CN117816360A - Combined activator for floatation desulfurization of pyrrhotite type tin-containing sulphide ore - Google Patents
Combined activator for floatation desulfurization of pyrrhotite type tin-containing sulphide ore Download PDFInfo
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- CN117816360A CN117816360A CN202410046486.6A CN202410046486A CN117816360A CN 117816360 A CN117816360 A CN 117816360A CN 202410046486 A CN202410046486 A CN 202410046486A CN 117816360 A CN117816360 A CN 117816360A
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- desulfurization
- pyrrhotite
- ton
- concentrate
- flotation
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052952 pyrrhotite Inorganic materials 0.000 title claims abstract description 44
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 31
- 230000023556 desulfurization Effects 0.000 title claims abstract description 31
- 239000012190 activator Substances 0.000 title claims abstract description 30
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005188 flotation Methods 0.000 claims abstract description 31
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 21
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 18
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 18
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 7
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229940001584 sodium metabisulfite Drugs 0.000 claims abstract description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 6
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000012141 concentrate Substances 0.000 claims description 59
- 229910052717 sulfur Inorganic materials 0.000 claims description 55
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 53
- 239000011593 sulfur Substances 0.000 claims description 52
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 40
- 239000011707 mineral Substances 0.000 claims description 40
- 230000002000 scavenging effect Effects 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 31
- 230000003213 activating effect Effects 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 19
- 239000004088 foaming agent Substances 0.000 claims description 11
- 238000007790 scraping Methods 0.000 claims description 11
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 46
- 230000000694 effects Effects 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 10
- 230000004913 activation Effects 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 description 39
- 235000010755 mineral Nutrition 0.000 description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- 239000004575 stone Substances 0.000 description 10
- 229910052683 pyrite Inorganic materials 0.000 description 9
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 9
- 239000011028 pyrite Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000012991 xanthate Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910001662 tin mineral Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 2
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical class C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a combined activator for floatation desulfurization of pyrrhotite type tin-containing sulphide ores, which comprises sulfuric acid, ferrous chloride, copper sulfate and CY100, wherein CY100 is one or a combination of more of sodium sulfite, sodium metabisulfite, sodium dithionite and sodium thiosulfate; the combined activator is applied to a technological process of firstly carrying out flotation desulfurization and then carrying out flotation recovery on the cassiterite, realizes a remarkable activation effect, solves the problem of difficult flotation desulfurization of the pyrrhotite type tin-containing sulfide ore in the prior art, realizes high-efficiency separation of the cassiterite and the pyrrhotite, and achieves a very satisfactory effect.
Description
Technical Field
The invention relates to a combined activator for floatation desulfurization of pyrrhotite type tin-containing sulphide ores, and belongs to the technical field of mineral processing medicaments.
Background
Tin is an indispensable material foundation in the life and work of all human beings, has a plurality of excellent characteristics, and has wide application and huge economic value. At present, mainly tin stone is industrially used for producing metallic tin, however, along with the development and utilization of tin resources, simple single-metal tin stone mines are fewer and fewer, and the multi-metal sulfide mines of the tin stone are mainly used at present, when the multi-metal sulfide mines of the tin stone are selected, the natural floatability of the sulfide ores is better than that of the tin stone, generally, sulfide ores are selected firstly and then oxidized ores are selected, and the sulfide ores are difficult to completely remove when the oxidized ores are selected, so that the prior desulfurization treatment is needed before the tin stone flotation, whether the prior desulfurization is completely removed directly affects the recovery of the subsequent tin stone, the desulfurization is not completely, the sulfide ores in ore pulp affect the floating of the tin stone, and a large amount of flotation agents are consumed by the sulfide ores, so that the recovery rate of the tin stone is lower, and the prior desulfurization is also a key problem of the tin stone flotation.
The sulfur content in the tin ore directly affects the grade and recovery rate of the tin concentrate, so that the desulfurization of the tin ore becomes a very important ring in the process of beneficiation of the tin ore.
The complex multi-metal tin ore desulfurization generally adopts a combined process of copper flotation, zinc separation, magnetic separation iron removal, desulfurization and tin separation, namely, raw ore is firstly ground to proper grinding granularity, sulfur inhibition copper flotation is firstly carried out for zinc separation, then magnetic separation is carried out for iron removal, and floatation desulfurization is carried out for tin separation.
