CN116516184A - Method for recycling indium from indium-iron-copper-zinc material - Google Patents
Method for recycling indium from indium-iron-copper-zinc material Download PDFInfo
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- CN116516184A CN116516184A CN202310481248.3A CN202310481248A CN116516184A CN 116516184 A CN116516184 A CN 116516184A CN 202310481248 A CN202310481248 A CN 202310481248A CN 116516184 A CN116516184 A CN 116516184A
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 124
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 35
- -1 indium-iron-copper-zinc Chemical compound 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000010949 copper Substances 0.000 claims abstract description 77
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 claims abstract description 75
- 229910052742 iron Inorganic materials 0.000 claims abstract description 60
- 239000011701 zinc Substances 0.000 claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 7
- 239000012074 organic phase Substances 0.000 claims description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- 239000008346 aqueous phase Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910001447 ferric ion Inorganic materials 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 3
- 239000011707 mineral Substances 0.000 claims 3
- 239000000243 solution Substances 0.000 abstract description 80
- 239000012535 impurity Substances 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 19
- 239000002184 metal Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000009854 hydrometallurgy Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 36
- 230000001276 controlling effect Effects 0.000 description 18
- 238000000605 extraction Methods 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 18
- 230000009467 reduction Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 238000003860 storage Methods 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- 238000005086 pumping Methods 0.000 description 10
- 239000012459 cleaning agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000008399 tap water Substances 0.000 description 6
- 235000020679 tap water Nutrition 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NYZRMWCPMJEXKL-UHFFFAOYSA-N [Fe].[Cu].[Zn] Chemical compound [Fe].[Cu].[Zn] NYZRMWCPMJEXKL-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B58/00—Obtaining gallium or indium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application discloses a method for recycling indium from indium-iron-copper-zinc materials, and relates to the technical field of hydrometallurgy. According to the method, after acid leaching of the indium-iron-copper-zinc material, metal iron is added to reduce ferric iron ions, the pH value of the obtained solution is regulated to be 2.2-2.4, a specific extractant is utilized to effectively separate indium from impurities such as iron, copper and zinc, the back extractant is utilized to enable the indium to return to a water phase, so that an aqueous solution which is rich in indium and has very low impurity content is obtained, the purity of the recovered metal indium is high, the recovery treatment difficulty is low, and meanwhile, the method is simple in process, less in equipment investment, pollution-free, low in cost and good in economic benefit.
Description
Technical Field
The application relates to the technical field of hydrometallurgy, in particular to a method for recycling indium from indium-iron-copper-zinc materials.
Background
Indium is currently refined in two types, namely primary indium and regenerated indium. Primary indium is mainly recovered from raw ores and is also a main source for smelting indium currently. The regenerated indium is produced by smelting after recovering waste metals, and is mainly a byproduct recovered from the smelting process of ores such as lead, zinc, copper, tin and the like, but the ratio of the regenerated indium is not large. In China mainly recovers and produces indium from byproducts of lead and zinc smelting. Along with the continuous improvement of indium production technology, the source of raw materials also shows a trend of diversification, and the soot, copper smelting slag, lead smelting slag and the like of steel factories start to become raw materials for refining indium.
The current method for separating and recovering indium from indium-iron-copper-zinc materials has poor separation effect on indium and other impurities and high cost, so that the separation efficiency of indium and other impurities is necessarily improved, and the cost is reduced.
Disclosure of Invention
Based on the defects existing in the prior art, the purpose of the application is to provide a method for recycling indium from indium-iron-copper-zinc materials, so that the separation efficiency of impurities such as indium, iron-copper-zinc and the like is improved, and the cost is reduced.
