, in the method provided by the present invention, in step S5, the flotation agent E is composed of sodium carbonate, water glass and fluorite collector, the fluorite collector is composed of sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate and tall oil, and the weight ratio of the sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate and tall oil is 4-8:0.5-1:0.5-1:1-2.

[0034] The present invention adopts a selectively compounded fluorite collector YZ-01 with good selectivity and strong collecting ability, that is, the above-mentioned flotation agent E, which can preferentially collect fluorite minerals with high monomer dissociation degree, good floatability and fast floating rate, thereby realizing the selective recovery of fluorite monomer minerals.

[0035] As an optional embodiment, in the method provided by the present invention, in step S6, during the selection process, the inhibitor used in the third or more selection processes is selected from two or more of acidified water glass, ethylenediaminetetramethylenephosphonic acid, tannin, and guar gum.

[0036] The present invention adopts a highly efficient inhibitor YY, i.e. the above inhibitor combination, and utilizes the synergistic effect of organic matter (ethylenediaminetetramethylenephosphonic acid, guar gum) and inorganic matter (acidified water glass) to target and inhibit calcite, significantly enlarge the hydrophobicity difference between fluorite and calcite, and successfully solve the technical difficulty in the industry of flotation separation of high-calcium fluorite.

[0037] As an optional embodiment, in the method provided by the present invention, in step S8, the reagent added to the fluorite roughing tailings is selected from two or more of ammonium chloride, sodium fluoride, sodium monofluorophosphate, and calcium chloride.

[0038] In the second stage roughing process of fluorite, adding fluorite activator YH-50, which is a combination of two or more of ammonium chloride, sodium fluoride, sodium monofluorophosphate and calcium chloride, can activate the surface of fluorite minerals with suppressed floatability and fluorite intergrowths with slow floating rate, greatly reducing the CaF 2 content and improve the comprehensive recovery rate of fluorite.

[0039] As an optional embodiment, in the method provided by the present invention, in step S6, the strong magnetic separation equipment used in the strong magnetic separation is a high gradient strong magnetic separator or a superconducting magnetic separator, and the magnetic field strength is 1.0T-5.0T.

[0040] As an optional embodiment, in the method provided by the present invention, the WO in the sulfide ore flotation tailings 3Content ≥ 0.10%, S ≥ 0.3%, CaF 2 Content ≥15%, CaCO 3 The content is 5-25%; the dissociation degree of fluorite monomer in the sulfide ore flotation tailings is ≥70%.

[0041] Compared with the prior art, the present invention has the following beneficial effects: (1) In the present invention, for the flotation tailings of sulfide ores with high pyrrhotite content (S≥0.3%), the activator in the reagent system is cleverly used to deeply activate the pyrrhotite before the flotation of black and white tungsten, and the pyrrhotite that is difficult to float is enhanced by flotation recovery, and the sulfur content in the flotation tungsten feed ore is reduced to about 0.05%, thereby eliminating the influence of sulfide minerals on the flotation process of tungsten. The dissociation degree characteristics of fluorite are used to carry out step-by-step enhanced flotation, and the selection differences of complex gangue minerals are used to carry out asynchronous separation and recovery, thereby achieving efficient recovery of low-grade, complex and difficult-to-separate associated fluorite resources, having significant economic benefits, and providing a new approach and idea for the comprehensive utilization of the same type of fluorite resources.

[0042] (2) The present invention utilizes the difference in fluorite flotation rate to preferentially capture coarse-grained fluorite minerals with high monomer dissociation degree in the flotation tailings of sulfide ore, and selects fluorite by flotation-magnetization process to obtain CaF 2 Grade> 97%, meeting the FC-97A quality requirements of the fluorite industry standard (YB / T 5217-2005) of the first-stage fluorite concentrate product; for fluorite minerals whose surface is contaminated by reagents and whose floatability is greatly reduced, and fine-grained and microcrystalline fluorite intergrowths with slow floating rate and low monomer dissociation degree, deep activation is carried out to greatly improve their floatability and significantly reduce CaF 2 content and improve the comprehensive recovery rate of fluorite.

[0043] (3) The present invention classifies the scavenging concentrate, the first-stage concentrate 2 middlings and the strong magnetic separation magnetic products, etc., and only finely grinds the obtained sediment, which greatly reduces the amount of regrinding feed and effectively avoids the over-powdering of fluorite and the mudification of gangue, which is conducive to obtaining CaF 2 Flotation index of grade >93%. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0045] Figure 1 is a process flow chart of the present invention; Figure 2 This is the process flow chart of Comparative Example 1. DETAILED DESCRIPTION

[0046] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and meticulously below in conjunction with the accompanying drawings and preferred embodiments of the present invention, but the protection scope of the present invention is not limited to the following specific embodiments.

[0047] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0048] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0049] Example 1 The sulfide ore flotation tailings WO 2 were processed by a large ore dressing plant in Hunan Province. 3 Content 0.40%, S content 0.35%, CaF 2 Content 20.15%, CaCO 3 The content is 22.45%. The main metal minerals in the tailings are scheelite, followed by pyrrhotite and wolframite, with occasional bismuthite, pyrite, cassiterite and magnetite; non-metallic minerals are mainly fluorite and calcite, followed by garnet, quartz and a small amount of pyroxene, amphibole, chlorite, etc.

