RU2048922C1 - Method of selective flotation of finely dispersed ores - Google Patents

Abstract

FIELD: concentration of minerals. SUBSTANCE: pulp is subjected for the successive conditioning with regulating agents of ionic composition, modifying agent, collecting agent and foaming agent, and valuable component is isolated into the foaming product. Hydrophobic organosilicon compound ГКЖ-94 is added additionally at conditioning which is fed with foaming agent in the mixture as an emulsion stabilized with sulfonol. At niobium ore flotation ИМ-50 is added as collecting agent and pine oil as foaming agent, and the ratio ИМ-50, pine oil, ГКЖ-94 and sulfonol is from 1:0.1:0.02:0.0005 to 1: 0.3:0.12:0.006. At rare-earth flotation asparal is added as collecting agent and pine oil as foaming agent, and the ratio of asparal, pine oil, ГКЖ-94 and sulfonol is from 1:0.5:0.05:0.00125 to 1:1:0.25:0.0125. At apatite ore flotation flotol-7,9 is added as collecting agent and pine oil as foaming agent, and the ratio of flotol-7,9, pine oil, ГКЖ-94 and sulfonol is from 1: 0.25: 0.1:0.0025 to 1:0.5:0.3:0.015. EFFECT: improved method of flotation. 4 cl, 11 tbl

Description

 The invention relates to mineral processing and can be used in the processing of fine ores and sludges, in particular in the flotation of niobium, rare earth and apatite ores.

Known methods for the selective flotation of finely dispersed materials, for example, sludges of gravity concentration of tin, rare metal and other ores, including conditioning pulp with regulators of ionic composition, modifier and collector [1]
The disadvantage of these methods is the low technological indicators of enrichment due to the need for preliminary removal of the finest particles (class -20, -15 microns).

Closest to the proposed one is a method of selective flotation of finely dispersed ores, including sequential conditioning of the pulp with regulators of ionic composition, a modifier, a collector and a foaming agent and the allocation of a valuable component in the foam product [2]
The disadvantage of this method is the low technological performance in the flotation of finely dispersed ores containing more than 50-80% of the -20 micron class. With such a content of fine particles, effective flotation requires not only preliminary aggregation of particles and a developed surface of thin air bubbles, but also certain surface properties of air bubbles and particle aggregates created by specially introduced reagents.

 The purpose of the invention is the improvement of technological indicators by enhancing aerofloculation of fine particles and their aggregates with thin air bubbles.

 The goal is achieved by the fact that in the method of selective flotation of finely dispersed ores, which includes sequential conditioning of the pulp with ionic composition regulators, a modifier, a collector and a foaming agent and isolating a valuable component into the foam product, a mixture of hydrophobic organosilicon compound GKZh-94 and a foaming agent in the form of an emulsion is additionally introduced into the conditioning process stabilized with sulfonol.

 IM-50 is introduced as a collector in the flotation of niobium ores, and pine oil is used as a foaming agent, while the ratio of IM-50, pine oil, GKZh-94 and sulfonol is from 1: 0.1: 0.02: 0.0005 to 1: 0.3: 0.12: 0.006.

 Asparal is introduced as a collector during the flotation of rare-earth ores, and pine oil is used as a foaming agent, while the ratio of asparal, pine oil, GKZh-94 and sulfonol is from 1: 0.5: 0.05: 0.00125 to 1: 1: 0.25: 0.0125.

 Flotol-7.9 is introduced as a collector for flotation of apatite ores, pine oil is used as a foaming agent, and the ratio of flotol is 7.9, pine oil. GKZH-94 and sulfonol is from 1: 0.25: 0.1: 0.0025 to 1: 0.5: 0.3: 0.015.

 The combined introduction of GKZh-94 and a foaming agent in the form of an emulsion stabilized by sulfonol provides a flow of air bubbles with a developed surface and, thanks to the high surface activity of GKZh-94 at the liquid-gas interface, promotes the formation of aggregates consisting of thin air bubbles and fine particles (and their aggregates). The aggregation of fine particles is facilitated by the adsorption of GKZh-94 on the surface of minerals after their treatment with a collector. When preparing the emulsion GKZh-94 and the blowing agent, the consumption of stabilizer-sulfonol is determined by the nature and concentrations of emulsifiable substances. Sulfonol helps to stabilize the emulsion and, accordingly, to keep it in a dispersed form for a sufficiently long time.

