JPS5949289B2 - Separate collection method of metals - Google Patents

Description

[Detailed Description of the Invention] Treatment methods that have been conventionally adopted as a method for separating and recovering various metals from electrolytic slime or ores include sulfation roasting method,
Dry chlorination method, soda roasting method, pressure leaching method (power soda,
There are pressurized methods using ammonia, sulfuric acid, or hydrochloric acid).

However, in the sulfation roasting method, As, Sb, or S generated during roasting
equipment for eliminating fumes such as e, sulfur oxides such as NO2 and S03, and their secondary pollution; skill is required to control the temperature of sulfuric acid roasting; soluble metals and insoluble metals are not completely separated; It had the disadvantage of requiring reprocessing in a separate process.

The chlorination method (a method that utilizes a chlorination reaction by thermal decomposition of C12 gas, NaC1, or CaC12) is also expensive to deal with the generated gas, generates highly toxic fumes and gases such as AsCl3, and has secondary Disadvantages include the risk of pollution, the danger of handling large amounts of dangerous C12 gas, and the difficulty of controlling the chlorination temperature.

In addition, the soda roasting method has the disadvantages that only a few types of metals can be solubilized, that extremely high skill is required to control the conditions of soda roasting, and that soda roasting is the only method used when processing raw materials containing various metals. The drawback is that it requires a combination of leaching steps.

Furthermore, the pressure leaching method requires a high-pressure melting method with a special structure, and the disadvantage common to all methods is that insoluble and soluble metals are not clearly separated, so both the leachate and the residue contain the same metal. The drawback is that it must be treated in two or more separate ways.

However, in the various conventional treatment methods described above, the chemicals used in roasting and reactions cannot be completely recycled or recovered, so they are not completely environmentally friendly or resource-saving.

It is an object of the present invention to provide a novel method for separating and recovering metals which substantially overcomes the drawbacks of the prior art described above.

The present invention provides a method for separately recovering various metals from raw materials containing divalent or higher valence metals such as electrolytic slime, metal-containing mixed catalysts, or complex ores, in which the metal-containing raw materials are blown with oxygen gas in the first step. Since it is a complex, it is treated with HNO3 to remove insoluble As, Au, Pt, Sb, Sio2, Al2O.
3 and dissolved in HNO3 in the second tank.
, Pb, Ag, Pd, Cu, Se, Te, C
o, Zn and Ni-containing NO3 solution is brought into contact with an organic solvent (5) to form Fe''+ ions in the organic solvent (5) described below.
In the third step, H2SO4 is added to the remaining metal ion-containing HNO3 solution in the raffinate to convert pb to PbS.
o 4, HCl or a metal chloride such as NaCl or Kcl is added to the remaining aqueous solution in the 4th step to precipitate Ag as AgC1, and the remaining metal ion-containing I (N03 aqueous solution is added to the remaining aqueous solution in the 5th step. The raffinate aqueous phase is brought into contact with the organic solvent (C) in the sixth step to extract HNO3 and Pd into the organic solvent phase (C). In the seventh step, SO2 gas is blown into the aqueous phase of the raffinate to reduce and separate Se and Te into metallic form, and the amount necessary to form a complex with Zn and Co remaining in the remaining aqueous solution is removed. After adding MCI, Co and Zn are brought into contact with 0 organic solvent in the 8th step.
The remaining aqueous liquid was extracted with HSO.
In the ninth step, NiSO4 and NH2O are separated and recovered from the recovered H2SO4 using known technology, and H2S
After concentration, O4 is recycled to the sulfation process in the second stage.
In the extraction process, Fe3+ is peeled off by contacting with hydrochloric acid, and the organic solvent (4) is recycled to the Ee3+ extraction process in the 5th step, and the organic solvent (in the 5th step) is extracted with HNO.
Pd by sequential contact with 3+NH4Cl and water
and HNO3 were collected separately, and the organic solution ff1B) was collected in the fifth
The recovered HNO3 is recycled to the HNO3 extraction process in the process.
After absorbing the NOx gas generated in the H03 melting process of the first process, it is recycled to the INOa melting process of the first process.
In the 6th step, the organic solvent (0 phase is brought into contact with H2S04 and peeled off as Cuf: CuSO4, and the solvent phase is replaced with H2SO4.
The organic solvent (0) is recycled to the Cu extraction step in the 6th step, and the organic solvent (0) phase in the 8th step is brought into contact with water to recover Co and Zn as chlorides. The organic solvent phase 0 is separated and collected, and the organic solvent phase 0 is used as C0 in the 8th step.
- A method for separately recovering various metals from the valuable metal-containing raw material, which comprises recycling to a ZnC1 extraction step.

