Concentration process of iron ore slimes

Abstract

The present application relates to a concentration process of iron minerals from ultrafine tailings (slimes) from iron ore processing through reverse flotation with pH between 8.5 and 10.5 with the addition of amide-amine type collector, or further a mixture thereof with traditional cationic collectors (amines), in the absence of any depressant, alternatively including a step of high field magnetic concentration, which allows to obtain a concentrate with iron content higher than 66% and contents of SiO2+Al2O3 below 4%.

Claims

1. A process of concentrating iron minerals from ultrafine tailings (slimes) from processing iron ore comprising: a) adjusting a pH of the slimes to a value in the range of 8.5 to 10.5 by adding a base; b) adding a collector, wherein the collector comprises an amidoamine cationic collector or a mixture of said amidoamine cationic collector with one or more other collectors, to the slimes and performing conditioning of said collector; c) adjusting a pulp percent solids by addition of water; d) performing reverse flotation, in the absence of depressant, to obtain an iron rich concentrate; and e) a high field wet magnetic concentration step.

2. The process according to claim 1, wherein the slimes comprise ultrafine particles comprising iron minerals and gangue minerals.

3. The process according to claim 2, wherein the iron minerals comprise hematite and goethite, and an iron content is 40 to 50%.

4. The process according to claim 2, wherein the ultrafine particles comprise quartz and kaolinite.

5. The process according to claim 1, wherein the slimes have 20 to 40% solids.

6. The process according to claim 1, wherein the base added in step (a) is sodium hydroxide (NaOH).

7. The process according to claim 1, wherein the amidoamine cationic collector is a straight-chain collector formulated from fatty acids of vegetable origin.

8. The process according to claim 7, wherein the amidoamine cationic collector comprises N-[3-(Dimethylamino)propyl]dodecanamide as an active molecule.

9. The process according to claim 1, wherein the one or more other collectors comprise an ether-amine class organic branched-chain cationic collector.

10. The process according to claim 1, wherein the collector is added in an amount in the range of 50 to 1000 g/t (grams of collector per ton of slimes).

11. The process according to claim 1, wherein a conditioning time of the collector in step (b) ranges from 10 to 30 minutes.

12. The process according to claim 11, wherein the conditioning time of the collector in step (b) is 20 minutes.

13. The process according to claim 1, wherein in step (c) adjusting the pulp percent solids is carried out so that the pulp percent solids is in the range of 15 to 25% solids.

14. The process according to claim 13, wherein the pulp percent solids is 20% solids.

15. The process according to claim 1, wherein in step (d), reverse flotation occurs in columns, with addition of water for washing a foam and directing iron minerals to a sunk.

16. The process according to claim 15, wherein the water is added in an amount which promotes dilution of pulp to a range of 15 to 20% solids.

17. The process according to claim 1, wherein a residence time of pulp in a column flotation in step (d) is from 20 to 60 minutes.

18. The process according to claim 17, wherein the residence time is 40 minutes.

19. The process according to claim 1, wherein a float overflow rate in step (d) is not more than 2 ton/h/m.sup.2.

20. The process according to claim 1, wherein the reverse flotation, in step (d), occurs in an open circuit and in one stage.

21. The process according to claim 1, wherein the reverse flotation, in step (d), occurs in open circuit in more than one stage with a cleaner stage.

22. The process according to claim 1, wherein in the high field wet magnetic concentration step, a field intensity is from 13,000 to 18,000 Gauss.

23. The process according to claim 1, wherein magnetic concentration equipment with horizontally or vertically disposed dies, with or without pulsing movement of pulp in a basin, is employed.

24. The process according to claim 1, wherein dispersing reagents selected from the group consisting of sodium hexametaphosphate and sodium silicate are employed.

25. The process according to claim 1, wherein colloidal magnetite is employed as a reagent.

26. The process according to claim 1, wherein an iron concentrate obtained has an iron content above 66% by weight and a SiO.sub.2+Al.sub.2O.sub.3content below 4.0% by weight.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present application is described in detail based on the respective figures.

