CN117599945A - Method for recycling micro-fine cassiterite - Google Patents
Method for recycling micro-fine cassiterite Download PDFInfo
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- CN117599945A CN117599945A CN202410070278.XA CN202410070278A CN117599945A CN 117599945 A CN117599945 A CN 117599945A CN 202410070278 A CN202410070278 A CN 202410070278A CN 117599945 A CN117599945 A CN 117599945A
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- Prior art keywords
- cassiterite
- flotation
- collector
- tin
- concentrate
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 364
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000004064 recycling Methods 0.000 title abstract description 6
- 238000005188 flotation Methods 0.000 claims abstract description 190
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000012141 concentrate Substances 0.000 claims abstract description 86
- 239000004088 foaming agent Substances 0.000 claims abstract description 47
- 239000004576 sand Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 41
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 34
- 230000023556 desulfurization Effects 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- 239000008394 flocculating agent Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 75
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 48
- 230000002000 scavenging effect Effects 0.000 claims description 43
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 25
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 24
- IVIFHBRWCULHPZ-UHFFFAOYSA-N n,1-dihydroxynaphthalene-2-carboxamide Chemical compound C1=CC=CC2=C(O)C(C(=O)NO)=CC=C21 IVIFHBRWCULHPZ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000003213 activating effect Effects 0.000 claims description 11
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims description 10
- QWENMOXLTHDKDL-UHFFFAOYSA-N pentoxymethanedithioic acid Chemical compound CCCCCOC(S)=S QWENMOXLTHDKDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 5
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 claims description 4
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 claims description 4
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 45
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 11
- 239000011707 mineral Substances 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000005189 flocculation Methods 0.000 description 12
- 230000016615 flocculation Effects 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002002 slurry Substances 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 7
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- 238000005273 aeration Methods 0.000 description 5
- 230000033558 biomineral tissue development Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010665 pine oil Substances 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910009027 Sn—OH Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- VDEUYMSGMPQMIK-UHFFFAOYSA-N benzhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1 VDEUYMSGMPQMIK-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D3/00—Differential sedimentation
- B03D3/06—Flocculation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of mineral separation, in particular to a method for recycling micro-fine cassiterite. A method of recovering micro-fine cassiterite comprising: carrying out cyclone classification treatment on the tin tailings to obtain an overflow phase and a sand setting phase; carrying out desulfurization flotation on the settled sand phase to obtain floating sulfur concentrate and desulfurization tailings; carrying out cassiterite flotation on the desulfurization tailings adopting a cassiterite collector; mixing the overflow phase with a flocculating agent, regulating the concentration, and then mixing with a third cassiterite collector and a second foaming agent for column flotation treatment to obtain tin flotation secondary concentrate and flotation tailings. According to the cassiterite collector disclosed by the invention, through the coordination and coordination actions of the components, the collecting efficiency of the collector molecules is higher, the binding capacity is stronger, and the recovery rate of cassiterite flotation operation can be greatly improved. The invention is more beneficial to improving the recovery rate of the cassiterite by applying the cassiterite collecting agent at different moments, the recovery rate of tin in tin concentrate can reach 70.54 percent or more, and the recovery rate of tin in tin concentrate can reach 74.68 percent or more.
Description
Technical Field
The invention relates to the technical field of mineral separation, in particular to a method for recycling micro-fine cassiterite.
Background
Cassiterite is commonly associated with sulphide ores, is brittle, and is wear-resistant, so that a large amount of secondary fine-grained cassiterite can be generated in the grinding process. The fine-fraction cassiterite has large specific surface area, is difficult to effectively collect and mineralize, and is easy to cause cassiterite to be lost in tailings.
At present, the conventional fine-fraction cassiterite recovery process mainly comprises flotation. The first prior art discloses a method for four-stage enrichment and recovery of tin polymetallic ore micro-particle cassiterite, which mainly reduces the influence of the micro-particle cassiterite on subsequent flotation by flocculation-concentration removal, but has a complex process flow and is not easy for industrial application. The second prior art discloses a beneficiation method for fine-grain cassiterite, which recovers fine-grain cassiterite through a classification-gravity separation-flotation mixing process, but the existence of a large amount of fine-grain cassiterite during desulfurization flotation results in serious tin inclusion and relatively low cassiterite recovery rate. The third prior art discloses a beneficiation method of micro-fine cassiterite, which recovers the micro-fine cassiterite through a magnetic separation-gravity separation-desulfurization flotation-cassiterite flotation process, and the recovery rate of the cassiterite is relatively high, but the medicament consumption in the flotation process is high due to the too high mud content, and the cost is high.
