AU2021103189A4 - Enhanced flotation collector for coarse-grained spodumene and use thereof - Google Patents
Enhanced flotation collector for coarse-grained spodumene and use thereof Download PDFInfo
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- AU2021103189A4 AU2021103189A4 AU2021103189A AU2021103189A AU2021103189A4 AU 2021103189 A4 AU2021103189 A4 AU 2021103189A4 AU 2021103189 A AU2021103189 A AU 2021103189A AU 2021103189 A AU2021103189 A AU 2021103189A AU 2021103189 A4 AU2021103189 A4 AU 2021103189A4
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- spodumene
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- grained
- flotation
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- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 128
- 238000005188 flotation Methods 0.000 title claims abstract description 83
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 68
- 239000012141 concentrate Substances 0.000 claims abstract description 37
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 34
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 26
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract description 24
- 238000000227 grinding Methods 0.000 claims abstract description 24
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 230000002000 scavenging effect Effects 0.000 claims abstract description 15
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 11
- 238000007885 magnetic separation Methods 0.000 claims abstract description 11
- 239000011707 mineral Substances 0.000 claims abstract description 11
- 235000010755 mineral Nutrition 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 9
- 239000000194 fatty acid Substances 0.000 claims abstract description 9
- 229930195729 fatty acid Natural products 0.000 claims abstract description 9
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 9
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims abstract description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940116411 terpineol Drugs 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 19
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 16
- 229960003237 betaine Drugs 0.000 claims description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012190 activator Substances 0.000 claims description 5
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229940117986 sulfobetaine Drugs 0.000 claims description 2
- 235000011148 calcium chloride Nutrition 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000008685 targeting Effects 0.000 abstract 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 11
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 11
- 239000005642 Oleic acid Substances 0.000 description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 11
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 11
- 229960002969 oleic acid Drugs 0.000 description 11
- 235000021313 oleic acid Nutrition 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 5
- 229940057995 liquid paraffin Drugs 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000005273 aeration Methods 0.000 description 2
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 2
- 229910052612 amphibole Inorganic materials 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 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
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 that is Substances 0.000 description 1
- 239000002699 waste material Substances 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
- 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
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B1/00—Conditioning for facilitating separation by altering physical properties of the matter to be treated
-
- 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
- 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
- B03D2203/04—Non-sulfide ores
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
OF THE DISCLOSURE
The present disclosure relates to the technical field of mineral flotation, in particular to an
enhanced flotation collector for coarse-grained spodumene and a use thereof. The collector includes
a specific content of sodium carbonate, fatty acid, betaine series surfactant, neutral oil and terpineol
or methyl isobutyl carbinol (MIBC). The present disclosure further provides a use of the collector,
targeting the enhanced flotation of coarse-grained spodumene in pegmatite. A flotation process of
the present disclosure only needs to grind a spodumene ore to a grinding fineness of 45-70%, -0.074
mm. A raw ore pulp is subjected to magnetic separation to remove a magnetic gangue mineral, and
then the collector is used to carry out one roughing, one cleaning and one scavenging to obtain a
spodumene concentrate product. By combining the process with the collector, the present disclosure
can increase a Li2 0 grade from 0.8-1.8% in the raw ore to 5.8-6.5% in the spodumene concentrate,
achieving a recovery rate of 80-90%. The present disclosure greatly reduces the grinding load and
cost of the spodumene ore, and can simplify the process flow and improve the separation efficiency.
11
DRAWINGS
Raw ore
Grinding fineness:
45-70%, -74 pm
Na2CO3: 2-4 kg/t
Magnetic separation
Magnetic
gangue CaC1 2
Collector
Roughing '0- CaC1 2
Na2CO3 lCollector
Spodumene Tailing
concentrate
FIG. 1
Description
Raw ore
Grinding fineness: -70%, -74 pm Na 2CO3: 2-4 kg/t
Magnetic separation
Magnetic gangue CaC1 2 Collector
Roughing '0- CaC1 2 Na2CO3 lCollector
Spodumene Tailing concentrate
FIG. 1
[01] The present disclosure relates to the technical field of mineral flotation, in particular to an enhanced flotation collector for coarse-grained spodumene and a use thereof.