 The selectivity of aggregation and flotation is ensured by the fact that the collector, as well as a mixture of GKZh-94 and a foaming agent, are introduced into the pulp when a high degree of physico-chemical dispersion of the finely divided pulp has been previously achieved due to the removal or binding of pulp ions to sparingly soluble compounds and the introduction of a modifier.

 Reagents used in the flotation process.

To control the ionic composition of the pulp, soda and sodium hydroxide, or combinations thereof, were used to bind liquid phase ions to sparingly soluble compounds, as well as exchange sorption on Ku-2-8 cation exchange resin in H ⁺ form.

Soda Na ₂ CO ₃ sodium carbonate, powder, is used as an aqueous solution.

 Caustic soda NaOH sodium hydroxide is available in the form of crystals and granules, used in the form of an aqueous solution.

KU-2-8 refers to monofunctional strongly acidic cation exchangers of the polarization type. It contains one type of ionogenic groups SO ₃ H. The use of cation exchange resin in the H ⁺ form made it possible to simultaneously control the pH value of the pulp and its ionic composition.

Sodium hexametaphosphate Na ₆ P ₆ O _{18, a} representative of condensed polyphosphates, is used as modifiers; it forms complex compounds with multivalent metal ions, is produced as a melt, and is used as an aqueous solution.

Liquid glass Na ₂ O ˙ mSiO ₂ soluble sodium silicate, m liquid glass module, is available in the form of 40% solutions, the most effective liquid glass with a module of 2.6-2.8
As a collector, asparal, tall oil, flotol-7.9, IM-50, butyl potassium xanthate were used.

 Asparal tetrasodium salt of N-alkyl-N-sulfosuccinoyl aspartic acid based on a mixture of technical amines, is produced in the form of 36% colloidized solutions.

 Tall oil is mainly a mixture of carboxylic and resin acids, as well as neutral substances. Of carboxylic acids it contains oleic, linoleic, linolenic, stearic, palmitic acids. Used in the form of soap or water emulsion.

 Xanthate potassium or sodium salts of xanthogenic acid, a solid powder, is used in the form of aqueous solutions.

IM-50 is a mixture of alkyl hydroxamic acids C ₇ -C ₉ or their salts. It is produced by industry with the following composition: 72-75% hydroxamic, 8-12% carboxylic acids, 10-15% moisture and 2.5-4% inorganic impurities. Used in flotation in the form of sodium salts after saponification. It has strong foaming properties.

 Flotol-7.9 is a mixture of diphosphonic acids, available in paste form.

 As a foaming agent used pine oil, T-80, OP-7.

 Pine oil the most active part is terpineol. Clear liquid.

 T-80 mixture of dioxane alcohols. Composition: monohydric and polyhydric alcohols 30-50% ethers 40-50% esters of oxalic acid 1-10% volatile components 5-10% A clear, non-stratifying liquid.

 OP-7 polyethylene glycol monoalkylphenyl ether, available as a paste or powder.

To increase the flotation efficiency of fine particles, an organosilicon compound GKZh-94 hydrophobizing liquid monoethylsiloxane [-C ₂ H ₅ Si (H) O-] _n ^- , where n 9-14, was used. Not miscible with water. The process is introduced in the form of an aqueous emulsion prepared in the presence of sulfonol.

 Sulfonol sodium benzenesulfonate based on propylene tetramers, powder, readily soluble in water.

 PRI me R 1 (prototype). Finely dispersed tin-containing ore is subjected to flotation; Sn content of 0.9%. Tin is represented by cassiterite, quartz minerals, feldspar, and gland hydroxides. The particle size distribution of the crushed ore is given in table. 1.

In the -20 μm class, 62.4% of tin is concentrated. The crushed ore is conditioned with Ku-2-8 cation exchanger in H ⁺ form (pH 5.0-5.5) for 10 min, liquid glass, aspartum collector, technical iso alcohols and OP-7 foaming agents.

 Flotation is carried out in a mechanical flotation machine with a chamber volume of 3 l, solid in a pulp 25. One foam flotation of the main flotation is carried out, the intermediate cleaning product is combined with the tailings of the main flotation.

Reagent mode of the prototype: Ku-2-8 in N ⁺ form 1.2˙10 ^-3 kg / kg,
pH 4.0-4.5 Water glass 0,5˙10 ^-3 kg / kg Asparal 0,2˙10 ^-3 kg / kg Technical izospirty C ₁₂ -C ₁₆ 0,1˙10 ^-3 kg / kg OP- 7 0.5˙10 ^-4 kg / kg Total hardness 0.42 mEq / L
The degree of dispersion in the class of -5 μm 89.2%
The flotation results of tin ore are given in table. 2.