[0050] Use Figure 1 The specific steps of the mineral processing method shown are as follows: (1) Add 3000 g / t of activator YH (sulfuric acid, oxalic acid, copper sulfate, and sodium fluorosilicate prepared in a mass ratio of 7:1:0.5:1.5) and 100 g / t+100 g / t of isopentyl xanthate and 100 g / t of butyl ammonium black powder to the sulfide ore flotation tailings of the concentrator. After sufficient stirring and a rough selection, pyrrhotite rough concentrate and enhanced flotation tailings are obtained.

[0051] (2) The pyrrhotite rough concentrate was subjected to four flotation separations. Water glass of 100 g / t, 50 g / t, 30 g / t and 30 g / t was added to the concentrates 1 to 4, respectively, to obtain pyrrhotite concentrate and concentrated middlings. The concentrated middlings were returned to the previous flotation process in sequence. The pyrrhotite concentrate yield was 0.98%, the S grade was 32.45% and the S recovery rate was 91.46%.

[0052] (3) Add 1000g / t sodium carbonate and salinized water glass (Al 2 (SO)4 :water glass = 1:6) 1000g / t, lead nitrate 800g / t, composite tungsten ore collector (prepared by salicylic hydroxamic acid, styrene phosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5) 1000g / t and 2 # Oil 30g / t, after fully stirring, black and white tungsten mixed flotation roughing is carried out to obtain black and white tungsten mixed rough concentrate and flotation tungsten roughing tailings.

[0053] (4) The black and white tungsten mixed rough concentrate is refined 4 times, and saline water glass (Al2O3) is added to refine 1 to refine 4 in sequence. 2 (SO) 4 :water glass = 1:6) 500g / t, 400g / t, 300g / t, 200g / t, tungsten concentrate and selected middlings are obtained, and the selected middlings are returned to the previous flotation operation in sequence. The yield of tungsten concentrate is 0.94%, WO 3 Grade 36.32%, WO 3 The recovery rate is 85.52%, and the S grade of tungsten concentrate is 0.70%.

[0054] (5) The rough tailings of black and white tungsten mixed flotation are subjected to two scavenging processes. The reagent systems for scavenging one and two are as follows: composite tungsten collector (prepared with salicylic acid, styrene phosphonic acid and benzoic acid in a mass ratio of 0.2:4:5) 300g / t, 2 # Oil 15g / t and composite tungsten ore collector (prepared with salicylic hydroxamic acid, styrene phosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5) 150g / t, 2 # Oil is 10g / t, and scavenging ore and floating tungsten tailings are obtained. The scavenging ore is returned to the previous flotation operation in sequence.

[0055] (6) Sodium carbonate 1177 g / t, water glass 1177 g / t, YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil prepared in a weight ratio of 6:0.5:0.5:2) 785 g / t are added to the mixed flotation tailings of black and white tungsten, and after being fully stirred, fluorite flotation roughing is carried out to obtain fluorite rough concentrate and fluorite roughing tailings.

[0056] (7) Fluorite roughing tailings were added with activator YH-50 (ammonium chloride and sodium fluoride prepared in a weight ratio of 6:4) 857 g / t and collector YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil prepared in a weight ratio of 6:0.5:0.5:2) 342 g / t for one scavenging to obtain scavenging concentrate and first-stage flotation tailings.

[0057] (8) Acidified water glass (294 g / t) was added to the fluorite rough concentrate for the first concentration to obtain fluorite concentrate 1 and concentrate 1 middlings. The concentrate 1 middlings were returned to the fluorite flotation roughing in sequence.

[0058] (9) Fluorite concentrate 1 was added with 147 g / t of acidified water glass for the second concentration to obtain fluorite concentrate 2 and first-stage concentrate 2 middlings; fluorite concentrate 2 was added with 98 g / t of inhibitor YY-20 (prepared with ethylenediaminetetramethylenephosphonic acid, guar gum and acidified water glass in a mass ratio of 1:1:8) for the third to sixth concentrations to obtain fluorite concentrate and concentrated middlings. The concentrated middlings were returned to the previous concentration operation in order.

[0059] (10) Flotation 6 fluorite concentrate is subjected to strong magnetic primary separation using a ZH flat ring high gradient strong magnetic separator with a magnetic field strength of 1.85T to obtain non-magnetic products and strong magnetic separation products. The non-magnetic product is the first-stage fluorite concentrate with a yield of 12.44%. CaF 2 Grade 97.38%, CaF 2 Recovery rate: 60.08%.

[0060] (11) The scavenging concentrate, the first-stage concentrate and the high-intensity magnetic separation magnetic products are concentrated and classified to obtain the classified overflow slurry and the classified sediment.

[0061] (12) The classified sand-set slurry is ground to obtain finely ground slurry with a particle size of -0.075 mm accounting for 95%, and the finely ground slurry is returned to the classification system.

[0062] (13) The overflow slurry is graded and concentrated and dehydrated to obtain a concentrated underflow slurry with a slurry concentration of 45%.

[0063] (14) The concentrated underflow pulp was added with 171 g / t of collector YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil in a weight ratio of 6:0.5:0.5:2) and stirred thoroughly before secondary flotation roughing of fluorite to obtain secondary fluorite rough concentrate and secondary roughing tailings.

[0064] (15) Acidified water glass (43 g / t) was added to the fluorite second-stage coarse concentrate for the first second-stage concentration to obtain fluorite second-stage concentrate 1 and second-stage concentrate 1 tailings.

[0065] (16) 34 g / t of acidified water glass was added to the second stage fluorite concentrate 1 to carry out the second stage concentrating, thereby obtaining the second stage fluorite concentrate 2 and the second stage concentrate 2 tailings.

