JPS5947338A - Method for removing iron from acidic solution containing nickel and cobalt - Google Patents

Abstract

PURPOSE:To separate and remove effectively Fe from an acidic soln. as hydroxide by adding an oxidizing agent and alkali to the soln. contg. Fe and MnO2 besides Ni and Co and by carrying out a reaction while controlling the pH and oxidation-reduction potential. CONSTITUTION:Mn in an acidic soln. of Ni and Co in sulfuric acid contg. Fe and Mn as impurities is precipitated as MnO2 and suspended in the soln. An oxidizing agent contg. Ni(OH)2 and/or Co(OH)2 as the principal component is added to the soln. to keep the oxidation-reduction potential of the soln. at 950- 1250mV (vs, S, C, E). The pH of the soln. is adjusted to 3.0-4.5 by adding alkali. A reaction is carried out under said conditions to precipitate and separate Fe as hydroxide. By this method iron can be continuously removed from the soln. with a small-sized apparatus.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has dissolved iron as an impurity, and manganese dioxide is 1'I'1. 192 solution of nickel and cobalt suspended as particles/I'1. relates to a method for removing iron without dissolving manganese dioxide particles.

For example, = t'r (7) 'In: expression 1;'f
I'j17 (') Ij', l (1, (h, wite, dinochelium sulfide, and fubalt sulfide mixture was made into a slurry and charged into an autoclave, and the mixture obtained by oxidation extraction and blowing air was added. nickel, ii, l2bi1]・le l-
4 containing A as the main component, bg Raman, and fIlfε acid) containing 41 as an impurity.
:j・llll solution J(l).Then, the impurity is removed from this solution as p liquid θ, which is usually used as manganese to +I+42. After converting manganese to +I+42. to make manganese dioxide (demanganization), F・11 tone! !: (Depending on the process, a force θg is used to precipitate iron as hydroxide (de↑g). If you use this gap to remove the button and remove the 11+a manganese, the pH will be adjusted. This is because there will be a large number of groups, which is undesirable.If you take the step of removing iron after applying manganese to II, the manganese dioxide generated in the demanganization process and the iron removed 1゛Iron hydroxide is not removed separately, for example, from the viewpoint of the filtration speed of 7) heavy filtration paste by a filter press, the omission of the steps related to a+W filtration, and the saving of equipment, but is removed by removing iron. Below (<1
After that, there are people who are expelled from the stripes every minute.

In the deiron removal step, the demanganized upper culm C
A sulfuric acid solution in which the generated manganese dioxide particles are suspended is treated with a sulfuric acid solution. Conventionally, iron is precipitated from such a solution with hydroxide and 1.
? 3- A,! What is the pH of the solution of i'U with a relatively low redox potential, using an alkali? , θ~ke, only adjustment to the left was performed. However, in this way, 1−
As the pH increases as shown above, manganese dioxide suspended in the solution dissolves into ITf and -C.
1. For example, what was demanganized to about 0.00n% in the previous demanganization step is -0.0n%, which is an order of magnitude higher. On%P1'
, the meaning of the previous demanganization-L culm is greatly diminished, and as a result, the demanganization process in the subsequent process, for example, the electrolytic refining process, becomes 8 times, making the process complicated. .

The invention is that when nickel and cobalt are dissolved as main components, manganese dioxide grains P are suspended, and iron is precipitated and separated as a hydroxide from a sulfuric acid solution containing iron as an impurity. The solubilization-reduction potential of the solution is 9. ff
O ~ 7.230 mV (VS, s, c, F,,
), (hereinafter simply referred to as mV) contains one or both of the following: 1-4rut
'Allowing the pH of the solution to alkaline while adding nitride powder]: So? , by changing the key signature to 0~/1.3, you can dissolve the man-can into ``1''/↓'' without making the second order or ``-I Hull'''s 1st order- 1L1. ↑The scales precipitate as hydroxide! ;1111).

The main component of the 11I sulfuric acid solution to which the present invention is applied is nickel (nickel) = C.
The oxidizing agent to be added is one containing a metal base other than Nisol and NiHard because it is not preferable to add it to the molten acid solution, for example, in the electrolytic refining process of metallic nickel or nickel matte. In order to remove cobalt from the electrolytic waste solution (anode jl'e) containing impurities produced in ? Ti decomposition waste liquid is subjected to "proofing treatment with If11 elemental gas and neutralization treatment with nickel carbonate to precipitate most of the cobalt, and nickel is co-precipitated and accompanied by 1: component / The cobalt precipitate is the most preferred. Add H, some iron is ai J
However, in addition to the fact that it contains almost no manganese, is it possible that the recovery process for Ni-no-U and cobalt, which are contained in high grade in the sediment, is carried out at the same time as this iron removal process? J no i u
This is because that. In addition, 111 self-lid items fI7
is the old ゛'' θ~lI0, Co 汐~, 20, F'e
: j; ~/3 XMn : 0. /Each city/inn%
It is F.

