RU2319550C1 - Collector for floatation of fluorite ores - Google Patents

Abstract

FIELD: mining industry; other industries; devices for concentration of minerals.

SUBSTANCE: invention is pertaining to concentration of minerals, in particular, to floatation of fluorite ores and is intended for industrial use at the concentration mills. Invention allows to reduce number of recleanings, to realize the flotation process in the cold mash, to simplify significantly flowsheet of the floatation concentration of fluorite ores and to reduce the power input and economical expenditures. In the capacity of the collector use dialkylarylpolyethyleneglycol ethers of the phosphoric acid of the general formula: [RC₆H₄O(CH₂CH₂O _m]₂P(O)OM, where R is alkyl C_nH_2n+1, n=6-9, m=4-12, M=H, K,HN (CH₂CH₂OH)₃.

EFFECT: invention ensures the reduced number of recleanings, realization of flotation process in the cold mash, significant simplification of the flowsheet of the floatation concentration of fluorite ores, the reduced power input and economical expenditures.

5 cl, 1 ex, 2 tbl, 1 dwg

Description

The invention relates to mineral processing, in particular to the flotation of fluorite ores, and is intended for industrial use in processing plants.

Fluorite ores are enriched by flotation using oxyhydryl collectors. To adjust the pH of the medium, soda is used to suppress calcite and depression of gangue minerals - sodium sulfide and water glass. After steaming the fluorite concentrate after steaming at 60-70 ° С, it is subjected to cleanings when liquid glass is fed (Bogdanov OS, Maksimov II, Podnek AK and others. Theory and technology of ore flotation / Ed. By OS Bogdanova. - 2 ed., Revised and additional - M .: Nedra, 1990, 363 p.).

As oxyhydryl collectors, oleic acid, fatty acids and waste products, tall oils, soap stocks, etc. are used.

Organophosphorus collectors are known — dialkyl polyethylene glycol esters of phosphoric acid, which are recommended for flotation of cassiterite [US Pat. UK No. 1451194. MKI B03D, NKI B2H, 1976], ores of rare metals and tin [A.S. No. 1645024 (USSR). The flotation method of ores of rare metals and tin // Utkelov B.A., Gak T.L., Abdurakhmanova I.K. and other MKI B03D 1/014. Publ. in BI 1991, No. 16], as well as for flotation of phosphate carbonate-containing ores [A.S. No. 1671359 (RF). MKI B03D 1/02. Publ. in BI 1991, No. 31]. However, dialkylpolyoxyethylene glycol esters of phosphoric acid, which are analogues of the claimed organophosphorus collectors, fluorite does not float.

The closest to the proposed invention in technical essence and the achieved result is oleic acid (Dudenkov S.V., Shubov L.Ya. et al. Fundamentals of theory and practice of using flotation reagents. M .: Nedra, 1969, 390 pp.) - prototype .

The disadvantages of this collector are: low selectivity, a large number of cleaning operations and the need for flotation at elevated temperatures. This requires large energy and economic costs.

The technical result of the invention is the creation of domestic industrial collectors that reduce energy and economic costs of the process of beneficiation of fluorite ores.

This result is achieved by using as a collector of flotation ores of fluorite ores of dialkylarylpolyethylene glycol esters of phosphoric acid of the general formula: [RC ₆ H ₄ O (CH ₂ CH ₂ O) _m ] ₂ P (O) OM,

where R is alkyl C _n H _{2n + 1} , n = 6-9, m = 4-12, M = H, K, HN (CH ₂ CH ₂ OH) ₃ , and the collector Fosphenox H 6B has R - alkyl C _{6 -9} , M = K, m = 6, collector. Metex has R - alkyl, C _9, M = K, m = 6, the collector phospholene 10T has R - alkyl, C _9, M = HN (CH ₂ CH ₂ OH) _3, m = 10, collector phospholene 10 has R - alkyl C ₉ , M = H, m = 10.

The collecting properties of dialkylarylpolyethylene glycol esters of phosphoric acid are due to structural features of the claimed reagents containing a complex set of functional groups, each of which contributes to the nature of the distribution of electron density in these groups and in the collector molecule as a whole.

The longer length of the hydrocarbon radicals (C _27-39) and the specific structure of the molecule organophosphorus collector having a hydrophilic group in the middle and two hydrophobic groups at the edges, ensure optimum surface hydrophobization fluorite.

The collector is fixed on its surface both by chemical interaction with the participation of the anion> P (O) O ^- and through physical adsorption with the participation of the group P = O. Since the oxygen atom of the phosphoryl group has a higher electron density than the oxygen atom of the carbonyl group, phosphorus-containing collectors are more firmly attached to fluorite by physical adsorption than oleic acid, which determines their higher selectivity. Fragments of the ethoxylated chain and double bonds of the aromatic ring of these reagents enhance this effect.

Phosphorus-containing collectors, due to the presence of more polar phosphorus groups than carboxyl collectors, are better soluble in water, less associated, have a higher emulsifying, wetting and dispersing ability. The consequence of this is their high stability under flotation conditions, including in a wide temperature range and a wide range of pH values, as well as moderate foaming.

The domestic industry produces a reagent under the brand name "Fosphenox N6B" (F N6B), TU 6-00-04691277-217-97. This reagent is used in the manufacture of detergents, in the oil, chemical, furniture, leather and fur industries.

The domestic industry produces a reagent under the brand name "Fosfol 10" (F 10), TU 38.507-63-0120-91. This reagent is used as a component in the preparation of complex inhibitors and demulsifiers in the oil industry.

According to TU 38.507-63-141-90, the domestic industry produces a reagent under the Fosfol 10T trademark (F 10T). This reagent is used as a dispersant and emulsifier for technical purposes.