(2) FIG. 1 shows a flowsheet comparing the state of the art and the slimes concentration route of the present application.

(3) FIG. 2 shows the typical size distribution of iron ore slimes.

(4) FIG. 3 shows a flowsheet detailing the steps of the iron ore slimes concentration process of the present application.

(5) FIG. 4 illustrates the typical mineralogical composition of iron ore slimes.

(6) FIG. 5 shows the iron (Fe) content in the concentrates obtained in the continuous column flotation pilot tests+magnetic concentration.

(7) FIG. 6 shows the silica (SiO.sub.2) content in the concentrates obtained in the continuous column flotation pilot tests+magnetic concentration.

(8) FIG. 7 shows the alumina (Al.sub.2O.sub.3) content in the concentrates obtained in the continuous column flotation pilot tests+magnetic concentration.

DETAILED DESCRIPTION

(9) Although the present application may be susceptible to different embodiments, preferred embodiments are shown in the drawings and in the following detailed discussion with the understanding that the present description should be considered an exemplification of the principles of the application and is not intended to limit the present application to what has been illustrated and described herein.

(10) Unless otherwise noted, all parts and percentages are by weight.

(11) The main approach of the present application relates to a process of concentration of iron ore from slimes generated in the processing of iron ore comprising the following steps: a) adjusting slimes pH to a value in the range of 8.5 to 10.5 by adding a base; b) adding amide-amine cationic collector, or a mixture of said collector with one or more other collectors, to the slimes and performing the conditioning of said collector; c) adjusting the pulp percent solids by addition of water; and d) performing reverse flotation, in the absence of depressant, to obtain an iron rich concentrate.

(12) The most used iron ore beneficiation process in the mining industry consists of flotation. The use of this process requires previous steps of desliming, which is the removal of the ultra-fine particles, which impairs the efficiency of the concentration process.

(13) The desliming of this ore is generally carried out by means of hydrocyclones. As shown in FIG. 1, the overflow from desliming, composed of ultrafine particles, is led to a subsequent process known as thickening. In this operation of slimes thickening, recovered process water and a thick product with 30% solids, the thickener underflow, are obtained. In the state of the art, the destination of these thickened slimes, or thickened ultrafines, are the tailings dams, as represented by FIG. 1A.

(14) The present application uses said slimes as a starting material, carries out a concentration process as shown in FIG. 1B, and obtains a concentrate containing more than 60% of iron content.

(15) The iron ore slimes of the present application are preferably derived from iron ore concentration operations in the Quadrilátero Ferrífero Area, of Minas Gerais State, and are basically composed of gangue minerals, mainly quartz and kaolinite, and iron minerals. Slimes iron content ranges from 40% to 50%.

(16) Preferably, the slimes used in the process of the application are approximately 30% solids and are composed of ultrafine ore particles. The typical size distribution of iron ore slimes can be visualized by means of FIG. 2. Typically, the slimes have about 50% particles below 10 μm and 20% below 3 μm, in addition to maximum particle size (top size) near to 45 μm.

(17) As shown by the flowsheet of FIG. 3, the first step of the process of the present application consists of adjusting the pH of the slimes by adding a base, preferably sodium hydroxide (NaOH), until achieving a pH between 8.5 and 10.5, the preferred pH range of the present application.

(18) The second step of the process consists of adding collectors and conditioning thereof. The collectors used in the present application are straight-chain amide-amine type formulated from vegetable fatty acids and are selective for the extraction of quartz and kaolinite. Preferably, the present application uses a commercially available collector called Flotinor-5530®, produced by the company Clariant®. The collector can be used alone, or in combination with traditional cationic organic branched-chain collectors, in different ratios.

(19) The collectors are preferably added in an amount ranging from 50 to 1000 g/t (grams of collector per ton of slimes). This value varies according to the surface area of the slimes and contaminants content (quartz and kaolinite).