(In order to precipitate and separate iron as a hydroxide by the method of the present invention from a me acid butyric acid solution, the solution is converted into a liquid l!ui' 33
~ Otsu 3 C, PH: 3.0 ~ months,! i, redox potential: qkθ~/2! It is 84' to manage to keep it within the range of i0mV. The liquid in my mouth; the crystal?
3-～Otsu 3C is 1. ys C, V: satisfies (<
De-ironization through an invented method? i), 3 filtration using a filter Fres, for example, after filtration is likely to result in trouble 111 due to II clogging of manganese and iron sludge (hereinafter referred to as iron-free sludge); on the other hand, If the temperature exceeds 43C, the effect on the dissolution of iron and manganese will be reduced.
Not only does σ not increase much more than in the case of sea lion temperature,
This is because measures against higher consumption of thermal energy, equipment such as reaction vessels, piping, pumps, etc. .1° (
Ru23, θ～Evening, the sea is [・II 3. o
A<fl;l:i is II(rri(lx Ic), and it takes 11 minutes to complete the 11th test of iron removal, -J5 PHh"1.3 Wom Erotoya 4.
'lsll1arJ, the anti-uniform core does not progress sufficiently, and fl; (water of nickel, cobalt, etc. in fL)) +2 compounds co-precipitate, and the 11-pronged ratio of nickel and cobalt is removed from Jliz1x. t'l+ru. The redox potential is 9! Adding an oxidizing agent containing one or both of hydroxide and hydroxide as the main components so that iθ~/part OmV and f:r is 9jOmV. Otherwise, the manganese dioxide produced tends to be easily dissolved in the liquid, and/or 2. Nickel added when SOmV is exceeded: 1 balt, >-i J
This is because there is too much oxidizing agent, and the oxidized 1111 is mixed into the A33 anti-luminous, non-luminous, and 1υζ precipitates, resulting in the collection of nickel and cobalt as described above.

Is the iron removal reaction possible under the following conditions? 1saDwaG1, ratioIj
・Continuously use a small device to adjust the magnification/gain θ degree in the liquid between / and /Iu:r to 0.0/g, and hold the thread 11 from /l to F:I", 1 .' to M' 7th culm degree l1itt n,
of? J Something will happen.

Hereinafter, 1.-1') f: /l will be explained together with 14 examples and a comparison example.

Example 1'1, Onibi Ω, Og/f of manganese as 1. afJ'4 as a blunt substance, a total of the sulfuric acid acidic solution of ninoral and cobalt, with most of the manganese in the solution as manganese dioxide? ! ; h<Usase 1; Eating l', manganese oxide is suspended as it is as a solution+'t, and then, in order to increase the amount of iron from the solution by 1, the solution Tff and Nj, , Co.
An oxidizing agent containing nickel-containing and cobalt grains containing 3 g/l and 10.9 ton h;% of Fe respectively, and a slurry of about 30 g/l of nickel-containing cobalt grains, and 5.0 g/l of nickel and cobalt grains for pH adjustment. ? θg/l
of sodium hydroxide solution, ′^ and continuously, using a stirrer f
+iif was supplied to the reaction tank, and the liquid that flowed was received in another reaction tank, and the pH was adjusted with thorium hydroxide solution as before. The iron removal reaction is completed at T. The final reaction solution is also removed from this reaction vessel by overflow.

Table 1 shows the composition of the acidic liquid tested on each side and the reaction condition f'1.
, and Table 2 shows the anti-1-no-shi corresponding to each side in Table 1.
It shows the concentration of the final solution and the quality of the iron-free grain.

As is clear from Tables 1 and 2, the preferred anti-ru L: fruit market example obtained under the condition /, ノ and 3 anti-1 misfortune,
Not only is the final solution sufficiently deironated, but the manganese concentration is fj (0.0/P/, which is similar to that in the test acidic solution).
1: is maintained. However, because of this, it is difficult to
However, since 11 nickel and cobalt grains were not added at 4 J, the redox potential did not increase sufficiently. The manganese concentration in the test acidic solution was 0.00g/JL, but due to the dissolution of the suspended manganese, the concentration of manganese was 0.3g/L. In addition, in Jt comparison example), conversely, there was too much addition of nickel-containing Kohar l-46 (1;), so even if the manganese concentration in the final reaction solution was low enough, unreacted Contains nickel and cobalt
It can be seen that I-Saimono is mixed in with the iron-free 11 items.

The examples in 1- below are nickel and = Jpal) Total dissolution +:
3 (1' f Le 4ii1 Severe l'I'Q property r* The case where a thickening agent containing liquid nickel and nickel is applied is explained, or it contains only either nickel or cobalt. The reaction can also be carried out under similar conditions for a charging agent.
'i similar article f'lte Jl-::, J river comes.

As is clear from the above, non-invention is
'rO'l'J Needlework (Anode waste liquid in Hy?',-1
The process that is inevitably generated when removing the bart is approximately 7% less than 11.
By adding 1), nickel and balt in the above additives are recovered while completely preventing the dissolution of manganese dioxide suspended in the burial. Conventional iron removal 1: Due to the increased manganese concentration in the culm, +j&%! 1. Chlorination: It eliminates or greatly reduces the number of demanganizing treatments in the Baltic solution,
It has extremely high economic value.

Applicant Sumitomo Metal Mining + llI, company agent patent attorney]
:Nakavisit 11A

Claims (1)

[Claims] (1) Molten f containing nickel and cobalt as main components
In the method of precipitating iron from sulfuric acid acidic solution C, which has a sulfuric acid solution and dissolves iron as an oxide, .1, the oxidation-reduction 'old position of the solution is q 0~/]!;Q
mV (vs, s, C, E,
(17, PI-1 with alkali at 3.0~/l-,
5. A method for removing iron from an acidic solution containing nickel and cobalt.