The method of the present invention will be explained with reference to the accompanying drawings.

FIG. 1 shows a process diagram of the method of the present invention.

Block S indicates various metal-containing raw materials such as electrolytic slag, waste catalyst, and complex ores.

1st step: This raw material is charged into a normal pressure sealed container in the "HNO3 dissolution" step of block 1, HNO3 is introduced into the container, and the raw material is dissolved under 02 gas blowing.

The 02 gas to be used is pure oxygen, and the reaction atmosphere is kept in a highly oxidizing state.Generally, when a metal is simply dissolved in HNO3, the result is 3Me+4HNO3, :3MeN03+NO+2H20 as shown in the formula below.
(Me=metal)... According to (1), 9NO gas is generated, and this NO gas causes a pollution problem, but when this is done in the presence of oxygen, the following formula % formula % (2) shows that NO gas is generated. The occurrence of is suppressed.

However, as a practical matter, there is a problem with the efficiency of the oxidation reaction by 02 gas, and some NOx is generated during this dissolution process, but since the atmosphere is 0.2 J, the conversion of NOx to NO is rapid, and thus NOx is generated. The NO□ produced in the block 1-2 "NOx absorption" process is processed in block 5 described below.
It is absorbed into the recovered HNO3 obtained in the "HNO3 stripping" step of -2 and recycled to the HNO3 dissolution step of Block 1.

HNO3 used in the HNO3 dissolution process of block 1
For example, a concentration of 50 to 60, for example, 50 to 55 is suitable.

However, it should be understood that more concentrated or dilute HNO3 can also be used.

The amount of oxygen is preferably at least the stoichiometric amount of formula C).

As oxygen, pure oxygen or an oxygen-containing gas can be used.

Au, Pt remaining as undissolved residue in HNO3 dissolution process
, As, Sb, Si02 and Al2O3 are separated (1-1 block).

Separation of these components is carried out by the steps described below with reference to FIG.

Second Step The solution from the HNO3 dissolution step in block 1 is then contacted in block 2 with an organic solvent (5).

The metal ions contained in the HNO3 solution of block 2 are Fe 3 +, Pb, Ag, Pd, Cu, Se
, Te, Co, Zn, Ni, etc.

The organic solvent (5) here refers to dialkyl acidic ethyl phosphate represented by 0)2[0)HC, where R is a C4 to 18 alkyl group, or these and hydrocarbons, or hydrocarbons and higher Mixtures with aliphatic alcohols can be used.

Di(2-
ethylhexyl) acidic phosphoric acid (D2EHPA) (R
=2-ethylhexyl group) is preferred.

In the "Fe3+ extraction" step of block 2, Fe3+ contacts the dialkyl acidic phosphate ester to form an adduct according to the following formula, and is extracted into the organic solvent phase.

F e ” ++3 ((RO) 2.KO)OH),
5"e [(RO) 2 [0) 0] 3+3H+ In Figure 3, a solution containing the above various ions was added to an HNO3 solution with a concentration of 180.4 t/lI) in an organic solvent (5) (D
2EHPA 50%, indecanol 3%, remainder kerosene) at room temperature shows the Fe3+ extraction curve.

In the figure, the horizontal axis is Fe3+ in the HNO3 solution (the sexual phase).
The vertical axis shows the concentration Cf/l) of Fe3+ in the organic solvent (organic phase).

