TUNGSTEN RECOVERY METHOD

Abstract

A tungsten recovery method including leaching tungsten while suppressing leaching of silicon by using a weak alkali compound with respect to a tungsten raw material containing silicon with tungsten oxide, separating most of the silicon as a residue during the leaching of the tungsten, and recovering a tungsten leachate having an extremely low silicon concentration.

Claims

1. A tungsten recovery method comprising leaching tungsten while suppressing leaching of silicon by weak alkali leaching using a weak alkali compound with respect to a tungsten raw material containing silicon and tungsten oxide.

2. The tungsten recovery method according to claim 1, wherein the weak alkali compound is sodium carbonate, aqueous ammonia, or sodium phosphate.

3. The tungsten recovery method according to claim 1, wherein the weak alkali compound having a molar equivalent of 1.5 to 3.0 times an amount of tungsten oxide in the raw material is added to the tungsten raw material to leach tungsten.

4. The tungsten recovery method according to claim 1, wherein the tungsten raw material is an oxidized roasted product of tungsten sludge containing tungsten carbide and silicon.

5. The tungsten recovery method according to claim 4, wherein the tungsten sludge is an oxidized roasted product containing 25 to 35 wt % of WO.sub.3, 15 to 20 wt % of CoWO.sub.4, and 25 to 50 wt % of SiO.sub.2.

6. The tungsten recovery method according to claim 2, wherein the weak alkali compound having a molar equivalent of 1.5 to 3.0 times an amount of tungsten oxide in the raw material is added to the tungsten raw material to leach tungsten.

7. The tungsten recovery method according to claim 2, wherein the tungsten raw material is an oxidized roasted product of tungsten sludge containing tungsten carbide and silicon.

8. The tungsten recovery method according to claim 3, wherein the tungsten raw material is an oxidized roasted product of tungsten sludge containing tungsten carbide and silicon.

9. The tungsten recovery method according to claim 6, wherein the tungsten raw material is an oxidized roasted product of tungsten sludge containing tungsten carbide and silicon.

10. The tungsten recovery method according to claim 7, wherein the tungsten sludge is an oxidized roasted product containing 25 to 35 wt % of WO.sub.3, 15 to 20 wt % of CoWO.sub.4, and 25 to 50 wt % of SiO.sub.2.

11. The tungsten recovery method according to claim 8, wherein the tungsten sludge is an oxidized roasted product containing 25 to 35 wt % of WO.sub.3, 15 to 20 wt % of CoWO.sub.4, and 25 to 50 wt % of SiO.sub.2.

12. The tungsten recovery method according to claim 9, wherein the tungsten sludge is an oxidized roasted product containing 25 to 35 wt % of WO.sub.3, 15 to 20 wt % of CoWO.sub.4, and 25 to 50 wt % of SiO.sub.2.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0026] FIG. 1 is a process step diagram representing an example of a recovery method according to an embodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

[0027] Next, an embodiment of the present invention will be described with reference to the drawing.

[0028] FIG. 1 is a process step diagram representing an example of a recovery method according to a first embodiment of the present invention.

<Silicon-Containing Tungsten Raw Material>

[0029] The tungsten recovery method according to the present embodiment is a method for selectively leaching and recovering tungsten from a tungsten raw material containing silicon together with tungsten oxide. As the tungsten raw material, an oxidized roasted product such as tungsten sludge containing tungsten carbide (WC) and silicon can be used. Examples of tungsten sludge containing WC and silicon include recovery sludge of cutting waste slurry discharged from a step of using a cemented carbide tool. In addition to tungsten carbide (WC) and cobalt (Co) derived from the cemented carbide tool component, diatomaceous earth (SiO.sub.2) which is used as a filtration aid during the solid-liquid separation and recovery, is mixed in the recovery sludge of the cutting waste.

[0030] In general, in a case where WC or Co contained in the recovery sludge is oxidatively roasted, the reaction occurs as the following formulae [1] and [2], and a roasted material containing approximately 25 to 35 wt % of WO.sub.3, 15 to 20 wt % of CoWO.sub.4, and 25 to 50 wt % of SiO.sub.2 is obtained.