 According to the prototype method, a concentrate containing 6.3% tin was obtained with extraction of 48.4%. Sedimentation analysis of flotation products showed that the extraction of tin from classes +20, -20 + 5 and -5 μm, respectively, is 70, 51.0 and 25 , 2% i.e. low extraction of tin in the concentrate is determined by the low flotability of particles of -20 + 5 and -5 microns.

 PRI me R 2 (according to the proposed method). Flotation is subjected to tin ore (example 1), crushed under the same conditions, the particle size distribution is given in table. 1.

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В качестве пенообразователя могут быть использованы ОП-7, сосновое масло, Т-80.The reagent mode of the proposed method: Ku-2-8 in N ⁺ form 1.2 · 10 ^-3 kg / kg
pH 4.0-4.5 Liquid glass 0.5˙ 10 ^-3 kg / kg Asparal 0.2˙ 10 ^-3 kg / kg

ovatel

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As the foaming agent can be used OP-7, pine oil, T-80.

The residual total stiffness of the pulp is 0.4 mEq / L; the degree of dispersion in the class of -5 μm 88.6%
The flotation results of tin ore by the proposed method are shown in table. 3.

 According to the proposed method, concentrates containing 7.9-8.22% of tin were obtained with the extraction of 81.3-84.2% (experiments 1-3). In the absence of GKZh-94 (experiment 4), the extraction of tin in the concentrate is sharply reduced, but if the emulsion of GKZh-94 and a foaming agent is prepared without a sulfonol stabilizer (experiment 5), there is a low extraction of tin in the concentrate.

The proposed method in comparison with the prototype allows to increase the extraction of the useful component by 35.8% while the quality of the concentrate is increased by 1.8%
The effectiveness of the proposed flotation method is confirmed on other types of finely dispersed fluorite and sulfide ores (examples 3 and 4).

PRI me R 3. Flotation was subjected to fine fluorite ore containing 12.1% CaF ₂ . Minerals of the quartz rock, feldspar and other silicates. In the -20 μm class, about 52% of CaF _{2 is} concentrated.

 The crushed ore is conditioned with soda and liquid glass, a tall soap collector, after which a mixture of hydrophobic organosilicon compound GKZh-94 and a T-80 foaming agent is additionally introduced in the form of an emulsion stabilized with sulfonol.

The reagent mode of the proposed method, kg / kg: Soda 3,5˙ 10 ^-3 Liquid glass 2,0˙ 10 ^-3 Tall oil 0,2˙ 10 ^-3 GKZH-94 2˙ 10 ^-5 T-80 1˙ 10 ^{- 4} Sulfonol 2.5˙ 10 ^-6
The flotation results are given in table. 4.

According to the proposed method obtained fluorite concentrate containing 95.3% CaF ₂ when extracting 86.1%
PRI me R 4. Flotation was subjected to finely dispersed copper ore. The main beneficial mineral is chalcopyrite. In the -20 μm class, 56.3% Cu is concentrated.

масло

Результаты флотации приведены в табл. 5.The reagent mode of the proposed method, kg / kg: NaOH 2˙ 10 ^-4 Na ₂ S 1,5˙ 10 ^-5 Liquid glass 1˙ 10 ^-4 Butyl potassium xanthate 2˙ 10 ^-5

butter

The flotation results are given in table. 5.

According to the proposed method, a copper concentrate containing 33.8% Cu was obtained with a recovery of 91.2%
Thus, the experimental data presented above show that high flotation rates of finely dispersed ores of various types were obtained under conditions when, after conditioning the pulp with ionic regulators, a modifier, and a collector, a mixture of hydrophobic organosilicon compound GKZh-94 and a foaming agent in the form of an emulsion stabilized sulfonol.

 PRI me R 5. Flotation was subjected to fine niobium ore, the content of niobium pentaxide 1.34% Niobium is represented by pyrochlore. The main minerals of the rocks: siderite, francolite, silicates, iron hydroxides. The particle size distribution of the crushed ore (T: W: W 1: 1: 6) is given in table. 6. In the -20 μm class, 76.2% of niobium pentaxide is concentrated.

