CN117965914A - Method for extracting and separating gallium and germanium from zinc replacement slag sulfuric acid leaching solution - Google Patents
Method for extracting and separating gallium and germanium from zinc replacement slag sulfuric acid leaching solution Download PDFInfo
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 75
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 43
- 239000002893 slag Substances 0.000 title claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000011701 zinc Substances 0.000 title claims abstract description 28
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002386 leaching Methods 0.000 title claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 116
- 239000012074 organic phase Substances 0.000 claims abstract description 93
- 238000005406 washing Methods 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012071 phase Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 15
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006073 displacement reaction Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003350 kerosene Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 239000012535 impurity Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- -1 Fe 3+ Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Abstract
The invention discloses a method for extracting and separating gallium and germanium from zinc displacement slag sulfuric acid leaching solution. The method comprises the following steps: (1) Extracting zinc displacement slag sulfuric acid leaching solution by adopting a first organic phase to obtain an iron-containing loaded organic phase and a raffinate water phase A; (2) Adding concentrated sulfuric acid to adjust the pH value of the raffinate water phase A to 1.0-1.2, and extracting by adopting a second organic phase to obtain an aluminum-gallium-germanium-containing loaded organic phase and a raffinate water phase B; (3) Washing the aluminum-gallium-germanium-containing loaded organic phase by adopting hydrochloric acid to obtain an aluminum washing liquid and a gallium-germanium loaded organic phase; (4) Extracting gallium germanium loaded organic phase by sulfuric acid to obtain gallium stripping solution and germanium loaded organic phase; (5) And (3) back-extracting the germanium loaded organic phase by adopting an ammonium fluoride solution to obtain germanium back-extracting solution and a blank organic phase. The method has the advantages of simple and continuous operation, easy industrialization, good separation effect and the like, and provides technical support for comprehensive recycling of gallium and germanium in zinc replacement slag by wet full extraction.
Description
Technical Field
The invention relates to the technical field of hydrometallurgy, in particular to a method for extracting and separating gallium and germanium from zinc replacement slag sulfuric acid leaching solution.
Background
The diluted gallium germanium is an important basic raw material for developing modern computers, 5G communication, new energy, aerospace, medical health and national defense and military high-new technology, and the stable resource supply guarantee of the diluted gallium germanium directly relates to economy and national defense safety and has strategic status.
The total reserve of gallium-germanium rare-earth metal resources in China stands in the front of the world. Because of the rare dispersed metal characteristics, gallium and germanium are rare in independent mineral deposits and exist in associated forms in mineral deposits such as lead zinc ore, lignite, bauxite and the like. In order to reduce the recovery and extraction cost, gallium and germanium are mostly fed into the byproduct slag for recovery in the main metal smelting process in the associated ore deposit. For example, in the smelting process of lead-zinc ore, gallium and germanium are enriched in the by-product of zinc replacement slag, and the zinc replacement slag is also an important gallium and germanium extraction raw material. The extraction separation and recovery of gallium and germanium are the main research ideas at present after the zinc replacement slag is leached by high-concentration oxygen sulfate. Except Ga 3+、Ge4+, other impurity metals such as Fe 3+、Al3+、Zn2+、Cu2+ with a certain concentration are often contained in the zinc replacement slag oxygen pressure sulfuric acid leaching solution, and the acidity is high. Making extraction of gallium and germanium more difficult. Particularly, due to the extremely similar chemical properties of Fe 3+、Al3+ and Ga 3+、Ge4+, the prior extraction system or technology is difficult to realize high-efficiency separation. Based on this, the present invention has been proposed.
Disclosure of Invention
The invention aims to provide a method for extracting and separating gallium and germanium from zinc displacement slag sulfuric acid leaching solution.