To achieve the above object, the present application provides a method for recovering indium from an indium-iron-copper-zinc material, comprising the steps of:
acid leaching is carried out on the indium-iron-copper-zinc material, and a first solution is obtained through solid-liquid separation;
adding metallic iron into the first solution to reduce ferric iron ions, and then carrying out solid-liquid separation to obtain a second solution;
adjusting the pH value of the second solution to 2.2-2.4, and extracting by using an extracting agent to separate indium from iron, copper and zinc so as to obtain a first aqueous phase and a first organic phase loaded with indium;
back-extracting the first organic phase by using a back-extracting agent to obtain a second organic phase and a second aqueous phase loaded with indium;
taking the second aqueous phase for indium recovery;
wherein the extractant comprises the following components in percentage by mass: 25-30% of di (2-ethylhexyl) phosphate (namely P204), 65-70% of kerosene and 0-10% of sec-octyl alcohol.
According to the method, firstly, the indium in the indium-iron-copper-zinc material is leached out through acid leaching, then, metal iron is added to reduce ferric iron ions, so that the problem that the indium and the iron cannot be effectively separated due to the fact that the iron is transferred into an organic phase in a subsequent extraction process is avoided, then, the pH value of a solution is controlled within a specific range, the indium is extracted by using a specific extractant, the effective separation of the indium from impurities such as iron, copper and zinc is achieved, a first organic phase rich in the indium is obtained, and then, the indium is returned to an aqueous phase by using a stripping agent, so that a second aqueous phase rich in the indium and very low in impurity content of zinc, copper and iron is obtained.
The pH of the second solution has a very large influence on the separation of indium and zinc by extraction, and when the pH is too high or too low, the separation of indium and zinc is not favored.
The second water phase can be used for preparing the metal indium by methods such as electrolysis, and the prepared metal indium has high purity, high product quality and low recovery treatment difficulty. The second aqueous phase may be used for other purposes than the preparation of metallic indium.
The method has the advantages of simple process, less equipment investment, no pollution, low cost and good economic benefit.
Preferably, the volume ratio of the extractant to the second solution is (0.5-3): 1. When the volume ratio of the extractant to the second solution is within the above range, the extraction of indium and the separation thereof from impurities such as iron, copper, zinc, and the like are more facilitated. More preferably, the volume ratio of the extractant to the second solution is (0.8-1): 1 to further improve the separation effect of indium from impurities such as iron, copper, zinc, etc.
Preferably, the stripping agent is hydrochloric acid. The stripping agent is not limited to hydrochloric acid, but may be other stripping agents. When the stripping agent is hydrochloric acid, the concentration of HCl in the stripping agent is preferably 5.5-6.5 mol/L, and the volume ratio of the first indium-loaded organic phase to the stripping agent is (4-8): 1. Under the stripping process conditions, indium is better transferred from the second organic phase into the aqueous phase. More preferably, the volume ratio of the first indium-loaded organic phase to the stripping agent is (4-5): 1, to further improve the stripping effect of indium.
The second organic phase can be recovered and used as an extractant for extracting the second solution, but the second organic phase contains more impurities after repeated use for a plurality of times, so that the obtained first organic phase contains more impurities, and the quality of the metal indium product is affected. Preferably, the method further comprises the steps of: before the back extraction, the first organic phase is washed by an inorganic acid solution to further remove impurities in the organic phase, so that the recycling frequency of the second organic phase is obviously increased, and the quality of the metal indium recovered by the second aqueous phase is better. Compared with the direct use of water as the cleaning liquid, the inorganic acid solution is used as the cleaning liquid, so that the cleaning effect is better.
Preferably, the inorganic acid in the inorganic acid solution used to clean the first organic phase is sulfuric acid. Compared with other acids, the sulfuric acid is stable, and can generate precipitation with other impurities, so that the comprehensive performance is better.
Preferably, the concentration of sulfuric acid in the inorganic acid solution used for cleaning the first organic phase is 1.8-2.0 mol/L, and the volume ratio of the first organic phase to the inorganic acid solution used for cleaning the first organic phase is (2-6): 1. Under the cleaning process conditions, impurities in the first organic phase can be better removed.
Preferably, in the step of adding metallic iron to the first solution to reduce ferric ions, the reaction end point potential is less than 360mV or red copper is separated out, so that ferric ions are completely reduced, extraction of ferric ions into the first organic phase is further reduced, and thus, indium and iron have better separation effect.
