Method for inhibiting extractant degradation of DSX process through metal extraction control

Abstract

Provided is a method for inhibiting extractant degradation in the DSX process through the metal extraction control, the method comprising steps of: (a) adding limestone to a copper solvent extraction-raffinate to precipitate iron (Fe) and aluminum (Al) as a slurry, recovering a clarifying liquid; and (b) adding sulfuric acid to the recovered clarifying liquid to adjust the pH thereof.

Claims

1. A method for inhibiting extractant degradation in a DSX process, the method comprising steps of: (a) adding limestone to a copper solvent extraction-raffinate to precipitate iron (Fe) and aluminum (Al) as a slurry; and (b) adding sulfuric acid to the copper solvent extraction-raffinate from which iron (Fe) and aluminum (Al) have been precipitated to adjust the pH thereof.

2. The method of claim 1, wherein the method further includes, after step (b), (c) further adding seawater to the copper solvent extraction-raffinate from which iron (Fe) and aluminum (Al) have been precipitated to adjust the temperature thereof.

3. The method of claim 1, wherein the copper solvent extraction-raffinate of step (a) includes cobalt (Co) and zinc (Zn), wherein the raffinate further includes manganese (Mn), and wherein the raffinate further includes at least one of cadmium (Cd), copper (Cu), potassium (K), magnesium (Mg), calcium (Ca), sodium (Na), and nickel (Ni).

4. The method of claim 1, wherein the concentration of sulfuric acid in step (b) is 10 g/L to 200 g/L.

5. The method of claim 1, wherein, in step (b), the sulfuric acid is added to adjust the copper solvent extraction-raffinate from which iron (Fe) and aluminum (Al) have been precipitated so as to have the pH of 3 to 6, and the sulfuric acid is not added to the precipitated slurry.

6. The method of claim 2, wherein, in step (c), the seawater is added to adjust the copper solvent extraction-raffinate from which iron (Fe) and aluminum (Al) have been precipitated so as to have a temperature of 30° C. to 50° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a flow chart of a method for inhibiting the DSX extractant degradation in a DSX process through metal extraction control of the present invention.

(2) FIG. 2 shows the extraction isotherm curve according to one embodiment of the present invention.

(3) FIG. 3 shows the correlation between the metal concentration and the oxime concentration contained in the solvent according to an embodiment of the present invention.

(4) FIG. 4 shows the inhibition of the extractant degradation according to one embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

(5) Hereinafter, embodiments of the present invention are described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

(6) FIG. 1 is a flow chart of a method for inhibiting the extractant degradation in a DSX process through metal extraction control of the present invention.

(7) The method for inhibiting extractant degradation in the DSX process through the metal extraction control according to the present invention includes (a) adding limestone to a copper solvent extraction-raffinate to precipitate iron (Fe) and aluminum (Al) as a slurry, recovering a clarifying liquid; and (b) adding sulfuric acid to the recovered clarifying liquid to adjust the pH thereof.

(8) The method may include, after step (b), step (c) of further adding seawater to the clarifying liquid to adjust the temperature thereof.

(9) In this regard, the copper solvent extraction-raffinate containing valuable metals includes cobalt (Co) and zinc (Zn), the raffinate further includes iron (Fe), aluminum (Al) and manganese (Mn), and the raffinate further includes at least one of cadmium (Cd), copper (Cu), potassium (K), magnesium (Mg), calcium (Ca), sodium (Na), and nickel (Ni).

(10) In step (a), the copper solvent extraction-raffinate containing valuable metals may include cobalt, zinc, and the like. In the valuable metals contained in the copper solvent extraction-raffinate, the amount of cobalt is about 100 ppm to about 300 ppm, and the amount of zinc is about 500 ppm to about 1000 ppm. However, they are contained together with other impurities, and themselves may be worthless.

