Methods for controlling iron via magnetite formation in hydrometallurgical processes
10689732 ยท 2020-06-23
Assignee
Inventors
- David John Chaiko (South Jordan, UT, US)
- Frank Baczek (Salt Lake City, UT, US)
- Sara (Sally) Rocks (Sandy, UT, US)
Cpc classification
C22B3/06
CHEMISTRY; METALLURGY
C22B23/0415
CHEMISTRY; METALLURGY
Y02P10/20
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C22B3/00
CHEMISTRY; METALLURGY
Abstract
A method of controlling iron in a hydrometallurgical process is disclosed. The method may comprise the steps of: leaching (14, 114) a feed slurry (2, 102); forming a pregnant leach solution (12a, 12b; 112a, 112b); removing a first leach residue (18, 118) from the pregnant leach solution (12a, 12b); and sending a portion (12b, 112b) of the pregnant leach solution (12a, 12b) and/or raffinate (22, 122) produced therefrom, to an iron removal process (34, 134). According to some preferred embodiments, the iron removal process (34, 134) may comprise the steps of: sequentially processing the pregnant leach solution (12a, 12b) and/or raffinate (22, 122) produced therefrom in a first reactor (R.sub.1) a second reactor (R.sub.2), and a third reactor (R.sub.3); maintaining a pH level of the first reactor (R.sub.1) above 4, by virtue of the addition of a first base; maintaining a pH level of the second (R.sub.2) and/or third (R.sub.3) reactors above 8.5, by virtue of a second base; and forming solids (46) comprising magnetite (68). The method may further comprise the steps of performing a solid liquid separation step (36) after the iron removal process (34, 134); and performing a magnetic separation step (64) to remove magnetite (68) from said solids comprising magnetite (68), without limitation. A system for performing the method is also disclosed.
Claims
1. A method of controlling iron in a hydrometallurgical leach process (1) comprising the steps of: leaching (14, 114) a feed slurry (2, 102); forming a pregnant leach solution (12a, 12b; 112a, 112b); removing a first leach residue (18, 118) from the pregnant leach solution (12a, 12b); and sending a portion (12b, 112b) of the pregnant leach solution (12a, 12b) and/or raffinate (22, 122) produced therefrom, to an iron removal process (34, 134); wherein the iron removal process (34, 134) comprises: sequentially processing the pregnant leach solution (12a, 12b) and/or raffinate (22, 122) produced therefrom in a first reactor (R.sub.1) a second reactor (R.sub.2), and a third reactor (R.sub.3); maintaining a pH level of the first reactor (R.sub.1) in the range of 4-5, by virtue of an addition of a first base; maintaining a pH level of the second (R.sub.2) and/or third (R.sub.3) reactors above 8.5, by virtue of an addition of a second base; and forming solids (46) comprising magnetite (68); performing a solid liquid separation step (36) after the iron removal process (34, 134); and performing a magnetic separation step (64) to remove magnetite (68) from said solids comprising magnetite (68).
2. The method of claim 1, further comprising a step of controlling the step of leaching (14, 114) a feed slurry (2, 102) such that the molar ratio of copper (Cu) to iron (Fe) is approximately 2:3.
3. The method of claim 1, further comprising a step of adding oxygen to the first reactor (R.sub.1).
4. The method of claim 3, wherein the feed slurry (2, 102) comprises a copper concentrate formed from chalcopyrite.
5. The method of claim 1, further comprising a step of leaching (44) a first metal value from the solids (46) comprising magnetite (68) to remove a first metal value before the step of performing a magnetic separation step (64) to remove magnetite (68).
6. The method of claim 5, wherein the first metal value comprises zinc, magnesium, and/or manganese.
7. The method of claim 5, further comprising a step of leaching (54) a second metal value from the solids (46) comprising magnetite (68) to remove a second metal value before the step of performing a magnetic separation step (64) to remove magnetite (68), and after the step of leaching (44) a first metal value.
8. The method of claim 7, wherein the first metal value comprises zinc, magnesium, and/or manganese in solution, and wherein the second metal value comprises copper in solution.
9. The method according to claim 8, wherein the copper in solution is combined with a portion (12a, 112a) of the pregnant leach solution (12a, 12b; 112a, 112b) entering a solvent extraction (24, 124) system.