In this way, in the Fe''+ extraction process, Fe3+ is selectively extracted into the organic solvent, and then the organic phase is blocked 2-1.
The organic phase is sent to the "Fe3+ washing" step, where it is subjected to MCI.
and recover it as a concentrated solution of Fe3+ in HC1 according to the formula below.

Fe((RO)2KO)0:13+3HC1;FeC1
The organic phase from which a +3((Ro)2p(ΩpH]Fe) has been removed is recycled to the Fe3+ extraction step of block 2.

H2SO4 can also be used in place of HCl in this step.

Figure 4 shows Fe”+ from the dialkyl acidic phosphoric acid-containing organic phase.
The figure shows the balance curve when washing (reverse extraction) with HCI solution.

Third step: The HNO3 solution from which Fe3+ has been removed in Niblock 2 is then sent to the "sulfation" step in Teblock 3, where H2SO4 in an amount approximately equivalent to the heavy metal ions contained is added to convert the metal into sulfate. Performs the conversion of chemical species to .

The concentration of sulfuric acid used is not critical. Pb in block 3
-bS04 is precipitated, so this is collected and sent to block 3-1.

The remaining aqueous solution in the fourth step is sent to the "salination" step in block 4, where HCl and ('-i or) NaCl are added to precipitate Ag as A C1, and AgC1 is separated in block 4-1. , the remaining aqueous solution is extracted from block 5 by “HNO3 extraction”.
Send to process.

In place of MCI, other metal chlorides of Group 1 or Group 2 of the Periodic Table, such as IC1.

CaC1□ etc. can be used.

The separated AgCl of block 4-1 may be appropriately shaped in a wet state, and then subjected to AgCl electrolysis in a NaOH bath to form electrolytic silver, or may be melted with NaOH and converted into Ag and NaCl.

Fifth step In the "HNO3 extraction" step of block 5, the aqueous liquid from block 4 is brought into contact with an organic solvent ().

Organic solvent [F]) refers to enthyl acids, such as tributyl phosphate (TBP),) lyoctyl phosphate (TOP), and dibutyl besidyl phosphate (D).
BBP), or trioctylphosphine oxide, etc., or mixtures thereof, or mixtures thereof with a hydrocarbon such as kerosene.

Extraction of HNO3 is performed according to the following formula.

) INO3+TBP, mHNO3·TBP The concentration of ethyl phosphate used is determined by the concentration of HNO3 in the aqueous solution to be extracted.

Figure 5 shows organic solvent (B) (-marked TBP 50% + T
OP 50%, X mark TBP 75% + TOP 25%)
The equilibrium curve at room temperature when extracting HNO3 is shown.

In the "HNO3 extraction" step of block 5, the Pd present is also extracted into the organic solvent.

FIG. 6 shows a Pd extraction equilibrium curve when Pd in a HNO3 solution (N0306/l to 1 mol/l) is brought into contact with an organic solvent (B) (TBP50 + kerosene 50).

In the figure, the horizontal axis shows the Pd concentration ('?/l) in the aqueous phase, and the vertical axis shows the Pd concentration (P/4) in the organic phase.

The organic phase of block 5 is then sent to the rPd cleaning step of block 5-1, where it is washed with more than 4N of-fNo. 3 and N
Pd ions are converted to Pd+ by contacting with a mixed solution with H4Cl.
2N1 (4C1 → Pd small H3) 2C1゜+2H+ ni P
The aqueous phase is recovered in the form of d(NH3)2Cl2.

The amount of NH4Cl in the mixed solution needs to be greater than the amount necessary for addition with Pd in the organic phase.

The HNO3 remaining in the organic phase is then sent to the "HNO3 stripping" step of block 5-2, where the organic phase is brought into contact with water to strip HNO3, and a portion of the recovered HNO3 is sent to block 5-1 as necessary. After concentrating to the concentration required for the Pd cleaning step, the remainder is sent to the "rNOx absorption" step in block 1-2.