(20) Preferably, the conditioning of the collectors is carried out in stirred tank, with residence time varying from 10 to 30 minutes, preferably 20 minutes, in order to promote and guarantee the adsorption of the collectors to the particles of quartz and kaolinite. The need for longer conditioning time compared to the conventional process, which takes about 1 minute, is explained by the high surface area of the iron ore slimes, which requires more time for the interaction between the mineral particles and the collecting reagents.

(21) Preferably, the process of the present application occurs without the addition of any type of depressant. It is observed that the depressants act in the depression of iron, as well kaolinite. Therefore, the addition of depressant would be detrimental to the process since it reduces the selectivity for the removal of this gangue mineral (kaolinite) present in iron ore slimes.

(22) The third step of the process of the present application is adding water to the process at the stirred tank output to ensure that the pulp has approximately 20% solids, a condition suitable for the next step (reverse flotation).

(23) The fourth step of the process of the present application is reverse column flotation, a method known in the state of the art. In this step, air, or any other suitable gas, is bubbled into the system, and the bubbles drags the particles of quartz and kaolinite to the surface.

(24) The reverse flotation step preferably occurs in an open circuit, which can be carried out in one stage or in more than one stage, with a cleaner stage. The cleaner stage is a flotation step which uses a relatively poor concentrate, from a previous flotation step, and produces a concentrate and tailings with higher grade.

(25) In the conventional column flotation process, the pulp residence time is approximately 20 min. In the present application a longer time (20 to 60 min, preferably 40 min) is used because slimes size characteristics: the thinner the particles, the longer the time required for sedimentation. In addition, the longer residence time is necessary in order to reach the appropriate overflow speed, reducing the hydrodynamic drag of iron particles together with the gangue. The overflow rate comprises the ratio of the float material rate which exits the top of the column (ton/h), by the cross-sectional area of the column (m.sup.2). The overflow rate in the conventional flotation is about 5 ton/h/m.sup.2. In the present application, the overflow rate is not more than 2 ton/h/m.sup.2.

(26) The use of washing water, added at the top of the column, promotes the washing of the foam and drives the iron minerals to the sunk, thereby increasing the separation efficiency. Therefore, washing water is necessary to reduce the hydrodynamic drag of iron minerals and direct them to the sunk.

(27) Washing water also promotes pulp dilution. In the present application the pulp should contain about 15 to 20% solids, preferably 15%. In the conventional flotation process, solids percent is about 40 to 50%. The granulometric characteristics of the slimes require a greater dilution in the flotation medium, for greater efficiency of contact of the gangue particles with the air bubbles, and less entrapment and dragging of iron particles by the foam (hydrodynamic drag). Therefore, the amount of water used should be such as to promote the dilution of the pulp to the range of 15 to 20% solids.

(28) Following the reverse flotation step, an iron concentrate is obtained. The present application allows the recovery of more than 90% of the iron present in the slimes and to obtain concentrates with iron contents above 60% with low impurities content, enabling a possible commercialization of this new product that was previously discharged as tailings.

(29) As described above, the process of application takes place at a pH range different from that conventionally used. The process proposes the use of collectors other than those traditionally used hitherto, with conditioning time much longer than the time adopted in conventional reverse flotation technology and even longer flotation time, higher dilution of the pulp during flotation, in addition to the absence of any depressant.

(30) In an alternative embodiment of the present application, after the reverse column flotation step, the obtained concentrate is sent to a high intensity magnetic concentration step, aiming at the removal of contaminants, mainly quartz and kaolinite not been removed by flotation. In this step, a magnetic field of 13,000 to 18,000 Gauss is applied, gap matrix of 1.1 to 1.5 mm, solids percent in the feed can vary from 15% to 35%, and washing water from 3 to 5 times the feed rate. Magnetic concentration equipment can be used with matrices arranged horizontally or vertically, the latter being combined with pulsation of the pulp in the basin.