(11) The copper solvent extraction-raffinate includes impurities such as manganese (Mn), cadmium (Cd), copper (Cu), iron (Fe), potassium (K), magnesium (Mg), calcium (Ca), sodium (Na), aluminum (Al) and nickel (Ni). In step (a), the limestone is added to the copper solvent extraction-raffinate.

(12) In step (a), in order to remove iron and aluminum from raffinate, which is copper solvent extraction-raffinate including valuable metals, limestone having a solid-liquid concentration of 20% by weight to 30% by weight, preferably 25% by weight may be added so as to allow the raffinate to have pH of 4 or more, preferably, pH of 4.5 to 6, more preferably pH of 5 to 5.5.

(13) After adding the limestone, in order to adjust the temperature of the liquid to be 30° C. to 60° C., preferably 35° C. to 50° C., more preferably about 40° C., the mixture is reacted for 0.5 hours to 4 hours, preferably 1.5 hours to 3.5 hours, more preferably about 3 hours.

(14) In this regard, the pH is adjusted to remove iron in the form of Fe.sub.2(SO.sub.4).sub.3 or Fe(OH).sub.3 and aluminum in the form of Al(OH).sub.3, minimizing the formation of crud which is a precipitate impurity in the DSX process.

(15) A feature of the process is that it is capable of selectively recovering valuable metal sulfides of cobalt and zinc from manganese, a major impurity.

(16) FIG. 2 shows the extraction isotherm curve according to one embodiment of the present invention.

(17) This graph is a graph showing the metal extraction rate according to pH change at the same temperature. In this graph, the starting pH and the limiting pH of the extraction are indicated, and the pH range used as an index of the operation is shown. This graph indicates that cobalt is extracted into the solvent in the range of pH 3 to pH 5.5, and the extraction rate is higher as the pH is closer to 5.5.

(18) Zinc is extracted into the solvent in the range of pH 3.5 to pH 6. As the pH is closer to the higher region, manganese, calcium, nickel and copper, which are impurities, are extracted into the solvent. Thus, pH control is necessary.

(19) In order to avoid the impurities such as manganese and copper, and to recover the maximum amount of cobalt and zinc, the pH used as an indicator of the operation in the DSX process is adjusted to 4 to 5.

(20) The reaction scheme of the above reaction is carried out according to the following reaction formula so that iron and aluminum may be removed from the copper solvent extraction-raffinate.
2FeSO.sub.4(a)+½O.sub.2+H.sub.2SO.sub.4.fwdarw.Fe.sub.2(SO.sub.4).sub.3(s)+H.sub.2O  [Reaction formula 1]
Fe.sub.2(SO.sub.4).sub.3(a)+3H.sub.2O.fwdarw.2Fe(OH).sub.3(s)+3H.sub.2SO.sub.4  [Reaction formula 2]
Al.sub.2(SO.sub.4).sub.3(a)+3H.sub.2O.fwdarw.2Al(OH).sub.3(s)+3H.sub.2SO.sub.4  [Reaction formula 3]

(21) Further, when iron and aluminum has been removed by the reaction formulas, step (a) may be repeated several times. Thereafter, a clarifier, which is a purifier, is used to remove the iron and aluminum as a slurry from the suspension containing the precipitated iron and aluminum, recovering the clarifying liquid.

(22) However, after the iron and aluminum are removed as the slurry, the pH of the clarifying liquid is adjusted to a high level of 4 to 6.

(23) Therefore, the present invention includes, after step (a), step (b) of adding sulfuric acid to the recovered clarifying liquid to adjust the pH thereof.

(24) In other words, in order to selectively add sulfuric acid to the slurry and clarifying liquid separated after step (a), the sulfuric acid is added to the point where the supernatant is separated in the clarifier, thereby adjusting the pH.

(25) That is, in step (b), sulfuric acid is added only to the supernatant, and thus, the sulfuric acid is not added to the slurry separated from the suspension to prevent the re-dissolution of iron and aluminum, which are impurities.

(26) FIG. 3 shows the correlation between the metal concentration and the oxime concentration contained in the solvent according to an embodiment of the present invention.

