JPS5818416B2 - A method of extracting metals, especially nickel, cobalt, and other materials such as rock powder and red mud from ultramafic rocks. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the extraction of rare metals, particularly nickel, cobalt, magnesium, or other materials such as rock powder and red mud from ultramafic rocks.

These metals can be extracted in the metallic state or in the form of oxides or chlorides.

"Ultrabasic rocks" include peridotite, dunite, Harzburgite, etc., their altered materials such as serpentein, serpenteinite, etc., debris of these rocks such as laterite, and other minerals and minerals related to these rocks. Sediment,
It means a group of oxide rocks consisting of semi-processed products and by-products produced when processing them, and has the following chemical composition: NiO, 05-5.0% Al2030.
05~25%CoO, 005~0.5%Fe2
03 0.5~65.0010Mg o 0.0~55
．． 0% Cr2 A3 o, o 05~5.0%C
ao O, 05~5.0% S i O20, 1~60
．． 0% Cuo O, 005~0.5% Loss on ignition 0.5
~5s,ofb Industrial by-products and waste materials having a similar composition can also be treated within the scope of the present invention by the methods described below.

Examples of ultramafic rocks that belong to non-natural products include flue dust produced in the production of ferronickel in metallurgical plants.

It is known to extract nickel from ores with low magnesia content (J, R, Boldt Jr., :P.

Queneau: The Winning
of NickelMethuen & Co.
, Led, , London (71967)).

Furthermore, treatment of serpenteinites using hydrochloric acid has been repeatedly attempted (R, 'M1111sr: Versu
chezur verwertung 5erpen
tinischer Gestein fur d
in N1ckel 'Berg-und Hu
ttenmannis'che l~fLonatsc
h-ete, Volume 9.5, Issues 4, 7 and 8 ('1950
),.

and R, Muller +-W, He5se, F, S
inigoi +Die Nufbereitung
von 5erpentini-ten und
1hren Verwitterungsprodu-
kton durch
In the above cited text, Volume 96, No. 10 (1951)).

Such methods do not yield pure substances as required for industrial applications.

Furthermore, it is common practice to make magnesium chloride solutions from magnesium-containing minerals (E, A, Gee,
M, T, Pavel, Productionnot Ma
Gnesium Chloride from Mag
ne-.

sium Si] 1cate Ore, US Patent No. 2
．． No. 549.798 (1951) and K, B-
+Beng,ts,on,',J,C.

A1mc+nd, L, N, Johanso, n, Ver.
4ahren ZurHeretellung Ko
nzentrierter, magnes-iumch
loridhaltiger Losungeny
German Published Specification No. 1.253.253 (196
4)).

This method cannot utilize the other metals in the snow contained in the mineral.

It is believed that all of these known methods suffer from some degree of drawbacks, such as: only one useful substance is extracted from the ore; a large proportion of the acid used is consumed; and the acid used is harmful or of no value. The proportion of waste materials generated is high.

In contrast to these processes, it is an object of the present invention to make it possible to extract a large number of useful components in pure form from the starting materials mentioned above, and to make such processes very economical and socio-ecological. The objective is to enable recirculation of the processing agent in order to achieve satisfactory results.

According to the invention, the feedstock is reacted with hydrogen chloride which is recovered in a further step of the process.

The obtained silica is collected and treated to form Wakamatsu.

When this r-liquid is treated with an oxidizing-neutralizing agent, iron-containing impurities are precipitated.

This is separated as red mud. According to another aspect of the invention, the remaining metal chloride solution is treated with one or more organic extraction solvents followed by washing to selectively recover nickel chloride and cobalt chloride; Subsequent thermal decomposition yields nickel oxide and/or cobalt oxide.

These may be ring-formed to give metallic nickel and/or
Or metal cobalt.

On the other hand, the hydrochloric acid produced by the decomposition is preferably reused for washing the organic extract mentioned above.

According to yet another aspect of the invention, the magnesium chloride remaining in solution after extraction of nickel and cobalt is thermally decomposed to pure magnesia, and the hydrogen chloride produced is reused to react as a raw material feed. , and some of the obtained magnesia is PH for the extraction of nickel or cobalt.
It is preferable to use it for adjusting the value.