Cassiterite (SnO) 2 ) Is a metal oxide which has high density, high hardness, easy pulverization, tetragonal system, is often brownish black and reddish brown, has metallic luster, has the hardness of 6-7 and the specific gravity of 68-7.0. Oxide inclusions are often formed with metals such as Fe, nb, and Ta, and Sn in the crystal may be replaced by Nb and Ta in a similar manner. The cassiterite crystal has a rutile structure and is generally in a biconical column shape or biconical aggregate shape formed by tetragonal biconical columns and tetragonal biconical columns. The contact angle of the cassiterite single mineral is 33 degrees, the natural floatability is poor, the gravity separation is a main method for recycling coarse cassiterite, and the micro-fine cassiterite is recycled by a flotation method.
Pyrite chemical composition is FeS 2 Pyrite is rich in sulfur and is therefore commonly used by sulfuric acid plants as the primary mineral raw material for sulfur extraction and sulfuric acid production. Light yellow, strong metallic luster, hardness of 6-6.5 and specific gravity of 4.9-5.2. In pyrite crystals, two S' S 2- Ion composition anion group [ S ] 2 ] 2- When the pyrite is crushed, the pyrite presents complete crystallization, the cleavage surface of the pyrite is oleophylic and hydrophobic, and the xanthate collector is easy to form hydrophobic double xanthates on the surface of the pyrite, which is beneficial to the floatation of the pyrite, so the floatation separation of the pyrite and the cassiterite is relatively easy.
Pyrrhotite Fe 1-X S (X=0.1-0.2) is a sulphide mineral of iron in the family of arsenical nickel ores, the content of which is up to 40% sulphur, and can be used as a raw material for producing sulfuric acid. Dark bronze yellow, metallic luster, hardness of 3.5-4.5, specific gravity of 4.6-4.7, and weak magnetism. The pyrrhotite has homogeneous multi-image variants of monoclinic, hexagonal and rhombic systems, and the pyrrhotite of the rhombic system is very little and basically a mixture of monoclinic and hexagonal systems, and the physical property, chemical composition and crystal structure of the pyrrhotite directly determine the floating characteristics, the easily oxidized degree of the surface, the brittleness and the like.
Sulfide minerals can affect recovery of cassiterite: on the one hand, the density of coarse-grain cassiterite is similar to that of sulfide minerals, the bed surface is not clear, and a large amount of heavy minerals such as sulfur, iron and the like are mixed in concentrate belts, so that the gravity separation efficiency and the grade of tin concentrate are seriously affected; on the other hand, the addition of inhibitor in copper flotation-zinc flotation results in oxidation of the surface of sulphide ore, hydroxamic acids are adopted as collectors, the floatability of sulphide ore and micro-size fraction cassiterite is similar, and the floatation of sulphide ore and micro-size fraction cassiterite together with the floatation of cassiterite not only seriously affects the recovery rate and grade of tin concentrate, but also greatly consumes floatation agents. The sulfur content in the tin concentrate exceeds the standard, which can lead to low selling price and influence the economic benefit of mines and the quality of smelted products.
Aiming at the problem that the pyrrhotite type tin-containing sulphide ore is difficult to carry out high-efficiency flotation desulfurization, related technicians are subjected to a great deal of work and research, and summarize that the existing pyrrhotite activators comprise copper sulfate, sodium sulfide, sodium fluosilicate, oxalic acid, sulfuric acid, copper sulfate+sulfuric acid, oxalic acid+copper sulfate, sulfuric acid+ferrous sulfate and the like, the activators are effective for carrying out flotation separation on part of cassiterite and pyrrhotite, but due to the fact that the difference of sulfur-containing minerals is large, the activators can not achieve satisfactory effects on the flotation separation effect of all pyrrhotite and cassiterite, for example: the method has the advantages that the effect of separating the tin ore and the pyrrhotite of certain pyrrhotite type tin sulfide ore in the Wenshan city of Yunnan province by adopting sulfuric acid as an activating agent through floatation is poor, the S grade of the raw ore is 2.57%, and 95% of sulfur-containing minerals are pyrrhotite, so that the research and development effect is excellent, and the pyrrhotite activating agent and the novel technique for removing sulfur from the tin sulfide ore with strong adaptability are scientific research projects to be attacked.