(27) In FIG. 3, each point shows the individual experimental result (each metal according to color) based on 41 days of a unit experimental day. FIG. 3 is a graph showing the concentration of oxime after 41 days according to the concentration of each metal.

(28) The higher the amount of metal loading in the solvent, the lower the concentration of oxime, indicating that the more the metal is extracted (loaded), the faster the degradation of the solvent.

(29) Therefore, it is important to lower the overall metal content in the DSX process to prevent oxime overload. In the DSX process feed solution and the extraction step, pH adjustment is necessary in conjunction with the extraction isotherm curve in FIG. 1 to prevent the total amount of metal loading from increasing by adjusting the pH. Further, the recovery rate should be considered from an economic point. Thus, it is not possible to lower the pH unconditionally in order to lower the metal amount, and it is important to maintain the balance of an appropriate level of pH and an appropriate concentration of oxime.

(30) In the present invention, the method of minimizing metal extraction to inhibit the extractant degradation may include step (b) of adding, to the separated clarifying liquid, the sulfuric acid having a concentration of 10 g/L to 200 g/L, preferably 50 g/L to 150 g/L, and more preferably 75 g/L to 125 g/L.

(31) Further, in step (b), the sulfuric acid may be added to the clarifying liquid to adjust the pH of 3 to 6, preferably pH of 3.5 to 5.5, and more preferably pH of 4 to 5.

(32) In step (b), the sulfuric acid may be added to adjust the pH, and the metal extraction may be inhibited in the DSX process.

(33) However, the temperature of the clarifying liquid with the pH adjusted is kept as high as 40° C. to 50° C.

(34) Therefore, the present invention includes step (c) of adding seawater to the pH-adjusted clarifying liquid to control the temperature thereof after step (b).

(35) In step (c), the seawater may be put into the pH-adjusted clarifying liquid reservoir to adjust the clarifying liquid temperature to be 30° C. to 50° C., preferably 30° C. to 45° C., and more preferably 30° C. to 40° C.

(36) Consequently, in step (c), the temperature of the clarifying liquid can be adjusted by the seawater input.

(37) FIG. 4 shows the inhibition of the extractant degradation according to one embodiment of the present invention.

(38) As shown in FIG. 4, the basic y-axis of the graph is the input amount (m.sup.3) of the extractant oxime (LIX 63), and the auxiliary y-axis of the graph is the analysis result of oxime (%).

(39) When the pH is maintained low, and the mol total metal/mol oxime is kept low in association with the above-described pH adjustment and the graph of the mol total metal/mol oxime, even when a similar amount of oxime is added, the oxime concentration (%) is increased, and the amount of the solvent degradation is decreased.

(40) A high oxime concentration means a high mol oxime, and it can be seen that a low value of mol total metal/mol oxime is maintained, indicating a virtuous cycle.

(41) The mol oxime is increased, and the mol total metal/mol oxime is lowered, and thus the degradation is reduced so that the oxime concentration is kept high. When the extractant is added, the mol total metal/mol oxime is further lowered.

(42) In this regard, the DSX feed solution in which iron is removed and recovered includes cobalt (Co) and zinc (Zn) the solution further includes aluminum (Al) and manganese (Mn), and the solution further includes at least one of cadmium (Cd), copper (Cu), potassium (K), magnesium (Mg), calcium (Ca), sodium (Na) and nickel (Ni).

(43) Further, the present invention can prolong the lifetime of the extractant used in the DSX process by the above-described method of inhibiting the extractant degradation.

(44) Hereinabove, although the present invention is described by specific matters such as concrete components, and the like, embodiments, and drawings, they are provided only for assisting in the entire understanding of the present invention. Therefore, the present invention is not limited to the embodiments. Various modifications and changes may be made by those skilled in the art to which the present invention pertains from this description. Therefore, the spirit of the present invention should not be limited to the above-described embodiments, and the following claims as well as all modified equally or equivalently to the claims are intended to fall within the scope and spirit of the invention.