[0066] (17) Fluorite second-stage concentrate 2 was added with inhibitor YY-20 (ethylenediaminetetramethylenephosphonic acid, guar gum, and acidified water glass in a mass ratio of 1:1:8) at 26 g / t per time for the 3rd to 6th rounds of concentrating, and the yield was 5.44%, CaF 2 Grade 93.12%, CaF 2The second-stage fluorite concentrate with a recovery rate of 25.15% and the second-stage concentrated middlings are returned to the previous concentration operation in sequence.

[0067] By adopting the ore dressing method of this embodiment, a sulfur concentrate with a yield of 0.98%, a sulfur grade of 32.45%, a sulfur recovery rate of 91.46%, and a yield of 0.94%, WO 3 Grade 36.32%, WO 3 The recovery rate of tungsten concentrate is 85.52% and the yield is 17.88%, CaF 2 Grade 96.08%, CaF 2 The recovery rate of the comprehensive fluorite concentrate is 85.23%. Compared with the original process production index of the concentrator, WO 3 The recovery rate increased by 12.52 percentage points, and the fluorite concentrate CaF 2 The grade increased by 9.08 percentage points, CaF 2 The recovery rate increased significantly by 20.23 percentage points.

[0068] Example 2 The sulfide ore flotation tailings WO 2 were processed by a large ore dressing plant in Hunan Province. 3 Content 0.42%, S content 0.50%, CaF 2 Content 22.32%, CaCO 3 The content is 5.73%. The valuable minerals in the tailings are tungsten ore and fluorite, and the main gangue is garnet, followed by quartz, calcite and a small amount of pyroxene, amphibole, chlorite, etc.

[0069] Use Figure 1 The specific steps of the mineral processing method shown are as follows: (1) Add activator YH 3500g / t, isopentyl xanthate + butyl ammonium black powder 120g / t + 120g / t respectively to the sulfide ore flotation tailings of the concentrator, stir thoroughly and carry out a rough selection to obtain pyrrhotite rough concentrate and enhanced flotation tailings.

[0070] (2) The pyrrhotite rough concentrate was subjected to four flotation separations. Water glass of 120 g / t, 80 g / t, 50 g / t and 30 g / t was added in turn in the flotation separations 1 to 4 to obtain pyrrhotite concentrate and concentrated middlings. The concentrated middlings were returned to the previous flotation separation in sequence. The pyrrhotite concentrate yield was 1.37%, the S grade was 32.92% and the S recovery rate was 90.14%.

[0071] (3) Add 1200g / t sodium carbonate and salinized water glass (Al 2 (SO) 4:water glass = 1:9) 1200g / t, lead nitrate 800g / t, composite tungsten ore collector (prepared by salicylic hydroxamic acid, styrene phosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5) 1000g / t, 2 # Oil 30g / t, after fully stirring, black and white tungsten mixed flotation roughing is carried out to obtain black and white tungsten mixed rough concentrate and flotation tungsten roughing tailings.

[0072] (4) The black and white tungsten mixed rough concentrate is refined 4 times, and saline water glass (Al2O3) is added to refine 1 to refine 4 in sequence. 2 (SO) 4 :water glass = 1:9) 500g / t, 400g / t, 300g / t, 300g / t, tungsten concentrate and selected middlings were obtained. The selected middlings were returned to the previous flotation operation in sequence. The yield of tungsten concentrate was 0.98%, WO 3 Grade 36.83%, WO 3 The recovery rate is 85.68%, and the S grade of tungsten concentrate is 0.88%.

[0073] (5) The rough tailings of black and white tungsten mixed flotation are subjected to two scavenging processes. The reagent systems for scavenging one and two are as follows: composite tungsten collector (prepared with salicylic acid, styrene phosphonic acid and benzoic acid in a mass ratio of 0.2:4:5) 300g / t, 2 # Oil 15g / t and composite tungsten ore collector (prepared with salicylic hydroxamic acid, styrene phosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5) 150g / t, 2 # Oil is 10g / t, and scavenging ore and floating tungsten tailings are obtained. The scavenging ore is returned to the previous flotation operation in sequence.

[0074] (6) Sodium carbonate 1172g / t, water glass 1172g / t and YZ-01 830g / t are added to the mixed flotation tailings of black and white tungsten, and after being fully stirred, fluorite flotation roughing is carried out to obtain fluorite rough concentrate and fluorite roughing tailings.

[0075] (7) Fluorite roughing tailings were added with activator YH-50 (ammonium chloride and sodium fluoride prepared in a weight ratio of 6:4) 830 g / t and collector YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil prepared in a weight ratio of 8:0.5:0.5:1) 332 g / t for one scavenging to obtain scavenging concentrate and first-stage flotation tailings.

[0076] (8) Acidified water glass (195 g / t) is added to the fluorite rough concentrate for the first concentration to obtain fluorite concentrate 1 and concentrate 1 middlings. The concentrate 1 middlings are returned to the fluorite flotation roughing in sequence.

[0077] (9) 98 g / t of acidified water glass was added to the fluorite concentrate 1 for the second concentration to obtain fluorite concentrate 2 and first-stage concentrate 2 middlings. 25 g / t of inhibitor YY-20 (prepared with ethylenediaminetetramethylenephosphonic acid, guar gum and acidified water glass in a mass ratio of 0.5:0.5:9) was added to the fluorite concentrate 2 for the third to fifth concentrations to obtain fluorite concentrate and concentrated middlings. The concentrated middlings were returned to the previous concentration operation in order.