Therefore, the method improves the recovery of the micro-particle cassiterite resources and has important significance for sustainable development and utilization of the tin resources.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for recovering micro-fine cassiterite, which aims to solve the problems of difficult mineralization and low recovery rate of the micro-fine cassiterite.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
a method of recovering micro-fine cassiterite comprising the steps of:
carrying out cyclone classification treatment on the tin tailings to obtain an overflow phase and a sand setting phase;
carrying out desulfurization flotation on the settled sand phase to obtain floating sulfur concentrate and desulfurization tailings;
adjusting the desulfurization tailings to a first concentration and a first pH value, and then mixing the desulfurization tailings with an activating agent, a first cassiterite collector and a first foaming agent to perform primary flotation roughing to obtain flotation roughing concentrate and flotation roughing tailings; mixing the flotation rougher tailings with a second cassiterite collector to perform secondary flotation scavenging to obtain scavenging concentrate and scavenging tailings, wherein the scavenging concentrate returns to the primary flotation rougher to form closed cycle; carrying out multistage concentration on the flotation rougher concentrate to obtain cassiterite flotation concentrate, and returning sulfur-containing tin middlings in the multistage concentration to the upper-stage concentration to form closed cycle;
mixing the overflow phase with a flocculating agent, adjusting the concentration, and then mixing with a third cassiterite collector and a second foaming agent for column flotation treatment to obtain tin flotation secondary concentrate and flotation tailings;
the first cassiterite collector, the second cassiterite collector and the third cassiterite collector respectively and independently comprise sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide, and the mass ratio of the sodium hydroxide to the sodium carbonate to the 1-hydroxy-2-naphthalhydroxamic acid to the N-hydroxyphthalimide is (4-6): 0.5-1.5): 1-2): 9-12.
In one embodiment, the first cassiterite collector is used in an amount of 100-400 g/t.
In one embodiment, the second cassiterite collector is used in an amount of 20-100 g/t.
In one embodiment, the amount of the third cassiterite collector is 100-200 g/t.
In one embodiment, the method of preparing the first cassiterite collector, the second cassiterite collector and the third cassiterite collector each independently comprises: and mixing the sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalimide, N-hydroxyphthalimide and water, wherein the mixing temperature is 70-80 ℃.
In one embodiment, the column flotation process includes one rougher, one beneficiation, and two sweeps.
In one embodiment, the column flotation process employs a cyclone-static microbubble flotation column; the circulation pressure of the cyclone-static micro-bubble flotation column is 0.15-0.22 mpa, the air charging amount is 1200-2000L/h, and the thickness of a foam layer is 5-15 cm.
In one embodiment, the first concentration is 30% -40%, and the first pH is 6-8.
In one embodiment, the activator comprises lead nitrate.
In one embodiment, the activator is used in an amount of 100 to 200g/t.
In one embodiment, the first foaming agent comprises No. two oils.
In one embodiment, the amount of the first foaming agent is 10-65 g/t.
In one embodiment, the multi-level beneficiation comprises four beneficiations.
In one embodiment, the flocculant comprises a polyacrylamide.
In one embodiment, the flocculant is used in an amount of 30-60 g/t.
In one embodiment, the overflow phase and flocculant are mixed and adjusted to a concentration of 30% -35%.
In one embodiment, the second foaming agent comprises No. two oils.
In one embodiment, the second foaming agent is used in an amount of 25-40 g/t.
In one embodiment, the desulphurized flotation specifically comprises: and adjusting the pH value of the sand sediment phase to 6-7, and then mixing the sand sediment phase with a flotation collector and a flotation foaming agent, and performing primary roughing, secondary fine selection and tertiary scavenging.
In one embodiment, the flotation collector includes at least one of amyl xanthate and butyl xanthate.
In one embodiment, the amount of the flotation collector is 50-100 g/t.
In one embodiment, the flotation frother comprises a pinitol oil;
in one embodiment, the amount of the flotation frother is 10-60 g/t.
In one embodiment, the average grade of tin in the tin tailings is 0.29% -0.33%.
In one embodiment, the cyclone classification process employs a cyclone; the operation pressure of the cyclone is 0.05-0.15 mpa.
In one embodiment, the overflow phase has a particle size of-0.037 mm and the sand precipitation phase has a particle size of +0.037mm.
Compared with the prior art, the invention has the beneficial effects that:
the novel cassiterite collector provided by the invention has the advantages that through the coordinated cooperation of sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide, the collecting efficiency of the collector molecules is higher, the binding capacity is stronger, and the recovery rate of cassiterite flotation operation can be greatly improved. The cassiterite collecting agent is applied at different moments, so that the recovery rate of cassiterite is improved. The method adopts proper additives to mix and carry out column recovery of the micro-fine cassiterite, thereby enhancing mineralization capability and improving flotation recovery rate. The method can realize the effective recovery of the micro-fine cassiterite, the recovery rate of tin in the tin concentrate can reach 70.54 percent or more, and the recovery rate of tin in the tin concentrate can reach 74.68 percent or more.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention relates to a method for recovering micro-fine cassiterite, comprising the following steps:
and carrying out cyclone classification treatment on the tin tailings to obtain an overflow phase and a sand setting phase.
And carrying out desulfurization flotation on the settled sand phase to obtain floating sulfur concentrate and desulfurization tailings.
Adjusting the desulfurization tailings to a first concentration and a first pH value, and then mixing the desulfurization tailings with an activating agent, a first cassiterite collector and a first foaming agent to perform primary flotation roughing to obtain flotation roughing concentrate and flotation roughing tailings; mixing the flotation rougher tailings with a second cassiterite collector to perform secondary flotation scavenging to obtain scavenging concentrate and scavenging tailings, wherein the scavenging concentrate returns to the primary flotation rougher to form closed cycle; and carrying out multistage concentration on the flotation rougher concentrate to obtain cassiterite flotation concentrate, and returning the sulfur-containing tin middlings in the multistage concentration to the upper-stage concentration to form closed cycle.