Almost 100% of HNO is recovered in this process, and the recovered HNO
The concentration of 3 can be adjusted from 4N to 6N by adjusting the number of extraction stages or flow rate ratio.
recovered at a concentration of

Back extraction of HNO3 is performed according to the following formula HNO3·TBP+H20=HN03+TBP.

Figure 7 shows TBP 20% TOP 45% kerosene 35%
Figure 2 shows an equilibrium curve of HNO3 back-extraction when HNO3 in an organic solvent is back-extracted with water at 60°C.

In the figure, the horizontal axis is the HNO3 concentration in the organic phase (g/13
), and the vertical axis shows the concentration (g/11) of recovered HNO3.

The aqueous phase of the HNO3 extraction step in block 5 of the sixth step is then sent to the "Cu extraction step" in block 6, where the Cu ions are extracted by contacting with an organic solvent (Q).

The organic solvent (C) refers to amines, such as Lix.
)64N, Lix65, Lix70 (all product names,
General Mills (General Mi-11s)
SME-529 (trade name, manufactured by Shell Oil), or these amines and hydrocarbon diluent solvents such as kerosene and/or higher aliphatic alcohols (
phase separation promoters) such as octatool, a mixture with indecanol.

The amount of hydrocarbon diluent solvent can be varied depending on the Cu concentration in the aqueous phase.

When the aliphatic higher alcohol phase separation accelerator is used, the amount thereof is preferably 2 to 5% (volume %) of the total organic solvent.

The aqueous phase after HNO3 extraction in block 5 contains the H2SO4 added in block 3 sulfation and a small amount of residual HC1 added in block 4.

For example, the extraction of Cu ions with an organic solvent (C) is performed using the following formula. %formula% Proceed according to

Figure 8 shows the L of Cu2+ in H2SO4 100 g/l solution.
ix64N 50% organic solvent consisting of 50% decakerosene (
Figure 2 shows the extraction equilibrium curve at room temperature with 0.

In the figure, the horizontal axis indicates the Cu ion concentration in the aqueous phase (<t/l'), and the vertical axis indicates the Cu ion concentration (g/1) in the organic phase.

The Cu ions extracted by the organic solvent (Q
Copper electrolysis... Contact with sulfuric acid solution or H2SO4 to recover Cu at high concentration in sulfuric acid, regenerate the organic solvent (C), and regenerate the organic solvent as a block. Recycle to 6-1.

The H2SO4 concentration used as a back-extractant here is not critical, but 150? / or more is preferable.

FIG. 9 shows an equilibrium curve when Cu in Lix64N 50%-+-kerosene 50% organic solvent was stripped (2) extracted) with 150 r/l H2SO4 (temperature 40 DEG C.).

In the figure, the horizontal axis shows the Cu concentration (f/7) in the organic phase, and the vertical axis shows the Cu concentration (S'/7) in the aqueous phase.

Seventh step: The aqueous phase from which the Cu ions have been extracted is sent to block 7, the “reduction step”.

Since Se and Te generally exist in this aqueous phase as H2Seo4 and H2TeO4, by blowing in a reducing gas such as SO3, Se and Te are reduced to elemental form and precipitated.

As the reducing agent used here, SO2, R28, etc. can be used, but SO□ is preferable.

The temperature used varies depending on the reducing agent, but is generally between 30°C and 50°C.
It is ℃.

The reduced Se and Te are separated by filtration and sent to block 7-1, where they are recovered as Se and Te.
o-ZnC1 extraction" process.

8th step d In block 8, C contained in the P liquid.

After addition of hydrochloric acid necessary for Zn and Zn to form a chloride complex, the mixture is brought into contact with organic solvent 0 to extract Co and Zn as a complex into the organic solvent, and the aqueous phase is recovered as sulfuric acid.

9th step: The recovered sulfuric acid is sent to the "concentration step" in block 9, where it is concentrated and N i S 04.6H20 is crystallized and separated, and the P solution is recycled to the sulfation step in block 3 to complete the recovery cycle. .