[0078] (10) Flotation 6 fluorite concentrate is separated by a ZH flat ring high gradient strong magnetic separator, with a magnetic field strength of 1.85T, to obtain non-magnetic products and strong magnetic separation products. The non-magnetic product is the first-stage fluorite concentrate with a yield of 14.62%. CaF 2 Grade 98.42%, CaF 2 The recovery rate is 64.46%.

[0079] (11) The scavenging concentrate, the first-stage concentrate and the high-intensity magnetic separation magnetic products are concentrated and classified to obtain the classified overflow slurry and the classified sediment.

[0080] (12) The classified sand-set slurry is ground to obtain finely ground slurry with a particle size of -0.075 mm accounting for 95%, and the finely ground slurry is returned to the classification system.

[0081] (13) The overflow slurry is graded and concentrated and dehydrated to obtain a concentrated underflow slurry with a slurry concentration of 45%.

[0082] (14) The concentrated underflow pulp was added with 166 g / t of collector YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil in a weight ratio of 8:0.5:0.5:1) and stirred thoroughly before secondary flotation roughing of fluorite to obtain secondary fluorite rough concentrate and secondary roughing tailings.

[0083] (15) 33 g / t of acidified water glass was added to the fluorite second-stage coarse concentrate for the second-stage first concentration to obtain fluorite second-stage concentrate 1 and second-stage concentrate 1 tailings.

[0084] (16) The second-stage fluorite concentrate 1 was added with 25 g / t of acidified water glass for the second-stage concentration to obtain the second-stage fluorite concentrate 2 and the second-stage concentrate 2 tailings.

[0085] (17) Fluorite second-stage concentrate was added with inhibitor YY-20 (prepared with ethylenediaminetetramethylenephosphonic acid, guar gum, and acidified water glass in a mass ratio of 0.5:0.5:9) at 12.5 g / t per ton for the 3rd to 5th rounds of concentrating, and the yield was 6.16%, CaF 2 Grade 93.79%, CaF 2 The second-stage fluorite concentrate with a recovery rate of 25.89% and the second-stage concentrated middlings are returned to the previous concentration operation in sequence.

[0086] The ore dressing method of the present invention can obtain a sulfur concentrate with a yield of 1.37%, a sulfur grade of 32.92%, a sulfur recovery rate of 90.14%, a yield of 0.98%, and a WO 3 Grade 36.83%, WO 3 The recovery rate of tungsten concentrate is 85.68% and the yield is 20.78%, CaF 2 Grade 97.05%, CaF 2 The recovery rate of the comprehensive fluorite concentrate is 90.35%. Compared with the original process production index of the concentrator, WO 3 The recovery rate increased by 12.68 percentage points, and the fluorite concentrate CaF 2 The grade of CaF increased significantly by 10.05 percentage points. 2 The recovery rate increased significantly by 25.35 percentage points.

[0087] Example 3 The sulfide ore flotation tailings WO 2 were processed by a sulfide ore flotation tailings from a ore dressing plant in Hunan Province. 3 Content 0.45%, S content 0.40%, CaF 2 Content 26.45%, CaCO 3 The content is 30.88%. The main minerals in the tailings are calcite, followed by garnet and a small amount of quartz, amphibole, chlorite, etc.

[0088] Use Figure 1 The specific steps of the mineral processing method shown are as follows: (1) Add 3000 g / t of activator YH (sulfuric acid, oxalic acid, copper sulfate, sodium fluorosilicate prepared in a weight ratio of 7:1:0.5:1.5) and 100 g / t+100 g / t of isopentyl xanthate and 100 g / t of butyl ammonium black powder to the sulfide ore flotation tailings of the concentrator. After sufficient stirring and a rough selection, pyrrhotite rough concentrate and enhanced flotation tailings are obtained.

[0089] (2) The pyrrhotite rough concentrate was subjected to four flotation separations. Water glass of 100 g / t, 50 g / t, 30 g / t and 30 g / t was added to the concentrates 1 to 4, respectively, to obtain pyrrhotite concentrate and concentrated middlings. The concentrated middlings were returned to the previous flotation process in sequence. The pyrrhotite concentrate yield was 1.07%, the S grade was 33.59% and the S recovery rate was 90.08%.

[0090] (3) Add 989g / t sodium carbonate and salinized water glass (Al 2 (SO) 4:water glass = 1:4) 989g / t, lead nitrate 791g / t, composite tungsten ore collector (prepared with salicylic hydroxamic acid, styrene phosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5) 989g / t, 2 # Oil 30g / t, after fully stirring, black and white tungsten mixed flotation roughing is carried out to obtain black and white tungsten mixed rough concentrate and flotation tungsten roughing tailings.

[0091] (4) The black and white tungsten mixed rough concentrate is refined 4 times, and saline water glass (Al2O3) is added to refine 1 to refine 4 in sequence. 2 (SO) 4 :water glass = 1:4) 450g / t, 350g / t, 270g / t, 180g / t, tungsten concentrate and selected middlings are obtained, and the selected middlings are returned to the previous flotation operation in sequence. The yield of tungsten concentrate is 0.94%, WO 3 Grade 36.32%, WO 3 The recovery rate is 85.52%, and the S grade of tungsten concentrate is 0.81%.

[0092] (5) The rough tailings of tungsten flotation obtained by mixed flotation of black and white tungsten were subjected to two scavengings. The reagent systems of scavenging one and two were as follows: 300g / t of composite tungsten collector (prepared by salicylic acid, styrene phosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5), 15g / t of 2# oil and 150g / t of composite tungsten collector (prepared by salicylic acid, styrene phosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5), 2 # Oil is 10g / t, and scavenging ore and floating tungsten tailings are obtained. The scavenging ore is returned to the previous flotation operation in sequence.