Disclosure of Invention
In order to solve the problems pointed out in the background art, the invention discloses a combined activator for floatation desulfurization of pyrrhotite type tin-containing sulphide ores. The combined activating agent comprises sulfuric acid, ferrous chloride, copper sulfate and CY100, wherein CY100 is one or a combination of more of sodium sulfite, sodium metabisulfite, sodium dithionite and sodium thiosulfate, and can effectively activate pyrrhotite, reduce the sulfur content in cassiterite and reduce the sulfur content in cassiterite to below 0.3%.
The combined activator comprises sulfuric acid, ferrous chloride, copper sulfate and CY100, wherein CY100 is one or a combination of more of sodium sulfite, sodium metabisulfite, sodium dithionite and sodium thiosulfate, and the mass ratio of each component in the combined activator is as follows
Sulfuric acid: ferrous chloride: copper sulfate: cy100=1-5:1-4:1-5.
For ore samples with lower grade, finer granularity and better monomer dissociation degree, sulfuric acid can not be added.
The invention relates to an application of a combined activator for floatation desulfurization of pyrrhotite type tin-containing sulphide ores,
the invention is realized by the following technical scheme.
The application of the combined activator for the floatation desulfurization of the pyrrhotite type tin-containing sulphide ore comprises the following specific steps:
(1) Crushing and grinding raw ore, wherein the solid-to-liquid ratio of grinding is 1:1, and grinding is carried out until the particle size is less than 0.074mm and accounts for 50% -90% by mass;
(2) Regulating the concentration of ore pulp to 30-40%, feeding the ore pulp into a flotation tank, calculating the dosage according to the dry weight of minerals, adding 200-2000 g/ton of combined activating agent, and stirring and activating for 3-5 min; the adding sequence of the activating agent is that firstly, activating agent sulfuric acid is added, then activating agent copper sulfate is added, and finally activating agent ferrous chloride and CY100 are added;
(3) Adding 50-200 g/ton of collecting agent butyl xanthate or amyl xanthate according to the dry weight of minerals in sequence, stirring and activating for 2-3 min, then adding 10-60 g/ton of foaming agent according to the dry weight of minerals, stirring and activating for 2-3 min, aerating and scraping sulfur concentrate;
(4) The flotation process comprises the following steps: and (3) separating the sulfur tailings by primary roughing and 2-3 times of scavenging, and purifying the sulfur concentrate by 1-3 times of concentration.
The invention is characterized in that:
the sulfuric acid of one of the combined activators can adjust the pH value of ore pulp, the separation of the pyrrhotite is usually arranged after other sulphide ores, caO is usually added to inhibit the pyrrhotite in the separation of other sulphide ores, and after the pyrrhotite is ground, part of the pyrrhotite is slimed and oxidized to cause the reduction of floatability, so that the surface of the pyrrhotite is required to be cleaned by adding the sulfuric acid, and the CaOH on the surface of the pyrrhotite is eliminated + 、Ca(OH) 2 、Fe(OH) 3 The hydrophilic film is favorable for forming hydrophobic biflava on the surface of the pyrrhotite, so that the flotation activity of the pyrrhotite is recovered.
Copper sulfate in the combined activator is widely used as a conventional activator of pyrrhotite, and the principle thereofThe double decomposition reaction occurs on the surface of the activated mineral, so that an activated film is formed on the surface of the mineral. So Cu is 2+ Can be preferentially adsorbed on the surface of pyrrhotite, and the anion adsorption stability of the pyrrhotite to xanthates is enhanced.
Combining ferrous chloride and CY100 in the activator can make Cu 2+ Reduction to Cu + Formation of Cu on mineral surface 2 S, the surface can absorb more Cu ions, and Cu + Has better adsorption effect on xanthate than Cu 2+ Thereby allowing the collector to better interact with the pyrrhotite surface.
The beneficial effects of the invention are as follows:
the combined activator is applied to a technological process of firstly carrying out flotation desulfurization and then carrying out flotation to recover the cassiterite, realizes remarkable activation effect, and tests prove that the sulfur content of ore feeding in the cassiterite flotation is reduced to about 0.3 percent, the S grade and the recovery rate of sulfur concentrate are 26.38 percent and 92.18 percent respectively, well solves the problem of difficult flotation desulfurization of the pyrite-type tin-containing sulfide ore in the prior art, realizes the efficient separation of the cassiterite and the pyrrhotite, and achieves quite satisfactory effect.