WC+5/2O.sub.2.fwdarw.WO.sub.3+CO.sub.2  [1]

WC+Co+3O.sub.2.fwdarw.CoWO.sub.4+CO.sub.2  [2]

<Weak Alkali Leaching Step S01>

[0031] In the tungsten recovery method according to the present embodiment, a weak alkali compound is used as a leaching agent. As the weak alkali compound, sodium carbonate, aqueous ammonia, sodium phosphate, or the like can be used. By using sodium carbonate, sodium phosphate, or the like, tungsten oxide (WO.sub.3) reacts as the following formula [3] to produce and leach sodium tungstate (Na.sub.2WO.sub.4). On the other hand, since silicon is difficult to be leached by a weak alkali compound, tungsten can be selectively leached.

WO.sub.3(s)+Na.sub.2CO.sub.3(aq)+H.sub.2O.fwdarw.Na.sub.2WO.sub.4(aq)+H.sub.2CO.sub.3(aq)  [3]

[0032] The amount of the weak alkali compound used is preferably 1.5 to 3.0 times the molar equivalent, and more preferably 2.0 to 2.5 times the molar equivalent with respect to the amount of tungsten oxide in the raw material. In a case where the amount thereof used is 3.5 times the molar equivalent or more than the amount of WO.sub.3, the leached amount of silicon increases. Accordingly, in order to suppress the leaching of silicon, the amount of the weak alkali compound used is preferably in the range described above (1.5 times to 3.0 times molar equivalent).

[0033] Water may be added to the tungsten raw material described above (oxidized roasted product of tungsten sludge or the like) to form slurry, and a weak alkali compound such as sodium carbonate may be added to the slurry for leaching. A solid content concentration of the slurry is preferably in a range of 10 to 600 g/L, and more preferably in a range of 300 to 350 g/L. In a case where the slurry concentration is lower than the range described above, the economic efficiency such as chemical cost and treatment amount is reduced, and in a case where the slurry concentration is higher than the range described above, the leaching time becomes long.

[0034] A leaching temperature is preferably 100° C. or higher and more preferably 150° C. to 200° C. A leaching time may be approximately 2.5 hours to 3.5 hours.

[0035] In a leaching step S01, for example, by using 1.5 to 3.0 times the molar equivalent of sodium carbonate with respect to the amount of tungsten oxide in the raw material, leaching of tungsten can be promoted while suppressing leaching of silicon. It is possible to obtain a leachate in which a WO.sub.3 leaching rate is 90% or more and a ratio of a Si concentration of the leachate to a WO.sub.3 concentration (Si [g/L]/WO.sub.3 [g/L]) is suppressed to less than 0.004.

[0036] Generally, in a case where the Si [g/L]/WO.sub.3 [g/L] concentration ratio in the liquid is less than 0.005, the Si concentration is sufficiently low. Accordingly, it is possible to prevent reprecipitation of Si in the leachate. In the recovery method of the present invention, the Si [g/L]/WO.sub.3 [g/L] concentration ratio of the leachate can be suppressed to less than 0.004. Accordingly, Si reprecipitation does not occur.

[0037] In case where the alkali leaching with NaOH is performed, as shown in the following formulae [4] and [5], a large amount of silicon is leached together with tungsten oxide (WO.sub.3). Accordingly, tungsten cannot be selectively leached.

WO.sub.3(s)+2NaOH(aq).fwdarw.Na.sub.2WO.sub.4(aq)+H.sub.2O  [4]

SiO.sub.2(s)+2NaOH(aq).fwdarw.Na.sub.2SiO.sub.3(aq)+H.sub.2O  [5]

<Recovery Step S02>

[0038] In a recovery step S02, a leachate and a leaching residue are separated into solid and liquid and recovered. Since this leachate contains almost no silicon, tungsten can be efficiently recovered. Meanwhile, water is added to the recovered leaching residue to perform repulping washing (S03) to wash out the leachate adhering to the residue. This is solid-liquid separated (S04) to recover the washed liquid (secondary leachate), and tungsten (Na.sub.2WO.sub.4) contained in the washed liquid (secondary leachate) can be recovered. The repulping washing (S03) of the leaching residue may be performed as necessary.

[0039] In the tungsten recovery method according to the present embodiment, the leaching of silicon is suppressed by the weak alkali leaching and the tungsten is leached. Accordingly, most of the silicon is separated as a residue during the leaching of the tungsten. Therefore, it is possible to obtain a tungsten leachate having an extremely low silicon concentration.

[0040] In addition, in the tungsten recovery method according to the present embodiment, in a case where the leaching of silicon and the solid-liquid separation, and the leaching of tungsten and the solid-liquid separation are performed, it is not necessary to perform the complicated process step described above, and the process step is simplified. Accordingly, the processing time can be shortened, the processing equipment can be simplified, and the productivity can be increased. In addition, since the number of times of solid-liquid separations is small, it is possible to suppress tungsten from migrating to a residue and lost due to coprecipitation, adsorption, adhesion, and the like of tungsten.