The method adopted by the present invention is thus novel, in that it allows the key components of the feedstock to be obtained in a pure and usable state, and that they can also be processed in such a way as to reduce the consumption rate of processing agents. It is recycled and reused, and virtually no waste material is produced.

Next, two embodiments of the method according to the invention are illustrated in FIGS. 1 and 2.
This will be explained in more detail with reference to the drawings.

The embodiment shown in Figure 1 is suitable for low cobalt feedstocks and will be described first.

The rock is previously heat treated and crushed in a known manner and then fed as ore 1 to step 10 of the method.

Step 320 or 330 to solubilize ore 1
The recovered hydrochloric acid 322 is used with a small amount of fresh acid to compensate for the loss.

Hydrochloric acid is heated between 115°C and 300°C depending on the nature of the feedstock.
Gas at a temperature of °C or 50°C to 115°C
It is supplied as an aqueous solution at a temperature of .

The action of hydrochloric acid on the ore produces a suspension consisting of aqueous solutions of various metal chlorides and filterable silica with titanium and chromium compounds.

Silica 11 is removed by a known method and treated in step 20 to obtain young pine.

In step 30, the chloride-containing solution 12 is treated with an oxidizing-neutralizing agent in a known manner to form a gel-like precipitate.

This includes water-containing oxide compounds of iron, manganese, aluminum, and possibly other metals.

This precipitate is filtered out and treated in step 40 to obtain red mud 41.

The filtered solution 32 contains mostly nickel chloride and cobalt chloride and is combined in step 210 with an organic extraction solvent 222 that is immiscible with the aqueous phase.

The selective solvent for the nickel extraction is preferably a liquid cation exchanger containing at least one C9-C11 tertiary carboxylic acid and/or at least one naphthenic acid.

The ratio of extraction solvent used is 0.2 nickel per mole of acid.
This corresponds to a molar ratio of 5 to 0.5 mol, and the temperature is 20°C to 50°C.

This extraction is performed at P I-(values of 5 to 7).

Preferably, a portion 323 of the magnesia recovered in step 320 is used to adjust the pH value.

Under the above conditions. During the extraction carried out, the nickel content of the solution 32 passes with a yield of more than 99.5% into the extraction solvent 222, where the nickel salt of the cation exchanger contained in this solvent is formed.

The nickel-containing organic extract 211 is subjected to precipitation.

and separated from the aqueous phase in step 220 with an aqueous hydrochloric acid solution, preferably the acid 251 recovered in steps 240 and 250.
Wash with

This cleaning is carried out at a temperature of 20°C to 50°C and a P and H value of 3 to 6.

During the washing operation under the above conditions, the nickel content of the organic extract 211 enters the aqueous solution 221 with a yield of more than 99.3%.

A corresponding proportion of cation exchanger is liberated in the organic phase,
The thus regenerated extraction solvent 222 is recycled to the extraction process 210.

In step 230, pure nickel chloride solution 221 is concentrated in a known manner by evaporation and drying to form a concentrate 2
31 is fed to step 240 as a concentrated solution or solid hydrate or in the molten state as required later.

In step 240, concentrate 231 is pyrolyzed at a temperature ranging from 500°C to 1500°C depending on the desired properties of the product.

Pyrolysis yields pure nickel oxide 241 with a yield of over 98 fb.

This nickel oxide can be reduced to metallic nickel by a known method if necessary.

During this decomposition hydrogen chloride 242 is liberated, which in step 2
At 50 it is cooled and absorbed into water.

The obtained hydrochloric acid aqueous solution 251 is the extract 211 of step 220.
It is preferable to reuse it for cleaning.

The pure magnesium chloride solution 212 remaining after the extraction is concentrated in a step 310 by evaporation and drying in a known manner, and the concentrate 311 is then passed to step 320 as a concentrated solution or in the solid or molten state, depending on subsequent requirements. Supplied.

In step 320, the concentrate 311 is pyrolyzed, with or without immediate post-treatment.