And mixing the overflow phase with a flocculating agent, regulating the concentration, and then mixing with a third cassiterite collector and a second foaming agent for column flotation treatment to obtain tin flotation secondary concentrate and flotation tailings.
The first cassiterite collecting agent, the second cassiterite collecting agent and the third cassiterite collecting agent respectively and independently comprise sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide, and under the action of the sodium hydroxide and the ammonium carbonate, hydroximoyl in the mixed medicament, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide is converted into hydroxyl, so that the hydrophilicity of the mixed medicament is increased, the hydroxyl on the surface of the medicament is increased, and the surface potential of cassiterite is reduced; when the pH is more than 8, pb is mainly Pb 2+ And Pb (OH) + Form of (B) Pb 2+ Sn with the surface of cassiterite 4+ A displacement reaction occurs. At this time, pb (OH) + The Sn-OH reaction with the surface of the cassiterite forms Sn-O-Pb + The complex increases the number of active coordination numbers of the cassiterite surface, improves the coordination numbers of the collector groups and the occurrence of cassiterite on the cassiterite surfaceCoordination, thereby realizing the activation of cassiterite. The mass ratio of the sodium hydroxide to the sodium carbonate to the 1-hydroxy-2-naphthalenic hydroxamic acid to the N-hydroxyphthalimide is (4-6): 0.5-1.5): 1-2): 9-12, for example, 4:0.5:1:9, 4.5:1:1.5:10, 5.5:1:1.5:10, 6:1.5:2:12 and the like.
The novel cassiterite collector provided by the invention has the advantages that through the coordinated cooperation of sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide, the collecting efficiency of the collector molecules is higher, the binding capacity is stronger, and the recovery rate of cassiterite flotation operation can be greatly improved. The cassiterite collecting agent is applied at different moments, so that the recovery rate of cassiterite is improved. The method adopts proper additives to mix and carry out column recovery of the micro-fine cassiterite, thereby enhancing mineralization capability and improving flotation recovery rate.
The average grade of tin in the tin tailings is 0.29% -0.33%. Firstly, cyclone classification treatment is carried out by adopting a cyclone, so that an overflow phase (the granularity is-0.037 mm, namely the granularity is less than 0.037 mm) and a sand setting phase (the granularity is +0.037mm, namely the granularity is more than 0.037 mm) are obtained. Tangentially feeding tin tailings into a cyclone with certain pressure, generating a high-speed rotating flow field in a cylindrical cavity, enabling components with high density in the tin tailings to move downwards along the axial direction under the action of the rotating flow field, moving outwards along the radial direction, moving downwards along the wall when reaching a cone section, and discharging from a bottom flow port to obtain a sand sedimentation phase; the components with small density move towards the central axis direction, form an upward moving inner vortex at the center of the axis, and then are discharged from the overflow port to obtain an overflow phase. The operation pressure of the cyclone is 0.05-0.15 Mpa, for example 0.05Mpa, 0.08Mpa, 0.1Mpa, 0.12Mpa, 0.13Mpa, 0.14Mpa, 0.15Mpa and the like. The cyclone of the invention adopts proper operating pressure, thereby obtaining overflow phase and sand setting phase with proper granularity range.
Further, carrying out desulfurization flotation on the sand setting phase to obtain floating sulfur concentrate and desulfurization tailings; the desulfurization flotation specifically comprises the following steps: and adjusting the pH value of the sand sediment phase to 6-7, and then mixing the sand sediment phase with a flotation collector and a flotation foaming agent, and performing primary roughing, secondary fine selection and tertiary scavenging. The invention adopts the sand setting phase with proper pH value, which is more beneficial to the desulfurization and floatation in the later stage.
In one embodiment, the flotation collector includes at least one of amyl xanthate and butyl xanthate. In one embodiment, the flotation collector comprises amyl xanthate and butyl xanthate, and the mass ratio of amyl xanthate to butyl xanthate is (1-2): (1-2), e.g., 1:1, 1:2, 2:1, etc. The invention can better carry out floatation on the sand setting phase by adopting the synergistic action of the amyl xanthate and the butyl xanthate with proper dosage ratio. In one embodiment, the amount of the flotation collector is 50-100 g/t, including but not limited to 50g/t, 70g/t, 80g/t, 90g/t, 100g/t, etc.
The foaming agent can greatly reduce the water surface tension, increase the dispersion of air in the ore pulp, change the size and the motion state of bubbles in the ore pulp, reduce the power consumption of air charging and stirring in the ore pulp, and form a foam layer required by flotation on the ore pulp surface; in the flotation process, the size of the generated bubbles is proper, and the strength of the bubbles is proper. In one embodiment, the flotation frother comprises a pinitol oil; in one embodiment, the amount of the flotation frother is 10 to 60g/t, e.g. 10g/t, 15g/t, 20g/t, 25g/t, 30g/t, 40g/t, 50g/t, 60g/t, etc. The invention adopts proper flotation foaming agent and flotation collector to perform synergistic effect, thereby ensuring flotation effect.