Examples of the organic solvent 0 include primary to quaternary amines, such as Primene JM-T (
Product name: Ro-hm an
dHaos) primary amine], LA-1, LA
-2 (trade name, manufactured by Rohm & Haas, secondary amine), Alamine 336 [trade name, manufactured by General Mills, trioctylamine (TOA)
) and Aliqut 336 (trade name, manufactured by General Mills, quaternary amine), and other amines can be used.

The organic solvent 0 is the above amine and a hydrocarbon such as a kerosene diluent and/or a higher alcohol such as octatool,
Mixtures with phase separation promoters such as decanol and indecanol can also be used.

Extraction of Co and Zn is performed as follows.

ZnC13-+(R3NH+)#(R3NH-)ZnC
13COCI,,””+2(R3NH+),=:(R3
NH+)・Q)Cl and Alamine 33 in Figure 10.
6 Using an organic solvent n consisting of 10% indecanol, 3% indecanol, and the remainder kerosene, the H2SO4 concentration in the solution was
The extraction equilibrium curve at room temperature is shown when o (marked with *) and Zn (marked with X) are extracted as chloride complexes.

In the figure, the horizontal axis shows the concentration of Co and Zn in the aqueous phase (J/l), and the vertical axis shows the concentration of Co and Zn in the organic phase (fii'/l).

The organic solvent ① in which Co and Zn were dissolved is then transferred to block 8.
Co and Zn are recovered as a concentrated aqueous solution of C(JC12 and ZnCl2) by being sent to the "co-2ncl stripping" step of Block 8, and the organic solvent 0 is regenerated. Recycle to 2ncl extraction step.

Peeling of Co and Zn is performed according to the following formula.

(R3NH+)"ZnC1'1-)R20;!R3N+
HC10nCl2 (R3NH”)2COC14+H2o, =2(R3N)
+2HC1+CoCl2 Figure 11 shows the equilibrium curve when a Co, Zn chloride complex in an organic solvent (Cl) (TOA 3% + indecanol 1% ten residual kerosene is extracted with water at 50°C on the peeling side) (Co is
Mark ZnI/'ix mark) is shown.

The horizontal axis in the figure shows the metal ion concentration in the organic phase (Cf/l),
The vertical axis indicates the metal ion concentration (f//, ) in the aqueous phase.

Au that was not dissolved in the HNO3 dissolution step of block 1,
P t, As, S b, S i 02 and Al2
The O3 separation operation will be explained with reference to FIG.

Figure 10 Step 2 Block 22 (7
) ICI (150y
7t~300? /l) to dissolve sb and Ae.

Hydrochloric acid solution containing dissolved Sb and As is block 22-1
Send to the "Sd extraction" process.

11th step: 1 (block 23 remaining from the HCI dissolution step of block 22 that was not dissolved in C1) is Pt, Au and 5to2,
Contains only gangue such as Al2O3, but the remainder contains pt and A.
When the quality of u is high, melt this in block 23-1.
The process melts to produce crude gold (block 23-2), and the Au is recovered by conventional means, such as electrolytic refining.

Further, if the quality of Au and Pt in the undissolved residue is low, the process is led to block 24, the "regia dissolving" step.

In the aqua regia dissolution step of block 24, the residue after dissolving and removing As and sb is put into a sealed container, and aqua regia is added while blowing in 02 to completely dissolve Au and pt.
The 2O3 gangue is separated as an undissolved residue.

In this step, for example, for pt, 3P t+ 18HCl
+4HN03 ;3 H2P t Cl 6+4NO
No (or NOx) generated by +8H20 is sent to the NOx absorption step of block 1-2 shown in FIG. 1 and recovered as HNO3.

12th round: The obtained aqua regia solution is then sent to the rAu/pt oil extraction step in block 25, where it is brought into contact with the organic solvent (2) to extract Au and pt into the organic phase.

Here, the same solvent as organic solvent 0 is used as the organic solvent [F].