[0093] (6) Sodium carbonate 977 g / t, water glass 977 g / t, and YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil prepared in a weight ratio of 5:1:0.5:2) 785 g / t are added to the mixed flotation tailings of black and white tungsten, and after being fully stirred, fluorite flotation roughing is carried out to obtain fluorite rough concentrate and fluorite roughing tailings.

[0094] (7) The fluorite roughing tailings were added with activator YH-50 (ammonium chloride and sodium fluoride prepared in a weight ratio of 6:4) 814 g / t and collector YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil prepared in a weight ratio of 6:0.5:0.5:2) 325 g / t for one scavenging to obtain scavenging concentrate and first-stage flotation tailings.

[0095] (8) Acidified water glass (293 g / t) was added to the fluorite rough concentrate for the first concentration to obtain fluorite concentrate 1 and concentrate 1 middlings. The concentrate 1 middlings were returned to the fluorite flotation roughing in sequence.

[0096] (9) 195 g / t of acidified water glass was added to the fluorite concentrate 1 for the second concentration to obtain fluorite concentrate 2 and first-stage concentrate 2 middlings. 98 g / t of inhibitor YY-20 (prepared with ethylenediaminetetramethylenephosphonic acid, guar gum and acidified water glass in a mass ratio of 1.5:1.5:7) was added to the fluorite concentrate 2 for the third to sixth concentrations to obtain fluorite concentrate and concentrated middlings. The concentrated middlings were returned to the previous concentration operation in order.

[0097] (10) Flotation 6 fluorite concentrate is separated by a ZH flat ring high gradient strong magnetic separator, with a magnetic field strength of 1.85T, to obtain non-magnetic products and strong magnetic separation products. The non-magnetic product is the first-stage fluorite concentrate with a yield of 16.38%. CaF 2 Grade 97.53%, CaF 2 Recovery rate: 60.52%.

[0098] (11) The scavenging concentrate, the first-stage concentrate and the high-intensity magnetic separation magnetic products are concentrated and classified to obtain the classified overflow slurry and the classified sediment.

[0099] (12) The classified sand-set slurry is ground to obtain finely ground slurry with a particle size of -0.075 mm accounting for 95%, and the finely ground slurry is returned to the classification system.

[0100] (13) The overflow slurry is graded and concentrated and dehydrated to obtain a concentrated underflow slurry with a slurry concentration of 45%.

[0101] (14) The concentrated underflow pulp was added with 195 g / t of collector YZ-01 (sodium sulfonated unsaturated fatty acid, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil in a weight ratio of 6:0.5:0.5:2) and stirred thoroughly before secondary flotation roughing of fluorite to obtain secondary fluorite rough concentrate and secondary roughing tailings.

[0102] (15) Acidified water glass (81 g / t) was added to the fluorite second-stage coarse concentrate for the first second-stage concentration to obtain fluorite second-stage concentrate 1 and second-stage concentrate 1 tailings.

[0103] (16) 41 g / t of acidified water glass was added to the second stage fluorite concentrate 1 to carry out the second stage of concentration, thereby obtaining the second stage fluorite concentrate 2 and the second stage concentrate 2 tailings.

[0104] (17) Fluorite second-stage concentrate 2 was added with inhibitor YY-20 (ethylenediaminetetramethylenephosphonic acid, guar gum, and acidified water glass in a mass ratio of 1.5:1.5:7) at 41 g / t / time for the 3rd to 6th rounds of concentration, and the yield was 7.70%, CaF 2 Grade 93.22%, CaF 2 The second-stage fluorite concentrate with a recovery rate of 27.18% and the second-stage concentrated middlings are returned to the previous concentration operation in sequence.

[0105] By adopting the ore dressing method of this embodiment, a sulfur concentrate with a yield of 1.07%, a sulfur grade of 33.59%, a sulfur recovery rate of 90.08%, a yield of 1.13%, and a WO 3 Grade 35.42%, WO 3 The recovery rate of tungsten concentrate is 87.01% and the yield is 24.07%, CaF 2 Grade 96.15%, CaF 2 The recovery rate of the comprehensive fluorite concentrate is 87.70%. Compared with the original process production index of the concentrator, WO 3 The recovery rate increased by 14.01 percentage points, and the fluorite concentrate CaF 2 The grade increased by 9.15 percentage points, CaF 2 The recovery rate increased significantly by 22.70 percentage points.

[0106] Comparative Example 1 The ore sample used is the same as that in Example 1, and the comprehensive recovery process of tungsten fluorite is as follows: Figure 2 As shown, the specific steps and pharmaceutical system are as follows: (1) Add 1000g / t of sodium carbonate and salinized water glass (Al 3+ :water glass = 1:10-1:2) 1000g / t, lead nitrate 800g / t, composite tungsten ore collector (same as Example 1) 1000g / t, 2 # Oil 30g / t, after fully stirring, black and white tungsten mixed flotation roughing is carried out to obtain black and white tungsten mixed rough concentrate and flotation tungsten roughing tailings.

[0107] (2) The mixed black and white tungsten rough concentrate was refined for 4 times. Acidified water glass 400g / t, 300g / t, 200g / t and 200g / t were added to refine 1 to refine 4 in turn to obtain tungsten concentrate and refined middlings. The refined middlings were returned to the previous flotation operation in sequence. The yield of tungsten concentrate was 1.15%, WO 3 Grade 27.12%, WO 3 The recovery rate is 74.15%, and the S grade of tungsten concentrate is 8%.