Drawings
FIG. 1 is a schematic illustration of the combined activated flotation desulfurization process flow in example 1.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific embodiments, but the scope of the invention is not limited to the description.
Example 1: the method comprises the steps of carrying out desulfurization and ore feeding on tin-containing secondary concentrate of Yunnan Wenshan, wherein the grades of S and Sn in a sample are respectively 2.58% and 0.31%, more than 95% of tin minerals are cassiterite, more than 95% of sulfur minerals are pyrrhotite, carrying out flotation desulfurization by using the combined activator, and the process flow is shown in a figure 1, and comprises the following specific steps:
1) Grinding the raw ore by a crushing and ball grinding machine, wherein the solid-to-liquid ratio of the grinding is 1:1, and the grinding fineness reaches-200 meshes and accounts for 60%;
2) Adjusting the concentration of ore pulp to be 35%, feeding the ore pulp into a flotation tank, calculating the dosage according to the dry weight of minerals, sequentially adding 500 g/ton of sulfuric acid, 200 g/ton of ferrous chloride, 200 g/ton of copper sulfate, 500 g/ton of CY100 (sodium sulfite 100 g/ton+sodium dithionite 200 g/ton+sodium thiosulfate 200 g/ton) and stirring and activating for 3min;
3) Adding 150 g/ton of collecting agent butyl xanthate according to the dry weight of minerals, and stirring for 2min;
4) Adding 40 g/ton of foaming agent according to the dry weight of minerals, stirring for 2min, performing primary roughing operation, aerating, and scraping sulfur concentrate for 5min to obtain roughed sulfur concentrate and roughed tailings;
5) After roughing, adding 50 g/ton of ferrous chloride, 100 g/ton of copper sulfate and 100100 g/ton of CY into the roughing tailings in sequence, and stirring and activating for 3min;
6) Adding 75 g/ton of collecting agent butyl xanthate according to the dry weight of minerals, and stirring for 2min;
7) Adding 20 g/ton of foaming agent according to the dry weight of minerals, stirring for 2min, carrying out scavenging operation, aerating and scraping sulfur concentrate for 3min to obtain scavenging concentrate and scavenging tailing;
8) Adding 25 g/ton of ferrous chloride, 50 g/ton of copper sulfate and 10050 g/ton of CY into the scavenging tailings after the scavenging operation is finished, and stirring and activating for 3min;
9) Adding 37.5 g/ton of collecting agent butyl xanthate according to the dry weight of minerals, and stirring for 2min;
10 Adding 10 g/ton of foaming agent according to the dry weight of minerals, stirring for 2min, carrying out scavenging operation, aerating and scraping sulfur concentrate for 3min to obtain scavenging secondary concentrate and scavenging secondary tailings, returning scavenging secondary concentrate to primary operation, forming closed cycle, and scavenging secondary tailings, namely tin-selecting and feeding;
11 Carrying out primary concentration operation on roughing sulfur concentrate without adding any medicament to obtain concentration primary concentrate and concentration primary tailings, combining the concentration primary tailings with scavenging primary concentrate, and returning to the roughing operation to form closed cycle;
12 The second operation of concentrating the first concentrate is carried out to obtain the second concentrate and the second tailings, the second concentrate is the final sulfur concentrate, and the second tailings are returned to the first operation of concentrating to form closed cycle.
Through detection, the tin-selecting ore-feeding tin-containing agent has the advantages of 0.28 percent of tin, 0.24 percent of sulfur, 26.38 percent of sulfur concentrate and 92.18 percent of sulfur recovery rate, thus obtaining excellent effects and solving the problems of mine enterprises. And simultaneously brings great economic benefit for the enterprises.