The temperature will depend on the desired activity of the magnesium oxide produced, but will be in the range 600°C to 2100°C.

Upon pyrolysis, pure magnesium oxide particles 21 and 323 with a surface area of 0.05 to 50 m/9 are obtained, depending on the selected conditions.

A portion of the magnesia 323 is preferably recycled to the extraction step 210 for pH adjustment.

The hydrochloric acid 322 liberated during the pyrolysis is carried out in step 10 as a gas or preferably as an aqueous solution after absorption in step 330.
used to solubilize the ore.

A further embodiment of the process according to the invention is suitable for feedstocks with a high cobalt content.

This will be explained with reference to FIG.

As previously discussed with respect to FIG. 1, the feedstock is first processed in steps 10 to 40.

In this case, solution 32 from step 30 contains mostly cobalt chloride, nickel chloride, and magnesium chloride.

Preferably, the selective extraction solvent for cobalt comprises a liquid ion exchanger containing at least one substituted ammonium, sulfonium or phosphonium group.

The concentration of chloride ions in solution 32 is in the range of 200 to 300 grams per liter.

The temperature during extraction should be in the range of 20°C to 50°C.

During the extraction under the above conditions, cobalt chloride in solution 32 enters extraction solvent 122 with a yield of more than 99.8% and solution 1
A complex salt of the ion exchanger contained in 22 is formed.

The cobalt-containing organic extract 111 is separated from the aqueous phase by sedimentation in step 120 at a temperature of 20°C to 50°C.
Wash with water 121.

As a result, cobalt chloride in the extract 111 enters the aqueous solution 123 with a yield of 99.5% or more.

In the organic phase, the ion exchanger is liberated in a corresponding proportion.

The thus regenerated extraction solvent 122 is recycled to the extraction process 110.

The pure cobalt chloride solution 123 is concentrated in step 130.

In step 140, the concentrate 131 is pyrolyzed to cobalt oxide 141.

It can also be reduced to metallic cobalt as described above for nickel.

Hydrogen chloride 142 liberated by this thermal decomposition is produced in step 15.
Hydrochloric acid aqueous solution for solubilization of ore by absorption in water at 0.1
Recirculate as 51.

The nickel chloride and magnesium chloride solution 112 remaining after extraction of the cobalt chloride is further processed in steps 210-250 and 310-350 according to embodiments of the invention as described above with respect to FIG.

In order to facilitate understanding of the present invention, the present invention will now be described by way of examples.

Example 1 This example applies the method according to the invention to the treatment of laterite ore having the following composition (expressed in weight percentages):

The ore was 100% ground to a fineness of less than 44 microns and then treated with 20 part strength hydrochloric acid at a temperature of 50°C to 105°C and atmospheric pressure in a stirred vessel equipped with a reflux condenser.

Table 1.1 shows that the percentage of dissolved nickel depends on the solvent temperature and dissolution time.

When hydrochloric acid was applied at 105° C. for 20 minutes, 39.5 parts out of 100 parts of the raw ore were dissolved.

60.5 parts of undissolved silica-containing residue are separated by filtration;
Dry.

Another part of the crushed ore was heated at a temperature of 100°C to 160°C under a pressure (absolute pressure) of 5 kg/cr&20
treated with hydrochloric acid at a concentration of

Under these conditions, 40.3 parts of 100 parts of raw ore were dissolved by the action of the solvent for 12 minutes.

The data analyzed for the filtered metal chloride solution produced by the first method described above is shown in Section A of Table 1.2.

The metals contained in the raw ore went into solution in yields ranging from 90 to 99 degrees.

Solution A was placed in a container under stirring at 50-60°C and neutralized with a magnetic screw "V" to a pH value of 6.2.

The formed precipitate was washed under vacuum and washed with distilled water.

The composition of the metal chloride solution after neutralization and filtration is shown in section B of Table 1.2.

The nickel lost in the iron-containing precipitate after filtration is dissolved in solution A.
This corresponds to a nickel content of 9.6%.

The above treatment yields iron and aluminum. A significant amount of chromium was removed from the solution.

