RU2381073C1 - Method for flotation of rare metal and tin ores - Google Patents

Abstract

FIELD: mining.

SUBSTANCE: method includes serial treatment of pulp with reagent-collector - ether of phosphorus-bearing compound with common formula: [RO(C₂H₄O)_m]₂P(O)OM, where R is alkyl C_4-20, alkyl (C_8-10)phenyl, M - H, K, HN(CH₂CH₂OH)₃ m=4-12, and sulphoxyl collector in ratio of (3:1)-(9:1) and extraction of concentrate. As sulphoxyl collector, amine salts of alkyl sulfates are used with common formula: ROSO₃NH_n(CH₂CH₂OH)_m (R=C_10-20, n, m=1-3), amine salts of alkylarylsulphonates with common formula: RC₆H₅SO₃NH_n(CH₂CH₂OH)_m (R=C_10-22, n, m=1-3), Asparal F.

EFFECT: improved quality of flotation concentrate.

4 cl, 2 dwg, 6 tbl, 2 ex

Description

The invention relates to the field of mineral processing by flotation and can be used in flotation processing of complex ores of rare metals and tin, including those containing topaz.

Known methods for the flotation of rare metals and tin, including the use of such collectors as: the tetrasodium salt of N-sulfosuccinoyl aspartic acid (Asparal F), triethanolamine salts of alkyl sulfates (TEACAS), amine salts of alkylarylsulfonates (AAS), hydroxamic acids (IM-50) .Ya., Ivankov SI, Shcheglova NK Flotation reagents in the processes of mineral processing: Handbook / edited by L.V. Kondratieva. - M .: Nedra, 1990, book 1, 400 pp.) . However, the application of methods using these collectors does not provide satisfactory flotation of useful minerals.

The closest technical solution, selected as a prototype, is a method of flotation of ores of rare metals and tin using as a collector a mixture of alkoxypolyalkylene oxide mono-, di- and triesters of phosphoric acid or its salts of the formula:

where R is the hydrocarbon radical C ₁ -C ₇ , n = 0-45, m = 45-0, n + m = 9-45, R '= H, CH ₃ , C ₂ H ₅ , k = 1-3, R '' - hydrogen or alkali metal (AS USSR No. 1645024. / Method of flotation of ores of rare metals and tin // Utkelov B.A., Gak T.L., Abdurakhmanova I.K. et al., B03D 1 / 014, published in B. I. 1991, No. 16).

The disadvantages of the method are: low quality flotation concentrate and the lack of industrial production of used collectors.

The technical result of the invention is improving the quality of flotation concentrate to the level of requirements of hydrometallurgical processing using available industrial domestic collectors.

It is achieved by the fact that in the proposed method of flotation of Ta-Nb-Sn ores, the pulp is sequentially treated with ether of an organophosphorus compound of the general formula: [RO (C ₂ H ₄ O) _m ] ₂ P (O) OM, where R is alkyl C _4-20 ; alkyl (C _8-10 ) phenyl, M - H, K, HN (CH ₂ CH ₂ OH) ₃ , m = 4-12, and a sulfoxyl collector in the ratio (3: 1) - (9: 1).

The difference of the proposed method from the prototype method is, firstly, that as organophosphorus collectors (FOS), esters of the general formula are used: [RO (C ₂ H ₄ O) _m ] ₂ P (O) OM, where R is alkyl C _4-20 , alkyl (C _8-10 ) phenyl, M - H, K, HN (CH ₂ CH ₂ OH) ₃ , m = 4-12, and TEACAS, AAC or Sulfoxyl collector (CC) are used Asparal F.

Another significant difference is that in the claimed method, FOS and a sulfoxyl collector are used together, because individually, none of them provides the quality of the concentrate that is necessary for subsequent hydrometallurgical processing.

An essential distinguishing feature of the proposed method is also the procedure for feeding collectors into the flotation pulp. Using physicochemical methods of analysis, it was established that the role of the main collector is played by FOS, and SS enhances its effect. For this reason, FOS is first added to the pulp, and only then the sulfoxyl collector. With the reverse order of addition of reagents, the technological parameters of flotation deteriorate.