[02] Known as the "new energy metal in the 21" century" and the "important element that drives the world forward", lithium has been widely used in the fields of batteries, lubricants, solid fuels, catalysts and nuclear industries. With the development and progress of science and technology, the market demand for the lithium resources continues to grow at a high speed.
[03] Spodumene is one of the main lithium resources that are currently available for development and utilization. Spodumene is found in pegmatite and generally has a large crystal grain size. The pegmatite spodumene ore has a grade of 1-2.5%. It is associated with gangue minerals such as quartz and feldspar, accompanied by a small amount of aluminosilicate minerals such as mica, amphibole and chlorite. The spodumene is usually separated by means of hand picking, flotation, gravity separation and flotation-gravity combined separation. Among them, flotation is the most common and effective method for spodumene processing. The typical agents used for spodumene flotation include three alkalis and two soaps, that is, sodium carbonate, sodium hydroxide and sodium sulfide serving as regulators and oxidized paraffin soap (OPS) and naphthenate soap serving as collectors.
[04] In the current agent system, if the grinding fineness is large, the coarse spodumene is difficult to float, resulting in a low recovery rate. Hence, most spodumene processing plants usually adopt a grinding fineness of 75% or more, -74 m, and some even increase the grinding fineness to % or more, -74 m. However, the flotation rate of spodumene decreases under fine grinding. In addition, since the aluminosilicate minerals such as feldspar, quartz, mica, chlorite and amphibole have similar surface properties to spodumene, they are easy to enter the spodumene concentrate along with the froth, thus making it hard to upgrade the spodumene concentrate. In recent years, there has been research on the flotation recovery of spodumene by using anion and cation combination agents. Due to the addition of a fatty amine collector in the agent, a large amount of sticky froths are produced during the flotation process, which makes it hard to apply the process in actual production. In order to balance the grade and recovery rate of the spodumene concentrate, it is necessary to develop an efficient flotation collector and process that enhance the flotation of coarse-grained spodumene. It is of great significance for maximizing the value of resources, building a resource-saving society and guaranteeing strategic resource reserves.
[05] In order to solve the problems of poor efficiency and energy waste in the flotation of coarse-grained spodumene, the present disclosure provides an enhanced flotation collector and process for coarse-grained spodumene. The collector can be used as a high-efficiency collector for spodumene of a conventional particle size, and can also significantly improve the flotation of coarse-grained spodumene. The collector can be used for flotation recovery of pegmatite spodumene under coarse grinding, and can obtain a spodumene concentrate with a high grade and recovery rate.
[06] In order to achieve the above objective, the present disclosure provides an enhanced flotation collector and process for coarse-grained spodumene.
[07] The enhanced flotation collector for coarse-grained spodumene includes the following components in parts by mass: 20-30 parts of sodium carbonate, 60-75 parts of fatty acid, 10-20 parts of betaine series surfactant, 5-10 parts of neutral oil and 3-6 parts of terpineol (2# oil) or methyl isobutyl carbinol (MIBC).
[08] Preferably, in the enhanced flotation collector for coarse-grained spodumene, the fatty acid may be a long-chain fatty acid with a carbon chain length greater than 12 or a compound thereof. Of course, oleic acid or an industrial product based on the oleic acid may be also applicable in the present disclosure.
[09] Preferably, in the enhanced flotation collector for coarse-grained spodumene, the betaine series surfactant may be at least one selected from the group consisting of carboxylic betaine, sulfobetaine, sulfate betaine and phosphate betaine, or may be an industrial product with the above substance as a main component. More preferably, the betaine surfactant may be C 12-C 14 alkyl dimethyl betaine.
[10] Preferably, in the enhanced flotation collector for coarse-grained spodumene, the neutral oil may be C 4 -C 16 alkane, aromatic hydrocarbon or a compound thereof that may be liquid or solid at room temperature, or may be an industrial product with the above substance as a main component. More preferably, the neutral oil may be kerosene or liquid paraffin.