600 ml of Solution B was placed in a stirred container at 40°C and mixed with Versatic-10 Acid (10 part concentration).
It was treated twice with 200 milliliters of a kerosene solution of (registered trademark).

(This Versat 1c-10Acid® is manufactured by Shell and is a mixture of branched saturated aliphatic carboxylic acids.

) PI (magnesia was added to adjust the value to 5.8.

The aqueous phase was separated from the organic phase by settling.

The data analyzed for the aqueous phase after this second treatment is shown in Section C of Table 1.3.

Nickel, cobalt, aluminum + of solution B during extraction
It can be seen that the iron t''Rom content enters the organic phase almost quantitatively and that solution C contains only magnesium and calcium.

Combine the organic phases and place in a shaking funnel at 40°C to reduce the concentration to 6%.
It was treated twice with hydrochloric acid at a concentration of 3 Q.

The phases were then separated by sedimentation. The two aqueous phase portions were mixed.

The analytical values for the combined aqueous phase are shown in Section D of Table 1.3.

It can be seen that the nickel, cobalt, aluminum, iron and chromium contents are considerably washed out of the organic phase by the hydrochloric acid.

Moreover, the solution contains higher concentrations of nickel and cobalt metals than solution B before extraction, and is substantially free of magnesium and calcium.

Solutions of metal chlorides listed in section C of Table 1.3 were brought into direct contact with hot steam containing magnesia powder produced by pyrolysis.

This direct heat exchange evaporated some of the water and free hydrochloric acid contained in the solution, thickening the fed magnesium chloride solution by 28.7%.

The concentrated magnesium chloride solution was thermally decomposed at 845° C. under oxidizing conditions.

At this temperature, magnesium chloride was thermally decomposed into magnesia and hydrogen chloride gas.

The calcium chloride content was not converted and was found intact in the baked goods.

The free time products had the chemical and physical properties listed in Section E of Table 1.4.

Hot steam containing hydrogen chloride was used to increase the concentration of the feed magnesium chloride solution.

Next, this hydrogen chloride gas was dissolved in water under adiabatic conditions, and 20
It was sent to the dissolution process as hydrochloric acid at a relevant concentration.

Next, residual chloride in the dried baked product was decomposed using a wet method or a dry method.

In the case of the former method, the Shu ware was washed with pure water to dissolve the calcium chloride, while the magnesia was reacted to form insoluble magnesium hydroxide.

After filtration, the filter cake was washed once again with pure water.

Next, this filtrate cake with a water content of 36.8% was placed in a drying oven and dried and baked at a temperature of 980° C. or lower.

This dried pottery consists of over 99.5% magnesia, with 0
, and contained 2% residual chloride.

In the case of the latter method, residual chloride in the roasted product was decomposed to 0.26% in an indirect heating furnace at 1380°C.

This treatment increased the maximum particle size of magnesia from 0.7 microns to 4.5 microns.

The purity of the obtained magnesia was 97.5% or more.

The concentration of the nickel chloride solution listed in section D of Table 1.3 is 16
After increasing the temperature to 0 &/l nickel, it was thermally decomposed at 790°C to obtain nickel oxide and hydrochloric acid.

The properties of the roasted shells are shown in Section F of Table 1.4. 6 Hydrogen chloride gas generated during concentration treatment and hydrogen chloride gas generated during thermal decomposition are recovered as hydrochloric acid with a concentration of 20 parts, and the organic phase is used for processing.

Example 2 In this example, a serpentine rock having the following composition was treated = (by weight) This rock was first crushed to a particle size of less than 1 mrIL.

Hydrochloric acid with a concentration of about 27 parts was added to a 50 kg sample of crushed rock.
001 was added and this was leached at 105°C for 60 minutes.

The resulting suspension was subjected to over-separation at 80°C.

The filter cake was a residue insoluble in hydrochloric acid and was weighed after drying and analyzed.

24.05 kg of dry material was obtained.

The yield of nickel and magnesium is 86.8 each.
% and 88.2%.