Example 2: the grade of S and Sn in the sample is 1.43% and 0.28%, respectively, more than 90% of tin mineral is cassiterite, and more than 95% of sulfur mineral is pyrrhotite. The combined activator is used for floatation desulfurization, and the specific steps are as follows:
1) Grinding the raw ore by a crushing and ball grinding machine, wherein the solid-to-liquid ratio of the grinding is 1:1, and the grinding fineness reaches-200 meshes and accounts for 90%;
2) Adjusting the concentration of ore pulp to be 30% and feeding the ore pulp into a flotation tank, calculating the dosage according to the dry weight of minerals, sequentially adding 100 g/ton of ferrous chloride, 100 g/ton of copper sulfate and 400 g/ton of CY100 (100 g/ton of sodium sulfite, 100 g/ton of sodium metabisulfite and 200 g/ton of sodium thiosulfate) serving as a combined activating agent in sequence, and stirring and activating for 3min;
3) 90 g/ton of the collecting agent amyl xanthate is added according to the dry weight of minerals, and the mixture is stirred for 3min;
4) Adding 40 g/ton of foaming agent according to the dry weight of minerals, stirring for 3min, performing primary roughing operation, aerating, and scraping sulfur concentrate for 5min to obtain roughed sulfur concentrate and roughed tailings;
5) After roughing, adding 50 g/ton of ferrous chloride, 50 g/ton of copper sulfate and 10200 g/ton of CY into roughing tailings in sequence, and stirring and activating for 3min;
6) 45 g/ton of the collecting agent amyl xanthate is added according to the dry weight of minerals, and the mixture is stirred for 2min;
7) Adding 20 g/ton of foaming agent according to the dry weight of minerals, stirring for 2min, carrying out scavenging operation, aerating and scraping sulfur concentrate for 3min to obtain scavenging concentrate and scavenging tailing;
8) Adding 25 g/ton of ferrous chloride, 25 g/ton of copper sulfate and 100100 g/ton of CY into the scavenging tailings after the scavenging operation is finished, and stirring and activating for 3min;
9) Adding 22.5 g/ton of collecting agent butyl xanthate according to the dry weight of minerals, and stirring for 2min;
10 Adding 10 g/ton of foaming agent according to the dry weight of minerals, stirring for 2min, carrying out scavenging operation, aerating and scraping sulfur concentrate for 3min to obtain scavenging secondary concentrate and scavenging secondary tailings, returning scavenging secondary concentrate to primary operation, forming closed cycle, and scavenging secondary tailings, namely tin-selecting and feeding;
11 Carrying out primary concentration operation on roughing sulfur concentrate without adding any medicament to obtain concentration primary concentrate and concentration primary tailings, combining the concentration primary tailings with scavenging primary concentrate, and returning to the roughing operation to form closed cycle;
12 The second operation of concentrating the first concentrate is carried out to obtain the second concentrate and the second tailings, the second concentrate is the final sulfur concentrate, and the second tailings are returned to the first operation of concentrating to form closed cycle.
The detection shows that the fine particle tin-selecting ore-feeding tin-containing agent has 0.28 percent, 0.27 percent of sulfur content, 21.60 percent of sulfur content in sulfur concentrate and 81.68 percent of sulfur recovery rate, thereby obtaining excellent effects and solving the problems of mine enterprises. And simultaneously brings great economic benefit for the enterprises.
Example 3: the grade of S and Sn in the sample is 0.80% and 0.31%, respectively, more than 90% of tin mineral is cassiterite, and more than 95% of sulfur mineral is pyrrhotite.
The combined activator is used for floatation desulfurization, and the specific steps are as follows:
1) Grinding the raw ore by a crushing and ball grinding machine, wherein the solid-to-liquid ratio of the grinding is 1:1, and the grinding fineness reaches-200 meshes and accounts for 50%;
2) Adjusting the concentration of pulp to 40% and feeding the pulp into a flotation tank, calculating the dosage according to the dry weight of minerals, sequentially adding 200 g/ton of sulfuric acid, 200 g/ton of ferrous chloride, 200 g/ton of copper sulfate, 400 g/ton of CY100 (200 g/ton of sodium sulfite and 200 g/ton of sodium metabisulfite) as combined activators, and stirring and activating for 3min;
3) 60 g/ton of collecting agent butyl xanthate is added according to the dry weight of minerals, and stirring is carried out for 2min;
4) Adding 40 g/ton of foaming agent No. 2 oil according to the dry weight of minerals, stirring for 2min, performing primary roughing operation, aerating, and scraping sulfur concentrate for 5min to obtain roughed sulfur concentrate and roughed tailings;
5) After roughing, adding 100 g/ton of ferrous chloride, 100 g/ton of copper sulfate and 100200 g/ton of CY into roughing tailings in sequence, and stirring and activating for 3min;