[0108] (3) The medium-floating tungsten roughing tailings in (2) are subjected to two sweepings. The reagent systems for sweeping one and sweeping two are: tungsten collector CYW 300g / t, 2 # Oil 15g / t and tungsten collector CYW 150g / t, 2 # Oil is 10g / t, and scavenging ore and floating tungsten tailings are obtained. The scavenging ore is returned to the previous flotation operation in sequence.

[0109] (4) Add 791 g / t of sodium carbonate, 1483 g / t of water glass, 99 g / t of tannin extract and 395 g / t of modified fatty acid sodium to the medium-floating tungsten tailings in (3), stir thoroughly and carry out fluorite flotation roughing 1 to obtain fluorite roughing 1 concentrate and fluorite roughing 1 tailings.

[0110] (5) Add 395 g / t of sodium carbonate, 1000 g / t of water glass and 200 g / t of modified fatty acid sodium to the fluorite roughing tailings in (4), stir thoroughly and carry out fluorite flotation roughing 2 to obtain fluorite roughing 2 concentrate and fluorite roughing 2 tailings.

[0111] (6) Add 400 g / t of water glass to the fluorite roughing concentrate 1 from (4) for concentration; obtain concentrate 1 and concentrate 1 tailings. The concentrate 1 is subjected to strong magnetic separation using a high gradient magnetic separator under 1.0 T conditions to obtain a magnetic product and a non-magnetic product.

[0112] (7) The non-magnetic separation product of (6) was added with 1500 g / t of hydrochloric acid, 200 g / t of acidified water glass (mass ratio of water glass to hydrochloric acid = 3:1), and 100 g / t of modified fatty acid sodium for concentration to obtain concentrate 2 and concentrate 2 tailings.

[0113] (8) The concentrate 2 in (7) was added with acidified water glass for 3 to 6 times of concentration, with the amount of acidified water glass being 150 g / t, 150 g / t, 100 g / t, and 50 g / t, respectively, to obtain fluorite concentrate 1 with a yield of 15.08%, CaF 2 Grade 87.66%, CaF 2 The recovery rate is 56.80%, and the selected middlings are returned to the previous selection operation in sequence.

[0114] (9) Add 200 g / t of water glass to the (5) intermediate roughing 2 concentrate for concentrating to obtain sweep concentrate and sweep concentrate tailings. The sweep concentrate tailings are returned to the previous operation fluorite roughing 2 together with the (6) intermediate concentrate 1 tailings.

[0115] (10) The (9) medium sweep concentrate is pre-classified together with the (6) medium magnetic product and the (7) medium concentrate 2 tailings to obtain a +0.045 mm particle size sediment and a -0.045 mm particle size overflow. The sediment is re-ground by a ball mill and then returned to the classification operation.

[0116] (11) The overflow in (10) is added with 400 g / t of sodium carbonate, 300 g / t of water glass and 100 g / t of modified fatty acid sodium to carry out low-grade fluorite roughing to obtain low-grade roughing tailings and low-grade rough concentrate; the low-grade roughing tailings are added with 20 g / t of modified fatty acid sodium to obtain low-grade scavenging concentrate and low-grade scavenging tailings.

[0117] (12) The low- and medium-grade scavenging concentrates from (11) are returned to the low-grade roughing operation, and the low-grade scavenging tailings are discharged into the tailings pond. (13) The low-middle coarse concentrate (11) was added with acidified water glass for four times of concentration. The reagent systems of concentration 2 to concentration 4 were as follows: 200 g / t of water glass was added to concentration 1, 350 g / t of hydrochloric acid and 200 g / t of acidified water glass were added to concentration 2, 150 g / t of acidified water glass was added to concentration 3, and 100 g / t of acidified water glass was added to concentration 4. The yield of fluorite concentrate 2 was 7.72%, and CaF 2 Grade 75.12%, CaF 2 The recovery rate is 25.04%, and the selected middlings are returned to the previous selection operation in sequence.

[0118] The sulfur content of tungsten concentrate obtained by the above process is significantly increased. 3 With a grade of only 27.12%, WO 3 The recovery rate was reduced by 11.37 percentage points compared with Example 1; the obtained fluorite comprehensive concentrate CaF 2 The grade is 83.40%, which is 12.68 percentage points lower than that of Example 1. 2 The recovery rate is 81.84%, which is 3.39 percentage points lower than that of Example 1. The quality of fluorite concentrate is poor, the cost per ton of mineral processing is high, and the economic benefit is not good.

[0119] Comparative Example 2 The ore sample used is the same as that in Example 1, and the specific steps and reagent system are as follows: (1) Add 100 g / t of isopentyl xanthate and 100 g / t of butyl ammonium black powder to the flotation tailings of the sulfide ore in the concentrator, stir them thoroughly and carry out a rough selection to obtain pyrrhotite rough concentrate and enhanced flotation tailings.

[0120] (2) The pyrrhotite rough concentrate was subjected to four flotation separations. Water glass of 100 g / t, 50 g / t, 30 g / t and 30 g / t was added to the concentrates 1 to 4, respectively, to obtain pyrrhotite concentrate and concentrated middlings. The concentrated middlings were returned to the previous flotation process in sequence. The pyrrhotite concentrate yield was 0.61%, the S grade was 34.73% and the S recovery rate was 60.93%.

[0121] (3) Add 1000g / t sodium carbonate and salinized water glass (Al 2 (SO) 4 :water glass = 1:6) 1000g / t, lead nitrate 800g / t, tungsten collector CYW (prepared by 731, styrene phosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5) 1000g / t, 2 # Oil 30g / t, after fully stirring, black and white tungsten mixed flotation roughing is carried out to obtain black and white tungsten mixed rough concentrate and flotation tungsten roughing tailings.