Preferably, in the step of adding metallic iron to the first solution to reduce ferric ions, the reaction endpoint potential is 355-360 mV, so that the precipitation amount of copper in the step is reduced while the complete reduction of the ferric ions is ensured, and the subsequent recovery of metallic copper is facilitated. More preferably, in the step of adding metallic iron to the first solution to reduce ferric ions, the reaction endpoint potential is 360mV to further reduce the amount of copper precipitation in this step while ensuring complete reduction of ferric ions.
Preferably, the method further comprises the following steps:
taking the first water phase, adding metallic iron for reaction, and then carrying out solid-liquid separation to obtain metallic copper and a third solution;
adding alkali to regulate the pH value of the third solution to be more than 9, and carrying out solid-liquid separation to obtain a mixture of metallic iron and zinc. By adjusting the pH of the third solution to 9 or more, iron and zinc are more effectively precipitated.
Taking the first aqueous phase, and adding metallic iron to react, wherein the mass ratio of copper ions in the first aqueous phase to the metallic iron added in the step affects the yield of metallic copper and the content of iron impurities introduced into the metallic copper. In order to avoid the introduction of iron impurities in the metallic copper while obtaining more metallic copper, it is preferable that the mass ratio is 1:0.8 to 1.1; more preferably, the mass ratio is 1:1.
Preferably, at least one of the following conditions is satisfied:
a. in the step of acid leaching of the indium-iron-copper-zinc material, the pH value of the reaction end point is below 0.6;
b. in the step of acid leaching of the indium-iron-copper-zinc material, the reaction temperature is 65-70 ℃;
c. in the step of acid leaching the indium-iron-copper-zinc material, the acid solution is sulfuric acid solution;
d. in the step of acid leaching the indium-iron-copper-zinc material, the concentration of acid in the acid solution is 1.6-1.9 mol/L.
The pH value of the reaction end point of the acid leaching is controlled below 0.6, so that the indium is leached more completely, and the recovery rate of the indium is improved. In order to reduce the cost, the pH at the end of the reaction is preferably 0.4 to 0.6.
The acid used for acid leaching satisfies the following two conditions: (1) leaching indium; (2) The extraction of indium in the second solution, such as sulfuric acid, nitric acid, etc., may not be affected, sulfuric acid being preferred to enhance the safety of the production.
The method for recovering and obtaining the metal indium from the second aqueous phase is not limited, and electrolysis and the like are adopted.
Compared with the prior art, the beneficial effect of this application lies in:
(1) Adding metallic iron into the indium-iron-copper-zinc material after acid leaching to reduce ferric iron ions, regulating the pH value of the obtained solution to 2.2-2.4, effectively separating indium from impurities such as iron, copper, zinc and the like by using a specific extractant, and returning the indium to a water phase by using a stripping agent to obtain an aqueous solution which is rich in indium and has very low impurity content, wherein the metallic indium prepared by using the aqueous solution has high purity and low recovery treatment difficulty;
(2) The method has the advantages of simple process, less equipment investment, no pollution, low cost and good economic benefit.
Drawings
FIG. 1 is a process flow diagram of various embodiments.
Detailed Description
For a better understanding of the objects, technical solutions and advantages of the present application, the present application will be further described with reference to specific examples and comparative examples, which are intended to be in detail, but are not to be construed as limiting the present application. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present application. The experimental reagents and apparatus according to the present application are common reagents and apparatus unless otherwise specified.
