CN112795795B - Method for separating gallium and germanium in sulfuric acid leaching solution through pressurized oxidation - Google Patents
Method for separating gallium and germanium in sulfuric acid leaching solution through pressurized oxidation Download PDFInfo
- Publication number
- CN112795795B CN112795795B CN202011473242.4A CN202011473242A CN112795795B CN 112795795 B CN112795795 B CN 112795795B CN 202011473242 A CN202011473242 A CN 202011473242A CN 112795795 B CN112795795 B CN 112795795B
- Authority
- CN
- China
- Prior art keywords
- gallium
- germanium
- solution
- sulfuric acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
- C22B41/00—Obtaining germanium
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Aiming at the characteristics that gallium-germanium lixivium generally contains arsenic, iron and antimony, especially contains iron element, neutralizing agent is added into sulfuric acid lixivium, when the pH value of the lixivium is neutralized to 1.0-2.0, solution is stopped to be added after ion hydrolysis precipitation, turbid neutralization lixivium is pumped into a pressurized reaction kettle and then is introduced with oxygen for oxidation, reaction solution is discharged after heating reaction is stirred for a period of time, solid-liquid separation is very easy, and after separation, pulping and washing are carried out, thus obtaining enriched slag with gallium content of more than 1%, germanium content is less than 0.05%, germanium loss is less, meanwhile, iron precipitation in the solution enters solid phase, arsenic and antimony mainly enter slag, and the germanium content of the solution is basically unchanged, thereby being convenient for the recovery of the subsequent adsorption or extraction process.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a process method for separating gallium and germanium in sulfuric acid leaching solution by pressurizing, oxidizing.
Background
For leaching the smelting slag rich in gallium and germanium by sulfuric acid, the produced solution contains valuable metals such as gallium, germanium, zinc, copper and the like and impurity elements such as iron, arsenic, antimony, fluorine, chlorine and the like, and the separation and enrichment of gallium and germanium are realized, the extraction process is widely adopted in a sulfuric acid system at present to realize high-efficiency separation, and the separation is generally realized by extracting gallium, extracting germanium or extracting gallium and germanium by co-extraction step-by-step back extraction according to different extraction mechanisms. The method for extracting gallium but not germanium mainly comprises the following steps: extracting gallium using P204, P507 without extracting germanium; the extraction of germanium but not gallium is mainly: the amine extractant is used for extracting germanium under the matching condition of organic acid (such as N235 is used for extracting germanium in a tartaric acid added solution), and LIX63 is used for extracting germanium under the high acid condition without extracting gallium, so that gallium and germanium separation is realized; the gallium and germanium co-extraction adopts different back extraction agents to realize separation, such as N235 gallium and germanium co-extraction under the matching condition of oxalic acid, hydrochloric acid back extraction of gallium and sodium hydroxide back extraction of germanium; the P204+ alkyl hydroxamic acid is used for co-extracting gallium and germanium, sulfuric acid is used for back extracting gallium, and ammonium fluoride is used for back extracting germanium.
Although the extraction process can well realize gallium and germanium separation under sulfuric acid leaching solution, the extraction process involves pollution of organic solvent to zinc smelting process, on the other hand, when extracting and separating gallium and germanium, iron element exists to influence gallium and germanium separation all the time, especially when P204 and P507 extract gallium, iron ions can be extracted into organic phase, and back extraction is very difficult, and can cause toxicity in organic phase after long-time operation, when gallium and germanium are co-extracted, iron ions preferentially enter extractant, iron is not removed in advance, gallium and germanium separation can be influenced, therefore, when part of extraction process is applied, iron needs to be removed first and then gallium and germanium separation is carried out.
In conventional hydrometallurgy, neutral precipitation pH values are mainly adopted for separating gallium and germanium in sulfuric acid leaching solution, hydrolysis precipitation is generally carried out on more ions at the pH value of gallium precipitation, such as iron, indium, tin, aluminum and the like precipitation, wherein the removal of impurity iron is the most important, and currently, an iron vitriol method, a goethite method, a neutral oxidation method and an iron phosphate method are mainly adopted, but no matter which iron removing method is adopted, the condition that iron slag adsorbs ionic elements exists, so that valuable metals are lost is caused, and the pure use of neutral hydrolysis precipitation separation of gallium and germanium is very difficult.