Obtaining a technological result with the combined use of FOS and SS can be explained by the phenomenon of a synergistic effect: SS, being an additional collector, increases the activity of FOS to such an extent that the activity of the mixture exceeds the sum of the effects of individual components.

FOS and SS are used in the ratio (3: 1) - (9: 1); outside these ratios, the technological parameters of flotation are reduced.

The inventive method can be used both for flotation beneficiation of Ta-Nb-Sn ores (Fig. 1), and for the refinement of gravity, flotation concentrates (Fig. 2) and other beneficiation products.

According to the flotation scheme, the process is carried out in two stages: first, in an alkaline medium at a pulp pH of 8.5-10.0, a flotation concentrate is obtained, and then in an acidic medium at a pH of 0.7-2.0, it is refined, and each of these stages, the pulp is treated with an organophosphorus collector of the general formula: [RO (C ₂ H ₄ O) _m ] ₂ P (O) OM, where R is alkyl C _4-20 , alkyl (C _8-10 ) phenyl, M - H, K, HN (CH ₂ CH ₂ OH) ₃ , m = 4-12, and CC with a ratio of reagents (3: 1) - (9: 1), and CC is added after the introduction of FOS (figure 1).

Carrying out alkaline flotation during the implementation of the proposed method allows you to remove the bulk of the ore material in the form of tails and significantly reduce the amount of material entering the lapping in an acidic environment. This leads to significant savings in reagents (sulfuric acid, soda, reduces the amount of wastewater and corrosion-resistant equipment).

Concentrates of alkaline flotation are obtained with high recovery, but the Ta ₂ O ₅ content in them is only 0.15-0.30%, while the concentrates for subsequent hydrometallurgical processing should contain at least 7% Ta.

Draft gravity concentrates obtained from the concentration of Ta-Nb-Sn ores, as well as flotation concentrates of the alkaline flotation cycle, contain impurities of quartz, feldspars and topaz. The main problems in the refinement of concentrates obtained from ores of the Etykinsk deposit are created by topaz, because it has physico-chemical properties close to valuable minerals and is concentrated with them.

Improving the quality of gravity and flotation concentrates to the level required for hydrometallurgical processing is achieved by flotation refinement in an acidic medium: sequential treatment of concentrates with an organophosphorus collector of the general formula: [RO (C ₂ H ₄ O) _m ] ₂ P (O) OM, where R is alkyl C _4-20 , alkyl (C _8-10 ) phenyl, M - H, K, HN (CH ₂ CH ₂ OH) ₃ , m = 4-12, and CC with a reagent ratio (3: 1) - (9 : 1) in the range of pH 0.7-2.0 (figure 2).

The choice of the pH range at this stage is due to the fact that the use of pH above 2.0 leads to a deterioration in the selectivity of the process, lowering the pH below 0.7 requires an unreasonably high consumption of sulfuric acid.

As the inventive organophosphorus collector (FOS) for the flotation of rare metal ores and tin, compounds of the general formula are used: [RO (C ₂ H ₄ O) _m ] ₂ P (O) OM, where R is C _4-20 alkyl, alkyl (C _8-10 ) phenyl, M - H, K, HN (CH ₂ CH ₂ OH) ₃ , m = 4-12.

These can be, in particular, dialkyl aryl polyethylene glycol esters of phosphoric acid:

- Fosphenox H 6B (F H 6B), R is alkyl C _6-9 phenyl, M = K, m = 6;

- Metex (MT), R is alkyl C ₉ phenyl, M = K, m = 10;

- Phosphol 6 (F 6), R is alkyl C ₉ phenyl, M = H, m = 6;

- Phosphol 10 (F 10), R is alkyl C ₉ phenyl, M = H, m = 10;

- Phosphol 12 (F 12) R is alkyl C ₉ phenyl, M = H, m = 12;

- Phosphol 6T (Ф 6Т) R is alkyl C ₉ phenyl, M = HN (CH ₂ CH ₂ OH) ₃ , m = 6;

- Phosphol 10T (Ф 10Т), R is alkyl C ₉ phenyl, M = HN (CH ₂ CH ₂ OH) ₃ , m = 10;

- Phosphol 12T (Ф 12Т) R - alkyl С ₉ phenyl, M = HN (CH ₂ CH ₂ OH) ₃ , m = 12 and dialkylpolyethylene glycol esters of phosphoric acid:

- Oksifos B (OB), R is alkyl C _8-10 , M = K, m = 6.