The invention is realized by the following technical scheme:
a method for extracting and separating gallium and germanium from a zinc displacement slag sulfuric acid leaching solution, the method comprising the steps of:
1) Extracting zinc displacement slag sulfuric acid leaching solution by adopting a first organic phase to obtain an iron-containing loaded organic phase and a raffinate water phase A; wherein the zinc replacement slag sulfuric acid leaching solution contains Ga3+ 0.1~0.5g/L、Ge4+ 0.1~0.5g/L、Fe3+ 0.5~1g/L、Al3+ 1~3g/L、Zn2+ 10~20g/L、Cu2+ 10~20g/L and Cd 2+ to 5g/L; the first organic phase is prepared from N1923 and sulfonated kerosene in a volume ratio of 1-3:7-9;
2) Adding concentrated sulfuric acid to adjust the pH value of the raffinate water phase A in the step 1) to 1.0-1.2, and extracting the raffinate water phase A in the step 1) by adopting a second organic phase to obtain an aluminum-gallium-germanium-containing loaded organic phase and a raffinate water phase B; the second organic phase is prepared from P204, YW100, TBP and sulfonated kerosene in a volume ratio of 1-2:0.25-0.5:0.25-0.5:7-8.5;
3) Washing the aluminum-gallium-germanium-containing loaded organic phase obtained in the step 2) by adopting hydrochloric acid to obtain an aluminum washing solution and a gallium-germanium loaded organic phase;
4) The gallium germanium loaded organic phase obtained in the sulfuric acid back extraction step 3) is adopted to obtain gallium back extraction liquid and germanium loaded organic phase;
5) And (3) back-extracting the germanium loaded organic phase obtained in the step (4) by adopting an ammonium fluoride solution to obtain germanium back-extracting solution and a blank organic phase.
Preferably, the pH of the sulfuric acid leaching solution of the zinc replacement slag is= -0.2-0.5.
Preferably, step 1) extraction employs cross-flow extraction; the extraction phase O/A is 1: (1-3); the extraction level is 1-3; the extraction time is 5-10 min.
Preferably, step 2) extraction employs countercurrent extraction; the extraction phase O/A is 1: (1-3); the extraction level is 3-5; the extraction time is 5-10 min.
Preferably, step 3) washing employs cross-flow washing; the concentration of hydrochloric acid is 6-10 mol/L; the washing ratio O/A is 1 (1-2); the washing level is 1-3; the washing time is 5-10 min.
Preferably, the counter-current back extraction is adopted in the back extraction in the step 4); the concentration of sulfuric acid is 200-300 g/L; the counter-current ratio O/A is (1-3): 1; the back extraction stage number is 3-5; the back extraction time is 5-10 min.
Preferably, step 5) back extraction employs counter-current back extraction; the concentration of the ammonium fluoride is 2-3 mol/L; the counter-current ratio O/A is (1-3): 1; the back extraction stage number is 3-5; the back extraction time is 5-10 min.
The beneficial effects of the invention are as follows: the invention skillfully utilizes the difference of the selective extraction and back extraction characteristics of the N1923-sulfonated kerosene mixed extractant and the P204-YW 100-TBP-sulfonated kerosene mixed extractant on Ga 3+, ge 4+, fe 3+、Al3+ and other impurities under different systems of sulfuric acid, hydrochloric acid, ammonium fluoride and the like, and finally realizes the separation of Ga 3+、Ge4+, fe 3+、Al3+ and other impurities and the mutual separation of Ga 3+ and Ge 4+, and has simple technological process operation, easy industrialization and good separation effect.
Detailed Description
The following is a further illustration of the invention and is not a limitation of the invention.
Example 1: method for extracting and separating gallium and germanium from zinc replacement slag sulfuric acid leaching solution
The main components of the zinc replacement slag sulfuric acid leaching solution are as follows ：Ga3+ 0.14g/L、Ge4+ 0.11g/L、Fe3+ 0.57g/L、Al3+ 2.28g/L,Zn2+ 10.22g/L,Cu2+ 19.83g/L,Cd2+ 4.29g/L,pH=-0.2.
30% N1923 and 70% sulfonated kerosene were formulated in volume ratio as the first organic phase. And 3-stage cross-flow extraction is carried out on the first organic phase and the zinc displacement slag sulfuric acid leaching solution according to the ratio O/A of 1:1.5, the extraction is carried out for 10min, the extraction rate of Fe 3+ is 98.53%, and the extraction rate of other ions is less than 3%, so that an iron-containing loaded organic phase and a raffinate water phase A are obtained.
15% P204, 2.5% YW100, 2.5% TBP and 85% sulfonated kerosene were formulated in volume ratio as a second organic phase. After the pH of the raffinate water phase A is regulated to 1.2 by adding concentrated sulfuric acid, 5-level countercurrent extraction is carried out with a second organic phase according to the ratio of O/A of 1:3 for 10min, wherein the Ga 3+ extraction rate is 98.12%, the Ge 4+ extraction rate is 98.43%, the Al 3+ extraction rate is 22.17%, and the other ion extraction rates are less than 3%, so as to obtain an aluminum-gallium-germanium-containing loaded organic phase and the raffinate water phase B.