[11] The enhanced flotation collector for coarse-grained spodumene may be prepared as follows:
[12] 1) dissolving the sodium carbonate prepared according to a set ratio in an appropriate amount of water to obtain a sodium carbonate solution A; and
[13] 2) adding the fatty acid, the betaine series surfactant, the neutral oil and the terpineol (2# oil) or the MIBC to the solution A according to a set ratio; mixing uniformly, heating and stirring to achieve a complete reaction, so as to obtain a homogeneous solution as the enhanced flotation collector for coarse-grained spodumene.
[14] The present disclosure provides a use of the enhanced flotation collector for coarse-grained spodumene. The enhanced flotation collector is used for a flotation process of coarse-grained spodumene, and the flotation process includes the following steps:
[15] 1) crushing a raw spodumene ore to -2 mm;
[16] 2) grinding the crushed spodumene ore according to a grinding fineness of 45-70%, -0.074 mm to obtain a spodumene ore pulp;
[17] 3) diluting the obtained spodumene ore pulp, and subjecting the ore pulp to magnetic separation to remove a magnetic gangue mineral;
[18] 4) adding a sodium carbonate solution to the ore pulp from which the magnetic gangue mineral is removed to adjust the pH of the ore pulp;
[19] 5) adding an alkaline earth metal ion as an activator of spodumene to the pH-adjusted ore pulp; and
[20] 6) adding the enhanced flotation collector for coarse-grained spodumene to the activated ore pulp, stirring, and then aerating for flotation to obtain a spodumene concentrate and a tailing product.
[21] In the use, in step 2), the heating and stirring may be conducted at 70-90°C for 10-30 min.
[22] In the use, all the agents may also be prepared without mixing and heating, and be added sequentially before flotation.
[23] In the use, in step 2), 2-4 kg/t of sodium carbonate may be added for grinding.
[24] In the use, in step 3), a magnetic field strength of the magnetic separation may be 0.6-1.2 T.
[25] In the use, in step 4), the ore pulp may have a mass concentration of 30-50% and a pH of 9.7-11.5. Preferably, the ore pulp may have a mass concentration of 35-45% and a pH of 10.3-11.2.
[26] In the use, in step 5), 100-200 g/t of alkaline earth metal ion activator, which may be represented by a calcium ion, may be added. Preferably, 200-400 g/t of calcium chloride activator may be added.
[27] In the use, in step 6), the flotation may include one roughing, one cleaning and one scavenging;
[28] in the roughing, 700-1,300 g/t of enhanced flotation collector for coarse-grained spodumene may be added; in the cleaning, no collector may be added; in the scavenging, 200-600 g/t of enhanced flotation collector for coarse-grained spodumene may be added. Preferably, in the roughing, 900-1,200 g/t of enhanced flotation collector for coarse-grained spodumene may be added; in the cleaning, no collector may be added, and the pH of the ore pulp may be adjusted to the same level in the roughing; in the scavenging, 300-500 g/t of enhanced flotation collector for coarse-grained spodumene may be added.