Further, in the process of cassiterite flotation, the desulfurization tailings are adjusted to be 30% -40% of the first concentration, the first PH is adjusted to be 6% -8, and the cassiterite flotation in the later stage is facilitated by adopting proper slurry concentration and pH. Mixing the slurry with the adjusted concentration and pH value with an activating agent, a first cassiterite collecting agent and a first foaming agent for primary flotation roughing to obtain flotation roughing concentrate and flotation roughing tailings; the activating agent comprises lead nitrate, and the dosage of the activating agent is 100-200 g/t, for example, 100g/t, 110g/t, 120g/t, 150g/t, 160g/t, 170g/t, 200g/t and the like; the first foaming agent comprises No. two oil, and the dosage of the first foaming agent is 10-65 g/t, for example 10g/t, 20g/t, 30g/t, 40g/t, 50g/t, 65g/t and the like. Mixing the flotation rougher tailings with a second cassiterite collector to perform secondary flotation scavenging to obtain scavenging concentrate and scavenging tailings, wherein the scavenging concentrate returns to the primary flotation rougher to form closed cycle; the flotation rougher concentrate is subjected to a multi-stage beneficiation, which in one embodiment comprises four beneficiations, resulting in a cassiterite flotation concentrate, the rougher ore in the multi-stage beneficiation being returned to the upper level beneficiation to form a closed cycle.
In one embodiment, the amount of the first cassiterite collector is 100-400 g/t, namely 100-400 g of the first cassiterite collector is added into each ton of slurry, and the amount of the first cassiterite collector is 100g/t, 150g/t, 200g/t, 250g/t, 300g/t, 350g/t, 380g/t, 400g/t and the like.
In one embodiment, the second cassiterite collector is added in an amount of 20-100 g/t, namely 20-100 g of the second cassiterite collector is added in each ton of slurry, and the amount of the second cassiterite collector comprises, but is not limited to, 20g/t, 25g/t, 30g/t, 40g/t, 50g/t, 60g/t, 70g/t, 80g/t, 90g/t, 100g/t and the like.
In one embodiment, the method of preparing the first cassiterite collector and the second cassiterite collector each independently comprises: mixing the sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalenic hydroxamic acid, N-hydroxyphthalimide and water at 70-80 ℃, such as 70 ℃, 72 ℃, 75 ℃, 78 ℃ or 80 ℃.
And further, mixing the overflow phase with a flocculating agent, adjusting the concentration to 30% -35%, such as 30%, 32%, 33%, 35%, and the like, and then mixing with a third cassiterite collector and a second foaming agent for column flotation treatment to obtain tin flotation secondary concentrate and flotation tailings.
In one embodiment, the flocculant comprises a polyacrylamide; the dosage of the flocculant is 30-60 g/t, for example 30g/t, 35g/t, 40g/t, 50g/t or 60g/t and the like; the second foaming agent comprises No. two oil, and the dosage of the second foaming agent is 25-40 g/t, for example 25g/t, 28g/t, 30g/t, 35g/t, 40g/t and the like. In one embodiment, the amount of the third cassiterite collector is 100-200 g/t, namely 100-200 g of the third cassiterite collector is added into each ton of slurry, and the amount of the third cassiterite collector comprises, but is not limited to, 100g/t, 120g/t, 135g/t, 150g/t, 170g/t, 200g/t and the like. In one embodiment, the method of preparing the third cassiterite collector each independently comprises: and mixing the sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalimide, N-hydroxyphthalimide and water, wherein the mixing temperature is 70-80 ℃. The invention adopts the coordination and cooperation of the third cassiterite collector and the second foaming agent, so that the column flotation treatment effect is better.
In one embodiment, the column flotation process comprises one rougher, one beneficiation, and two sweeps; the column flotation treatment adopts a rotational flow-static micro-bubble flotation column; the circulation pressure of the cyclone-static micro-bubble flotation column is 0.15-0.22 Mpa, such as 0.15Mpa, 0.16Mpa, 0.17Mpa, 0.18Mpa, 0.19Mpa, 0.2Mpa, 0.21Mpa, 0.22Mpa and the like, and the aeration amount is 1200-2000L/h, such as 1200L/h, 1400L/h, 1500L/h, 1600L/h, 1700L/h, 1800L/h, 2000L/h and the like; the thickness of the foam layer is 5-15 cm, such as 5cm, 8cm, 10cm, 12cm, 15cm, etc. By using column flotation treatment under suitable conditions, can enhance mineralization capacity and improve flotation recovery rate.