6Mol/L hydrochloric acid is adopted, and the ratio O/A is 1:1, carrying out 2-level cross-flow washing, wherein the washing rate of Al 3+ is 98.12 percent, and the washing rate of Ga 3+、Ge4+ is less than 3 percent, so as to obtain an aluminum washing liquid and a gallium germanium loaded organic phase; the gallium germanium loaded organic phase adopts 250g/L sulfuric acid according to the O/A ratio of 3: and (3) carrying out 5-stage countercurrent stripping, wherein the Ga 3+ stripping rate is 99.03%, and Ge 4+ is not stripped, so as to obtain gallium stripping solution and germanium loaded organic phase. The germanium-loaded organic phase adopts 2mol/L ammonium fluoride solution, and the ratio O/A is 1: and (3) carrying out 3-stage countercurrent stripping, wherein the Ge 4+ stripping rate is 99.17%, and obtaining germanium stripping liquid and a blank organic phase.
Example 2: method for extracting and separating gallium and germanium from zinc replacement slag sulfuric acid leaching solution
The main components of the zinc replacement slag sulfuric acid leaching solution are as follows ：Ga3+ 0.48g/L、Ge4+ 0.41g/L、Fe3+ 0.89g/L、Al3+ 2.28g/L,Zn2+ 10.22g/L,Cu2+ 19.83g/L,Cd2+ 4.29g/L,pH=0.5.
30% N1923 and 70% sulfonated kerosene were formulated in volume ratio as the first organic phase. And 2-level cross-flow extraction is carried out on the first organic phase and the zinc replacement slag sulfuric acid leaching solution according to the ratio O/A of 1:3, the extraction is carried out for 5min, the extraction rate of Fe 3+ is 98.29%, and the extraction rate of other ions is less than 3%, so as to obtain an iron-containing loaded organic phase and a raffinate water phase A.
The second organic phase was formulated from 20% p204, 5% yw100, 2.5% tbp and 72.5% sulfonated kerosene, by volume. After the pH of the raffinate water phase A is regulated to 1.0 by adding concentrated sulfuric acid, 5-level countercurrent extraction is carried out with the second organic phase according to the ratio of O/A of 1:2, the extraction is carried out for 5min, the Ga 3+ extraction rate is 97.79%, the Ge 4+ extraction rate is 98.02%, the Al 3+ extraction rate is 18.43%, and the other ion extraction rate is less than 3%, so that an aluminum-gallium-germanium-containing loaded organic phase and the raffinate water phase B are obtained.
10Mol/L hydrochloric acid is adopted, and the ratio O/A is 1:2, carrying out 1-level cross-flow washing, wherein the washing rate of Al 3+ is 97.11%, and the washing rate of Ga 3+、Ge4+ is less than 3%, so as to obtain an aluminum washing liquid and a gallium germanium loaded organic phase; the gallium germanium loaded organic phase adopts 200g/L sulfuric acid according to the ratio O/A of 1: and (3) carrying out 3-stage countercurrent stripping, wherein the Ga 3+ stripping rate is 99.07%, and Ge 4+ is not stripped, so as to obtain gallium stripping solution and germanium loaded organic phase. The germanium-loaded organic phase adopts 3mol/L ammonium fluoride solution, and the ratio O/A is 1: and (3) carrying out 5-level countercurrent stripping, wherein the Ge 4+ stripping rate is 99.46%, and obtaining germanium stripping liquid and a blank organic phase.
Example 3: method for extracting and separating gallium and germanium from zinc replacement slag sulfuric acid leaching solution
The main components of the zinc replacement slag sulfuric acid leaching solution are as follows ：Ga3+ 0.14g/L、Ge4+ 0.11g/L、Fe3+ 0.89g/L、Al3+ 2.90g/L、Zn2+ 19.27g/L、Cu2+ 11.53g/L、Cd2+ 1.67g/L,pH=0.5.
20% N1923 and 80% sulfonated kerosene were formulated in volume ratio as the first organic phase. And carrying out 1-level cross-flow extraction on the zinc replacement slag sulfuric acid leaching solution and the first organic phase according to the ratio O/A of 1:1, wherein the extraction rate of Fe 3+ is 97.12%, the extraction rate of other ions is less than 3%, and obtaining an iron-containing loaded organic phase and a raffinate water phase A.