[29] The present disclosure provides an enhanced flotation collector and process for coarse-grained spodumene. The key to the collector is that it innovatively adds the betaine surfactant, the neutral oil and the frothing agent 2# oil or the MIBC to the fatty acid and the sodium carbonate of a specific content. The betaine, the neutral oil and the frothing agent serve as auxiliary agents, which can enhance the flotation of coarse-grained spodumene, adjust the froth structure, and significantly improve the recovery rate of coarse-grained spodumene. These agents can be added sequentially, and can also be added in form of a mixed solution. The enhanced flotation collector is prepared as follows: dissolving the sodium carbonate in an appropriate amount of water to obtain a sodium carbonate solution; adding the fatty acid, the betaine series surfactant, the neutral oil and the #2 oil or the MIBC to the solution, mixing uniformly, heating and stirring to achieve a complete reaction, so as to obtain a homogeneous solution as the enhanced flotation collector for coarse-grained spodumene. The present disclosure further provides a flotation process matching the enhanced flotation collector for coarse-grained spodumene. The process only needs to grind the spodumene ore to a grinding fineness of 45-70%, -0.074 mm. The raw ore pulp is first subjected to magnetic separation to remove a magnetic gangue mineral, and the pH of the ore pulp is adjusted to 9.7-11.5. Then the above collector is used to carry out one roughing, one cleaning and one scavenging to obtain a spodumene concentrate product. The collector of the present disclosure can enhance the flotation of coarse-grained spodumene and has desirable selectivity. By means of the above process, the present disclosure can increase a Li 2 0 grade from 0.8-1.8% in the raw ore to 5.8-6.5% in the spodumene concentrate, achieving a recovery rate of 80-90%. The collector and process greatly reduce the grinding load and cost of the spodumene ore, and can simplify the process flow and improve the separation efficiency. The present disclosure is of great significance for maximizing the value of resources, building a resource-saving society and guaranteeing strategic resource reserves.
[30] FIG. 1 is a flowchart of a flotation process according to the present disclosure.
[31] In order to facilitate a better understanding of the present disclosure, the content of the present disclosure is further described below in conjunction with the examples, but the content of the present disclosure is not limited to the following examples. Other substitutions, modifications, changes and deletions may be made to the design, operating conditions and parameters of the following exemplary examples without departing from the spirit of the present disclosure, but all such adjustments should be included in the scope of the present disclosure. The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to include values close to these ranges or values. In terms of numerical ranges, one or more new numerical ranges can be derived by combining the end values of each range, combining the end values of each range and the individual point values and combining the individual point values, and these numerical ranges should be considered as specifically disclosed herein.
[32] The present disclosure is described in below with reference to the specific examples.
[33] Example 1
[34] 15 g of sodium carbonate was added to an appropriate amount of water and stirred well until it was completely dissolved to obtain a sodium carbonate solution. 35 g of oleic acid, 12 g of tetradecyl dimethyl betaine, 8 g of liquid paraffin and 4 g of 2# oil were added to the sodium carbonate solution. These substances were heated and stirred at 90°C for 20 min to achieve a complete reaction, so as to obtain a homogeneous solution as an enhanced flotation collector for coarse-grained spodumene. When in use, the enhanced flotation collector was diluted to a specific concentration.
[35] Example 2
[36] 8 g of sodium carbonate was added to an appropriate amount of water and stirred well until it was completely dissolved to obtain a sodium carbonate solution. 20 g of linoleic acid, 10 g of octadecyl dimethyl betaine, 3 g of liquid paraffin and 2 g of methyl isobutyl carbinol (MIBC) were added to the sodium carbonate solution. These substances were heated and stirred at 80°C for 30 min to achieve a complete reaction, so as to obtain a homogeneous solution as an enhanced flotation collector for coarse-grained spodumene. When in use, the enhanced flotation collector was diluted to a specific concentration.
[37] Example 3
[38] 25 g of sodium carbonate was added to an appropriate amount of water and stirred well until it was completely dissolved to obtain a sodium carbonate solution. 60 g of oleic acid, 20 g of dodecyl dimethyl betaine, 10 g of liquid paraffin and 8 g of 2# oil were added to the sodium carbonate solution. These substances were heated and stirred at 90°C for 30 min to achieve a complete reaction, so as to obtain a homogeneous solution as an enhanced flotation collector for coarse-grained spodumene. When in use, the enhanced flotation collector was diluted to a specific concentration.