(31) Optionally, chemical reagents can be used in the magnetic concentration step, aiming at greater selectivity in the separation between iron minerals and gangue minerals, mainly quartz and kaolinite. The chemical reagents are dispersants, selected from the group consisting of sodium hexametaphosphate and sodium silicate, and also the reagent called colloidal magnetite. Colloidal magnetite increases the magnetic susceptibility of iron minerals, while the dispersants promote the greater dispersion between the iron minerals and the gangue minerals, promoting a greater separation between them.

(32) Said chemical reagents are added to the process in a stirred conditioning tank, with residence time varying from 2 to 5 minutes, following to the magnetic concentration step.

(33) The dosages of the reagents applied during the magnetic concentration step are 200 to 400 g/t for the dispersants and 300 to 700 g/t for the colloidal magnetite.

(34) The combination of flotation steps and magnetic concentration promotes the removal of quartz higher than 95% and kaolinite higher than 85%, allowing the final concentrate to be obtained with an iron content higher than 66% and SiO.sub.2+Al.sub.2O.sub.3 lower than 4, 0%, in addition to a global recovery of more than 45% and metallic recovery of more than 70%.

(35) Thus, although only some embodiments of the application have been shown, it will be understood that various omissions, substitutions and alterations may be made by a person skilled in the art without departing from the spirit and scope of the present application. The embodiments described should be considered in all aspects only as illustrative and not restrictive.

(36) It is expressly provided that all combinations of the elements performing the same function in substantially the same manner to achieve the same results are within the scope of the application. Substitutions of elements from one described embodiment to another are also fully intended and contemplated. It is also necessary to understand that the drawings are not necessarily in scale, but that they are only of a conceptual nature. The intention is, therefore, to be limited, as indicated by the scope of the appended claims.

(37) The following examples are offered in the sense of aiding the understanding of the present application and should not be considered as limiting its scope.

EXAMPLE 1

(38) Iron minerals concentration tests were performed using slimes's samples from iron ore processing. These slimes samples were from iron ore operations located in the Quadrilátero Ferrífero Area (state of Minas Gerais, Brazil) and had chemical, mineralogical and size distribution typical of this region.

(39) Table 1 shows chemical composition of the sample having the content of about 45% Fe, 28% SiO.sub.2 and 3% Al.sub.2O.sub.3. It is important to remember that kaolinite is the main Al.sub.2O.sub.3 bearing mineral.

(40) TABLE-US-00001 TABLE 1 Chemical composition of iron ore slimes Fe SiO.sub.2 P Al.sub.2O.sub.3 Mn TiO.sub.2 CaO MgO IL (%) (%) (%) (%) (%) (%) (%) (%) (%) Ignition Loss 45.19 28.69 0.076 3.11 0.103 0.116 0.019 0.019 2.87

(41) Regarding the size distribution, the slimes sample had about 50% particles below 10 μm and a maximum particle size (top size) near to 45 μm, as shown in the graphic of FIG. 2.

(42) Regarding the mineralogical composition, the samples had about 63% of iron minerals (mainly haematite and goethite), 25% of quartz and 8% of kaolinite, as shown in the graphic of FIG. 4.

(43) The pH adjustment of the slimes, which had 30% solids, was performed in stirred tank with the addition of sodium hydroxide (NaOH) until pH 10.5 was reached.

(44) 152 g/t of Flotinor-5530® collector, produced by the company Clariant®, was used and the conditioning time was 20 minutes. Water was added to the process in the stirred tank pipe output such that the slimes reached 20% solids.

(45) Slimes samples were subjected to flotation tests on a single stage, 6-meter-high, 8-inch-diameter column with feed rate of 80 kg/h. The residence time in the column was approximately 30 minutes and pulp solids percent remained in the range of 20 to 15%. No depressant was added.

(46) The final concentrate successfully achieved high iron content and low quartz and kaolinite contents. The results presented in Table 2 show the results obtained, with a concentrate containing 62.81% Fe and only 3.21% SiO.sub.2 (quartz). A substantial portion of quartz was removed for the flotation tailings, and also a certain amount of kaolinite. In addition, the metallurgical recovery of iron was quite high: 93.83%.