10% P204, 2.5% YW100, 5% TBP and 82.5% sulfonated kerosene were formulated in volume ratio as a second organic phase. After the pH of the raffinate water phase A is regulated to 1.05 by adding concentrated sulfuric acid, 3-stage countercurrent extraction is carried out with a second organic phase according to the ratio of O/A of 1:1 for 10min, wherein the Ga 3+ extraction rate is 98.09%, the Ge 4+ extraction rate is 98.25%, the Al 3+ extraction rate is 21.32%, and the other ion extraction rate is less than 3%, so as to obtain an aluminum-gallium-germanium-containing loaded organic phase and the raffinate water phase B.
8Mol/L hydrochloric acid is adopted, and the ratio O/A is 1:1, carrying out 3-level cross-flow washing, wherein the washing rate of Al 3+ is 99.37%, and the washing rate of Ga 3+、Ge4+ is less than 3%, so as to obtain an aluminum washing liquid and a gallium germanium loaded organic phase; the gallium germanium loaded organic phase adopts 200g/L sulfuric acid according to the ratio O/A of 1: and (3) carrying out 5-stage countercurrent stripping, wherein the stripping rate of Ga 3+ is 99.27%, and Ge 4+ is not stripped, so as to obtain gallium stripping solution and germanium loaded organic phase. The germanium-loaded organic phase adopts 2mol/L ammonium fluoride solution, and the ratio O/A is 1: and (3) carrying out 3-stage countercurrent stripping, wherein the stripping rate of Ge 4+ is 98.97%, and obtaining germanium stripping liquid and a blank organic phase.
Comparative example 1
Reference to example 1 only differs in that: n1923 is not added when the first organic phase is selected, and 100% sulfonated kerosene is used according to the volume ratio. In the first organic phase extraction process, fe 3+ and other ions are not extracted; in the second organic phase extraction process, fe 3+ is extracted into an aluminum gallium germanium loaded organic phase, fe 3+ is not washed by hydrochloric acid, and an iron gallium germanium organic phase is obtained, and in the sulfuric acid and ammonium fluoride back extraction process, fe 3+ respectively enters a gallium back extraction liquid and a germanium back extraction liquid and cannot be separated.
Comparative example 2
Reference to example 1 only differs in that: when the first organic phase is selected, the similar extractant N263 is adopted to replace N1923, and 30% of N263 and 70% of sulfonated kerosene are used according to the volume ratio. In the first organic phase extraction process, the extraction rate of Fe 3+ is 8.25%, and other impurity ions are not extracted; in the second organic phase extraction process, fe 3+ is extracted into an aluminum gallium germanium loaded organic phase, fe 3+ is not washed by hydrochloric acid, and an iron gallium germanium organic phase is obtained, and in the sulfuric acid and ammonium fluoride back extraction process, fe 3+ respectively enters a gallium back extraction liquid and a germanium back extraction liquid and cannot be separated.
Comparative example 3
Reference to example 1 only differs in that: when the first organic phase is selected, the similar extractant N235 is adopted to replace N1923, and 30% of N235 and 70% of sulfonated kerosene are used according to the volume ratio. In the first organic phase extraction process, the extraction rate of Fe 3+ is 68.27%, and other impurity ions are not extracted; in the second organic phase extraction process, fe 3+ is extracted into an aluminum gallium germanium loaded organic phase, fe 3+ is not washed by hydrochloric acid, and an iron gallium germanium organic phase is obtained, and in the sulfuric acid and ammonium fluoride back extraction process, fe 3+ respectively enters a gallium back extraction liquid and a germanium back extraction liquid and cannot be separated.
Comparative example 4
Reference to example 1 only differs in that: the second organic phase was selected without TBP added, 15% p204, 2.5% yw100 and 87.5% sulfonated kerosene, by volume. In the second organic phase extraction process, the Ga 3+ extraction rate is 98.02%, the Ge 4+ extraction rate is 98.63%, the Al 3+ extraction rate is 19.21%, and the other ion extraction rate is less than 3%, so that an aluminum-gallium-germanium-containing loaded organic phase and a raffinate water phase B are obtained. The washing with hydrochloric acid gave an Al 3+ washing rate of 98.12% but a Ga 3+、Ge4+ washing loss rate of 25.56% (significantly higher than in example 1).
Comparative example 5
Reference example 2 differs only in that: the second organic phase was selected without the addition of P204, 5% YW100, 2.5% TBP and 92.5% sulfonated kerosene, by volume. The second organic phase extraction procedure had a Ga 3+.42% extraction and Ge 4+ extraction of 32.15% (significantly lower than example 2).
Comparative example 6
Reference example 3 differs only in that: YW100 is not added in the second organic phase, and 10% P204, 5% TBP and 85% sulfonated kerosene are added according to the volume ratio. The second organic phase extraction procedure, ga 3+ extraction 84.17%, ge 4+ extraction 4.62% (significantly lower than example 3).