[39] Application Example 1
[40] A spodumene ore, with a Li2 0 content of 1.45%, was mined from the Jiajika mine in Sichuan, China. The spodumene ore was ground to a grinding fineness of 55%, -0.074 mm, and was subjected to magnetic separation to remove a magnetic gangue mineral. Then sodium carbonate was added to adjust the pH of an ore pulp to 10.3, and stirring was carried out for 3 min. A calcium chloride solution with a mass concentration of 2.5%, prepared from 250 g/t of calcium chloride, was added, and stirring was carried out for 3 min. The collector prepared in Example 1 was added in an amount of 1,100 g per ton of spodumene ore, and stirring was carried out for 5 min. Then aeration was carried out for flotation to obtain a roughing concentrate and tailing. 100 g/t of calcium chloride was added to the roughing tailing, and stirring was carried out for 3 min. 400 g/t of collector prepared in Example 1 was added, and stirring was carried out for 5 min. Then scavenging was carried out to obtain a scavenging middling and tailing, and the scavenging middling was returned to the roughing task. Sodium carbonate was added to the roughing concentrate to adjust the pH to 10.3, and stirring was carried out for 3 min. Then cleaning was carried out to obtain a cleaning middling and concentrate. The cleaning middle was returned to the roughing task, and the cleaning concentrate was a spodumene concentrate. The scavenging tailing was a spodumene tailing. FIG. 1 shows a specific flotation process, and Table 1 provides flotation indexes. Through the collector and process of the present disclosure, the spodumene concentrate separated from the Jiajika spodumene ore with a Li 2 0 content of 1.45% increased the Li 2 0 grade to 6.19%, achieving a recovery rate of 89.07%.
[41] Table 1 Flotation indexes of enhanced flotation collector for Jiajika spodumene ore Product Yield /% Li 2 0 grade /% Recovery rate /% Magnetic product 1.73 1.12 1.33 Spodumene concentrate 20.90 6.19 89.08 Spodumene tailing 77.37 0.18 9.59 Total 100 1.45 100
[42] Comparative Example 1
[43] The raw materials and processes were the same as those in Experimental Example 1, except that other combination agents were used to replace the enhanced flotation collector for coarse-grained spodumene. The experimental results are shown in Table 2.
[44] Table 2 Flotation indexes of Jiajika spodumene ore Collector Product Yield /% Li2 0 grade /% Recovery rate /% Magnetic product 1.71 1.21 1.43
Spodumene concentrate 19.43 5.65 75.73 Oleicacid Spodumene tailing 78.86 0.42 22.85 Total 100 1.45 100 Magnetic product 1.89 1.11 1.44 Oleicacid+liquid Spodumene concentrate 18.24 6.41 79.99 paraffin Spodumene tailing 79.87 0.34 18.58 (massratio5:1) Total 100 1.46 100 Oleic acid + betaine Magnetic product 2.06 1.1 1.57
(mass ratio 3:1) Spodumene concentrate 25.36 4.93 86.83 Spodumene tailing 72.58 0.23 11.59 Total 100 1.44 100 Magnetic product 1.56 1.32 1.43 Oleicacid+liquid Spodumene concentrate 23.51 5.38 87.67 paraffin+betaine(mass Spodumene tailing 74.93 0.21 10.91 ratio15:3:5) Total 100 1.44 100
[45] Experimental Example 2
[46] An experiment spodumene ore, with a Li2 0 content of 1.49%, was mined from Lijiagou in Sichuan, China. The spodumene ore was ground to a grinding fineness of 61%, -0.074 mm, and was subjected to magnetic separation to remove a magnetic gangue mineral. Then sodium carbonate was added to adjust the pH of an ore pulp to 10.5, and stirring was carried out for 3 min. A calcium chloride solution with a mass concentration of 2.5%, prepared from 300 g/t of calcium chloride, was added, and stirring was carried out for 3 min. The collector prepared in Example 2 was added in an amount of 1,200 g per ton of spodumene ore, and stirring was carried out for 5 min. Then aeration was carried out for flotation to obtain a roughing concentrate and tailing. 120 g/t of calcium chloride was added to the roughing tailing, and stirring was carried out for 3 min. 450 g/t of collector prepared in Example 3 was added, and stirring was carried out for 5 min. Then scavenging was carried out to obtain a scavenging middling and tailing, and the scavenging middling was returned to the roughing task. Sodium carbonate was added to the roughing concentrate to adjust the pH to 10.5, and stirring was carried out for 3 min. Then cleaning was carried out to obtain a cleaning middling and concentrate. The cleaning middle was returned to the roughing task, and the cleaning concentrate was a spodumene concentrate. The scavenging tailing was a spodumene tailing. FIG. 1 shows a specific flotation process, and Table 2 provides flotation indexes. Through the collector and process of the present disclosure, the spodumene concentrate separated from the Lijiagou spodumene ore with a Li 2 0 content of 1.49% increased the Li 2 0 grade to 6.14%, achieving a recovery rate of 88.23%.