In a preferred embodiment, a method of recovering micro-fine-grained cassiterite comprises the steps of:
(a) Carrying out cyclone classification treatment on tin tailings, wherein the average grade of tin in the tin tailings is 0.29% -0.33%, and a cyclone is adopted in the cyclone classification treatment; the operation pressure of the cyclone is 0.05-0.15 mpa; obtaining an overflow phase and a sand setting phase; the granularity of the overflow phase is-0.037 mm, and the granularity of the sand deposition phase is +0.037mm;
(b) Performing desulfurization flotation on the settled sand phase, wherein the desulfurization flotation specifically comprises the following steps: the pH value of the sand sediment phase is adjusted to 6-7, and then the sand sediment phase is mixed with a flotation collector and a flotation foaming agent to carry out primary roughing, secondary fine selection and tertiary scavenging; the flotation collector comprises at least one of amyl xanthate and butyl xanthate; the consumption of the flotation collector is 50-100 g/t; the flotation foaming agent comprises pinitol oil; the consumption of the flotation foaming agent is 10-60 g/t; obtaining floating sulfur concentrate and desulfurization tailings;
(c) Adjusting the desulfurization tailings to a first concentration of 30% -40% and a first pH value of 6-8, and mixing with an activating agent, a first cassiterite collecting agent and a first foaming agent to perform primary flotation roughing to obtain flotation roughing concentrate and flotation roughing tailings; the activator comprises lead nitrate; the dosage of the activating agent is 100-200 g/t; the first foaming agent comprises No. two oil; the dosage of the first foaming agent is 10-65 g/t; the consumption of the first cassiterite collector is 100-400 g/t; mixing the flotation roughing tailings with a second cassiterite collector for secondary flotation scavenging to obtain scavenging concentrate and scavenging tailings, wherein the dosage of the second cassiterite collector is 20-100 g/t; the scavenger concentrate returns to the primary flotation rougher to form a closed cycle; carrying out multistage concentration on the flotation rougher concentrate to obtain cassiterite flotation concentrate, and returning sulfur-containing tin middlings in the multistage concentration to the upper-stage concentration to form closed cycle;
the first cassiterite collecting agent and the second cassiterite collecting agent respectively and independently comprise sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide, and the mass ratio of the sodium hydroxide to the sodium carbonate to the 1-hydroxy-2-naphthalhydroxamic acid to the N-hydroxyphthalimide is (4-6): 0.5-1.5): 1-2): 9-12;
(d) Mixing the overflow phase with a flocculating agent, adjusting the concentration to be 30% -35%, mixing the mixture with a third cassiterite collecting agent and a second foaming agent, performing column flotation treatment, wherein the third cassiterite collecting agent comprises sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalic acid and N-hydroxyphthalimide, the mass ratio of the sodium hydroxide to the sodium carbonate to the 1-hydroxy-2-naphthalic acid to the N-hydroxyphthalimide is (4-6): (0.5-1.5): (1-2): (9-12), the dosage of the third cassiterite collecting agent is 100-200 g/t, and the flocculating agent comprises polyacrylamide; the dosage of the flocculant is 30-60 g/t; the second foaming agent comprises No. two oil; the dosage of the second foaming agent is 25-40 g/t; the column flotation treatment comprises one roughing, one carefully selecting and two scavenging; the column flotation treatment adopts a rotational flow-static micro-bubble flotation column; the circulation pressure of the cyclone-static micro-bubble flotation column is 0.15-0.22 mpa, the aeration quantity is 1200-2000L/h, and the thickness of a foam layer is 5-15 cm, so that tin flotation secondary concentrate and flotation tailings are obtained;
the preparation method of the first cassiterite collector, the second cassiterite collector and the third cassiterite collector each independently comprises: and mixing the sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalimide, N-hydroxyphthalimide and water, wherein the mixing temperature is 70-80 ℃.
The following is a further explanation in connection with specific examples and comparative examples.
Example 1
The embodiment is an example of the method for recycling micro-fine cassiterite by the grading flocculation linkage based on the novel collecting agent, and the mineral raw material is tin polymetallic ore in Guangxi province; the main mineral components in the table tailing are cassiterite, pyrite, quartz, calcite and the like. The average grade of tin in the ore is 0.29%.
A method of recovering micro-fine cassiterite comprising the steps of:
(1) Desliming of the cyclone: feeding the table tailings into a cyclone for classification, feeding overflow-0.037 mm of the cyclone into a sloping plate thickener for flocculation sedimentation, and feeding the cyclone sand setting plus 0.037mm into subsequent flotation operation.
(2) Desulfurizing and floatation: adding sulfuric acid into the cyclone sand for size mixing, controlling the pH value to be 6, and adopting amyl xanthate and butyl xanthate as flotation collectors according to the mass ratio of 1:1, mixing, and carrying out primary roughing, secondary concentration and tertiary scavenging, wherein the consumption of a flotation collector is 72g/t, and the consumption of a roughing foaming agent, namely, pine oil is 60g/t, so as to obtain floating sulfur concentrate and desulfurization tailings.
(3) Cassiterite flotation: the desulfurization flotation tailings are slurried until the concentration of the ore pulp is 35%, the pH value of the ore pulp is regulated to 6 by sulfuric acid, 200g/t of lead nitrate serving as an activating agent is added, 400g g/t of a first cassiterite collecting agent and 45g/t of No. 2 oil serving as a foaming agent are added, and primary flotation roughing is carried out, so that flotation roughing concentrate and flotation roughing tailings are obtained; adding 50g/t of a second collector into the roughing tailings for secondary flotation scavenging to obtain scavenging concentrate and scavenging tailings, and returning the scavenging concentrate to primary flotation roughing operation to form closed cycle; carrying out four times of concentration on the flotation roughing concentrate to obtain cassiterite flotation concentrate, and returning sulfur-containing tin middlings subjected to each stage of flotation to the upper-stage operation to form closed cycle;
(4) Column flotation: adding 60g/t of polyacrylamide flocculant into the inclined plate thickener in the step (1) for flocculation sedimentation to obtain overflow and settled sand, regulating the slurry concentration of the settled sand to be 35%, feeding the settled sand into a cyclone-static micro-bubble flotation column for one-time roughing one-time concentration and two-time scavenging operation, wherein a third cassiterite collector is adopted in roughing and concentration, the dosage is 175g/t and 130g/t respectively, the dosage of a foaming agent is 40g/t, and tin flotation secondary concentrate and flotation tailings are obtained, wherein the circulating pressure of the cyclone-static micro-bubble flotation column is 0.15Mpa, the aeration amount is 1200L/h, and the thickness of a foam layer is 10cm.
