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Registered Patent No. 10-1662725

(19) Korean Intellectual Property Office (KR) (45) Date of announcement October 5, 2016 (11)

Registration number 10-1662725 (24) Date of

(12) Registered Patent Publication (B1) registration September 28, 2016

(51) International Patent Classification (Int. (73) Patent Holder

C22B 23/00 Cl.) (2006.01) C22B 3/00 (2006.01) Pohang Industrial Science Research
C22B 3/24 (2006.01) C22B 3/42 (2006.01) Institute 67 Cheongam-ro (Hyoja-dong), Nam-gu,
(52) CPC Patent Pohang-si,
C22B 23/00
Classification (2013.01)
C22B 23/0453 (2013.01) (21)
Gyeongsangbuk-do (72) Inventor Lee Chang-gyu , Building 7, Room
Application number 10-2015-0129967 (22) Application
1101 (Jigok-dong, Professor Apartment)
date September 14, 2015 Examination date September

14, 2015 (56) Prior art search literature

KR1020080093146 A (continued on reverse side)

JP05212382 A (74) Agent Yumi

KR100772967 B1 Patent & Law Firm

Total number of claims: 7 in total (54) Examiner: Lee Cheol-hwan

Title of invention Nickel and cobalt extraction method

(57) Summary

It relates to a method for extracting nickel and cobalt, comprising: preparing a solution containing cobalt and nickel; adsorbing the ions including cobalt and nickel to an
ion exchange resin through an ion exchange process; backwashing the ion exchange resin adsorbed with the ions; obtaining a desorption solution in which the adsorbed
ions are desorbed by injecting a solution containing an acid into the ion exchange resin to which the ions are adsorbed; and injecting water into the ion exchange resin
from which the ions are desorbed to obtain a liquid after washing, wherein an acid is injected into the ion exchange resin to which the ions are adsorbed to obtain a
desorption liquid from which the adsorbed ions are desorbed. In the step of obtaining, some of the desorption liquid is recycled as a solution containing acid, and the
remaining desorption liquid is used as a recovery liquid for nickel and cobalt together with the cleaning liquid. Extraction method of cobalt and nickel can provide.

Dae Pyo Do - Figure 2

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Registered Patent No. 10-1662725

(52) CPC Patent Classification Hyunwook

C22B 3/24 3/42 (2013.01) Jin 7, Songlim-ro 90beon-gil, Nam-gu, Pohang-si, Gyeongsangbuk-do (Songdo-dong)

C22B (2013.01)

(72) Inventor Kim

Byeong-

won, 1235, 101-1402, Saecheonnyeon-ro, Buk-gu, Pohang-si, Gyeongsangbuk-do

(Jangseong-dong, Doosan We've the Zenith Apt.)

National R&D project that supported this invention Project

identification number G031677411 Ministry name

Ministry of Industry Research management

specialized agency Research Korea Institute of Energy Technology Evaluation and Planning

project name Energy technology development project Research

project name Low-grade nickel oxide ore effective resource recovery technology development of overseas mining rights by beneficiation and hybrid smelting Supervised by rate of contribution

institution 1/1

research period Korea Institute of Energy Technology

Evaluation and Planning 2014.12.01 ~ 2015.09.30

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Registered Patent No. 10-1662725

three
signatures

claims

claim 1

preparing a solution containing cobalt and nickel;

adsorbing the ions including cobalt and nickel to an ion exchange resin through an ion exchange process;

backwashing the ion exchange resin adsorbed with the ions;

obtaining a desorption liquid in which the adsorbed ions are desorbed by injecting a solution containing an acid into the ion exchange resin to which the

ions are adsorbed; and

Injecting water into the ion exchange resin from which the ions are desorbed to obtain a liquid after washing;

In the step of obtaining a desorption liquid in which the adsorbed ions are desorbed by adding acid to the ion exchange resin on which
the ions are adsorbed, some of the desorption liquid is recycled as a solution containing an acid, The remaining desorption liquid is
used as a nickel and cobalt recovery liquid together with the after-cleaning liquid.

claim 2

According to claim 1,

In the step of preparing a solution containing cobalt and nickel,

The method of extracting cobalt and nickel, wherein the solution containing cobalt and nickel is a filtrate after the Fe-Ni precipitation step during the Fe-Ni

manufacturing process.

claim 3

According to claim 1,

In the step of obtaining a desorption liquid in which the adsorbed ions are desorbed by adding acid to the ion exchange resin on which
the ions are adsorbed, when some of the desorption liquid is recycled as a solution containing an acid. , A method for extracting cobalt
and nickel that replenishes consumed acid.

claim 4

According to claim 1,

The ion exchange resin is a method for extracting cobalt and nickel, wherein the bis-picolylamine resin is used.