10. The method of claim 7, wherein the step of leaching (44) a first metal value is performed at a pH level above 5, and wherein the step of leaching (54) a second metal value is performed at a pH level below 4 and above 0.5.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) To complement the description which is being made, and for the purpose of aiding to better understand the features of the invention, a set of drawings illustrating non-limiting preferred embodiments of new methods for precipitating iron in hydrometallurgical processes is attached to the present specification as an integral part thereof, in which the following has been depicted with an illustrative and non-limiting character. It should be noted that elements sharing similar features may be represented with similar reference numerals, without limitation. A non-limiting list of identifying numerals and definitions thereof appear at the end of this description.
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(10) In the following, the invention will be described in more detail with reference to drawings in conjunction with exemplary embodiments.
SUMMARY OF THE INVENTION
(11) Disclosed, is a method of controlling iron in a hydrometallurgical process, via magnetite formation, separation and recovery. According to some embodiments, the method may comprise the steps of: leaching 14, 114 a feed slurry 2, 102; forming a pregnant leach solution 12a, 12b; 112a, 112b; removing a first leach residue (18, 118 from the pregnant leach solution (12a, 12b; and sending a portion 12b, 112b of the pregnant leach solution 12a, 12b and/or raffinate 22, 122 produced therefrom, to an iron removal process 34, 134. The iron removal process 34, 134 may comprise the steps of: sequentially processing the pregnant leach solution 12a, 12b and/or raffinate 22, 122 produced therefrom in a first reactor (R.sub.1), a second reactor (R.sub.2), and a third reactor (R.sub.3); maintaining a pH level of the first reactor (R.sub.1) in the range of 4-5, by virtue of the addition of a first base; maintaining a pH level of the second (R.sub.2) and/or third (R.sub.3) reactors above 8.5, by virtue of a second base; and forming solids 48 comprising magnetite 68, without limitation. Methods according to the invention may further comprise the steps of performing a solid/liquid separation step 36 after the iron removal process 34, 134; and performing a magnetic separation step 64 to remove magnetite 68 from said solids 48 comprising magnetite 68, without limitation.
(12) According to some embodiments, the method may further comprise the step of controlling the step of leaching 14, 114 a feed slurry 2, 102 such that the molar ratio of copper (Cu) to iron (Fe) is approximately 2:3. According to some embodiments, the method may further comprise the step of maintaining more than 95% of the iron (Fe) in the 2+ state.
(13) According to some embodiments, the method may further comprise the step of discouraging the formation of iron hydroxide during the step of forming solids 48 comprising magnetite 68.
(14) According to some embodiments, the method may further comprise the step of adding oxygen to the first reactor (R.sub.1)in particular, for embodiments wherein the feed slurry 2, comprises a copper concentrate formed from chalcopyrite.
(15) According to some embodiments, the method may further comprise the step of leaching 44 a first metal value from the solids 38 comprising magnetite 68, in order to remove a first metal value, before the step of performing a magnetic separation step 64 to remove magnetite 68 is performed. For example, the first metal value may comprise zinc, magnesium, and/or manganese, without limitation. According to some embodiments, the method may further comprise the step of leaching 54 a second metal value from the solids 48 comprising magnetite 68, in order to remove a second metal value, before the step of performing a magnetic separation step 64 to remove magnetite 68 is performed, but after the step of leaching 44 a first metal value, without limitation. For instances wherein a second metal value recovery step is utilized, the first metal value may comprise zinc, magnesium, and/or manganese in solution, and the second metal value comprises copper in solution, without limitation.
(16) According to some embodiments, the method may further comprise the copper in solution produced during the second metal value recovery step 54 may be combined with a portion 12a, 112a of the pregnant leach solution 12a, 12b; 112a, 112b entering a solvent extraction 24, 124 system, without limitation. According to some embodiments, the step of leaching 44 a first metal value may be performed at a pH level above 5, and the step of leaching 54 a second metal value may be performed at a pH level below 4 and above 0.5, without limitation. According to some embodiments, the method may further comprise the step of adding a reductant to the first reactor (R.sub.1)in particular, if the feed slurry 102 comprises nickel laterite. Seeding of the first reactor (R.sub.1), second reactor (R.sub.2), and/or third reactor (R.sub.3) may be performed using some of the solids 48 comprising magnetite 68, which may be recovered during solid/liquid separation step 46.
DETAILED DESCRIPTION OF THE INVENTION
(17) The following description of the non-limiting embodiments shown in the drawings is merely exemplary in nature and is in no way intended to limit the inventions disclosed herein, their applications, or uses.