Wherein the first cassiterite collector, the second cassiterite collector and the third cassiterite collector are respectively prepared from sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide according to the mass ratio of 5:2:1:10 is compounded in warm water at 80 ℃.
The tin concentrate and the tin secondary concentrate are obtained through the linkage process of classification, flocculation, desulfurization, floatation and cassiterite floatation by being assisted by a novel cassiterite collector. The grade of tin in the tin concentrate is 6.08%, the tin recovery rate is 71.15%, the grade of tin in the tin sub concentrate is 4.58%, and the tin recovery rate is 75.18%.
Example 2
The embodiment is another example of the method for recycling micro-fine-particle cassiterite by means of grading flocculation linkage based on the novel collecting agent, and the mineral raw material is tin polymetallic ore in Yunnan. The main mineral composition of the ore is cassiterite, pyrite, limonite, quartz, calcite and the like. The average grade of tin in the ore was 0.33%.
The method for recovering the micro-fine cassiterite mainly comprises the following steps:
(1) Desliming of the cyclone: feeding the tin tailings from the shaking table into a cyclone for classification, feeding overflow-0.037 mm of the cyclone into a sloping plate thickener for flocculation sedimentation, and feeding the sand sediment +0.037mm of the cyclone into subsequent flotation operation.
(2) Desulfurizing and floatation: adding sulfuric acid into the cyclone sand for size mixing, controlling the pH value to be 6, and adopting a flotation collector to be amyl xanthate and butyl xanthate according to the mass ratio of 1:2, mixing, namely carrying out primary roughing, secondary concentration and tertiary scavenging, wherein the consumption of a flotation collector is 65g/t, and the consumption of a flotation foaming agent, namely 35g/t of pine oil is used for obtaining the floating sulfur concentrate and the desulfurization tailings.
(3) Cassiterite flotation: the desulfurization flotation tailings are slurried until the concentration of the ore pulp is 36%, the pH value of the ore pulp is regulated to 7 by sulfuric acid, 100g/t of lead nitrate serving as an activating agent is added, 250g/t of a first cassiterite collecting agent and 30g/t of No. 2 oil serving as a foaming agent are added, primary flotation roughing is carried out, and flotation roughing concentrate and flotation roughing tailings are obtained; adding 70g/t of a second collector into the roughing tailings to perform secondary flotation scavenging to obtain scavenging concentrate and scavenging tailings, and returning the scavenging concentrate to primary flotation roughing operation to form closed cycle; carrying out four times of concentration on the flotation roughing concentrate to obtain cassiterite flotation concentrate, and returning sulfur-containing tin middlings subjected to each stage of flotation to the upper-stage operation to form closed cycle;
(4) Column flotation: adding 30g/t of polyacrylamide flocculant into the inclined plate thickener in the step (1) for flocculation sedimentation to obtain overflow and settled sand, regulating the slurry concentration of settled sand to be 30%, feeding the settled sand into a cyclone-static micro-bubble flotation column for one-time roughing one-time concentration and two-time scavenging operation, wherein a third cassiterite collector is adopted in roughing and concentration, the dosage is 170g/t,100g/t and a roughing foaming agent is 25g/t respectively, and tin flotation secondary concentrate and flotation tailings are obtained, wherein the circulating pressure of the cyclone-static micro-bubble flotation column is 0.20Mpa, the aeration quantity is 1800L/h and the thickness of a foam layer is 15cm.
The first cassiterite collector, the second cassiterite collector and the third cassiterite collector are respectively prepared from sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide according to a mass ratio of 5:2:1.5:10 are compounded in warm water at 70 ℃.
The tin concentrate and the tin secondary concentrate are obtained through the linkage process of classification, flocculation, desulfurization, floatation and cassiterite floatation by being assisted by a novel cassiterite collector.
The grade of tin in the tin concentrate is 6.35%, the tin recovery rate is 72.35%, the grade of tin in the tin sub-concentrate is 4.35%, and the tin recovery rate is 74.89%.
Example 3
This example is a further example of the method for recovering micro-fine cassiterite based on the staged flocculation linkage of the novel collector according to the present invention, and the mineral raw material is a certain tin polymetallic ore. The main mineral composition of the ore is cassiterite, pyrite, limonite, quartz, etc. The average grade of tin in the ore was 0.31%.
The method for recovering the micro-fine cassiterite mainly comprises the following steps:
(1) Desliming of the cyclone: mineral raw materials are fed into a cyclone for classification, overflow of the cyclone is-0.037 mm, the mineral raw materials are fed into an inclined plate thickener for flocculation sedimentation, and the sand setting of the cyclone is +0.037mm and enters the subsequent flotation operation.