[0041] In the tungsten recovery method according to the present embodiment, a chemical agent such as hydrogen fluoride is not used, and accordingly, it is possible to reduce the cost of the chemical cost and stably perform the process operation. In addition, in the tungsten recovery method according to the present embodiment, a chemical agent of a calcium compound as in the method of the related art is not used. Accordingly, no extra precipitation occurs, and it is possible to save time and effort in wastewater treatment and sludge disposal and reduce the process cost and environmental load.

EXAMPLES

[0042] Hereinafter, examples of the recovery method according to the present invention will be shown together with comparative examples.

[0043] The WO.sub.3 concentration in the tungsten raw material and the leaching residue was measured according to a measurement method specified in the standard (JIS M 8128 method for quantifying tungsten in ore). In addition, the Si concentration was measured by fluorescence X-ray analysis. The WO.sub.3 concentration and Si concentration in the leachate were measured by ICP-AES analysis.

[0044] As the silicon-containing tungsten raw material, an oxidized roasted product containing the WO.sub.3 concentration of 59.6 wt % and the Si concentration of 14.7 wt % was used.

[0045] The WO.sub.3 leaching rate was calculated by an equation of WO.sub.3 leaching rate [%]=WO.sub.3 [g] in the leachate/(WO.sub.3 [g] in the leachate+WO.sub.3 [g] in the leaching residue).

[0046] The Si/WO.sub.3 concentration ratio of the leachate was defined as the Si [g/L]/WO.sub.3 [g/L] ratio.

Example 1

[0047] 150 g of a silicon-containing tungsten raw material (the oxidized roasted product described above) was put in an autoclave container, and 500 mL of water was added to have the slurry concentration to 300 g/L. 81.7 g of sodium carbonate ([Na.sub.2CO.sub.3]/[WO.sub.3] molar ratio=2.0 times equivalent) was added thereto, heated to 200° C., and held for 1 hour to leach WO.sub.3.

[0048] A volume of the leachate after leaching was 540 mL, and in the composition, the WO.sub.3 concentration was 157.2 g/L, the Si concentration was 0.21 g/L, the Si/WO.sub.3 concentration ratio was 0.0013, and the Si concentration was sufficiently lower than 0.004 which is the target Si/WO.sub.3 concentration ratio. The dry leaching residue was 68.0 g, and the WO.sub.3 concentration in the leaching residue was 6.4 wt %. From this result, the WO.sub.3 leaching rate was 95.1%, and a high leaching rate was obtained.

Example 2

[0049] The amount of sodium carbonate added was 102.2 g ([Na.sub.2CO.sub.3]/[WO.sub.3] molar ratio=2.5 times equivalent), and leaching was performed in the same manner as in Example 1 under other conditions. As a result, a volume of the leachate after leaching was 550 mL, and in the composition, the WO.sub.3 concentration was 157.5 g/L, the Si concentration was 0.22 g/L, the Si/WO.sub.3 concentration ratio was 0.0014, and the Si concentration was sufficiently lower than 0.004 which is the target Si/WO.sub.3 concentration ratio. The dry leaching residue was 66.5 g, and the WO.sub.3 concentration in the leaching residue was 3.9 wt %. From this result, the WO.sub.3 leaching rate was 97.1%, and a high leaching rate was obtained.

Example 3

[0050] The amount of sodium carbonate added was 122.6 g ([Na.sub.2CO.sub.3]/[WO.sub.3] molar ratio=3.0 times equivalent), and leaching was performed in the same manner as in Example 1 under other conditions. As a result, a volume of the leachate after leaching was 560 mL, and in the composition, the WO.sub.3 concentration was 156.9 g/L, the Si concentration was 0.23 g/L, the Si/WO.sub.3 concentration ratio was 0.0015, and the Si concentration was sufficiently lower than 0.004 which is the target Si/WO.sub.3 concentration ratio. The dry leaching residue was 64.1 g, and the WO.sub.3 concentration in the leaching residue was 2.1 wt %. From this result, the WO.sub.3 leaching rate was 98.5%, and a high leaching rate was obtained.