Example 1
The embodiment provides a method for recycling indium from indium-iron-copper-zinc materials, which comprises the following steps:
1. acid leaching: after checking the leaching tank and its exhaust, stirring and valve of the matched pipeline are normal, adding tap water 18m into the leaching tank 3 Stirring, adding 8000kg of indium, iron, copper and zinc materials (comprising the following components by mass percent: 52% of water, 14% of copper, 4% of indium, 12% of iron and 18% of zinc) at a speed of 2000kg/h, adding 1800L of concentrated sulfuric acid (98% by mass percent) at a speed of 15L/min under the stirring and air suction starting state, detecting the pH value after adding the concentrated sulfuric acid, if the pH value is more than 0.5, supplementing the sulfuric acid, controlling the pH value at the end point of the reaction to be 0.5, then raising the temperature of a leaching kettle to 65 ℃, preserving the temperature for 3 hours, sampling, detecting the concentration of In, ag, cu, ge, zn, fe in the leaching liquid, cooling to 50 ℃, checking the trivalent iron reduction tank and the air suction, stirring and matched pipeline valves thereof, and pumping the filtrate into the trivalent iron reduction tank after the trivalent iron reduction tank is normally circulated and clear, thus obtaining a first solution of 22m 3 The filter residue is then rinsed in a filter press with tap water, the water consumption being 3m 3 The water washing liquid is returned to be used as the feed water for acid leaching, and the filter residue is dried by compressed air to obtain acid leaching byproducts and the In, ag, ge, cu content of the acid leaching byproducts is detected.
2. A ferric iron reduction step: slowly adding 100kg of iron powder while stirring filtrate in a ferric iron reduction tank at room temperature, controlling the adding speed to be 1kg/min, controlling the potential of a reaction end point to be 360mV (adopting Ag/AgCl reference electrode for detection), sampling to detect the potential and observing whether red copper is separated out from the solution after the total amount of the iron powder is 90%, stopping adding the iron powder if the potential reaches 360mV or the red copper is separated out, continuing to react for 40 minutes, filtering, circularly clearing the filtrate, and then pumping the filtrate into an indium extract storage tank to obtain a second solution; if 100kg of iron powder solution is added and the potential is still more than 360mV or no red copper is precipitated, continuously adding iron powder, adding 3kg each time, completely sampling to detect the potential value, observing whether copper is precipitated or not until the potential reaches 360mV or the red copper is precipitated, stopping adding the iron powder, continuously reacting for 40 minutes, and after the reaction is finished, circularly clearing filtrate to obtain a second solution;
3. and (3) indium extraction: adding alkali solution into the second solution to adjust pH value to 2.2, and adding extractant (comprising the following components by mass percent: P204% 25%, kerosene 65%, and sec-octanol 10%) to 1m 3 Pumping the flow rate of/h into an indium extract storage tank at the same time to separate indium, iron, copper and zinc, controlling the volume ratio of the indium to be 1:1, stirring for 5min, standing and clarifying for 20min to obtain a first aqueous phase and a first organic phase loaded with indium, feeding the first aqueous phase into a copper precipitation process, mixing the first organic phase with a cleaning agent (sulfuric acid solution with the sulfuric acid concentration of 1.8 mol/L), controlling the volume ratio of the first organic phase to the sulfuric acid solution to be 4:1, stirring for 5min, standing and clarifying for 20min to obtain an aqueous phase and a cleaned organic phase, wherein the aqueous phase is returned to the storage tank to be used as a cleaning agent of the next batch, mixing the cleaned organic phase with a back extractant (hydrochloric acid with the HCl concentration of 5.5 mol/L), controlling the volume ratio of the cleaned organic phase to be 4:1, and standing and clarifying for 20min after stirring for 5min to obtain a second organic phase loaded with indium, wherein the second organic phase is returned to the extractant to be used as an extractant of the next batch, and the second organic phase is subjected to extraction by the second phase to clarification tankElectrolyzing to obtain metal indium;
4. copper deposition process: checking whether the stirring, air suction and matched pipeline valves of the copper precipitation tank are normal, adding the obtained first water phase into the tank for 24m 3 Stirring and heating to 60 ℃, preserving heat, adding industrial iron powder at a speed of 1kg/min, wherein the mass ratio of copper ions in the first water phase to the industrial iron powder is 1:1, sampling and detecting whether the copper content in the solution is the copper content after the heat preservation reaction is carried out for 2 hours after the iron powder is added<100ppm, if<100ppm, stopping adding the iron powder, otherwise continuing to add the iron powder until the copper content in the solution is reached<100ppm, then press-filtering to obtain copper byproducts and a third solution, and enabling the third solution to enter an iron and zinc precipitation process;
5. iron and zinc depositing process: checking whether the stirring, air suction and matched pipeline valve of the iron-zinc sink are normal. Adding the third solution into the tank, starting stirring, adding liquid caustic soda with the mass concentration of 32% of NaOH to adjust the pH value to be 9, stabilizing the pH value to be 9 at the speed of 20L/min, reacting for 1.5 hours, performing pressure filtration to obtain an iron-zinc byproduct, and allowing the filtrate to enter a sewage treatment process.