Figure 12 shows Au and pt in aqua regia with an organic solvent (TO).
Extraction equilibrium curves of Au (■ mark) and PT (x mark) when extracted with A3% + indecanol 3% + residual kerosene at room temperature are shown.

In the figure, the horizontal axis shows the Au and Pt concentrations (r/z) in the aqueous phase, and the vertical axis shows the Au and Pt concentrations C? in the organic phase. /l).

The organic phase of the extract is then sent to the "Pt stripping" step in block 25-1, where pt is isolated as Na2PtC16 by contacting with an alkaline aqueous solution such as a NaOH aqueous solution (soy7 or higher is sufficient). (Block 25-z).

The organic phase of block 25-1 is rAu of block 25-3.
A reducing solution such as Na2SO is added to the stripping process.
3. Au is reductively peeled off by contacting with a solution such as NaNO2 or N2H4, and recovered as metallic gold in block 25-4, and the tetraorganic solvent (g) is recycled to block 25.

Note that since the Au that was not completely peeled off in block 23 tends to increase as the number of steps increases, a part of the organic layer is sent to the "incineration" step of block 25-5, where it is incinerated and the Au is recovered. .

Sb and A dissolved in the 13th step “rHc1 dissolution of Niblock 22” step
The HCI solution containing s (Pt) is
sb is recovered in the organic solvent, and the organic phase is contacted with water in the "Sb stripping" step of block 23-2. sb is stripped and the organic phase is recycled to block 22-1.

The raffinate aqueous phase (block 26 rA s -HC1 solution is sent to the "neutralization" step of block 27 where it is combined with the raffinate aqueous phase of the "rAu-Pt extraction" step of block 25 by known neutralization means). Neutralize and release.

The method of the present invention is suitable for processing raw materials containing polyvalent metals such as electrolytic slum, and as mentioned above, it is a closed circuit type that can recycle most of the chemicals used, has high purity and recovery rate of recovered metals, and prevents pollution. The industrial significance of the above is also that of a dog.

Next, the present invention will be explained with reference to Examples.

As a raw material, electrolytic slum produced in a copper electrolysis process with the following composition (wt%) was used.

(Unit weight section) Au -Pt Ag Se T
e Pd Pb1.14 0.085.36 8.
67 0.880.0011.46Cu Fe Z
n Ni Co Sb As30.57 0.
05 0.04 0.79 0.03 18.436.
09 The above raw material 502 was placed in a closed container, and 60% HN0310ktj was poured into the container while blowing 0° to dissolve it.

The blowing rate of No. 02 was adjusted to match the injection of HNO3, and the reaction proceeded at about 40° C. to 80° C. due to self-heating.

When treated at a slime dissolution rate of about 10 ky/hour, the NOx at the outlet of a packed column with a diameter of 500 square meters and a height of 3,000 square meters was 10 to 20 ppm.

After 30 minutes, the undissolved residue was separated from P to give a residue of approximately 1.3%.

Add the washing liquid of undissolved residue to the f liquid to bring the total liquid volume to 29.4t.
And so.

The concentration of each component in the liquid is as follows.

(Unit: r/7) Fe Pb Ag Cu
Pd Se Te0.8 2.5 9.1 5
1.90<0.01 14.70.15CoZn
Ni HNO3 0,050,070,13204,0 This was di(2-ethylhexyl)phosphoric acid (D2EHPA
) and separated the organic phase at 150 ? /1HcA to peel off Fe as FeCl3.

Fe, yield is quantitative.

PbSO4 was precipitated and removed by adding 50% H2SO40.2ky to the HNO3 solution of the sediment.

Is pb in the solution 0.001? / became below.

0.26ky of 35% HCl was added to the remaining slurry to separate the precipitated Ag.

The amount of P solution including the AgC1 water washing solution was 40 tons, and the composition was as follows.