[47] Table 3 Flotation indexes of enhanced flotation collector for Lijiagou spodumene ore Product Yield /% Li 2 0 grade /% Recovery rate /% Magnetic product 1.08 1.20 0.87 Spodumene concentrate 21.45 6.14 88.23 Spodumene tailing 77.47 0.21 10.90 Total 100 1.49 100
[48] Comparative Example 2
[49] The raw materials and processes were the same as those in Experimental Example 2, except that other combination agents were used to replace the enhanced flotation collector for coarse-grained spodumene. The experimental results are shown in Table 4.
[50] Table 4 Flotation indexes of Lijiagou spodumene ore Collector Product Yield /% Li2 0 grade /% Recovery rate /% Magnetic product 1.12 1.18 0.88 Spodumene concentrate 20.36 5.73 78.09 Spodumene tailing 78.52 0.4 21.02 Total 100 1.49 100 Magnetic product 1.37 1.16 1.07 Oleic acid + liquid Spodumene concentrate 19.25 6.33 82.31 paraffin (mass ratio 6:1) Spodumene tailing 79.38 0.31 16.62 Total 100 1.48 100 Magnetic product 1.53 1.22 1.24 Oleic acid + betaine (mass Spodumene concentrate 23.74 5.44 85.84 ratio 2:1) Spodumene tailing 74.73 0.26 12.92 Total 100 1.50 100 Magnetic product 1.34 1.22 1.11 Oleicacid+liquid Spodumene concentrate 22.82 5.64 87.09 paraffin+betaine(mass Spodumene tailing 75.84 0.23 11.80 ratio6:1:3) Total 100 1.48 100
[51] Comparative Example 3
[52] Only the grinding fineness was changed, that is, 82.17% and 88.32%, -0.074 mm, and other conditions such as raw materials and experimental procedures were the same as those in Experimental Example 2. The experimental results are shown in Table 5. When the grinding fineness exceeded the optimal range, the grade of spodumene decreased significantly, and the recovery rate remained basically unchanged.
[53] Table 5 Flotation indexes of Lijiagou spodumene ore under different grinding fineness Grinding fineness Product Yield /% Li 2 0 grade /% Recovery rate /% Magnetic product 1.76 1.12 1.34 Spodumene concentrate 24.64 5.34 89.19 82.17%,-0.074 mm Spodumene tailing 73.6 0.19 9.48 Total 100 1.48 100 Magnetic product 1.92 1.09 1.40 Spodumene concentrate 26.04 5.16 89.92 88.32%,-0.074 mm Spodumene tailing 72.04 0.18 8.68 Total 100 1.49 100
Claims (5)
1. An enhanced flotation collector for coarse-grained spodumene, comprising the following components in parts by mass: 20-30 parts of sodium carbonate; 60-75 parts of fatty acid; 10-20 parts of betaine series surfactant; 5-10 parts of neutral oil; and 3-6 parts of terpineol or methyl isobutyl carbinol (MIBC).
2. The enhanced flotation collector for coarse-grained spodumene according to claim 1, wherein the fatty acid is a long-chain fatty acid with a carbon chain length greater than 12 or a compound thereof; wherein the betaine series surfactant is at least one selected from the group consisting of carboxylic betaine, sulfobetaine, sulfate betaine and phosphate betaine, or is an industrial product with the above substance as a main component; wherein the neutral oil is C4 -C1 6 alkane, aromatic hydrocarbon or a compound thereof that is liquid or solid at room temperature, or is an industrial product with the above substance as a main component.