(18) The inventors have developed a novel process 1 which can use copper and iron to precipitate magnetite, cuprite, gypsum, and metal-oxide phases from hydrometallurgical liquors. Through stepwise leaching of the precipitate, pay metals, such as zinc (Zn) and copper (Cu), can optionally be selectively captured from the residue and also processed (see
(19) The iron removal process 34, 134 may serve to remove bulk cations from solution through pH changes which are much greater than those currently known in the art (e.g., pH levels above 9). As suggested in the figures (e.g.,
(20) As suggested in the figures, a continuous magnetite formation process may be employed. For instance, magnetite may be continuously formed, in order to economically remove iron from chalcopyrite leach pregnant leach solution (PLS). Iron may be removed from the chalcopyrite PLS while: i.) recovering copper as an acid soluble phase and/or ii.) forming magnetite as the sole iron phase for easy separation, without limitation.
(21) Benefits of this process over conventional iron hydroxide precipitation are many. For example, without limitation, a saleable, dense, and easily separable/filterable iron product may be produced. Moreover, a recoverable copper product may be produced (i.e., downstream of iron removal), thereby resulting in negligible copper losses as compared to current state-of-the-art processes. Additionally, with embodiments of the present invention, there may be no need for an external oxidant (which, thereby, reduces reagent costs). Lastly, the potential exists that methods, systems, and flowsheets described herein could eventually replace conventional solvent extraction (SX) systems.
(22) The chemistry involved in preferred embodiments is preferably as follows. Copper (Cu.sup.2+) and iron (Fe.sup.2+) react with one another to form goethite (FeOOH), which further reacts with Fe.sup.2+ to product magnetite (Fe.sub.3O.sub.4). Cuprite (Cu.sub.2O) may also be produced during the process. Ideal stoichiometry may be found in Equation (1) below. Additional chemical details may be found in Equations (2) through (5). If there is not enough OH.sup. in a particular embodiment, then equation (6) may apply. If there is not enough Fe.sup.2+ in a particular embodiment, then residual goethite may be present in the iron product.
2Cu.sup.2++3Fe.sup.2++5H.sub.2O.fwdarw.Cu.sub.2O+Fe.sub.3O.sub.4+10H.sup.+(1)
2Cu.sup.2++2Fe.sup.2+.fwdarw.2Cu.sup.++2Fe.sup.3+(2)
2Cu.sup.++OH.sup..fwdarw.Cu.sub.2O+H.sup.+(3)
2Fe.sup.3++4H.sub.2O.fwdarw.2FeOOH+6H.sup.+(4)
2FeOOH+Fe.sup.2++2OH.sup..fwdarw.Fe.sub.3O.sub.4+2H.sub.2O(5)
2Cu+.fwdarw.Cu.sup.0+Cu.sup.2+(6)
(23) According to some preferred embodiments, as shown in flowsheet depicted in
(24) The second PLS stream 12b may enter a magnetite iron removal process step 34 of the third stage 30. Details of a preferred embodiment of the iron removal step 34 of the third stage 30 may be found in
EXAMPLE
(25) An example of magnetite processing according to a particular embodiment of the invention follows. The purpose of the test was to produce magnetite and cuprite as solid products from synthetic hydrometallurgical liquor.
(26) The experiment was conducted by providing a solution of 5.2 g L.sup.1 Cu and 8 g L.sup.1 Fe(II) and pH 2.8. The solution was placed in a magnetically-stirred beaker. The pH was adjusted step-wise, over a thirty minute period, with addition of sodium carbonate, to reach a final pH of 9.9. The system temperature was gradually increased from ambient (20 C.) to reach 50 C. after 20 minutes, and then allowed to gradually fall back to ambient temperature (20 C.) for the remainder of the experiment.
(27) The results of the experiment were as follows. The iron and copper were completely removed from solution to form a dense, black precipitate. Analysis of the final liquor by ICP-AES indicated that copper and iron, if present, were below detection levels (approximately less than about 0.008 ppm Cu and approximately less than about 0.02 ppm Fe). Because sodium carbonate was used as the base in this example, no solid byproducts (e.g., such as gypsum) were formed in this reaction. Other tests (outside of the purview of this example) have indicated that the chemistry can be just as effective with the use of limestone, lime, caustic, or other bases in lieu of sodium carbonate.
(28) An examination of the solid product by X-ray diffraction (XRD) found only magnetite and cuprite (Cu.sub.2O) to be present (see Table 1,
(29) TABLE-US-00001 TABLE 1 Composition of solid residue by X-ray diffraction indicates only two phases are present- magnetite and cuprite. Phase Weight Percent Magnetite 77 Cuprite 23
(30) An example flowsheet for implementation of the magnetite iron removal process 34 in the leaching of primary copper sulfide concentrates is provided in
(31) A bulk 12a of the PLS may travel to an SX/EW circuit 24, 26, and although not expressly shown, downstream copper products 52 may be combined therewith. Dissolved metals in the impurities bleed stream 12b are precipitated as magnetite 66 and other metal-oxides. After a solid/liquid separation step 36, basic clean water 38 can be recycled to one or more reactors (R.sub.1, R.sub.2, R.sub.3) within the iron removal process 34. Solids 38 procured through the iron removal process 34 may undergo downstream selective leaching using stepwise pH changes as shown. Some of the solids 38 recovered from solid/liquid separation 36 may be recycled to the one or more reactors (R.sub.1, R.sub.2, R.sub.3) within the iron removal process 34 for seeding purposes, without limitation.