Disclosure of Invention
Based on the problems that gallium-germanium lixivium generally contains arsenic, iron and antimony, and particularly contains iron elements, the invention provides a method for separating gallium-germanium from sulfuric acid lixivium, wherein the gallium-containing grade of enriched slag obtained by the method is more than 1%, and the germanium-containing grade is less than 0.05%.
A method for separating gallium and germanium from sulfuric acid leaching solution by pressurized oxidation comprises the following steps:
s1: adding a neutralizing agent into the sulfuric acid leaching solution, stirring, stopping adding the neutralizing agent after the solution is turbid, and controlling the pH value of the solution to be 1.0-2.0; the neutralizer is one of sodium carbonate, ammonium carbonate and sodium hydroxide;
s2: introducing oxygen into the turbid leaching solution in the step S1 under the condition of pressurization, and heating and stirring for reaction to obtain a mixed solution A;
s3: carrying out solid-liquid separation on the mixed solution A to obtain gallium-containing solid slag and germanium-containing leaching solution;
compared with the prior art, the invention has the following beneficial effects:
the neutralizing agent added in the neutralization process in the step S1 brings monovalent cations, so that arsenicum, antimonite or jarosite slag is easily formed by the neutralizing agent and iron, arsenic and antimony, and gallium is precipitated into slag in the form of gallium hydroxide and aluminum hydroxide together with the jarosite slag.
The oxidation reaction in the step S2 oxidizes the iron, arsenic and antimony in the solution into high valence state, so that the subsequent reaction is convenient, meanwhile, under the condition of high pressure and high temperature, the oxidation reaction of the iron, the arsenic and the antimony is more thorough, the neutralization and the hydrolysis reaction of the gallium are also more thorough, meanwhile, the precipitation of gallium, iron, arsenic and antimony is easier, the generated iron vitriol slag type is more single, the solution obtained after the reaction is easier to filter, and the problem of difficult filtration of jelly such as ferric hydroxide, gallium hydroxide and aluminum hydroxide does not occur.
The iron vitriol slag is utilized to change slag type under the condition of pressurization, is not easy to adsorb germanium, and is beneficial to reducing the loss of germanium.
Further, the pressure of step S2: 0.2 to 0.5mpa, and the reaction temperature is: 105-155 ℃, oxygen flow: 20-200 Nm 3 Reaction time/h: and 1-4 h.
Further, in the step S2, before the pressurized oxidation reaction of the turbid leaching solution, a neutralizing agent is added, and 0.05-5 g of the neutralizing agent is added for every 1L of the turbid leaching solution. The supplemental neutralizing agent is mainly used for neutralizing acid continuously generated in the reaction process by supplementing a small amount of neutralizing agent before the reaction because the acid is generated in the pressure oxidation process of impurity ions such as iron, antimony, arsenic and the like, so that the reaction is more thoroughly carried out.
Further, washing the gallium-containing solid slag obtained in the step S3 by slurrying water, wherein the solid ratio of slurrying liquid to solid is 4:1, the reaction time is 1-2 h, and the reaction temperature is 60-80 ℃ to obtain gallium-containing enriched slag.
Further, the neutralizing agent is preferably sodium carbonate.
Further, the oxygen introduced in the step S2 is oxygen with the oxygen concentration being more than 93%.
Further, the gallium grade of the gallium-containing enriched slag is more than 1%, and the germanium grade is less than 0.05%, so that the gallium-containing enriched slag can be used for recycling gallium.
Compared with the traditional method, the separation process does not involve an organic extraction reagent, the solid-liquid separation in the step S3 is very easy, the separated solid slag is pulpified and washed with water to obtain enriched slag with the gallium content of more than 1 percent and the germanium content of less than 0.05 percent, the enriched slag can be used for comprehensively recycling gallium, the loss of germanium is less, meanwhile, iron in the solution is precipitated into a solid phase, most of arsenic and antimony are in the slag, the germanium content of the solution is basically unchanged, and the subsequent adsorption or extraction process recycling is facilitated.