Example 2
The only difference from example 1 is that: adding alkali into the second solution to adjust the pH value to 2.4, and simultaneously pumping the second solution and the extractant into an indium extract liquid storage tank for extraction so as to separate indium from iron, copper and zinc.
Example 3
The only difference from example 1 is that: the extractant comprises the following components in percentage by mass: p20430% and kerosene 70%.
Example 4
The only difference from example 1 is that: the extractant comprises the following components in percentage by mass: p20427%, kerosene 68%, sec-octanol 5%.
Example 5
The only difference from example 1 is that: the first organic phase is not washed with a washing agent in the indium extraction process.
Example 6
A method for recovering indium from indium-iron-copper-zinc material, comprising the following steps:
1. acid leaching: inspection leaching tankAfter the air draft, stirring and the valve of the matched pipeline are normal, adding tap water 18m into the leaching kettle 3 Stirring, adding 8000kg of indium, iron, copper and zinc materials (comprising the following components by mass percent: 52% of water, 14% of copper, 4% of indium, 12% of iron and 18% of zinc) at a speed of 3000kg/h, adding 1800L of concentrated sulfuric acid (98% by mass percent) at a speed of 20L/min under the stirring and air suction starting state, detecting the pH value after adding the concentrated sulfuric acid, if the pH value is more than 0.6, supplementing the sulfuric acid, controlling the pH value at the end point of the reaction to be 0.6, then raising the temperature of a leaching kettle to 70 ℃, preserving the temperature for 3h, sampling, detecting the concentration of In, ag, cu, ge, zn, fe in the leaching liquid, cooling to 65 ℃, checking the trivalent iron reduction tank and the air suction, stirring and matched pipeline valves thereof, pumping the trivalent iron reduction tank after the filtrate is normally circulated and clear, obtaining the first solution, and obtaining 16m in total 3 The filter residue is then rinsed in a filter press with tap water, the water consumption being 3m 3 The water washing liquid is returned to be used as the feed water for acid leaching, and the filter residue is dried by compressed air and the In, ag, ge, cu content of the filter residue is detected.
2. A ferric iron reduction step: slowly adding 100kg of iron powder while stirring filtrate in a ferric iron reduction tank at room temperature, controlling the adding speed to be 1kg/min, controlling the potential of a reaction end point to be 360mV (adopting Ag/AgCl reference electrode for detection), sampling to detect the potential and observing whether red copper is separated out from the solution after the total amount of the iron powder is 90%, stopping adding the iron powder if the potential reaches 360mV or the red copper is separated out, continuing to react for 40 minutes, filtering, circularly clearing the filtrate, and then pumping the filtrate into an indium extract storage tank to obtain a second solution; if 100kg of iron powder solution is added and the potential is still more than 360mV or no red copper is precipitated, continuously adding iron powder, adding 3kg each time, completely sampling to detect the potential value, observing whether copper is precipitated or not until the potential reaches 360mV or the red copper is precipitated, stopping adding the iron powder, continuously reacting for 40 minutes, and after the reaction is finished, circularly clearing filtrate to obtain a second solution;