(32) Zinc oxide (as well as other oxides including Mn, Mg, etc.) may be dissolved at a pH above 5 (e.g., between 5 and 7; 5<pH<7) in a first base metal value recovery step 44, in order to generate a first metal value PLS 48 (e.g., a zinc PLS as shown). The metal value PLS 48 can be purified by solvent extraction (SX), followed by electrowinning; or, the PLS 48 may be used for the production of pure zinc carbonate (not shown). Solids 48 from a subsequent solid/liquid separation step 46 (following the base metal recovery step 44) may be washed at a pH less than 4 (i.e., 0.5<pH<4), in a subsequent base metal recovery step 54. The subsequent base metal recovery step 54 may comprise, for instance, a copper recovery step, where cuprite is dissolved into solution, without limitation. Slurry 58 from the second base metal recovery step 54 may undergo a solid/liquid separation step 56, for example, in order to produce a copper-rich liquor 52 as shown. In some embodiments, copper-rich liquor 52 produced in the fifth stage 50 of the process 1 can be combined with the original PLS stream 12a entering copper SX/EW circuits 24, 26, without limitation. Solids 58 from the solid/liquid separation step 56 may then undergo magnetic separation 64, for example, in order to pull clean magnetite 66 therefrom. The remaining residue 62 from the magnetite recovery step 64 may primarily comprise gypsum 62, and may be sent to a tailings impoundment or processed further, without limitation.
(33) In some embodiments, it is envisaged that a flowsheet could treat raffinate 22, 122 as opposed to a pregnant leach solution (PLS) 12b,112b, without limitation. In some embodiments, it is envisaged that a flowsheet could treatment both raffinate 22, 122 and pregnant leach solution (PLS) 12b,112b, together, at the same time, without limitation. In some embodiments, while not shown, portions of the flowsheets shown in
(34) It should be made known that the particular features, processes, and benefits which are shown and described herein in detail are purely exemplary in nature and should not limit the scope of the invention. For example, for copper concentrate leach circuits, oxygen (O.sub.2) may be bubbled into the first reactor (R.sub.1) of the iron removal process 34, in order to promote a 1:2 Fe(II) to Fe(III) ratio, without limitation. At pH levels greater than 4, where Fe(II) and Cu(II) are present, Cu(I) and Fe(III) is typically produced and therefore, it may not be necessary to bubble oxygen (O.sub.2) into the first reactor (R.sub.1). For embodiments where raffinate 22 is used in an iron removal process 34 within a copper concentrate 2 processing plant (whether alone, or in combination with copper-rich PLS 12b), it may be necessary to increase the amount of oxygen and/or the amount base agent added to the first reactor (R.sub.1), because the incoming feed stream 22, 112b to the iron removal process 34 may have a lower copper tenor and/or a lower pH, without limitation. As suggested in
(35) Although the invention has been described in terms of particular embodiments and applications, one of ordinary skill in the art, in light of this teaching, can generate additional embodiments and modifications without departing from the spirit of or exceeding the scope of the claimed invention. Accordingly, it is to be understood that the descriptions herein are proffered by way of example to facilitate comprehension of the invention and should not be construed to limit the scope thereof.
REFERENCE NUMERAL IDENTIFIERS
(36) 1, 100 hydrometallurgical process 2, 102 feed slurry (e.g., concentrate, metal sulfide concentrate, copper concentrate) 10, 110 first stage (e.g., primary leach circuit) 12a, 112a liquids fraction 1, first pregnant leach solution (PLS) stream (e.g., bulk stream @>50%) 12b, 112b liquids fraction 2, second pregnant leach solution (PLS) stream (e.g., bleed stream @<50%) 14, 114 leach step (e.g., vat leaching, heap leaching) 16, 116 solid/liquid separation step (e.g., thickener) 18, 118 solids fraction (e.g., leach residue) 20, 120 second stage (e.g., solvent extraction circuit) 22, 122 raffinate stream 24, 124 solvent extraction step 26, 126 electrowinning step (shown as optional in