[0122] (4) The black and white tungsten mixed rough concentrate is refined 4 times, and saline water glass (Al2O3) is added to refine 1 to refine 4 in sequence. 2 (SO) 4 :water glass = 1:6) 500g / t, 400g / t, 300g / t, 200g / t, tungsten concentrate and selected middlings are obtained, and the selected middlings are returned to the previous flotation operation in sequence. The yield of tungsten concentrate is 1.00%, WO 3 Grade 31.76%, WO 3 The recovery rate is 79.63%, and the S grade of tungsten concentrate is 3.82%.

[0123] (5) The rough tailings of tungsten flotation obtained by mixed flotation of black and white tungsten were subjected to two scavengings. The reagent systems for scavenging one and two were as follows: tungsten collector CYW (prepared by 731, styrenephosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5) 300g / t, 2# oil 15g / t and tungsten collector CYW (prepared by 731, styrenephosphonic acid and benzohydroxamic acid in a mass ratio of 0.2:4:5) 150g / t, 2 # Oil is 10g / t, and scavenging ore and floating tungsten tailings are obtained. The scavenging ore is returned to the previous flotation operation in sequence.

[0124] (6) Sodium carbonate 1177 g / t, water glass 1177 g / t, YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil prepared in a weight ratio of 6:0.5:0.5:2) 785 g / t are added to the mixed flotation tailings of black and white tungsten, and after being fully stirred, fluorite flotation roughing is carried out to obtain fluorite rough concentrate and fluorite roughing tailings.

[0125] (7) Fluorite roughing tailings were added with activator YH-50 (ammonium chloride and sodium fluoride prepared in a weight ratio of 6:4) 857 g / t and collector YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil prepared in a weight ratio of 6:0.5:0.5:2) 342 g / t for one scavenging to obtain scavenging concentrate and first-stage flotation tailings.

[0126] (8) Acidified water glass (294 g / t) was added to the fluorite rough concentrate for the first concentration to obtain fluorite concentrate 1 and concentrate 1 middlings. The concentrate 1 middlings were returned to the fluorite flotation roughing in sequence.

[0127] (9) 147 g / t of acidified water glass was added to the fluorite concentrate 1 for the second concentration to obtain fluorite concentrate 2 and first-stage concentrate 2 middlings. 98 g / t of inhibitor YY-20 (ethylenediaminetetramethylenephosphonic acid, guar gum, and acidified water glass in a mass ratio of 1:1:8) was added to the fluorite concentrate 2 for the third to sixth concentrations to obtain fluorite concentrate and concentrated middlings. The concentrated middlings were returned to the previous concentration operation in sequence.

[0128] (10) Flotation 6 fluorite concentrate is subjected to strong magnetic primary separation using a ZH flat ring high gradient strong magnetic separator with a magnetic field strength of 1.85T to obtain non-magnetic products and strong magnetic separation products. The non-magnetic product is the first-stage fluorite concentrate with a yield of 12.04%. CaF 2 Grade 96.81%, CaF 2 The recovery rate is 58.04%.

[0129] (11) The scavenging concentrate, the first-stage concentrate and the high-intensity magnetic separation magnetic products are concentrated and classified to obtain the classified overflow slurry and the classified sediment.

[0130] (12) The classified sand-set slurry is ground to obtain finely ground slurry with a particle size of -0.075 mm accounting for 95%, and the finely ground slurry is returned to the classification system.

[0131] (13) The overflow slurry is graded and concentrated and dehydrated to obtain a concentrated underflow slurry with a slurry concentration of 45%.

[0132] (14) The concentrated underflow pulp was added with 171 g / t of collector YZ-01 (sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate, and tall oil in a weight ratio of 6:0.5:0.5:2) and stirred thoroughly before secondary flotation roughing of fluorite to obtain secondary fluorite rough concentrate and secondary roughing tailings.

[0133] (15) Acidified water glass (43 g / t) was added to the fluorite second-stage coarse concentrate for the first second-stage concentration to obtain fluorite second-stage concentrate 1 and second-stage concentrate 1 tailings.

[0134] (16) 34 g / t of acidified water glass was added to the second stage fluorite concentrate 1 to carry out the second stage concentrating, thereby obtaining the second stage fluorite concentrate 2 and the second stage concentrate 2 tailings.

[0135] (17) Fluorite second-stage concentrate 2 was added with inhibitor YY-20 (ethylenediaminetetramethylenephosphonic acid, guar gum, and acidified water glass in a mass ratio of 1:1:8) at 26 g / t per time for the 3rd to 6th rounds of concentrating, and the yield was 5.25%, CaF 2 Grade 92.54%, CaF 2 The second-stage fluorite concentrate with a recovery rate of 24.17% and the second-stage concentrated middlings are returned to the previous concentration operation in sequence.

[0136] The above process flow is different from that of Example 1 in that no activator YH is used in step (1). The S removal rate of the flotation desulfurization operation is only 60.93%, resulting in a significant increase in the sulfur content of the tungsten concentrate to 3.82%. 3 The grade and recovery rate decreased by 4.56 and 5.89 percentage points respectively. 2The grade also decreased from 96.08% to 95.51%, CaF 2 The recovery rate decreased by 3.01 percentage points.