The filtered metal chloride solution was further treated in substantially the same manner as in Example 1 to generate Nio.

After removing the nickel, the magnesium chloride solution was first dried in a spray dryer at a temperature of about 260°C to obtain magnesium chloride trihydrate.

Next, this was thermally converted at a temperature of 860°C to obtain magnesia and hydrochloric acid.

The surface area of the produced magnesia is 2.25 rrl/! 9
Its bulk density was 425 g/11.

Magnesia was further processed in the same steps as in Example 1.

The gases generated during pyrolysis are 22 volumes of hydrogen chloride, 23
Contains 55 volumes of water and 55 volumes of inert gas,
When this was treated in a single-stage adiabatic absorption column, 27% concentration of hydrochloric acid was obtained.

This was used to dissolve serpentein in the circulatory system.

Example 3 This example relates to partial treatment of metal chloride solutions in accordance with one aspect of the present invention.

The composition of the feed solution is shown in Section A of Table 3.1.

A total volume of 6,001 liters of solution A was added to 30 volumes of xylene in a counter-current extraction column at 35°C.
s), a solution containing t-octylamine].

The aqueous phase after extraction was separated by sedimentation.

The average analytical data for the separated aqueous phase is shown in Table 3.1, section B.

It can be seen that this solution contains only small amounts of cobalt, aluminum and iron.

The combined organic eggs were then washed in the same extraction column at 35°C with a total volume of 241 co-flowing distilled water.

The aqueous phase was separated by settling. The average analytical data is shown in Section C of Table 3.1.

Solution C contained cobalt, aluminum and iron washed out of the organic phase, and also contained only small amounts of nickel and magnesium.

The total yield of cobalt for solution A was 98% or higher.

It was possible to process solution B to produce nickel oxide by the method of Example 11 and to obtain cobalt oxide by processing solution C in a similar manner.

Preferred embodiments of the present invention are listed below.

1 Extraction of nickel is carried out at a temperature of 20-50°C, preferably 35-40°C, and a pH value of 5-7, preferably 5.7-6.
3, using a liquid cation exchanger containing at least one tertiary carboxylic acid having 9 to 11 carbon atoms and/or at least one naphthenic acid,
At this time, the molar ratio of nickel to 1 mole of acid was set at 025 to 0.
．． 5 mol, preferably 0.3-0.35 mol, then using an aqueous hydrochloric acid solution at a temperature of 20-50 °C, preferably 30-40 °C and a pH value of 3-6, preferably 5-5.5. 2. A process as claimed in claim 1, characterized in that the nickel is washed out from the organic phase and the regenerated cation exchanger is reused in the extraction.

2 Obtained nickel chloride solution;
℃, preferably at a temperature of 700 to 900℃, absorbing the hydrogen chloride gas generated during the decomposition into water,
The method according to claim 1 and the method according to claim 1, characterized in that the aqueous hydrochloric acid solution thus produced is used for washing the organic phase.

3 Cobalt and nickel are recovered separately and 20-5
0°C1, preferably a temperature of 35-40°C and a chloride ion concentration of 200-300. ! i2/l.

The cobalt is extracted in one step by treatment with a liquid shadow ion exchanger containing at least one of substituted ammonium, sulfonium aluminum or phosphonium groups, preferably under conditions of 250-270 g/l, followed by 20-270 g/l. washing out the cobalt chloride from the organic phase using water at 50° C., preferably between 35 and 40° C., recovering this as a cobalt chloride solution and reusing the regenerated ion exchanger for the extraction; A method according to claim 1, characterized in that the solution remaining after cobalt has been extracted is treated in a separate step under the conditions described in paragraphs 1 and 2 above to extract nickel.

4. Heat the obtained cobalt chloride solution to 500 to 15,000C.
, preferably at a temperature of 600 to 800°C, and the hydrogen chloride produced during the cracking is recycled to solubilize the feedstock. The method described in.

600-2 immediately after pyrolyzing the magnesia chloride solution remaining after the extraction of nickel and/or cobalt.
The method according to claim 1, characterized in that the treatment is carried out at 100°C, and the temperature is selected so that the surface area of the produced magnesia is from 0.05 to 5 om/9 as required.