(47) TABLE-US-00002 TABLE 2 Results from the iron ore slimes concentration route IL Fe Ignition Mass Rec. Fe SiO.sub.2 P Al.sub.2O.sub.3 Mn Loss Flow (%) (%) (%) (%) (%) (%) (%) (%) Feed 100.00 100.00 44.52 29.44 0.077 3.04 0.075 2.60 Concentrate 66.51 93.83 62.81 3.21 0.104 2.50 0.109 3.12 Tailings 33.49 6.17 8.20 81.54 0.024 4.12 0.007 1.57

EXAMPLE 2

(48) The same slimes samples used in the previous example were tested with different process parameters, as reported in Table 3: Type of collector: traditional (ether-amine) or Flotinor-5530® (amide-amine) Collector dosage: 50 to 500 g/t Use of depressant: with or without starch pH: 8.5 to 10.5

(49) Slimes samples were subjected to flotation tests on a single stage, 6-meter-high, 8-inch-diameter column with a feed rate of 80 kg/h.

(50) The results presented in Table 3 show that using traditional ether-amine collectors, the best metallurgical result of iron recovery is about 93%, however, a high impurity concentrate (SiO.sub.2>10%) is obtained. And, in order to obtain a low silica content in the concentrate (3.73%), a high amount of iron is drawn into the float (hydrodynamic drag), which can be proven with the low metallurgical recovery of iron (about 67%).

(51) Tests using at least 100 g/t of Flotinor-5530®, an amide-amine type collector, at high pH, showed good results. The best result was the test using 152 g/t Flotinor-5530®, at pH 10.5, obtaining a concentrate with 63% iron, 3% silica and 94% of metallurgical recovery.

(52) The use of depressant (starch) impaired results even using Flotinor-5530® as a collector. The results showed a reduction of the metallurgical recovery to about 64%, because it reduces the selectivity of the process.

(53) TABLE-US-00003 TABLE 3 Process parameters and results obtained in each test Metallic Concen- Concen- Starch Rec. trate trate Collector (g/t) (g/t) pH (%) % Fe % SiO.sub.2 Traditional 105 0 8.5 89.23 57.71 10.70 Traditional 113 0 9.5 67.59 64.01 3.73 Traditional 115 0 10.5 34.91 55.67 6.48 Traditional 112 552 8.5 92.58 57.66 10.31 Traditional 101 497 9.5 70.12 59.28 5.85 Flotinor 199 0 8.5 88.11 61.63 4.55 5530 ® Flotinor 49 0 8.5 96.63 58.43 7.96 5530 ® Flotinor 51 0 9.5 96.87 58.98 7.35 5530 ® Flotinor 47 0 10.5 95.67 53.72 15.3 5530 ® Flotinor 127 0 10.5 95.85 63.68 4.66 5530 ® Flotinor 108 0 9.5 86.18 61.37 4.18 5530 ® Flotinor 101 0 8.5 91.24 61.04 4.74 5530 ® Flotinor 152 0 8.5 87.03 61.94 4.1 5530 ® Flotinor 149 0 9.5 79.04 62.00 3.64 5530 ® Flotinor 152 0 10.5 93.83 62.81 3.21 5530 ® Flotinor 184 0 10.5 93.23 62.32 3.34 5530 ® Flotinor 472 263 8.5 63.73 59.56 4.86 5530 ® Flotinor 508 563 8.64 64.52 60.65 4.60 5530 ®

EXAMPLE 3

(54) Magnetic concentration tests were performed with the concentrate from the pilot scale flotation, with a feed rate ranging from 80 kg/h to 200 kg/h. Equipment with horizontally disposed matrix without pulsation of pulp and equipment with vertically disposed matrix with pulsation of the pulp in the basin were tested, both with percent solids ranging from 15 to 35%, magnetic field of 13,000 to 18,000 Gauss and gap matrix, from 1.1 to 1.5 mm. The tests were performed with and without addition of chemical reagents. The results obtained are shown in Table 4 below.