Detailed Description
Aiming at the characteristics that gallium-germanium lixivium generally contains arsenic, iron and antimony, especially contains iron elements, a neutralizing agent is added into the lixivium, the solution is stopped to be added after ion hydrolysis precipitation when the pH value of the lixivium is neutralized to 1.0-2.0, the turbid neutralization lixivium is pumped into a pressurized reaction kettle, a small amount of neutralizing agent is added again, oxygen is introduced for oxidation, after heating reaction is carried out for a period of time while stirring, reaction solution is discharged, solid-liquid separation is very easy, slurry water washing is carried out after separation, enriched slag with gallium content of more than 1 percent is obtained, germanium content of less than 0.05 percent, germanium loss is less, meanwhile, iron in the solution is precipitated into solid phase, most of the arsenic and antimony enter the slag, and the germanium content of the solution is basically unchanged, thereby being convenient for the recovery of subsequent adsorption or extraction process.
A method for separating gallium and germanium from sulfuric acid leaching solution by pressurizing and oxidizing,
firstly, adding a neutralizing agent into sulfuric acid leaching solution, stopping adding the neutralizing agent until clear solution becomes turbid, and measuring the pH value to be controlled to be 1.0-2.0. The neutralizing agent is one of sodium carbonate, ammonium carbonate and sodium hydroxide, preferably sodium carbonate. Reaction principle: neutralizing and inducing precipitation, adding neutralizing agent into the leaching solution at normal temperature, continuously consuming acid radical ion in the leaching solution by using alkaline neutralizing agent, continuously adding neutralizing agent to make Fe, ga and Al in the leaching solution start to produce hydrolytic precipitation, stopping adding alkaline neutralizing agent when solution turbidity appears, at this time the pH value of solution is 1.0-2.0, and introducing monovalent cation (Na + 、NH 4 + ) Providing monovalent cations necessary for the subsequent formation of arsenical, antimonite or jarosite slag;
then adding the turbid solution into an autoclave, and adding a small amount of neutralizing agent again, wherein the adding amount is 0.05-5 g of neutralizing agent per 1L of turbid leaching solution. Then oxygen is introduced for oxidation, heating and stirring are carried out for reaction for a period of time, after the solution is discharged, solid-liquid separation is realized by natural standing or suction filtration, and the obtained solid mainly contains iron gallium arsenic. Wherein, autoclave reaction pressure is: 0.2 to 0.5mpa, and the reaction temperature is: 105-155 ℃, and the reaction time is as follows: 1-4 hours, oxygen flow: 20-200 Nm 3 And/h, oxygen refers to oxygen-enriched gas containing more than 93% of oxygen. After the reaction is finished, the obtained solution is subjected to solid-liquid separation by a filtering device, solid slag is subjected to slurrying water washing, the solid-liquid ratio of slurrying liquid is 4:1, the reaction time is 1-2 hours, and the reaction temperature is 60-80 ℃.
Reaction principle: neutralizing to pH 1.0-2.0, pumping into a pressurized reaction kettle, introducing oxygen-enriched gas with concentration greater than 93%, and neutralizing part of Fe in the solution 2+ 、As 3+ 、Sb 3+ Under the conditions of high temperature, high pressure and low acid, the low valence ions can rapidly and possibly lead the low valence Fe in the solution to be as low as possible 2+ 、As 3+ 、Sb 3+ All oxidized to Fe 3+ 、As 5+ 、Sb 5+ Thereby completely converting arsenic, iron and antimony in the leaching solution into arsenicum, antimonite or jarosite slag solid slag, and releasing acid in the reaction processThe pH of the process is stabilized by adding a neutralizing agent added before, under conditions in which the iron precipitate can enter the solid phase in the form of iron vitriol slag, avoiding the formation of Fe (OH) 3 The colloid adsorbs germanium, which causes incomplete gallium-germanium separation.
Gallium ions, aluminum ions, iron, arsenic and antimony in the sulfuric acid leaching solution are neutralized to form arsenicum, antimonite or jarosite slag which are coprecipitated into a slag phase, a mixed solid phase is formed, the characteristic that arsenicum, antimonite or jarosite slag is easy to filter is fully utilized to mix and match with the gallium hydroxide and aluminum hydroxide colloidal substances which are generated by hydrolysis and are difficult to filter, and the problem that gallium hydroxide and aluminum hydroxide are difficult to filter at normal temperature is solved.