6. Evaporating and/or drying solutions of nickel chloride, cobalt chloride and magnesia chloride or one or two of these solutions before their pyrolysis and concentrating the products.

6. The method according to claim 2 and items 2, 4 and 5 above, characterized in that the pyrolysis is carried out as a liquid or solid hydrate or in a molten state.

7 Hydrogen chloride generated by thermal decomposition of magnesium chloride at 1 to 50 kg/cr? The hydrogen chloride is used to solubilize the feedstock at an absolute pressure of
00-450°C, preferably 120-150°C, preferably at an absolute pressure of 1 kg/c11L, as a gas or absorbed in water at a temperature of 50-115°C1
Preferably at 85-105°C and preferably at an absolute pressure of 5-1
6. Process according to claim 5, characterized in that it is used as an aqueous solution of hydrochloric acid at 0 kg/ffl, and that the solubilization is carried out under temperature and pressure conditions selected with regard to the nature of the feedstock.

[Brief explanation of drawings]

1 and 2 are flow sheets for implementing the present invention. . In Figures 1 and 2, 1 is ore, 2 is HCI, 10 is a solubilization/filtration process, 11 is silica, 12
is a chloride-containing solution, 20 is a drying/classification process, 21 is Wakamatsu, 30 is a precipitation/filtration process, 31 is a gel-like precipitate, 32
is the filtered solution, 40 is the drying/classification process, 41 is the red mud, 11
'0 is a cobalt extraction process, 111 is an organic extract containing cobalt, 112' is a solution of nickel chloride and magnesium chloride, 120 is a washing process, 121 is water 1.122 is an extraction solvent, 129 is a cobalt chloride aqueous solution, 130 is Concentration step, 131 concentrate, 140 thermal decomposition step, 141 cobalt oxide, 142 hydrogen chloride, 150 absorption step, 15
1 is a hydrochloric acid aqueous solution, 210 is a nickel extraction step, 211 is a nickel-containing organic extract, 212 is a whole solution of magnesila chloride, 220 is a washing step, 221 is a nickel chloride aqueous solution, 222 is an extraction solvent, 230 is a concentration step, 231 is a concentrate, 240 pyrolysis process, 241 nickel oxide, 24
2 is hydrogen chloride, 250 is an absorption process, 251 is an aqueous hydrochloric acid solution, 310 is a concentration process, 311 is a concentrate, 320 is a thermal decomposition process, 321 is magnesium oxide, 322 is hydrochloric acid, 32
3 means magnesium oxide and 330 means absorption process.

Claims (1)

[Claims] 1. Peridotite, dunite, Harzburgite, etc., their altered products, such as serpentein, serpenteinite, etc., debris of these rocks, such as laterite, other minerals and sediments associated with these rocks, and those produced by their processing. In a process for the extraction of metals, in particular nickel, cobalt and other substances such as rock powder and red mud, from ultramafic rocks belonging to the group consisting of semi-processed products and by-products and non-natural substances of similar composition, The above process solubilizes the feedstock with hydrogen chloride, separates the resulting silica, processes it into rock powder, adds an oxidizing-neutralizing agent to precipitate impurities in the remaining solution, and converts this precipitate into a red powder. The nickel and/or cobalt contained in the chloride-containing solution are extracted with one or more selective organic extraction solvents, and the resulting extract is washed with an aqueous phase to remove the nickel and/or cobalt as a slurry. and/or the cobalt is recovered as a pure solution of nickel chloride and/or cobalt chloride, and the extraction solvent after removing nickel and/or cobalt is reused for the above extraction, and the resulting nickel chloride and/or cobalt chloride solution is pyrolyzed to produce nickel oxide and/or cobalt oxide, the hydrogen chloride produced is recovered as an aqueous solution and reused for washing the organic phase and/or solubilizing the feedstock, and the remaining after the extraction is A method for extracting metals as described above, characterized in that the magnesium chloride solution is thermally decomposed and the generated hydrogen chloride is reused for solubilizing the feedstock.