- Oxyfos KD-6 (O KD-6), R is alkyl C _8-10 , M = H, m = 6.

All of the listed reagents are produced by domestic industry at several enterprises in significant quantities.

Dialkylarylpolyethylene glycol esters of phosphoric acid, where R = alkyl (C _8-10 ) phenyl, M - H, K, N (CH ₂ CH ₂ OH)] ₃ , m = 4-12, are used in the manufacture of detergents as an adhesive additive , in the oil industry as a demulsifier, in the heavy industry as a lubricant, in the leather and fur industries as a filler, wetting, degreasing and detergent with an antistatic effect, as well as in the chemical and furniture industry.

We have declared compounds of this class as collectors for flotation of fluorite ores (RF Patent No. 2319550, 2008. Collector for flotation of fluorite ores // Kurkov A.V., Pastukhova I.V., B03D 1/014. Publ. In B.I. No. 8, 2008). For the flotation of rare metals and tin, these reagents have not been used to date.

Phosphoric acid dialkyl polyethylene glycol esters of the general formula: [RO (C _n H _2n O) _m ] _x P (O) OH _3-x , where R is C _8-20 alkyl, alkenyl, n = 2-4, m = 1- 8, x = 1-2, in the form of alkaline, alkaline-earth or ammonium salts are proposed for the enrichment of oxidized tin ores. Cassiterite flotation is carried out by FOS synthesized based on a trioxyethylated mixture of saturated alcohols C ₁₁ -C ₁₅ at a pH of 2-7 (preferably 4) in the presence of xylene. (US Pat. UK No. 1451194, MKI B03D, NCI B2H, 1976). However, technological indicators of the flotation of ores of rare metals and tin, especially in the presence of topaz, are unsatisfactory.

As the sulfoxyl collector, amine salts of alkyl sulfates of the general formula are used: ROSO ₃ NH _n (CH ₂ CH ₂ OH) _m (R = C _10-22 , n, m = 1-3) (TEACAC); amine salts of alkylarylsulfonates of the general formula: RC ₆ H ₅ SO ₃ NH _n (CH ₂ CH ₂ OH) _m (R = C _10-22 , n, m = 1-3) (AAS) or Asparal F.

Thus, to achieve a technical result, it is necessary to implement the whole new set of developed distinctive features of the proposed method.

The invention is illustrated by examples, which show the results of flotation of tantalum, niobium and tin from complex rare-metal ore, gravity and flotation concentrates according to the claimed method using collectors MT and SS and the prototype method using a collector - a mixture of phosphoric acid mono, butoxypolyethylene oxide and triester (BPEO): [C ₄ H ₉ O (CH ₂ CH ₂ O) ₃ O] ₂ PO (OH).

Example 1. Flotation from complex Ta-Nb-Sn ore using MT and Asparal F collectors (flotation scheme).

For the experiments, an ore sample of the Etykinsk deposit was used, the characteristics of which are given in Table 1.

Ore is pre-crushed to a grade of 0.074 mm at a level of 60% in the finished product grinding (feeding flotation) class.

The method includes the following operations:

Obtaining flotation concentrate (pH 8.5-10.0);

- treatment of pulp with soda (Na ₂ CO ₃ 0.5 kt / t);

- sequential processing of pulp FOS (0.2 kg / t) and SS (0.05 kg / t);

- treatment with apolar oil (0.1 kg / t);

alkaline flotation (15 min) to obtain a coarse collective concentrate and the allocation of the bulk of the ore material in the form of tailings of the main production.

Finishing the flotation concentrator (pH 0.7-2.0):

- processing of coarse collective concentrate with sulfuric acid to pH 1.5 (2 kg / t) and a flotation regulator (apolar oil - 0.1 kg / t);

- sequential processing of pulp FOS (0.1 kg / t) and SS (0.03 kg / t);

- treatment with tripolyphosphate (TPF - 0.3 kg / t kg / t);

- main lapping flotation (20 min) to obtain lapping concentrate.