Under the high temperature condition, the ion activity is increased, the acidity of the inorganic compound precipitation endpoint is higher, according to the potential-pH diagram under the thermodynamic principle and under the high temperature, the situation that the ion activity coefficient and the pH value change along with the temperature is considered, on one hand, the ion activity coefficient is increased under the high temperature, the iron, the arsenic and the antimony can realize rapid oxidation, the reaction of generating alum slag is more thorough, the ion activity of the iron and the gallium is increased under the high temperature, the pH value of the neutralization hydrolysis reaction can be completed under the condition of being lower than the normal temperature, meanwhile, the acid generated by the reaction in the process of generating the precipitation of the iron, the arsenic, the antimony, the gallium and the aluminum continuously reacts with the neutralizing agent to reach balance, under the high temperature condition, the reaction speed is faster and more thorough along with the temperature rise, the complete precipitation of the gallium can be realized under the lower pH value, the same effect that the neutralization pH value can be realized to 4.5 under the normal temperature is effectively avoided, the dosage of the neutralizing agent is greatly saved under the normal temperature condition, meanwhile, the precipitation of the iron and the arsenic and the antimony is easier, the generated alum slag is more single, the solution is easy to obtain, and the solution, the problem of the iron, the hydroxide, the colloid and the like is difficult to filter after the reaction.
Wherein, the reaction equation for producing the iron vitriol is:
2Fe(OH) 3 +4SO 4 2- +3Fe 3+ +3H 2 O+2M + →2MFe 3 (SO 4 ) 2 (OH) 6 +3H + (M＝Na + 、NH 4 + )
the iron ion hydrolysis reaction formula is:
Fe 3+ +nH 2 O→Fe(OH) n (3-n)+ +nH + (n＝1，2)
the slag type formed by the iron vitriol slag under the conditions of high temperature and pressure and low acid is not adsorbed with germanium, which is favorable for reducing the loss of germanium, and germanium does not participate in the related generation reaction in the reaction process, so that the germanium contained in the slag produced by precipitation in the reaction process is less and is only entrained by solution, and the germanium contained in the slag after water washing can be controlled below 0.05%.
Example 1
Zinc powder is leached by sulfuric acid to replace gallium and germanium slag, and the leaching solution is filtered to obtain 344mg/L of gallium, 409mg/L of germanium, 15.3g/L of zinc, 3.7g/L of iron, 3.5g/L of arsenic, 0.025g/L of antimony, 32g/L of acid and 14.7g/L of copper.
A method for separating gallium and germanium from sulfuric acid leaching solution by pressurized oxidation comprises the following steps:
s1: slowly adding sodium carbonate into 1L leaching solution, starting stirring when adding sodium carbonate, observing the condition of the solution while adding, and measuring the pH value of the solution to be 1.5 by using a pH meter when turbidity appears;
s2: stopping neutralizing and stirring, pouring the neutralized solution into a pressurized reaction kettle, adding 2g of sodium carbonate, starting stirring, introducing pure oxygen at the flow rate of 200L/min, heating to the temperature of 150 ℃ and the pressure of 0.4mpa, and reacting for 5 hours;
s3: after the reaction is finished, opening the pressurized reaction kettle to filter the solution by using vacuum suction filtration equipment to obtain solid slag and filtrate, wherein the filtrate is germanium-containing solution for separating gallium;
s4: the solid slag is stirred and washed for 1 hour by hot water at 60 ℃, and is filtered again, and the solid slag is enriched slag containing gallium.
The typical composition of each solution is as follows:
| project | Zn | Ge | Ga | Cu | Fe | Co | Ni | Mn | Mg | Cd | As | Sb |
| Immersion liquid | 15.3 | 409 | 344 | 14.7 | 3.7 | 366 | 346 | 465 | 438 | 2757 | 3575 | 25 |
| After neutralization and pressurization reaction | 13 | 399 | 8.3 | 11.8 | 0.4 | 350 | 295 | 392 | 358 | 2415 | 1373 | 25 |
Note that: zn, fe and Cu are in g/L units, and the rest are in mg/L units
| Item (%) | Zn | Ge | Ga | Cu | Fe | As |
| Gallium precipitate slag | 3.74 | 0.005 | 2.47 | 8.6 | 6.6 | 2.1 |
Example 2
The zinc powder is leached by sulfuric acid to replace gallium and germanium slag, and the leaching solution is filtered to obtain 704mg/L gallium, 588mg/L germanium, 25g/L zinc, 1.7g/L iron, 2.08g/L arsenic, 22g/L acid and 70g/L copper.