Example 4

[0051] The amount of sodium carbonate added was 57.2 g ([Na.sub.2CO.sub.3]/[WO.sub.3] molar ratio=1.4 times equivalent), and leaching was performed in the same manner as in Example 1 under other conditions. As a result, a volume of the leachate after leaching was 530 mL, and in the composition, the WO.sub.3 concentration was 140.7 g/L, the Si concentration was 0.16 g/L, the Si/WO.sub.3 concentration ratio was 0.0012, and the Si concentration was sufficiently lower than 0.004 which is the target Si/WO.sub.3 concentration ratio. However, the dry leaching residue was 71.2 g, and the WO.sub.3 concentration in the leaching residue was 21.1 wt %. From this result, it was confirmed that, the WO.sub.3 leaching rate was 83.2%, and in order to increase the WO.sub.3 leaching rate to 95% or more, the [Na.sub.2CO.sub.3]/[WO.sub.3] molar ratio is preferably 1.5 times equivalent or more.

Example 5

[0052] By using sodium phosphate instead of sodium carbonate, the amount thereof added was set to 158.0 g ([Na.sub.2CO.sub.3]/[WO.sub.3] molar ratio=2.5 times equivalent), and leaching was performed in the same manner as in Example 1 under other conditions. As a result, a volume of the leachate after leaching was 580 mL, and in the composition, the WO.sub.3 concentration was 149.6 g/L, the Si concentration was 0.20 g/L, the Si/WO.sub.3 concentration ratio was 0.0013, and the Si concentration was sufficiently lower than 0.004 which is the target Si/WO.sub.3 concentration ratio. The dry leaching residue was 66.9 g, and the WO.sub.3 concentration in the leaching residue was 4.1 wt %. From this result, the WO.sub.3 leaching rate was 96.9%, and a high leaching rate was obtained.

Comparative Example 1

[0053] By using sodium hydroxide instead of sodium carbonate, the amount thereof added was set to 61.7 g ([Na.sub.2CO.sub.3]/[WO.sub.3] molar ratio=4.0 times equivalent), and leaching was performed in the same manner as in Example 1 under other conditions. As a result, a volume of the leachate after leaching was 530 mL, and in the composition, the WO.sub.3 concentration was 165.2 g/L, the dry leaching residue was 68.6 g, and the WO.sub.3 concentration in the leaching residue was 2.5 wt %. From this result, the WO.sub.3 leaching rate was 98.1%. However, the Si concentration of the leachate was 42.9 g/L, and a large amount of silicon was leached. As a result, the Si/WO.sub.3 concentration ratio was as high as 0.26, which was not suitable to suppress silicon leaching and selectively leaching tungsten.

TABLE-US-00001 TABLE 1 Process condition Processing WO.sub.3 Si Process Process Leaching material concentration concentration temperature time agent [g] [%] [%] [° C.] [hour] [g] Example 1 Si-containing W 59.6 14.7 200 1.0 Na.sub.2CO.sub.3 oxidized roasted 81.7 product 150 g Example 2 Si-containing W 59.6 14.7 200 1.0 Na.sub.2CO.sub.3 oxidized roasted 102.2 product 150 g Example 3 Si-containing W 59.6 14.7 200 1.0 Na.sub.2CO.sub.3 oxidized roasted 122.6 product 150 g Example 4 Si-containing W 59.6 14.7 200 1.0 Na.sub.2CO.sub.3 oxidized roasted 57.2 product 150 g Example 5 Si-containing W 59.6 14.7 200 1.0 Na.sub.3PO.sub.4 oxidized roasted 158.0 product 150 g Comparative Si-containing W 59.6 14.7 200 1.0 NaOH Example 1 oxidized roasted 61.7 product 150 g Process condition Leaching Leachate WO.sub.3 agent/WO.sub.3 Slurry WO.sub.3 Si Si[g/L]/ leaching molar ratio concentration concentration concentration WO.sub.3[g/L] rate [—] [g/L] [g/L] [g/L] [—] [%] Example 1 2.0 300 157.2 0.21 0.0013 95.1 Example 2 2.5 300 157.5 0.22 0.0014 97.1 Example 3 3.0 300 156.9 0.23 0.0015 98.5 Example 4 1.4 300 140.7 0.16 0.0012 83.2 Example 5 2.5 300 149.6 0.20 0.0013 96.9 Comparative 4.0 300 165.2 42.9 0.26 98.1 Example 1

INDUSTRIAL APPLICABILITY

[0054] The present invention provides the method for efficiently and selectively recovering tungsten from a tungsten raw material containing silicon together with tungsten.