[0137] In summary, enhanced flotation desulfurization has a certain impact on tungsten ore flotation and fluorite recovery. Especially in tungsten ore flotation operations, reducing the S content in the flotation tungsten feed to less than 0.05% is the key to obtaining good tungsten flotation indicators.

[0138] The above contents are further detailed descriptions of the present invention in combination with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the field to which the present invention belongs, several simple deductions or substitutions can be made without departing from the concept of the present invention, which should be regarded as falling within the scope of protection of the present invention.

Claims

1. A method for enhanced recovery of tungsten and fluorite from sulfide ore flotation tailings, characterized in that: The following steps are involved: S1. Add flotation agent A to the sulfide ore flotation tailings, stir thoroughly, and then perform pyrrhotite enhanced flotation roughing to obtain enhanced flotation tailings; S2, adding flotation reagent B to the enhanced flotation tailings and fully stirring them, and then performing black and white tungsten mixed flotation roughing to obtain black and white tungsten mixed rough concentrate and flotation tungsten roughing tailings; S3, adding flotation reagent C to the black and white tungsten mixed rough concentrate obtained in step S2 for at least one concentration to obtain tungsten concentrate; S4, adding flotation reagent D to the rough tungsten flotation tailings obtained in step S2 for at least one scavenging to obtain tungsten flotation tailings; S5, adding flotation reagent E to the tungsten tailings obtained in step S4 and stirring them thoroughly, and then performing fluorite flotation roughing to obtain fluorite rough concentrate and fluorite roughing tailings; S6, adding reagents to the fluorite rougher tailings obtained in step S5 for scavenging, obtaining scavenging concentrate and first-stage flotation tailings, and further concentrating the fluorite rougher concentrate at least 3 times to obtain fluorite concentrate and selected middlings, and performing strong magnetic separation to remove impurities from the fluorite concentrate, and the non-magnetic product is a first-stage high-quality fluorite concentrate; S7, the scavenged concentrate obtained in step S6, the fluorite coarse concentrate, the selected middlings obtained by secondary selection, and the magnetic product obtained by strong magnetic separation and impurity removal of the fluorite concentrate are classified through a cyclone to obtain a classified overflow slurry; S8, after concentrating the classified overflow pulp obtained in step S7, adding reagents and stirring sufficiently, performing second-stage flotation roughing of fluorite to obtain second-stage fluorite rough concentrate; S9, the fluorite second-stage rough concentrate obtained in step S8 is subjected to at least three rounds of beneficiation to obtain a second-stage fluorite concentrate.

2. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: In step S1, after the pyrrhotite enhanced flotation roughing, a pyrrhotite rough concentrate is obtained. After the pyrrhotite rough concentrate is subjected to 1-3 times of concentrating, a pyrrhotite concentrate and a concentrating middling are obtained. The concentrating middling is sequentially returned to the previous flotation operation; In step S3, after the concentration, the concentrated middlings are obtained, and the concentrated middlings are sequentially returned to the previous flotation operation; In step S4, after scavenging, the scavenged minerals are obtained, and the scavenged minerals are returned to the previous flotation operation in sequence; In step S7, after classification, classified sand is obtained, and the classified sand slurry is ground to obtain finely ground slurry, so that the dissociation degree of fluorite monomer in the finely ground slurry is ≥80%, and the finely ground slurry is returned to the classification operation to form a closed-loop process.

3. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: In step S1, the flotation reagent A contains an activator, and the activator is selected from two or more of ammonium fluorosilicate, ammonium persulfate, oxalic acid, sulfuric acid, copper sulfate, and ammonium chloride; the flotation reagent A is prepared by the activator, isopentyl xanthate and butyl ammonium black medicine in a mass ratio of 300-350:10-12:10-12.

4. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: In step S2, the flotation reagent B contains a composite tungsten ore collector, which is composed of salicylic acid, styrene phosphonic acid and benzoic acid; the flotation reagent B is composed of sodium carbonate, salinized water glass, lead nitrate, a composite tungsten ore collector and 2 # Oil composition.

5. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: In step S3, the flotation reagent C is salted water glass, and the salted water glass is prepared by mixing Al2(SO)4 and water glass in a mass ratio of 1:10-1:

2.

6. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: In step S4, the flotation reagent D is composed of a composite tungsten ore collector and 2 # The composite tungsten ore collector is composed of salicylic acid, styrene phosphonic acid and benzoic acid.

7. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: In step S5, the flotation reagent E is composed of sodium carbonate, water glass and fluorite collector, the fluorite collector is composed of sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate and tall oil, and the weight ratio of the sulfonated unsaturated fatty acid sodium, oxidized paraffin soap, sodium dodecyl sulfate and tall oil is 4-8:0.5-1:0.5-1:1-2.

8. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: In step S6, the strong magnetic separation equipment used in the strong magnetic separation is a high gradient strong magnetic separator or a superconducting magnetic separator, and the magnetic field strength is 1.0T-5.0T; in the selection process, the inhibitor used in the third or more selection processes is selected from two or more of acidified water glass, ethylenediaminetetramethylenephosphonic acid, tannin, and guar gum.

9. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: In step S8, the reagent added to the fluorite roughing tailings is selected from two or more of ammonium chloride, sodium fluoride, sodium monofluorophosphate, and calcium chloride.

10. The ore dressing method for enhanced recovery of tungsten and fluorite in sulfide ore flotation tailings according to claim 1, characterized in that: The WO3 content in the sulfide ore flotation tailings is ≥0.10%, S ≥0.3%, CaF2 content ≥15%, and CaCO3 content 5-25%; the dissociation degree of fluorite monomer in the sulfide ore flotation tailings is ≥70%.

Images