3. and (3) indium extraction: adding alkaline solution into the second solution to adjust pH to 2.3, and simultaneously pumping into indium extract storage tank with extractant (comprising components of (by mass fraction: P204%, kerosene 68%, and sec-octanol 5%) to extractSeparating indium from iron, copper and zinc, controlling the volume ratio O/A=3:1, and the adding speed of the extractant is 1.5m 3 Stirring for 5min, standing and clarifying for 20min to obtain a first aqueous phase and a first organic phase loaded with indium, allowing the first aqueous phase to enter a copper precipitation process, mixing the first organic phase with a cleaning agent (sulfuric acid solution with sulfuric acid concentration of 2.0 mol/L), controlling the volume ratio of the first organic phase to the sulfuric acid solution to be 6:1, stirring for 5min, standing and clarifying for 20min to obtain the aqueous phase and a cleaned organic phase, wherein the aqueous phase is returned to a cleaning agent storage tank to be used as a cleaning agent of the next batch, mixing the cleaned organic phase with a stripping agent (hydrochloric acid with HCl concentration of 6.5 mol/L), controlling the volume ratio of the cleaned organic phase to be 8:1, stirring for 5min, standing and clarifying for 20min to obtain a second organic phase and a second aqueous phase loaded with indium, wherein the second organic phase is returned to the extraction agent storage tank to be used as an extraction agent of the next batch, and the second aqueous phase is electrolyzed to obtain metal indium;
4. copper deposition process: checking whether the stirring, air suction and matched pipeline valves of the copper precipitation tank are normal, adding the obtained first water phase into the tank for 26m 3 Stirring and heating to 60 ℃, preserving heat, adding industrial iron powder at a speed of 1kg/min, wherein the mass ratio of copper ions in the first water phase to the industrial iron powder is 1:1.2, sampling and detecting whether the copper content in the solution is the copper content after the heat preservation reaction is finished for 2 hours<100ppm, if<100ppm, stopping adding the iron powder, otherwise continuing to add the iron powder until the copper content in the solution is reached<100ppm, then press-filtering to obtain copper byproducts and a third solution, and enabling the third solution to enter an iron and zinc precipitation process;
5. iron and zinc depositing process: checking whether the stirring, air suction and matched pipeline valve of the iron-zinc sink are normal. Adding the third solution into the tank, starting stirring, adding alkali liquor with the mass concentration of 32% of NaOH to adjust the pH value to be 9, stabilizing the pH value to be 9 at the speed of 20L/min, reacting for 1.5 hours, performing pressure filtration to obtain an iron-zinc byproduct, and allowing the filtrate to enter a sewage treatment process.
Example 7
A method for recovering indium from indium-iron-copper-zinc material, comprising the following steps:
1. acid leaching: inspection leaching tank and pump thereofAfter the air, stirring and matched pipeline valves are normal, adding tap water 17.5m into the leaching kettle 3 Stirring, adding 8000kg of indium, iron, copper and zinc materials (comprising the following components by mass percent: 52% of water, 14% of copper, 4% of indium, 12% of iron and 18% of zinc) at a speed of 1500kg/h, adding 1800L of concentrated sulfuric acid (98% by mass percent) at a speed of 7L/min under the stirring and air suction starting state, detecting the pH value after adding the concentrated sulfuric acid, if the pH value is more than 0.4, supplementing the sulfuric acid, controlling the pH value at the end point of the reaction to be 0.4, then raising the temperature of a leaching kettle to 65 ℃, sampling and detecting the concentration of In, ag, cu, ge, zn, fe in the leaching solution after 2h of heat preservation reaction, cooling to 50 ℃, checking a trivalent iron reduction tank and an air suction pipe valve thereof, stirring and matching the trivalent iron reduction tank, pumping the trivalent iron reduction tank after the filtrate is normally circulated and clear, obtaining a first solution by 16m 3 The filter residue is then rinsed in a filter press with tap water, the water consumption being 3m 3 The water washing liquid is returned to be used as the feed water for acid leaching, and the filter residue is dried by compressed air and the In, ag, ge, cu content of the filter residue is detected.