(2) Desulfurizing and floatation: adding sulfuric acid into the cyclone sand for size mixing, controlling the pH value to be 7, and adopting a flotation collector to be amyl xanthate and butyl xanthate according to the mass ratio of 2:1, mixing, and carrying out primary roughing, secondary concentration and tertiary scavenging, wherein the consumption of a flotation collector is 65g/t, and the consumption of a flotation foaming agent, namely pine oil is 15g/t, so as to obtain floating sulfur concentrate and desulfurization tailings.
(3) Cassiterite flotation: regulating the slurry concentration of the desulfurization flotation tailings to be 30%, regulating the pH value of the slurry to be 6 by sulfuric acid, roughing, adding 100g/t of activator lead nitrate, 100g/t of first cassiterite collector and 40g/t of foaming agent No. 2 oil, and performing primary flotation roughing to obtain flotation roughing concentrate and flotation roughing tailings; adding 45g/t of collector into the roughing tailings to perform secondary scavenging operation to obtain scavenging concentrate and scavenging tailings, and returning the scavenging concentrate to primary flotation roughing operation to form closed cycle; and (3) carrying out four times of concentration on the flotation roughing concentrate to obtain cassiterite flotation concentrate, and returning sulfur-containing tin middlings subjected to each stage of flotation to the upper-stage operation to form closed cycle.
(4) Column flotation: adding 30g/t of polyacrylamide flocculant into the inclined plate thickener in the step (1) for flocculation sedimentation to obtain overflow and settled sand, regulating the slurry concentration of settled sand to be 30%, feeding the settled sand into a cyclone-static micro-bubble flotation column for one-time roughing one-time concentration and two-time scavenging operation, wherein a third cassiterite collector is adopted in roughing and concentration, the dosage is 160g/t and 130g/t respectively, and the foaming agent is 30g/t, so as to obtain tin flotation secondary concentrate and flotation tailings, wherein the circulating pressure of the cyclone-static micro-bubble flotation column is 0.22Mpa, the aeration amount is 2000L/h, and the thickness of a foam layer is 15cm.
The first cassiterite collector, the second cassiterite collector and the third cassiterite collector are respectively prepared from sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide according to the mass ratio of 5:2:1:10 are compounded in warm water at 70 ℃.
The tin concentrate and the tin secondary concentrate are obtained through the linkage process of classification, flocculation, desulfurization, floatation and cassiterite floatation by being assisted by a novel cassiterite collector.
The grade of tin in the tin concentrate is 6.25%, the tin recovery rate is 74.56%, the grade of tin in the tin sub-concentrate is 4.88%, and the tin recovery rate is 75.17%.
Example 4
In the method for recovering fine-grained cassiterite, except that the first cassiterite collector, the second cassiterite collector and the third cassiterite collector are each independently formed by compounding sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide in the mass ratio of 4:1.5:2:9 in warm water at 70 ℃, the other conditions are the same as in example 3.
The grade of tin in the tin concentrate is 6.12%, the tin recovery rate is 70.54%, the grade of tin in the tin sub-concentrate is 4.24%, and the tin recovery rate is 74.68%.
Example 5
In the method for recovering fine-grained cassiterite, except that the first cassiterite collector, the second cassiterite collector and the third cassiterite collector are each independently formed by compounding sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide in the mass ratio of 6:0.5:1:12 in warm water at 70 ℃, the other conditions are the same as in example 3.
The grade of tin in the tin concentrate is 5.98%, the tin recovery rate is 70.69%, the grade of tin in the tin sub concentrate is 4.37%, and the tin recovery rate is 74.79%.
Comparative example 1
The mineral feedstock of this comparative example was identical to that of example 3, except that the crude ore was not cyclone classified, the conventional cassiterite collector, the benzoate hydroxamic acid, was used as the flotation collector, and a conventional aerated flotation machine was used as the comparative example, otherwise identical to that described above. The tin concentrate obtained in this comparative example had a tin content of 3.68%, a tin recovery of 55.48%, a tin grade of 1.70% in the secondary tin concentrate, and a tin recovery of 47.15%.
Comparative example 2
In this comparative example, the first cassiterite collector, the second cassiterite collector and the third cassiterite collector were each benzohydroxamic acid, with the other conditions being the same as in example 3.
The tin concentrate obtained in this comparative example had a tin content of 3.59%, a tin recovery of 54.69%, a tin grade of 1.67% in the secondary tin concentrate, and a tin recovery of 48.97%.
Comparative example 3
In this comparative example, the conditions were the same as in example 3 except that the first cassiterite collector, the second cassiterite collector, and the third cassiterite collector were each independently composed of sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid, and N-hydroxyphthalimide in a mass ratio of 2:5:4:7 in 70 ℃ warm water.
The tin concentrate obtained in this comparative example had a tin content of 3.03%, a tin recovery of 55.34%, a tin grade of 1.61% in the secondary tin concentrate, and a tin recovery of 46.58%.