The domestic industry produces a reagent under the trademark Meteks (MT), TU 2484-184-05744685-01. The reagent is used as a wetting and washing substance in the textile industry.

Phosphoric acid dialkylaryl polyethylene glycol esters of the general formula: [RC ₆ H ₄ O (CH ₂ CH ₂ O) _m ] ₂ P (O) OM,

where R is alkyl C _n H _2n +1, n = 6-9, m = 4-12, M = H, K, HN (CH ₂ CH ₂ OH) ₃ , until now, fluorite ore collectors have not been used, therefore, the claimed technical solution meets the criterion of "novelty."

From the known properties of dialkylarylpolyethylene glycol esters of phosphoric acid does not follow with all the evidence that they should float fluorite. Therefore, the claimed technical solution meets the criterion of "inventive step".

Example. Flotation of fluorite ore of the Suransky deposit with organophosphorus collectors (FOS).

For the experiments, poor fluorite ore was used, the basis of which is fluorite, quartz and mica. The mineral composition of the ore sample is shown in table 1.

Table 1 The mineral composition of the sample Mineral Amount, % Fluorite 22 Sellait 2 Quartz 36.5 Mica (muscovite, biotite, sericite) 35.5 Calcite 3 Chlorite one Pyrites traces Sphen traces Barite traces Apatite traces

The scheme and reagent mode of laboratory experiments are shown in the drawing, the test results using the inventive organophosphorus collectors and prototype are shown in table 2.

table 2 FOS fluorite flotation indices from the ore sample of the Suransky deposit,% Flotation product Exit, % Content% Extraction Experience Conditions CaF ₂ CaCO ₃ CaF ₂ ,% one 2 3 four 5 6 Fluorite Conc. 19.7 97.7 0.47 79.1 Oleic acid - 0.5 kg / t steaming 5 cleanings (prototype) Industrial product1 12.6 10.18 9.3 5.3 Intermediates 2-5 3.8 71.74 11.9 11,2 Total: rough conc-t 36.1 64,42 4.76 95.6 Tails 63.9 1,67 0.96 4.4 Total: ore 100.0 24.32 2,33 100.0 Fluorite Conc. 20,0 98.80 0.26 81.1 F N 6B - 0.5 kg / t without steaming 3 recycle (claimed collector) Industrial product 1 10.1 14.70 8.90 6.1 Intermediates 2-3 5.5 37.0 15,2 8.4 Total: rough conc-t 35.6 65.39 5.02 95.6 Tails 64,4 1,67 0.95 4.4 Total: ore 100.0 24.35 2.40 100.0 Fluorite Conc. 19.8 98.68 0.16 80.1 MT - 0.5 kg / t without steaming 3 recycle (claimed collector) Industrial product 1 14,4 15.18 9.66 9.0 Intermediates 2-3 2,5 52.86 15,64 5,4 Total: rough conc-t 36.7 62.80 4.94 94.5 Tails 63.3 2.13 0.88 5.5 Total: ore 100.0 24.39 2,37 100.0 Fluorite Conc. 19.6 98.0 0.45 79.1 F 10 -0.5 kg / t without steaming 2 refining (the claimed collector) Industrial product 1 11.9 11.09 9.5 5,4 Industrial product 2 3.9 68,42 12.03 11.0 Total: rough conc-t 35,4 65.53 4.77 95.5 Tails 64.6 1.70 1,02 4,5 Total: ore 100.0 24.29 2,35 100.0 Fluorite Conc. 19.5 97.7 0.31 78.5 Ф 10Т - 0.5 kg / t without steaming 2 recycle (claimed collector) Industrial product 1 11.3 10.18 9.48 4.7 Industrial product 2 3.8 72.31 12.3 11.3 Total: rough conc-t 34.6 66.33 4.62 94.5 Tails 65,4 2.04 1,08 5.5 Total: ore 100.0 24.28 2,31 100.0

From the table it follows that the new organophosphorus collectors are more selective than oleic acid: to ensure similar flotation performance to the prototype, fewer cleaning operations are required: two (F 10, F 10T) or three (MT, FN 6B) instead of five for oleic acid . In addition, the use of the proposed collectors makes it possible to eliminate steaming and reduce heat consumption.

Declare FOS well soluble in water, do not form precipitation during storage and in the process of flotation. They are non-toxic, explosion and fireproof. The cost of the proposed collectors is at the level of oleic acid. They are produced by domestic industry in significant quantities and can successfully replace oleic acid during flotation of fluorite ores.

Thus, the use of the inventive dialkyl aryl polyethylene glycol esters of phosphoric acid as a collector of fluorite ores can reduce the number of purifications, carry out the flotation process in cold pulp, significantly simplify the technological scheme of flotation concentration of fluorite ores and reduce energy and economic costs.

The proposed collectors are produced by domestic industry and can be sold in concentration plants processing fluorite ores.

Claims (5)

1. The collector for flotation of fluorite ores, characterized in that the collector used dialkylarylpolyethylene glycol esters of phosphoric acid of the General formula

where R is alkyl C _n H _{2n + 1} , n = 6-9, m = 4-12, M = H, K, HN (CH ₂ CH ₂ OH) ₃ . 2. The collector according to claim 1, characterized in that R is alkyl C _6-9 , M = K, m = 6 - Fosphenox H 6B. 3. The collector according to claim 1, characterized in that R is alkyl C ₉ , M = K, m = 6 - Metex. 4. Collector according to claim 1, characterized in that the R - C ₉ alkyl, M = HN (CH ₂ CH ₂ OH) _3, m = 10 - phospholene 10T. 5. The collector according to claim 1, characterized in that R is alkyl C ₉ , M = H, m = 10 - Phosphol 10.