масло

Остаточная общая жесткость жидкой фазы пульпы после обработки содой и едким натром составила 0,6 мгэкв/л.The reagent mode of the proposed method, kg / kg: Soda 4˙ 10 ^-3 Caustic soda 1˙ 10 ^-3 Sodium hexametaphosphate 0.8˙ 10 ^-3 IM-50 0.8˙ 10 ^-3

butter

The residual total hardness of the liquid phase of the pulp after treatment with soda and caustic soda was 0.6 mEq / L.

The degree of dispersion of the pulp in the class of -5 μm was 89.7%
The results of ore flotation according to the proposed method with proof of the selected range of changes in the consumption of reagents are given in table. 7.

Tests 1-3 show the flotation results of the proposed method within the optimal ratios of additional reagents. The extraction of niobium pentaxide in concentrates containing 9.25-10.3% Nb ₂ O ₅ amounted to 78.4-83.4%
If you go beyond the stated ratio of additionally introduced reagents (experiments 4 and 5), flotation performance decreases.

If the ratio of the reactants is lower than stated, the recovery of Nb ₂ O ₅ drops sharply (experiment 4). If, on the contrary, the ratio is higher than stated, the quality of the concentrate significantly decreases (experiment 5). With the exclusion of one of the additional reagents, the extraction of niobium pentaxide in the concentrate decreases (experiments 6-8). Moreover, in the absence of an emulsion stabilizer, the quality of the concentrate also decreases (experiment 6). The reduction in extraction is determined by the low flotation efficiency of fine particles in the absence of reagents that promote aerofloculation of fine particles and thin air bubbles.

 Thus, the experimental data presented show that the optimal results of selective flotation of finely dispersed niobium ores are obtained under conditions when, after introducing ionic regulators, a modifier, an IM-50 collector into the pulp, a mixture of hydrophobic organosilicon compound GKZh-94 and pine oil are additionally introduced into the conditioning in the form of an emulsion stabilized by sulfonol, and the ratio of IM-50, pine oil, GKZH-94 and sulfonol is from 1: 0.1: 0.002: 0.0005 to 1: 0.3: 0.12: 0.006.

PRI me R 6. Flotation was subjected to fine-dispersed rare-earth ore, the content of Σ TR ₂ O ₃ 10.8% Rare-earth minerals are represented by monazite, xenotime, etc. Minerals of the rock calcite, silicates, iron hydroxides.

 The particle size distribution of the crushed ore (T: W: W 1: 1: 6) is given in table. 8.

In the -20 μm class, 81.1% TR ₂ O _{3 is} concentrated.

Остаточная общая жесткость жидкой фазы пульпы составила 0,6 мгэкв/л, степень дисперсности по классу -5 мкм 84,7%
Результаты флотации руды по предложенному способу с доказательствами выбранного диапазона реагентов приведены в табл. 9.The reagent mode of the proposed method, kg / kg: Soda 4˙ 10 ^-3 Liquid glass 3˙ 10 ^-3 Asparal 2˙ 10 ^-4

The residual total hardness of the liquid phase of the pulp was 0.6 mEq / L, the degree of dispersion in the -5 μm class was 84.7%
The results of ore flotation according to the proposed method with evidence of the selected range of reagents are given in table. nine.

Tests 1-3 show the flotation results of the proposed method within the optimal ratios of the reagents. The recovery of TR ₂ O ₃ in concentrates containing 26.9-28.4% TR ₂ O ₃ is 80-85.1%
If you go beyond the stated ratio of additionally introduced reagents (experiments 4 and 5), flotation performance decreases. If the ratio of the reactants is lower than stated, the recovery of TR ₂ O _{3 is} significantly reduced and amounts to 66.3% (experiment 4). If, on the contrary, the reagent ratio is higher than stated, the quality of the concentrate (experiment 5) decreases due to the flotation of minerals that are close in their surface properties to rare-earth minerals. With the exclusion of one of the additional reagents, the recovery of TR ₂ O ₃ falls into the concentrate (experiments 6-8).

 The reduction in extraction is determined by the low flotation efficiency of fine particles in the absence of reagents that contribute to the aerofloculation of fine particles and thin air bubbles.

 Thus, the experimental data presented show that the optimal results of the selective flotation of finely divided rare-earth ores were obtained under conditions when, after conditioning the pulp with ionic regulators, a modifier, and a collector, an additional mixture of hydrophobic organosilicon compound GKZh-94 and pine oil in the form of an emulsion stabilized sulfonol, and as a collector asparagus, while the ratio of asparal, pine oil, GKZH-94 and sulfonol is from 1: 0.5: 0.05: 0.00125 to 1: 1: 0.25: 0.0125.

