Method for preparing nickel sulfate aqueous solution from nickel-containing raw material
View Patent ↗Provided herein is a method for preparing a nickel sulfate aqueous solution, comprising: (A-i) a reduction heat treatment process for thermally treating a first raw material containing nickel and lithium; (B) a first leaching process for leaching the heat-treated product produced by the reduction heat treatment process; (A-ii) a roasting process for thermally treating a second raw material containing nickel and sulfur; (C) a second leaching process for leaching the first leaching residue produced by the first leaching process and the calcine produced by the roasting process; (D) a neutralization process for neutralizing the second leached solution produced by the second leaching process; and (E) a solvent extraction process for refining nickel in the neutralized solution produced by the neutralization process.
1 . A method for preparing a nickel sulfate aqueous solution, the method comprising:
(A-i) a reduction heat treatment process for thermally treating a first raw material containing nickel and lithium;
(B) a first leaching process for leaching the heat-treated product produced by the reduction heat treatment process;
(A-ii) a roasting process for thermally treating a second raw material containing nickel and sulfur;
(C) a second leaching process for leaching the first leaching residue produced by the first leaching process and the calcine produced by the roasting process;
(D) a neutralization process for neutralizing the second leached solution produced by the second leaching process; and
(E) a solvent extraction process for refining nickel in the neutralized solution produced by the neutralization process to prepare the nickel sulfate aqueous solution.
2 . The method of claim 1 , wherein the first raw material and the second raw material each independently comprises at least one selected from the group consisting of an oxide, a hydroxide, a sulfide, and a sulfur oxide,
the oxide, hydroxide, sulfide, and sulfur oxide each independently containing ore, matte, black mass (BM), black powder (BP), mixed hydroxide precipitate (MHP), mixed carbonate precipitate (MCP), mixed sulfide precipitate (MSP), or a mixture thereof.
3 . The method of claim 1 , wherein the first raw material comprises nickel in a form of nickel oxide or nickel metal composite oxide.
4 . The method of claim 1 , wherein the second raw material comprises nickel in a form of nickel sulfide.
5 . The method of claim 1 , wherein the reduction heat-treatment process is carried out at 650 to 950° C. in a manner of introducing the first raw material into a thermal treatment equipment and injecting nitrogen gas.
6 . The method of claim 1 , wherein the first leaching process is carried out using a first leaching agent including an inorganic acid, water, or a mixture thereof.
7 . The method of claim 1 , wherein the first leached solution obtained by the first leaching process contains lithium and the first leaching residue contains nickel.
8 . The method of claim 1 , wherein the roasting process is carried out at 650 to 950° C. in a manner of introducing the second raw material into a thermal treatment equipment and injecting oxygen gas.
9 . The method of claim 1 , wherein, in the second leaching process, the first leaching residue and the calcine are leached in an atmospheric reactor and a high-temperature, high-pressure reactor, respectively.
10 . The method of claim 1 , wherein the neutralizing process is carried out using a neutralizing agent including MHP, MCP, nickel hydroxide (Ni(OH) 2 ), nickel carbonate (NiCO 3 ), sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ), calcium hydroxide (Ca(OH) 2 ), magnesium hydroxide (Mg(OH) 2 ), calcium oxide (CaO), magnesium oxide (MgO), or a mixture thereof.
11 . The method of claim 1 , wherein the neutralization process is carried out at 80° C. and a pH of 2 to 4.5.
12 . The method of claim 1 , wherein the neutralization is carried out for 2 hours or more and the neutralized solution produced by the neutralization process has a residual acidity of 10 g/L or less.
13 . The method of claim 1 , wherein the solvent extraction process comprises:
(E-i) a first solvent extraction process for refining nickel from the neutralized solution produced by the neutralization process; and
(E-ii) a second solvent extraction process for refining nickel from the post-first extraction solution produced by the first solvent extraction process.
14 . The method of claim 13 , wherein the first solvent extraction process is performed by:
(i) a first loading process for loading nickel into an organic phase by adding a first organic extractant to a nickel sulfate aqueous solution;
(ii) a first extraction process for back extracting nickel into an aqueous phase by adding the post-first loading organic extractant to the neutralized solution;
(iii) a first scrubbing process for recovering cobalt into an aqueous phase by adding an inorganic extractant into the post-first extraction organic extractant;
(iv) a first stripping process for recovering copper into an aqueous phase by adding an inorganic extractant to the post-first scrubbing organic extractant; or
a combination of the above steps, as follows: (i) and (ii); (i), (ii), and (iii); or (i), (ii), (iii), and (iv).
15 . The method of claim 14 , wherein the first organic extractant in the first loading process is used at a volume ratio of 3.5 to 6.5 to the nickel sulfate aqueous solution.
16 . The method of claim 14 , wherein after the post-first loading solution produced by the first loading process is allowed to undergo precipitation, the nickel-containing byproduct thus precipitated is used as a neutralization agent in the neutralization process.
17 . The method of claim 14 , wherein after the post-first loading in the first extraction process, the organic extractant is used at a volume ratio of 1.5 to 4.5 to the neutralized solution in the first extraction process.
18 . The method of claim 14 , wherein volume ratios of the inorganic extractants to the organic extractants in the first scrubbing process and the first stripping process each range from 9.5 to 12.5.
19 . The method of claim 14 , wherein the first scrubbing process is carried out at a pH of 2 to 3.
20 . The method of claim 14 , wherein the first stripping process is carried out at a pH of 0.5 to 1.5.
21 . The method of claim 14 , wherein the post-first stripping organic extractant is reused as the first organic extractant.
22 . The method of claim 14 , further comprising a first precipitation process for recovering cobalt by adding a first precipitation agent to the post-first scrubbing solution produced by the first scrubbing process.
23 . The method of claim 14 , further comprising a second precipitation process for recovering copper by adding a second precipitation agent to the post-first stripping solution produced by the first stripping process.
24 . The method of claim 13 , wherein the second solvent extraction process is carried out by:
(i) a second loading process for loading nickel into an organic phase by adding a second organic extractant to a nickel sulfate aqueous solution;
(ii) a second extraction process for back extracting nickel into an aqueous phase by adding the post-second loading organic extractant to the post-first extraction solution;
(iii) a second stripping process for recovering impurities into an aqueous phase by adding an inorganic extractant to the post-second extraction organic extractant; or
a combination of the above steps, as follows: (i) and (ii); or (i), (ii), and (iii).
25 . The method of claim 24 , wherein the second organic extractant is used at a volume ratio of 4.5 to 8.5 to the nickel sulfate aqueous solution in the second loading process.
26 . The method of claim 24 , wherein after the post-second loading solution produced by the second loading process is allowed to undergo precipitation, the nickel-containing byproduct thus precipitated is used as a neutralization agent in the neutralization process.
27 . The method of claim 24 , wherein the post-second loading organic extractant is used at a volume ratio of 0.3 to 1.5 to the post-first extraction solution in the second extraction process.
28 . The method of claim 24 , wherein the organic extractant is used at a volume ratio of 3.5 to 7.5 to the inorganic extractant in the second stripping process.
29 . The method of claim 24 , wherein the second stripping process is carried out at a pH of 0.25 to 1.5.
30 . The method of claim 24 , wherein the post-second stripping organic extractant is reused as a second organic extractant.