(r/, a) HNO3H2SO4C1' Pd C
u 5e149.9 100 3. s<o:oO
x3s, x51o, sTe Zn Te Co
Zn Ni PdO, 110,050,110,
03-0,050,09<0.001g<0. o 01 The above r liquid was brought into contact with a mixed solvent of 75% TBP + 25% TOP, and the resulting organic phase was heated at 250 t/11 (No3+
Contact with 120t/1NH4C1 solution, HNO of oil liquid
From a 3+NH4Cl mixed solution, Pd becomes P as the concentration increases.
dCNH3)2C12 was isolated in crystalline form.

The organic phase was contacted with water at about 60°C to recover HNO3 as about 3.5N HNO3.

The aqueous phase of the raffinate after contact with TBP-TOP solvent was socked with 54Nb, the organic phase was contacted with 15% H2SO4, the Ct was extracted as CuSO4 into H2SO4, and the aqueous phase was injected with SO.
2 gases were blown into the reactor, and Se and Te were recovered in elemental form.

Add 0.01 kg of 35% HCl to the remaining aqueous liquid, and add TO
It was brought into contact with an organic solvent of A3% + isodecal 1% and residual kerosene, the organic phase was separated, and it was brought into contact with water at 30° C. or above to recover Co and Zn as ZnC12 and COCl2.

The aqueous phase of the raffinate contained 100 v/l of H2SO4 and was recycled to the sulfation step in block 3 after concentration.

25 minutes after thoroughly washing the undissolved residue from the first step (block 1) with water.
HCl was added and dissolved at 40°C for 180 minutes.

After cooling, the undissolved solids were separated, and the solids were dissolved in aqua regia while blowing 02, and the insolubles were separated as Al2O35102.

The aqua regia solution was extracted at room temperature with an organic solvent of 3% TOA + 1 g of isodecanol + residual kerosene, and the organic phase was extracted with 8% NaOH.
Wash with solution and recover as PtNa2Ptc16 (0,
08y) The raffinate organic phase was washed with water and brought into contact with Na2SO4 solution to recover Au in metallic form (as in 8.2).

The remaining non-reverse extraction material was incinerated and recovered.

The sludge after separating the insoluble solids F was brought into contact with an organic solvent consisting of TOAIO%, decanol 3 thikerosine, the organic phase was washed with water, and MCI was added to the extracted sb by hydrolysis in water to form 5bC13 ( 173f) and the aqueous phase was neutralized with Ca(OH)2 to convert As to HASo4.1
) ■Recovered as 20 (51, 11).

[Brief explanation of drawings]

FIG. 1 is a schematic process diagram of the method of the present invention, and FIG. 2 is a process diagram for treating undissolved residue in the first step of the method of the present invention. Figure 3 is the Fe3+ extraction equilibrium curve with organic solvent, Figure 4 is the back extraction curve of HF e Cl 4, Figure 5 is the HNO3 extraction equilibrium curve with organic solvent, Figure 6 is the Pd extraction curve with organic solvent, and Figure 7 is the extraction equilibrium curve of HNO3 with organic solvent. The figure shows the HNO3 exfoliation curve with water, Figure 8 shows the Cu extraction equilibrium curve with organic solvent, and Figure 9 shows the H2
α bacteria release curve by SO4, Figure 10 shows c by organic solvent.
o-ZnC1 extraction equilibrium curve, Figure 11 shows Co by water
*Zn peeling equilibrium curve; FIG. 12 is an Au-Pt extraction equilibrium curve using an organic solvent.

Claims (1)