PRI me R 7. Flotation was subjected to finely divided apatite ore, the content of P ₂ O ₅ 19.3%. The main minerals are apatite, francolite. Minerals of the rock calcite, siderite, silicates, iron hydroxides. The particle size distribution of the crushed ore (T: W: W 1: 1: 6) is given in table. 10.

In the -20 μm class, 72.3% of P ₂ O _{5 is} concentrated.

масло

Остаточная общая жесткость жидкой фазы пульпы после обработки содой и едким натром составила 0,58 мгэкв/л. Степень дисперсности пульпы по классу -5 мкм составила 96,4%
Результаты флотации руды по предложенному способу с доказательством выбранного диапазона изменений расхода реагентов приведены в табл. 11.The reagent mode of the proposed method, kg / kg: Soda 3˙10 ^-3 Caustic soda 1,5˙10 ^-3 Liquid glass 2˙10 ^-3 Flotol-7.9 4˙10 ^-4

butter

The residual total hardness of the pulp liquid phase after treatment with soda and caustic soda was 0.58 mEq / L. The degree of dispersion of the pulp in the class of -5 μm was 96.4%
The results of ore flotation according to the proposed method with proof of the selected range of changes in the consumption of reagents are given in table. eleven.

Tests 1-3 show the flotation results of the proposed method within the optimal ratios of additional reagents. The recovery of P ₂ O ₅ in concentrates containing 38.0% P ₂ O ₅ amounted to 82.1-85.9%. When the limits of the declared ratio of additionally introduced reagents (experiments 4 and 5) were exceeded, flotation indices decreased.

If the ratio of reagents is lower than stated, the recovery of P ₂ O _{5 is} significantly reduced and is 67.2% (experiment 4). If, on the contrary, the reagent ratio is higher than stated, the quality of the concentrate (experiment 5) is significantly reduced due to the flotation of minerals that are close in surface properties to apatite (carbonates, etc.). With the exclusion of one of the additional reagents, the extraction of P ₂ O ₅ falls into the concentrate (experiments 6–8). In the absence of an emulsion stabilizer (experiment 8), the quality of the concentrate decreases (experiment 8). The reduction in extraction is determined by the low flotation efficiency of fine particles in the absence of reagents that contribute to the aerofloculation of fine particles and thin air bubbles.

 Thus, the experimental data presented show that the optimal results of the selective flotation of finely dispersed apatite ores were obtained under the conditions when, after the modifier was added to the pulp in an alkaline medium, the flotol-7.9 collector was additionally mixed with a hydrophobic organosilicon compound GKZh-94 and pine oil in the form emulsion stabilized with sulfonol, while the ratio of flotol-7.9, pine oil, GKZH-94 and sulfonol is from 1: 0.25: 0.1: 0.0025 to 1: 0.5: 0.3: 0.015.

 In general, the proposed method for the selective flotation of finely dispersed ores allows a 25-30% increase in the extraction of valuable components due to the effective flotation of particles less than 20 microns.

Claims (4)

 1. METHOD FOR SELECTIVE FLOTATION OF THIN DISPERSED ORES, including sequential conditioning of the pulp with ionic composition regulators, a modifier, a collector and a foaming agent and isolating a valuable component into the foam product, characterized in that, when conditioning, the hydrophobic organosilicon compound GKZh-94 is added, which is fed from the foam mixtures in the form of an emulsion stabilized by sulfonol.  2. The method according to claim 1, characterized in that when flotation of niobium ores, IM-50 is introduced as a collector, and pine oil is used as a foaming agent, while the ratio of IM-50, pine oil, GKZh-94 and sulfonol is 1 0, 1 0.02 0.0005 1 0.3 0.12 0.006.  3. The method according to claim 1, characterized in that when flotation of rare-earth ores, asparal is introduced as a collector, and pine oil is used as a foaming agent, while the ratio of asparal, pine oil, GKZh-94 and sulfonol is 1 0.5 0.05 0.00125 1 1 0.25 0.125.  4. The method according to claim 1, characterized in that when flotation of apatite ores, flotol-7.9 is introduced as a collector, and pine oil is used as a foaming agent, while the ratio of flotol-7.9, pine oil, GKZh-94 and sulfonol is 1 0.25 0.1 0.0025 1 0.5 0.3 0.015.

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