Table 1 The chemical and mineral composition of the initial ore sample,% Chemical composition Mineral composition Components Content Minerals Content Ta ₂ O ₅ 0.013 Columbite 0,03 Nb ₂ O ₅ 0,023 Microlite 0.01 Sn 0,038 Cassiterite 0.02 U 0.0019 Albite 63,2 SiO ₂ 69.12 Microcline 13.3 Al ₂ O ₃ 13.54 Quartz 16,2 Fe ₂ O ₃ 2,8 Topaz 1,1 Mo 0.015 Mica 1.3 Wo ₃ 0.02 Clay minerals 4.2 K ₂ O 3.75 Sulfides 0.02 Na ₂ O 4.20 Zirtolit 0.02 Cao 1,2 Fluorite, tourmaline, amphiboles, pyroxenes characters pp 5.2791 Enclosing rocks 0.60 Hydroxides of Fe and Mn characters TOTAL 100.0 TOTAL 100.0

At the stage of flotation concentrate production, the action of analog collectors (Asparal F, AAS and TEASAS), declared by FOS in an individual form, as well as the combined action of FOS and SS, was tested. The test results shown in table 2, allow to draw the following conclusions:

- the independent use of both analog collectors and FOS does not provide sufficient completeness of the extraction of valuable minerals in an alkaline environment;

- the addition of SS to FOS leads to an increase in the selectivity of flotation at its minimum cost;

- the optimal ratio of FOS and SS is in the range (3: 1) - (9: 1);

- the optimal consumption of FOS is 0.2 kg / t. When the FOS consumption is less than 0.2 kg / t, the extraction of useful minerals in the foam product is lower; when the FOS consumption is more than 0.2 kg / t, the flotation results do not improve;

- to achieve the maximum effect of the reagents in the flotation pulp SS serves after processing pulp FOS;

- flotation is carried out at a pH of 8.5-10.0. At pH values below 8.5, the recovery of useful components drops sharply, with increasing pH above 10.0, extraction decreases and the quality of the resulting concentrate decreases;

- from the results of table 2 it follows that the use of the claimed FOS in combination with SS provides a high (~ 30 times) degree of concentration of useful components, which allows to reduce the amount of material entering the lapping in an acidic environment by more than 3 times.

table 2 Indicators of alkaline flotation with the use of analog collectors (Asparal F, IM-50, TEASAS), the claimed FOS in an individual form and FOS with SS Product Exit, % Ta,% Collector consumption, kg / t Content Extraction Alkaline Flotation Concentrate 3.4 0.28 70.9 AAS-0.2 Alkaline flotation tails 96.6 0.0040 29.1 (analog) Ref. ore 100.0 0.0133 100.0 Alkaline Flotation Concentrate 2.0 0.2 30.5 Asparal F-0.2 Alkaline flotation tails 98.0 0.0094 69.5 (analog) Ref. ore 100.0 0.0133 100.0 Alkaline Flotation Concentrate 2.1 0.250 40.3 TEASAS-0.2 Alkaline flotation tails 97.9 0.0081 59.7 (analog) Ref. ore 100.0 0.0133 100.0 Alkaline Flotation Concentrate 5.3 0.19 75.1 MT-0.2 Alkaline flotation tails 94.7 0.0035 24.9 Ref. ore 100.0 0.0133 100.0 Alkaline Flotation Concentrate 4.9 0.20 74.3 F10T-0.2 Alkaline flotation tails 95.1 0.0036 25.7 Ref. ore 100.0 0.0133 100.0 Alkaline Flotation Concentrate 4.3 0.23 73.5 Oxyfos B-0.20 Alkaline flotation tails 95.7 0.0037 26.5 Ref. ore 100.0 0.0133 100.0 Alkaline Flotation Concentrate 3.9 0.27 78.9 OksifosB-0.20 Asparal F-0.05 Alkaline flotation tails 96.1 0.0029 21.1 (the claimed method) Ref. ore 100.0 100.0 Alkaline Flotation Concentrate 3.6 0.29 79.5 F10T-0.20 TEASAS-0.05 Alkaline flotation tails 96.4 0.0028 20.5 (the claimed method) Ref. ore 100.0 0.0133 100.0 Alkaline Flotation Concentrate 3.8 0.28 79.1 FN6B-0.20 AAS-0.05 Alkaline flotation tails 96.2 0.0029 20.9 (the claimed method) Ref. ore 100.0 0.0133 100.0 Alkaline Flotation Concentrate 3.6 0.30 80.3 MT-0.20 Asparal F-0.05 Alkaline flotation tails 96.4 0.0027 19.7 (the claimed method) Ref. ore 100.0 0.0133 100.0