From the above, the novel cassiterite collector provided by the invention has the advantages that the collecting efficiency of the collector molecules is higher, the binding capacity is stronger, and the recovery rate of cassiterite flotation operation can be greatly improved through the coordination and coordination of sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide. The invention is more beneficial to improving the recovery rate of the cassiterite by applying a proper amount of the cassiterite collecting agent at different moments. The method adopts proper additives to mix and carry out column recovery of the micro-fine cassiterite, thereby enhancing mineralization capability and improving flotation recovery rate. The method can realize the effective recovery of the micro-fine cassiterite, the recovery rate of tin in the tin concentrate can reach 70.54 percent or more, and the recovery rate of tin in the tin concentrate can reach 74.68 percent or more.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A method of recovering micro-fine cassiterite, comprising the steps of:
carrying out cyclone classification treatment on the tin tailings to obtain an overflow phase and a sand setting phase;
carrying out desulfurization flotation on the settled sand phase to obtain floating sulfur concentrate and desulfurization tailings;
the desulfurization tailings are regulated to a first concentration and a first pH value, and then are mixed with an activating agent, a first cassiterite collector and a first foaming agent for primary flotation roughing, so that flotation roughing concentrate and flotation roughing tailings are obtained; mixing the flotation rougher tailings with a second cassiterite collector to perform secondary flotation scavenging to obtain scavenging concentrate and scavenging tailings, wherein the scavenging concentrate returns to the primary flotation rougher to form closed cycle; carrying out multistage concentration on the flotation rougher concentrate to obtain cassiterite flotation concentrate, and returning sulfur-containing tin middlings in the multistage concentration to the upper-stage concentration to form closed cycle;
mixing the overflow phase with a flocculating agent, adjusting the concentration, and then mixing with a third cassiterite collector and a second foaming agent for column flotation treatment to obtain tin flotation secondary concentrate and flotation tailings;
the first cassiterite collector, the second cassiterite collector and the third cassiterite collector respectively and independently comprise sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalhydroxamic acid and N-hydroxyphthalimide, and the mass ratio of the sodium hydroxide to the sodium carbonate to the 1-hydroxy-2-naphthalhydroxamic acid to the N-hydroxyphthalimide is (4-6): 0.5-1.5): 1-2): 9-12.
2. The method for recovering micro-fine cassiterite according to claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) The consumption of the first cassiterite collector is 100-400 g/t;
(2) The dosage of the second cassiterite collector is 20-100 g/t;
(3) The consumption of the third cassiterite collector is 100-200 g/t.
3. The method for recovering micro-fine-particle cassiterite according to claim 1, wherein the preparation method of the first cassiterite collector, the second cassiterite collector and the third cassiterite collector each independently comprises: and mixing the sodium hydroxide, sodium carbonate, 1-hydroxy-2-naphthalimide, N-hydroxyphthalimide and water, wherein the mixing temperature is 70-80 ℃.
4. The method for recovering micro-fine cassiterite according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The column flotation treatment comprises one roughing, one refining and two scavenging;
(2) The column flotation treatment adopts a rotational flow-static micro-bubble flotation column; the circulation pressure of the cyclone-static micro-bubble flotation column is 0.15-0.22 mpa, the air charging amount is 1200-2000L/h, and the thickness of a foam layer is 5-15 cm.
5. The method for recovering micro-fine cassiterite according to claim 1, comprising at least one of the following steps (1) to (6):
(1) The first concentration is 30% -40%, and the first pH is 6-8;
(2) The activator comprises lead chloride;
(3) The dosage of the activating agent is 100-200 g/t;
(4) The first foaming agent comprises No. two oil;
(5) The dosage of the first foaming agent is 10-65 g/t;
(6) The multi-level beneficiation comprises four beneficiations.
6. The method for recovering micro-fine cassiterite according to claim 1, comprising at least one of the following steps (1) to (5):
(1) The flocculant comprises polyacrylamide;
(2) The dosage of the flocculant is 30-60 g/t;
(3) Mixing the overflow phase with a flocculating agent and adjusting the concentration to 30% -35%;
(4) The second foaming agent comprises No. two oil;
(5) The dosage of the second foaming agent is 25-40 g/t.
7. The method for recovering micro-fine cassiterite according to claim 1, characterized in that said desulphurisation flotation comprises in particular: and adjusting the pH value of the sand sediment phase to 6-7, and then mixing the sand sediment phase with a flotation collector and a flotation foaming agent, and performing primary roughing, secondary fine selection and tertiary scavenging.
8. The method for recovering micro-fine cassiterite according to claim 7, characterized by comprising at least one of the following features (1) to (4):
(1) The flotation collector comprises at least one of amyl xanthate and butyl xanthate;
(2) The consumption of the flotation collector is 50-100 g/t;
(3) The flotation foaming agent comprises pinitol oil;
(4) The consumption of the flotation foaming agent is 10-60 g/t.
9. The method of recovering micro-fine cassiterite according to claim 1, wherein the average grade of tin in the tin tailings is 0.29% -0.33%.
10. The method for recovering micro-fine cassiterite according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The cyclone classification treatment adopts a cyclone; the operation pressure of the cyclone is 0.05-0.15 mpa;
(2) The granularity of the overflow phase is-0.037 mm, and the granularity of the sand deposition phase is +0.037mm.
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