Comparative example 7
Reference example 3 differs only in that: when the second organic phase is selected, the same type of extractant P507 is used for replacing P204, and 10 percent of P507, 2.5 percent of YW100, 5 percent of TBP and 82.5 percent of sulfonated kerosene are used according to the volume ratio. The second organic phase extraction procedure had a Ga 3+ extraction of 72.02% and Ge 4+ extraction of 74.25% (significantly lower than in example 3).
Comparative example 8
Reference example 3 differs only in that: the second organic phase is selected by using the same kind of extractant Cyanex272 to replace P204, and 10% Cyanex272, 2.5% YW100, 5% TBP and 82.5% sulfonated kerosene are used according to the volume ratio. The second organic phase extraction procedure, ga 3+ extraction 59.02%, ge 4+ extraction 65.25% (significantly lower than example 3).
By comparing the examples with the comparative examples, the extraction and separation effects of gallium and germanium in the comparative examples are far less than those of the examples, so that it can be demonstrated that the extraction system and the extraction process for extracting and separating gallium and germanium in the zinc-substituted slag sulfuric acid leaching solution are not simple in combination of the extractant and the extraction process or similar conventional replacement, and have unexpected synergistic remarkable gain effects; and the extraction mode, the stage number, the time and the like can further ensure the extraction rate and the separation recovery rate of gallium when the extraction mode, the stage number, the time and the like are in the range required by the invention.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for extracting and separating gallium and germanium from zinc displacement slag sulfuric acid leaching solution, which is characterized by comprising the following steps:
1) Extracting zinc displacement slag sulfuric acid leaching solution by adopting a first organic phase to obtain an iron-containing loaded organic phase and a raffinate water phase A; wherein the zinc replacement slag sulfuric acid leaching solution contains Ga3+ 0.1~0.5g/L、Ge4+ 0.1~0.5g/L、Fe3+ 0.5~1g/L、Al3+ 1~3g/L、Zn2+ 10~20g/L、Cu2+ 10~20g/L and Cd 2+ to 5g/L; the first organic phase is prepared from N1923 and sulfonated kerosene in a volume ratio of 1-3:7-9;
2) Adding concentrated sulfuric acid to adjust the pH value of the raffinate water phase A in the step 1) to 1.0-1.2, and extracting by adopting a second organic phase to obtain an aluminum-gallium-germanium-containing loaded organic phase and a raffinate water phase B; the second organic phase is prepared from P204, YW100, TBP and sulfonated kerosene in a volume ratio of 1-2:0.25-0.5:0.25-0.5:7-8.5;
3) Washing the aluminum-gallium-germanium-containing loaded organic phase obtained in the step 2) by adopting hydrochloric acid to obtain an aluminum washing solution and a gallium-germanium loaded organic phase;
4) The gallium germanium loaded organic phase obtained in the sulfuric acid back extraction step 3) is adopted to obtain gallium back extraction liquid and germanium loaded organic phase;
5) And (3) back-extracting the germanium loaded organic phase obtained in the step (4) by adopting an ammonium fluoride solution to obtain germanium back-extracting solution and a blank organic phase.
2. The method of claim 1, wherein the pH of the zinc displacement slag sulfuric acid leach solution is = -0.2-0.5.
3. The method according to claim 1, wherein step 1) extraction employs cross-flow extraction; the extraction phase O/A is 1: (1-3); the extraction level is 1-3; the extraction time is 5-10 min.
4. The method according to claim 1, wherein step 2) extraction employs countercurrent extraction; the extraction phase O/A is 1: (1-3); the extraction level is 3-5; the extraction time is 5-10 min.
5. The method of claim 1, wherein step 3) washing employs cross-flow washing; the concentration of hydrochloric acid is 6-10 mol/L; the washing ratio O/A is 1 (1-2); the washing level is 1-3; the washing time is 5-10 min.
6. The method according to claim 1, wherein step 4) of back-extraction employs counter-current back-extraction; the concentration of sulfuric acid is 200-300 g/L; the counter-current ratio O/A is (1-3): 1; the back extraction stage number is 3-5; the back extraction time is 5-10 min.
7. The method according to claim 1, wherein step 5) of back-extraction employs counter-current back-extraction; the concentration of the ammonium fluoride is 2-3 mol/L; the counter-current ratio O/A is (1-3): 1; the back extraction stage number is 3-5; the back extraction time is 5-10 min.
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