At the flotation stage of concentrate refinement, the influence of the main process parameters on its technological indicators: expenses and reagent supply methods was checked. The test results allow the following conclusions:

- as in the alkaline cycle, a synergistic effect is observed with the combined use of FOS and SS: a small addition of SS, in a fairly narrow concentration range increases flotation performance with a decrease in the main collector (FS) consumption with a residual acid concentration in the pulp of 10-15 g / l;

- SS in accordance with its role in the flotation process serves after FOS;

- the optimal range of pH values is 0.7-2.0: above pH 2.0, the selectivity of the process decreases, at pH below 0.7 an unreasonably high consumption of sulfuric acid is required;

- as a regulator of foaming in the present method using apolar oil IS 45, the supply of which improves the nature of the foam. In the absence of IS 45, strong foaming and deterioration in the quality of the final concentrate are observed. IS-45 is served together with sulfuric acid;

- the optimal consumption of reagents in kg / t of food at a pulp density of 12% solid are: sulfuric acid - 130-180; IS-45 - 1-2; FOS - 2-3; SS - 0.30; TPF - 20-25.

Thus, only the combined use of the proposed FOS and SS in the claimed conditions provides the most effective indicators of the flotation of rare metals and tin.

Flotation indices of tantalum, niobium and tin from ore according to the flotation scheme are presented in Table 5.

Example 2. Flotation refinement of gravity concentrate.

From the ore sample of the Etykinsk deposit, the characteristics of which are given in Table 1, a navigation concentrate was obtained, the mineral and particle size distribution of which is presented in Tables 3 and 4, respectively. This concentrate, after regrinding to the grade of 0.21 mm ~ 95.0%, is fed to flotation finishing.

Table 3 The mineral composition of gravity concentrate,% Mineral Content Mineral Content Columbite 1,1 Zircon 0.2 Pyrochlore microlite Zn Biotite 0.2 Cassiterite Zn Muscovite Zn Topaz 65.7 Enclosing rocks 0.3 Quartz + Field Pshat 18.5 Scrap 5.1 Amazonite 0.1 Sludge 7.0 Pyrites 1,0 Total 100.0 Amphibole 0.8

Table 4 Granulometric composition of gravity concentrate with the distribution of metals by particle size,% Size classes, mm Exit Content Distribution That Nb Sn That Nb Sn +0.21 4.1 0.163 0.277 0.474 1.65 2.5 3.0 -0.21 + 0.15 2,4 0.109 0.177 0.294 0.65 0.9 1,1 -0.15 + 0.074 62,2 0,096 0,110 0.148 14.6 15,2 14.0 -0.0774 31.3 1,086 1,173 1,714 83.1 81.4 81.9 Ref. to-t 100.0 0.407 0.451 0.655 100.0 100.0 100.0

Flotation lapping (pH 0.7-2.0):

- treatment of gravity concentrate with sulfuric acid to pH 1.5 (5 kg / t) and flotation regulator (apolar oil - 0.1 kg / t);

- sequential processing of pulp FOS (0.1 kg / t) and SS (0.03 kg / t) (10 min);

- treatment with tripolyphosphate (TPF - 0.3 kg / t kg / t) (10 min);

- main lapping flotation (20 min) to obtain lapping concentrate.

The flotation results of tantalum, niobium and tin from the gravity concentrate ore of the Etykinsk deposit according to the claimed method and the prototype method are shown in table.6.