[Claims] 1. At least Fe, Pb, 'AgJPd, Cu, Se,
Te. Raw materials containing Co, Zn, and Ni are heated with H in the presence of oxygen.
Treat with NO3 to separate the insoluble residue, contact the remaining HNO3 solution with an organic solution medium (a) containing dialkyl phosphoric acid or a mixture thereof to extract Fe+3, and convert the metals contained in the raffinate solution into sulfates. at least the required amount of H
2SO4 is added to convert the metal salt to sulfate and HN
O3 is liberated, pb is removed as PbSO4, Ag is removed by adding a chlorine-containing compound to the resulting fcRNO3 solution, and the F solution is treated with a phosphoric acid ester or a mixture thereof or a phosphine oxide-containing organic solvent Q3). The raffinate H2S04-HCI acidic solution was brought into contact with an amine-containing organic solution F to extract Cu into an organic solvent (Q), and the raffinate aqueous solution was extracted with a reducing agent. After treatment, Se and Te are reduced and recovered in elemental form, and after adding a predetermined amount of MCI to the remaining solution, it is brought into contact with an amine-containing organic solvent 0 to extract Co and Zn as chloride complexes.
After crystallizing N I So 4 from the raffinate sulfuric acid solution, the raffinate sulfuric acid solution is recycled to the sulfate conversion step, the organic solvent residue is treated with MCI to recover Fe, and the organic solution I is treated with water or Treat with NO3+N and H4Cl to recover N03 and Pd, and treat the organic solvent with H2SO4 to recover CuS.
Collect O4 and treat organic solvent 0 with water to make CuS04
A method for the fractional recovery of metals, which comprises recovering Co and Zn as chlorides by treating the organic solvent (c) with water. 2 Di(2-ethylhexyl) as dialkyl phosphate
2. The method according to claim 1, wherein phosphoric acid is used. 3. The method according to claim 1, wherein tributyl phosphate is used as the phosphoric acid ester. 4. The method according to claim 1, wherein trioctyl phosphate is used as the phosphoric acid ester. 5. The method according to claim 1, wherein trioctylphosphine oxide is used as the phosphine oxide. 6. The method according to claim 1, wherein the organic solvents 0 and 0 use an amino acid or an amine, a hydrocarbon diluent, and/or a higher alcohol phase separation promoter. 7 At least Fe, Pb, Ag, Pd, Cu
, Se, Te, Co, Zn, Ni, Pt, Au, A
s, Sb-containing raw material is treated with HNO3 in the presence of oxygen to separate the insoluble residue, and the remaining H
Fe+3 is extracted by contacting the NO3 solution with an organic solution medium containing dialkyl phosphoric acid or a mixture thereof, and the raffinate solution is injected with the necessary amount of H2SlO to convert the contained metal to sulfate.
4 is added to convert the metal salt into sulfate, HNO3
, pb is removed as PbSO4, a chlorine-containing compound is added to the resulting HNO3 solution to remove the Ag, and the sludge is treated with ethyl phosphate or a mixture thereof or a phosphine oxide-containing organic solvent). HNO3 and Pd were extracted into an organic solution tm), and the raffinate was extracted with HNO3 and Pd.
2S04-HCI acidic solution is brought into contact with an amine-containing organic solvent (0) to extract Cu into an organic solvent (Q), the raffinate aqueous solution is treated with a reducing agent to reduce and recover Se and Te to elemental form, and the remaining After adding a predetermined amount of HCI to the solution, it is brought into contact with an amine-containing organic solvent (2) to extract Co and Zn as a chloride complex, and after crystallizing NISO4 from the raffinate sulfuric acid solution, the raffinate sulfuric acid solution is added to the sulfuric acid solution. Recycled in the conversion process to salt,
The HNO3 insoluble residue is treated with HCI to dissolve the sb and As compounds, the insoluble residue is dissolved in aqua regia, and the aqua regia solution is treated with an organic amine-containing organic solvent to extract pt and Au into the organic phase. is contacted with an alkaline aqueous solution to peel off the PT, the remaining organic phase is treated with a reducing agent to recover Au in elemental form, and a solution containing Az-8b is contacted with an organic solution containing an organic amine to remove sb from an organic solvent. The organic solvent (g) was extracted with water and treated with water to peel off the sb, and the organic solvent (g) was extracted with water or HN.
Treated with O3+NH4C■ to recover No3 and Pd, treated with organic solvent (0 was treated with H2SO4 to remove CuS0
4 was recovered and the organic solvent 0)) was treated with water to remove Co and Zn.
A method for separating metals and recovering them as chlorides.