claim 5

According to claim 1,

In the step of injecting a solution containing an acid into the ion exchange resin adsorbed with the ions to obtain a desorption solution in
which the adsorbed ions are desorbed, the acid used is hydrochloric acid.

claim 6

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Registered Patent No. 10-1662725

According to claim 1,

In the step of obtaining a desorption solution in which the adsorbed ions are desorbed by injecting a solution containing an acid into the ion exchange resin to

which the ions are adsorbed, the acid used is hydrochloric acid at a concentration of 3 to 10 wt% Cobalt and a method for extracting nickel.

claim 7

According to claim 1,

The method of extracting cobalt and nickel in which the ion adsorption rate and desorption rate are maintained at 90% or more and 100% or less compared to

the initial level even after repeated process use.

description of the invention

technical field

[0001] It relates to a method for extracting nickel and cobalt.

Bae KiSul
Kyung

[0003] In the conventionally developed Fe-Ni manufacturing process through hydrogen reduction (KR 10-2010-0128249), laterite ore is reduced to hydrogen,

A portion of the reduced light is used as seed light for cementation of Ni in a later process.

[0004] Thereafter, Fe and Ni are leached from the remaining reduced ore with hydrochloric acid, and then Fe-Ni is precipitated by mixing with the seed ore prepared in

the previous step.

[0005] After the precipitation process, the generated Fe-Ni is recovered as a product through solid-liquid separation, and the precipitation filtrate, most of which is Fe, is subjected

to a crystallization process to produce FeCl2 hydrate, followed by a high-temperature oxidation process Manufacture iron oxide (Fe2O3) through

while recovering hydrochloric acid.

[0006] The precipitation filtrate in the precipitation process contains non-precipitated Ni and Co at several hundred ppm levels.

content of invention

challenge to solve

[0008] It is intended to provide an effective method for extracting nickel and cobalt.

means of solving the problem

[0010] In one embodiment of the present invention, preparing a solution containing cobalt and nickel; adsorbing the ions including cobalt and nickel to an ion exchange

resin through an ion exchange process; backwashing the ion exchange resin adsorbed with the ions; obtaining a desorption liquid in which the adsorbed ions

are desorbed by injecting a solution containing an acid into the ion exchange resin to which the ions are adsorbed; and injecting water into the ion exchange

resin from which the ions are desorbed to obtain a solution after washing, wherein an acid is introduced into the ion exchange resin to which the ions are

adsorbed to obtain a desorption solution in which the adsorbed ions are desorbed. In the step of obtaining;, a part of the desorption liquid is recycled as a

solution containing an acid, and the remaining desorption liquid is used as a recovery liquid for nickel and cobalt together with the after-cleaning liquid. provides

[0011] In the step of preparing a solution containing cobalt and nickel, the solution containing cobalt and nickel is Fe—Ni

It may be a filtrate after the Fe-Ni precipitation step during the manufacturing process.

[0012] In the step of obtaining a desorption liquid obtained by desorbing the adsorbed ions by injecting an acid into the ion exchange resin to which the ions are adsorbed, some of

the desorption liquid is converted into a solution containing an acid. When recycled, it can replenish consumed acid.

[0013] The ion exchange resin may be a bis-picolylamine resin.

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Registered Patent No. 10-1662725

[0014] In the step of obtaining a desorption solution in which the adsorbed ions are desorbed by injecting a solution containing an acid into the ion exchange resin to which the ions are

adsorbed, the acid used may be hydrochloric acid.

[0015] A desorption solution obtained by desorbing the adsorbed ions by injecting a solution containing an acid into the ion exchange resin to which the ions are adsorbed can be obtained.

In the step of obtaining, the acid used may be at a concentration of 3 to 10 wt%.

[0016] In the method of concentrating cobalt and nickel, the ion adsorption rate and desorption rate are 90% or more compared to the initial level even after repeated use of the process.

can be maintained as

Effects of the Invention

[0018] Nickel and cobalt can be effectively extracted by using a method with excellent adsorption and desorption efficiency while reducing the amount of acid used.

[0019] More specifically, a method capable of maintaining the adsorption efficiency of a resin by increasing the desorption efficiency in an ion exchange process even when using the

same amount of acid is proposed.

Brief description of the drawing

1 and 2 is an exemplary view of a nickel and cobalt extraction process using an ion exchange resin .

Specific details for carrying out the invention

[0022] Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited

thereby, and the present invention is only defined by the scope of the claims to be described later.

[0024] As described above, cobalt and nickel in the filtrate after the Fe-Ni precipitation step during the Fe-Ni manufacturing process are ion exchange processes (Ion

It can be recovered through the exchange process (hereafter IX process).