3. The enhanced flotation collector for coarse-grained spodumene according to claim 1, wherein the enhanced flotation collector is prepared as follows: 1) dissolving the sodium carbonate prepared according to a set ratio in an appropriate amount of water to obtain a sodium carbonate solution A; and 2) adding the fatty acid, the betaine series surfactant, the neutral oil and the terpineol or the MIBC to the solution A according to a set ratio; mixing uniformly, heating and stirring to achieve a complete reaction, so as to obtain a homogeneous solution as the enhanced flotation collector for coarse-grained spodumene; wherein in step 2), the heating and stirring are conducted at 70-90°C for 10-30 min.
4. A use of the enhanced flotation collector for coarse-grained spodumene according to any one of claims 1 to 3, wherein the enhanced flotation collector is used for a flotation process of coarse-grained spodumene, and the flotation process comprises the following steps: 1) crushing a raw spodumene ore to -2 mm; 2) grinding the crushed spodumene ore according to a grinding fineness of 45-70%, -0.074 mm to obtain a spodumene ore pulp; 3) diluting the obtained spodumene ore pulp, and subjecting the ore pulp to magnetic separation to remove a magnetic gangue mineral; 4) adding a sodium carbonate solution to the ore pulp from which the magnetic gangue mineral is removed to adjust the pH of the ore pulp; 5) adding an alkaline earth metal ion as an activator of spodumene to the pH-adjusted ore pulp; and 6) adding the enhanced flotation collector for coarse-grained spodumene to the activated ore pulp, stirring, and then aerating for flotation to obtain a spodumene concentrate and a tailing product.
5. The use of the enhanced flotation collector for coarse-grained spodumene according to claim 4, wherein in step 2), 2-4 kg/t of sodium carbonate is added for grinding; in step 3), a magnetic field strength of the magnetic separation is 0.6-1.2 T; in step 4), the pH of the ore pulp is 9.7-11.5; wherein in step 5), 100-200 g/t of alkaline earth metal ion activator, which is represented by a calcium ion, is added; wherein in step 6), the flotation comprises one roughing, one cleaning and one scavenging; in the roughing, 700-1,300 g/t of enhanced flotation collector for coarse-grained spodumene is added; in the cleaning, no collector is added; in the scavenging, 200-600 g/t of enhanced flotation collector for coarse-grained spodumene is added.
Page 1/1
08 Jun 2021
DRAWINGS
Raw ore
Grinding fineness: 45-70%, -74 μm Na2CO3: 2-4 kg/t 2021103189
Magnetic separation
Magnetic Na2CO3 gangue CaCl2 Collector
Roughing CaCl2 Na2CO3 Collector
Spodumene Tailing concentrate
FIG. 1
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| CN202110420554.7A CN115213019A (en) | 2021-04-19 | 2021-04-19 | Coarse-grained spodumene enhanced flotation collecting agent and application thereof |
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| CN113976329A (en) * | 2021-12-01 | 2022-01-28 | 天齐创锂科技(深圳)有限公司 | Flotation and desulfurization collecting agent for tailings generated in lithium extraction by spodumene sulfuric acid process and application of flotation and desulfurization collecting agent |
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| CN118268139B (en) * | 2024-05-30 | 2024-07-26 | 矿冶科技集团有限公司 | Hard rock type lithium ore shunt differential speed flotation method for multi-mineral-phase lithium ore |
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| CN113976329A (en) * | 2021-12-01 | 2022-01-28 | 天齐创锂科技(深圳)有限公司 | Flotation and desulfurization collecting agent for tailings generated in lithium extraction by spodumene sulfuric acid process and application of flotation and desulfurization collecting agent |
| CN113976329B (en) * | 2021-12-01 | 2024-04-09 | 天齐创锂科技(深圳)有限公司 | Spodumene sulfuric acid method lithium extraction tailings flotation desulfurization collecting agent and application thereof |
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