2. A ferric iron reduction step: slowly adding 90kg of iron powder while stirring filtrate in a ferric iron reduction tank at room temperature, controlling the adding speed to be 0.5kg/min, controlling the potential of a reaction end point to be 360mV (adopting Ag/AgCl reference electrode for detection), sampling to detect the potential and observing whether red copper is separated out from the solution after the total amount of the iron powder is 90%, stopping adding the iron powder if the potential reaches 360mV or the red copper is separated out, continuing to react for 40 minutes, filtering, circularly clearing the filtrate, and then pumping the filtrate into an indium extract storage tank to obtain a second solution; if 100kg of iron powder solution is added and the potential is still more than 360mV or no red copper is precipitated, continuously adding iron powder, adding 3kg each time, completely sampling to detect the potential value, observing whether copper is precipitated or not until the potential reaches 360mV or the red copper is precipitated, stopping adding the iron powder, continuously reacting for 40 minutes, and after the reaction is finished, circularly clearing filtrate to obtain a second solution;
3. and (3) indium extraction: adding alkaline solution into the second solution to adjust pH to 2.4, and simultaneously pumping into indium extract tank together with extractant (comprising components of (by mass) P204% 29%, kerosene 69%, and sec-octanol 2%) to extract indium and indiumIron, copper and zinc are separated, the volume ratio of the iron to the copper to the zinc is controlled to be O/A=0.5:1, and the adding speed of the extractant is 0.5m 3 Stirring for 5min, standing and clarifying for 20min to obtain a first aqueous phase and a first organic phase loaded with indium, allowing the first aqueous phase to enter a copper precipitation process, mixing the first organic phase with a cleaning agent (sulfuric acid solution with sulfuric acid concentration of 1.8 mol/L), controlling the volume ratio of the first organic phase to the sulfuric acid solution to be 2:1, stirring for 5min, standing and clarifying for 20min to obtain the aqueous phase and a cleaned organic phase, wherein the aqueous phase is returned to a cleaning agent storage tank to be used as a cleaning agent of the next batch, mixing the cleaned organic phase with a stripping agent (hydrochloric acid with HCl concentration of 5.5 mol/L), controlling the volume ratio of the cleaned organic phase to be 4:1, stirring for 5min, standing and clarifying for 20min to obtain a second organic phase and a second aqueous phase loaded with indium, wherein the second organic phase is returned to the extraction agent storage tank to be used as an extraction agent of the next batch, and the second aqueous phase is electrolyzed to obtain metal indium;
4. copper deposition process: checking whether the stirring, air suction and matched pipeline valves of the copper precipitation tank are normal, adding the obtained first water phase into the tank for 24m 3 Stirring and heating to 55 ℃, preserving heat, adding industrial iron powder at a speed of 0.5kg/min, wherein the mass ratio of copper ions in the first water phase to the industrial iron powder is 1:1, sampling and detecting whether the copper content in the solution is the copper content after the heat preservation reaction is carried out for 2 hours after the iron powder is added<100ppm, if<100ppm, stopping adding the iron powder, otherwise continuing to add the iron powder until the copper content in the solution is reached<100ppm, then press-filtering to obtain copper byproducts and a third solution, and enabling the third solution to enter an iron and zinc precipitation process;
5. iron and zinc depositing process: checking whether the stirring, air suction and matched pipeline valve of the iron-zinc sink are normal. Adding the third solution into the tank, starting stirring, adding alkali liquor with the mass concentration of 32% of NaOH to adjust the pH value to be 9, stabilizing the pH value to be 9 at the speed of 20L/min, reacting for 1.5 hours, performing pressure filtration to obtain an iron-zinc byproduct, and allowing the filtrate to enter a sewage treatment process.
Comparative example 1
The only difference from example 1 is that: before the second solution is extracted by the extractant, the pH of the second solution is adjusted to 0.6.
Comparative example 2
The only difference from example 1 is that: before the second solution is extracted by the extractant, the pH of the second solution is adjusted to 3.
Comparative example 3
The only difference compared to example 1 is that the extractant comprises the following components in mass fraction: p204.35%, kerosene 56.3%, sec-octyl alcohol 8.7%.
The indium, iron, copper, zinc concentrations of the solutions obtained in the middle of each example and comparative example are shown in table 1.