[0025] This ion exchange process can be broadly divided into an adsorption process, a backwashing process, a desorption process, and a washing process.

there is.

1 is an exemplary view of an ion exchange process of cobalt and nickel in the filtrate after the Fe-Ni precipitation step.

[0027] Usually, in the Fe-Ni manufacturing process (10-2010-0128249), in the precipitation filtrate containing Fe as the main component and Co and Ni at several hundred ppm levels,

Through an ion exchange process, a process of recovering Co and Ni is performed.

[0028] When the adsorption process and backwashing process of the ion exchange process are performed, the ion exchange resin (usually Bis-picolylamine resin)

Trace amounts of Co and Ni are adsorbed.

[0029] The bispicolylamine-based resin used at this time strongly adsorbs Ni, Co, and Fe in that order. The stronger the adsorbed ion, the stronger the acid (in the present

invention, hydrochloric acid is used) for desorption.

[0030] If the adsorption rate cannot be maintained, the efficiency of the process is reduced because a regeneration process in which the resin is washed with a strong acid must be

added during the operation of the process.

[0031] Maintaining the adsorption rate requires the use of strong acids in desorption, but when strong acids are used, the amount of acid required increases, resulting in permeability.

The cost of the input acid will increase.

[0032] More specifically, in the desorption process during the ion exchange process, diluted hydrochloric acid is used to desorb the adsorbed metal ions.

can

[0033] When diluted hydrochloric acid passes through the resin column in which metal ions are adsorbed, a desorption solution containing metal ions and having a low pH is discharged, and the

solution is used as a raw material for a subsequent process.

[0034] As described above, the adsorption efficiency in the adsorption process of Co and Ni metal ions of the next precipitation filtrate is maintained only when the desorption is good.

Therefore, it is necessary to induce desorption as completely as possible using a strong acid.

2 is an example of an ion exchange process of cobalt and nickel in the filtrate after the Fe—Ni precipitation step according to an embodiment of the present invention

it's a try

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Registered Patent No. 10-1662725

[0036] The method of FIG. 2 changes the flow of the desorption liquid discharged in the desorption process in the method of FIG. 1 described above, so that ions can be more effectively

desorbed even when a small amount of acid is used.

[0037] In the method according to an embodiment of the present invention, a part of the desorption liquid maintaining a low pH is transferred to a post-process, and the rest is supplemented

by the amount of strong acid used to make diluted hydrochloric acid again, and then the desorption process again can be put into

[0038] In the case of using the method shown in FIG. 2, Ni and Co, which are metal ions to be recovered, may be continuously concentrated in the circulating desorption liquid.

[0039] After the desorption process is completed, when the cleaning process is performed, the circulating desorption liquid with high Co and Ni content remaining in the ion exchange resin

is washed out in the cleaning process, so that some of the circulating desorption liquid and If mixed and transported to a later process, the yield of the recovered metal

can be increased.

[0040] More specifically, in one embodiment of the present invention as shown in FIG. 2, since the desorption is performed by mixing a circulating desorption liquid having a low pH and a

strong acid (eg, hydrochloric acid) in the same ratio, the ion exchange is more efficient. Co and Ni in the resin can be desorbed.

[0042] Preferred examples and comparative examples of the present invention are described below. However, the following examples are only preferred examples of the

present invention, but the present invention is not limited to the following examples.

[0044] Example

[0045] After the precipitation process by applying the method of the Fe-Ni manufacturing process (10-2010-0128249), the precipitation filtrate was prepared and analyzed (ICP

analysis). liter, Ni showed a content of about 150mg/liter.

[0046] The temperature of this solution was raised to about 60 ° C, the pH was adjusted to around 4.0, and a circulation experiment was performed 6 times using a

bispicolylamine-based ion exchange resin (Lewatit MDS TP 220) according to the method proposed in the present invention. (Using the method of FIG. 2)

[0047] The results obtained are schematized in Table 1. Circulates the components of six streams that can analyze adsorption and desorption rates through ICP analysis

It was analyzed by round.

[0048] [Analysis samples: (1) precipitation filtrate, (2) solution after IX, (3) solution after backwashing, (4) solution after circulation desorption, (5) solution after circulation desorption, (6) solution after washing, see

FIG. 2]