(55) TABLE-US-00004 TABLE 4 Process parameters and results obtained in magnetic concentration tests Colloidal Met. Conc. Field Gap Dispersant Magnetite Rec. Conc. % SiO.sub.2 + Matrix (Gauss) (mm) (g/t) (g/t) (%) % Fe % Al.sub.2O.sub.3 Vertical 13,000 1.5 0 0 74.86 67.33 3.08 Vertical 13,000 1.5 0 0 73.18 67.69 2.10 Vertical 13,000 1.5 0 0 73.10 66.35 3.46 Vertical 13,000 1.5 0 0 49.42 57.43 11.75 Vertical 13,000 1.5 300 0 69.34 63.63 4.17 Vertical 13,000 1.5 0 0 64.54 64.42 6.38 Vertical 13,000 1.5 0 500 69.84 64.71 5.32 Horizontal 13,000 1.1 0 0 70.50 65.23 5.83 Horizontal 18,000 1.1 0 0 66.30 66.40 4.09

(56) The results of Table 4 show that the application of the high field magnetic concentration, after the flotation step, allows the obtainment of concentrate with iron content above 67%. The addition of 300 g/t of sodium hexametaphosphate as a dispersant allows increasing the iron content in the concentrate from 57.43% to 63.63% and reduce SiO.sub.2+Al.sub.2O.sub.3 contents from 11.75% to 4.17%. The addition of 500 g/t of colloidal magnetite promoted an increase in metallic recovery from 64.54% to 69.84% and reduction in SiO.sub.2+Al.sub.2O.sub.3 contents from 6.38% to 5.32%.

(57) The tests presented in Table 4 also prove that the increase of the magnetic field from 13,000 Gauss to 18,000 Gauss promotes an increase in the iron content from 65.23% to 66.40% and reduction in SiO.sub.2+Al.sub.2O.sub.3 content from 5, 83% to 4.09%.

EXAMPLE 4

(58) In addition, continuous pilot scale tests were carried out using a flotation column of 508 mm diameter and 4 meters height in the rougher stage and a magnetic concentration with a field of 13,000 Gauss, gap of 1.5 mm and a pulsating bed in Longi LGS-500EX 1.3 T equipment in cleaner step. The tests were carried out with a feed rate of 500 kg/h, 35% solids, 200 g/t Flotinor 5530 collector, pH 10.5, 700 liters/h wash water, magnetic field of 13,000 Gauss, gap of 1.5 mm and 300 rpm of basin pulsation. The results obtained are shown in Table 5 below and in FIGS. 5, 6 and 7.

(59) TABLE-US-00005 TABLE 5 Results on pilot scale in flotation column + magnetic concentration Circuit: Column (rougher) + magnetic concentration (cleaner) Mass Metallic Rec. Rec. chemistry (%) Blaine Flow (%) (%) Fe SiO.sub.2 Al.sub.2O.sub.3 (cm.sup.2/g) Feed 100.00 100.00 44.79 30.87 2.70 Xx RG Concentrate 78.15 92.69 53.13 17.40 2.98 Xx RG Tailings 21.85 7.31 14.98 73.08 3.78 Xx CL Concentrate 51.78 76.50 66.18 2.68 0.84 2,500 a 3,500 CLTailings 26.36 16.19 27.51 63.18 7.17 XX

(60) The results show that column flotation followed by magnetic concentration allows obtaining concentrate with iron content higher than 66% and SiO.sub.2+Al.sub.2O.sub.3 contents below 4%. In addition, this route allows obtaining iron concentrate with a specific surface (blaine) of more than 2,500 cm.sup.2/g, which allows the use of this concentrate as a feedstock (pellet feed) for the pelletizing process, and may also promote energy consumption reduction in the grinding step to obtain feed with a mean surface of 1,500 cm.sup.2/g.