From the data of tables 5 and 6 it follows that:

- according to the flotation scheme:

- using collectors of the proposed method, a concentrate was obtained with a Ta content of 8.5% when extracting 72.4% from ore (90.1% from the operation), niobium 13.6% when extracting 66.8% from ore (87.2% from the operation) and tin 16.7% when extracting 58.9% from the ore (80.2% from the operation). The concentrate may be directed to hydrometallurgical processing;

- when using the collector of the prototype method, a concentrate was obtained with a content of 6.8% Ta when extracting 55.6% from ore (80.2% from the operation), niobium 8.6% when extracting 52.5% from ore (76.8 % of the operation) and tin 10.1% when extracting 42.6% of the ore (68.8% of the operation). The low quality of the concentrate in terms of Ta (<7%) does not allow its use for hydrometallurgical redistribution;

- according to the gravity-flotation scheme:

- according to the claimed method, a concentrate was obtained with a tantalum content of 9.1% when extracting 57.2% from ore (90.6% from operation), niobium 13.7% when extracting 60.5% from ore (87.4% from operation ) and tin 17.0% when extracting 53.3% of ore (79.8% of the operation), the quality of which allows you to send it to hydrometallurgical processing;

- according to the prototype method, a concentrate was obtained with a tantalum content of 6.9% when extracting 47.1% from ore (74.5% from the operation), niobium 10.0% when extracting 44.4% from ore (63.8% from operations) and tin 11.0% when extracting 39.1% of ore (58.6% of the operation), the quality of which does not allow using it for hydrometallurgical processing.

Thus, the use of the inventive collectors makes it possible to increase the quality of the concentrate in terms of Ta content by 1.2-1.25 times, while increasing Ta extraction by 16.8% for ore (9.9% for operations) by flotation scheme and by 9, 3% for ore (14.7% for operations) according to the gravity-flotation scheme.

Based on the test results of the proposed method of flotation of ores of rare metals and tin, we can draw the following conclusions:

- the inventive method can be used both in an alkaline environment (pH 8.5-10.0) for flotation of Ta-Nb-Sn ores, including those containing topaz, followed by refinement of the flotation concentrate in an acidic environment (pH 0.7-2, 0), so as to improve the quality of gravity concentrates;

- the use of the claimed FOS in combination with SS in an alkaline medium (pH 8.5-10.0) allows you to concentrate tantalum by 23 times and reduce the amount of material entering the finishing in an acidic environment by more than 3 times;

- carrying out the stage of flotation refinement of gravity and flotation concentrates in an acidic environment in the claimed conditions makes it possible to significantly increase the concentration of the target components in concentrates and their extraction into the foam product compared to the prototype method; after acid finishing, the tantalum content in the finishing concentrate is 640-680 times higher than the initial one;

- the quality obtained by the present method of concentrates flotation refinement on the content of the target minerals and impurities allows you to use them for hydrometallurgical processing;

- in the inventive method using affordable industrial collectors, the range of which is quite diverse.

Thus, the proposed method of flotation of ores of rare metals and tin can be recommended for industrial use in processing plants for flotation of Ta-Nb-Sn ores.

Claims (4)

1. A method of flotation of ores of rare metals and tin, including treating the pulp with a reagent - collector - ether phosphorus-containing compounds and the allocation of concentrate, characterized in that the pulp is sequentially treated with ether phosphorus-containing compounds of the General formula
[RO (C ₂ H ₄ O) _m ] ₂ P (O) OM,
where R is alkyl C _4-20 , alkyl (C _8-10 ) phenyl, M is H, K, HN (CH ₂ CH ₂ OH) ₃ , m = 4-12, and a sulfoxyl collector in the ratio (3: 1) - (9: 1). 2. The method according to claim 1, characterized in that the sulfoxyl collector uses amine salts of alkyl sulfates of the general formula: ROSO ₃ NH _n (CH ₂ CH ₂ OH) _m (R = C _10-22 , n, m = 1-3 ) (TEASAS). 3. The method according to claim 1, characterized in that as the sulfoxyl collector amine salts of alkylaryl sulfonates of the general formula are used
RC ₆ H ₅ SO ₃ NH _n (CH ₂ CH ₂ OH) _m (R = C _10-22 , n, m = 1-3) (AAC). 4. The method according to claim 1, characterized in that Asparal F. is used as a sulfoxyl collector.

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