Table 1

[0049] 1st round of Analytical flow Fe Co In Volume [liter] 1.600

circulation Precipitate filtrate 103,100.0 241.0 125.0 1.600

Liquid after IX 89,400.0 32.0 10.0

liquid after backwashing 24,570.0 43.0 10.0 0.805

circulating desorption 0.0 0.0 0.0 0.450

liquid after circulating desorption 860.0 632.0 302.0 0.437

liquid after washing 42.0 25.0 52.0 0.403

Secondary liquid precipitated filtrate 109,400.0 254.0 135.0 1.600

Liquid after IX 95,100.0 40.0 10.0 1.560

liquid after backwashing 47,690.0 65.0 13.0 0.400

circulating desorption 742.0 527.0 249.0 0.450

liquid after circulating desorption 1,888.0 1,008.0 501.0 0.428

liquid after washing 394.0 224.0 136.0 0.390

tertiary liquid precipitated filtrate 107,800.0 253.0 131.0 1.600

Liquid after IX 92,000.0 36.0 10.0 1.560

liquid after backwashing 46,150.0 63.0 10.0 0.404

circulating desorption 1,649.0 858.0 425.0 0.450

liquid after circulating desorption 2,229.0 1,235.0 648.0 0.428

liquid after washing 381.0 185.0 100.0 0.816

4th liquid precipitated filtrate 104,000.0 244.0 125.0 1.600

Liquid after IX 91,900.0 27.0 10.0 1.560

Liquid after backwashing 27,640.0 36.0 10.0 0.768

Liquid after circulation 1,908.0 1,003.0 530.0 0.450

Desorption liquid After circulation 2,235.0 1,333.0 709.0 0.455

liquid after desorption Washing liquid 802.0 408.0 222.0 0.402

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Registered Patent No. 10-1662725

5th Precipitate filtrate 107,800.0 245.0 125.0 1.600

Liquid after IX 95,700.0 38.0 10.0 1.570

liquid after backwashing 48,560.0 67.0 10.0 0.404

circulating desorption 1,930.0 1,078.0 577.0 0.450

liquid after circulating desorption 2,364.0 1,351.0 752.0 0.442

liquid after washing 780.0 433.0 231.0 0.400

6th liquid precipitated filtrate 103,100.0 239.0 122.0 1.600

Liquid after IX 92,500.0 33.0 10.0 1.580

Liquid after backwashing 48,460.0 58.0 10.0 0.403

Liquid after circulation 2,057.0 1,132.0 630.0 0.450

Desorption liquid After circulation 2,653.0 1,411.0 808.0 0.444

liquid after desorption Washing liquid 449.0 242.0 134.0 0.778

[0051] The concentration of hydrochloric acid used for desorption in this example was 6% hydrochloric acid by weight. Based on the results of Table 1,

The adsorption and desorption rates of Co and Ni, which are metals to be collected, are shown in Table 2.

Table 2

[0052] 1st round of Category Co In

circulation Adsorption Rate 77.75% 87.98%

Desorption Rate 95.49% 86.92%

Secondary Adsorption Rate 78.25% 90.37%

Desorption Rate 88.56% 79.62%

tertiary Adsorption Rate 79.84% 90.63%

Desorption Rate 90.80% 88.28%

4th Adsorption Rate 82.13% 88.36%

Desorption Rate 99.55% 98.09%

5th Adsorption Rate 77.88% 90.13%

Desorption Rate 93.44% 91.61%

6th Adsorption Rate 80.25% 89.84%

Desorption Rate 99.50% ~100.00%

The adsorption rate and desorption rate in Table 2 were defined as follows.

[0055] [Adsorption rate definition]

[0056]

[0057] [Definition of desorption rate]

[0058]

[0060] As suggested in the present invention, the desorption rate of Co increased from 95.49% in the first cycle to 99.50% in the sixth cycle. Even in the case of Ni, which has an easy

adsorption behavior and is difficult to desorb, the desorption is well performed from 86.92% to ~100.00% in the first round.

[0061] This means that desorption of the ion exchange resin can be performed smoothly even if the same hydrochloric acid is introduced, if desorption is performed by

circulation using a low pH after the desorption process.

[0062] In this embodiment, although this is an example for 6 rounds of circulation, in an actual commercial process, these effects are stabilized as the rounds are repeated, so

that a more stable ion exchange process can be operated.

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Registered Patent No. 10-1662725

[0064] Comparative Example

[0065] The first cycle of the above embodiment can be viewed as a comparative example.

[0066] As shown in the first cycle result, the desorption of Co and Ni does not work well even if the same hydrochloric acid is used. If the desorption is not performed well, the

adsorption rate of the ion exchange resin will continue to decrease as the number of cycles of the ion exchange process is repeated, and to prevent this, a separate ion

regeneration process must be performed.

[0067] In this case, disadvantages such as stopping all front and rear processes due to the ion exchange process or having to build a separate ion exchange facility for operation

are expected.

[0069] The present invention is not limited to the above embodiments and can be manufactured in various different forms, and those skilled in the art to which the present

invention pertains can do other specific things without changing the technical spirit or essential features of the present invention. It will be understood that it can be

implemented in the form. Therefore, the embodiments described above should be understood as illustrative in all respects and not limiting.

floor plan

drawing 1

drawing 2

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