TABLE 1
The first aqueous phase obtained In examples 1 to 7 has an In concentration of 50ppm or less, a Cu concentration of 28000ppm or more, an Fe concentration of 26000ppm or more, and a Zn concentration of 39000ppm or more, and indium is effectively purified In each example; the obtained second water phase has an In concentration of 50000ppm or more, a Cu concentration of 50ppm or less, an Fe concentration of 50ppm or less, and a Zn concentration of 50ppm or less, and can satisfy the requirement of purifying indium. In comparison with comparative examples 1 to 2, examples 1 to 2 effectively separated indium from zinc by controlling the pH of the second solution within a reasonable range. Compared with comparative example 3, examples 1 and 3 to 4 have better separation effect of indium from other impurities due to the specific extractant, because the comparative example 3 uses the extractant having higher content of P204 and lower content of diluent, resulting in poor fluidity and unfavorable extraction. Both pH values outside the present application and varying the ratio of the extractant components outside the present application affect the extraction effect, the latter being relatively less affected.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present application and not for limiting the scope of protection of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application.
Claims (10)
1. A method for recovering indium from indium-iron-copper-zinc material, which is characterized by comprising the following steps:
acid leaching is carried out on the indium-iron-copper-zinc material, and a first solution is obtained through solid-liquid separation;
adding metallic iron into the first solution to reduce ferric iron ions, and then carrying out solid-liquid separation to obtain a second solution;
adjusting the pH value of the second solution to 2.2-2.4, and extracting by using an extracting agent to separate indium from iron, copper and zinc so as to obtain a first aqueous phase and a first organic phase loaded with indium;
back-extracting the first organic phase by using a back-extracting agent to obtain a second organic phase and a second aqueous phase loaded with indium;
taking the second aqueous phase for indium recovery;
wherein the extractant comprises the following components in percentage by mass: 25-30% of di (2-ethylhexyl) phosphate, 65-70% of kerosene and 0-10% of sec-octyl alcohol.
2. The method of recovering indium from a material of indium, iron, copper, and zinc according to claim 1, wherein a volume ratio of said extractant to said second solution is from (0.5 to 3): 1.
3. The method for recovering indium from a material of indium, iron, copper, and zinc according to claim 1, wherein the stripping agent is hydrochloric acid.
4. A method for recovering indium from a material of indium, iron, copper and zinc according to claim 3, wherein the concentration of HCl in said stripping agent is between 5.5 and 6.5mol/L, and the volume ratio of said first indium-loaded organic phase to said stripping agent is between (4) and (8): 1.
5. The method of recovering indium from an indium-iron-copper-zinc material according to claim 1, further comprising the steps of: the first indium-loaded organic phase is washed with a mineral acid solution prior to the stripping.
6. The method of recovering indium from a material containing indium, iron, copper, and zinc according to claim 5, wherein the mineral acid in the mineral acid solution used to clean the first organic phase is sulfuric acid.
7. The method according to claim 6, wherein the concentration of sulfuric acid in the inorganic acid solution used for cleaning the first organic phase is 1.8 to 2.0mol/L, and the volume ratio of the first organic phase to the inorganic acid solution used for cleaning the first organic phase is (2 to 6): 1.
8. The method of recovering indium from a material of indium, iron, copper, and zinc according to claim 1, wherein in the step of adding metallic iron to the first solution to reduce ferric ions, a reaction endpoint potential is less than 360mV or red copper is precipitated.
9. The method for recovering indium from an indium-iron-copper-zinc material according to claim 8, further comprising the steps of:
taking the first water phase, adding metallic iron for reaction, and then carrying out solid-liquid separation to obtain metallic copper and a third solution;
adding alkali to regulate the pH value of the third solution to be more than 9, and carrying out solid-liquid separation to obtain a mixture of metallic iron and zinc.
10. The method of recovering indium from an indium, iron, copper, and zinc material according to claim 1, wherein at least one of the following conditions is satisfied:
a. in the step of acid leaching of the indium-iron-copper-zinc material, the pH value of the reaction end point is below 0.6;
b. in the step of acid leaching of the indium-iron-copper-zinc material, the reaction temperature is 65-70 ℃;
c. in the step of acid leaching the indium-iron-copper-zinc material, the acid solution is sulfuric acid solution;
d. in the step of acid leaching the indium-iron-copper-zinc material, the concentration of acid in the acid solution is 1.6-1.9 mol/L.
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