6) Adding 30 g/ton of collecting agent butyl xanthate according to the dry weight of minerals, and stirring for 2min;
7) Adding 20 g/ton of foaming agent according to the dry weight of minerals, stirring for 2min, carrying out scavenging operation, aerating and scraping sulfur concentrate for 3min to obtain scavenging concentrate and scavenging tailing;
8) Adding 50 g/ton of ferrous chloride, 50 g/ton of copper sulfate and 100100 g/ton of CY into the scavenging tailings after the scavenging operation is finished, and stirring and activating for 3min;
9) Adding 15 g/ton of collecting agent butyl xanthate according to the dry weight of minerals, and stirring for 2min;
10 Adding 10 g/ton of foaming agent according to the dry weight of minerals, stirring for 2min, carrying out scavenging operation, aerating and scraping sulfur concentrate for 3min to obtain scavenging secondary concentrate and scavenging secondary tailings, returning scavenging secondary concentrate to primary operation, forming closed cycle, and scavenging secondary tailings, namely tin-selecting and feeding;
11 Carrying out primary concentration operation on roughing sulfur concentrate without adding any medicament to obtain concentration primary concentrate and concentration primary tailings, combining the concentration primary tailings with scavenging primary concentrate, and returning to the roughing operation to form closed cycle;
12 The second operation of concentrating the first concentrate is carried out to obtain the second concentrate and the second tailings, the second concentrate is the final sulfur concentrate, and the second tailings are returned to the first operation of concentrating to form closed cycle.
The detection shows that the fine particle tin-selecting ore-feeding tin-containing agent has 0.31 percent, 0.08 percent of sulfur content, 23.56 percent of sulfur content in sulfur concentrate and 90.67 percent of sulfur recovery rate, thus obtaining excellent effect and solving the difficult problem for mine enterprises. And simultaneously brings great economic benefit for the enterprises.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (6)
1. A combined activator for floatation desulfurization of pyrrhotite type tin-containing sulfide ores is characterized by comprising sulfuric acid, ferrous chloride, copper sulfate and CY100, wherein the CY100 is one or a combination of more of sodium sulfite, sodium metabisulfite, sodium dithionite and sodium thiosulfate.
2. The combined activator for the flotation desulfurization of pyrrhotite type tin-containing sulphide ores according to claim 1, wherein the combined activator is characterized in that: the mass ratio of each component in the combined activator is as follows
Sulfuric acid: ferrous chloride: copper sulfate: cy100=1-5:1-4:1-5.
3. The use of a combined activator for the flotation desulfurization of pyrrhotite type tin-containing sulphide ores according to claim 1, characterized by the specific steps of:
(1) Crushing and grinding raw ore, wherein the solid-to-liquid ratio of grinding is 1:1, and grinding is carried out until the particle size is less than 0.074mm and accounts for 50% -90% by mass;
(2) Regulating the concentration of ore pulp to 30-40%, feeding the ore pulp into a flotation tank, calculating the dosage according to the dry weight of minerals, adding 200-2000 g/ton of combined activating agent, and stirring and activating for 3-5 min;
(3) Adding 50-200 g/ton of collecting agent butyl xanthate or amyl xanthate according to the dry weight of minerals in sequence, stirring and activating for 2-3 min, then adding 10-60 g/ton of foaming agent according to the dry weight of minerals, stirring and activating for 2-3 min, aerating and scraping sulfur concentrate;
(4) The flotation process comprises the following steps: and (3) separating the sulfur tailings by primary roughing and 2-3 times of scavenging, and purifying the sulfur concentrate by 1-3 times of concentration.
4. The use of a combined activator for the flotation desulfurization of pyrrhotite type tin-containing sulphide ores according to claim 1, characterized in that: the dosing sequence of the activating agent in the step (2) is sulfuric acid, copper sulfate, ferrous chloride and CY100 in sequence.
5. The use of a combined activator for the flotation desulfurization of pyrrhotite type tin-containing sulphide ores according to claim 1, characterized in that: and (3) roughing to obtain roughing concentrate and roughing tailings, carrying out 2-3 scavenging operations on the roughing tailings, returning the tailings subjected to scavenging each time to the previous stage to form closed cycle, and carrying out 1-3 concentration operations on the roughing concentrate to obtain the final sulfur concentrate.
6. The use of a combined activator for the flotation desulfurization of pyrrhotite type tin-containing sulphide ores according to claim 5, wherein: the dosage of the medicament in the scavenging operation is halved compared with that in the roughing operation, and the medicament is not added in the refining operation.
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