A method for separating gallium and germanium from sulfuric acid leaching solution by pressurized oxidation comprises the following steps:
s1: slowly adding sodium hydroxide into 1L leaching solution, starting stirring when adding sodium hydroxide, observing the condition of the solution while adding, and measuring the pH value of the solution to be 1.8 by using a pH meter when turbidity appears;
s2: stopping neutralizing and stirring, pouring the neutralized solution into a pressurized reaction kettle, adding 2g of sodium hydroxide, starting stirring, introducing 93% oxygen, heating to 135 ℃ at 0.4mpa at 180L/min, and reacting for 2 hours;
s3: after the reaction is finished, opening the pressurized reaction kettle to filter the solution by using vacuum suction filtration equipment to obtain solid slag and filtrate, wherein the filtrate is germanium-containing solution for separating gallium;
s4: the solid slag is stirred and washed for 1 hour by hot water at 60 ℃, and is filtered again, and the solid slag is enriched slag containing gallium.
Typical components of each solution:
| project | Zn | Ge | Ga | Cu | Fe | Co | Ni | Mn | Cd | As |
| Immersion liquid | 25 | 588 | 701 | 70 | 1.7 | 173 | 411 | 1082 | 1734 | 2080 |
| After neutralization and pressurization reaction | 24.7 | 584 | 7.3 | 67 | 0 | 175 | 410 | 1079 | 1720 | 369 |
Note that: the units of Zn, fe and Cu are g/L, and the rest are mg/L.
Example 3
The zinc powder is leached by sulfuric acid to replace gallium and germanium slag, and the leaching solution is filtered to obtain the leaching solution containing gallium 504mg/L, germanium 488mg/L, zinc 45g/L, iron 3.2g/L, arsenic 4.08g/L, acid 25g/L and copper 40g/L.
A method for separating gallium and germanium from sulfuric acid leaching solution by pressurized oxidation comprises the following steps:
s1: slowly adding ammonium carbonate into 2L of leaching solution, starting stirring when adding ammonium carbonate, observing the condition of the solution while adding, and measuring the pH value of the solution to be 1.2 by using a pH meter when turbidity appears;
s2: stopping neutralizing and stirring, pouring the neutralized solution into a pressurized reaction kettle, adding 5g of ammonium carbonate, starting stirring, introducing 93% pure oxygen, heating to 145 ℃ at a flow rate of 200L/min and a pressure of 0.35mpa, and reacting for 4 hours;
s3: after the reaction is finished, opening the pressurized reaction kettle to filter the solution by using vacuum suction filtration equipment to obtain solid slag and filtrate, wherein the filtrate is germanium-containing solution for separating gallium;
s4: the solid slag is stirred and washed for 1 hour by hot water at 60 ℃, and is filtered again, and the solid slag is enriched slag containing gallium.
Typical components of each solution:
| project | Zn | Ge | Ga | Cu | Fe | Co | Ni | Mn | Cd | As |
| Immersion liquid | 45 | 488 | 504 | 40 | 3.2 | 170 | 211 | 1582 | 1024 | 4010 |
| After neutralization and pressurization reaction | 44.7 | 486 | 1.3 | 38 | 0.1 | 170 | 210 | 1479 | 1020 | 460 |
Note that: the units of Zn, fe and Cu are g/L, and the rest are mg/L.
| Item (%) | Zn | Ge | Ga | Cu | Fe | As |
| Gallium precipitate slag | 0.84 | 0.004 | 4.57 | 14.6 | 10.6 | 12.1 |
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention.
Claims (6)
1. A method for separating gallium and germanium from sulfuric acid leaching solution by pressurized oxidation, which is characterized by comprising the following steps:
s1: adding a neutralizing agent into the sulfuric acid leaching solution, stirring, stopping adding the neutralizing agent after the solution is turbid, and controlling the pH value of the solution to be 1.0-2.0; the neutralizer is one of sodium carbonate, ammonium carbonate and sodium hydroxide; the sulfuric acid leaching solution at least contains gallium, germanium and iron elements;
s2: introducing oxygen into the turbid leaching solution in the step S1 under the condition of pressurization, and heating and stirring for reaction to obtain a mixed solution A; wherein the pressure of the reaction is 0.2-0.5 mpa, the reaction temperature is 105-155 ℃, and the oxygen flow is 20-200 Nm 3 And/h, wherein the reaction time is 1-4 h;
s3: and (3) carrying out solid-liquid separation on the mixed solution A to obtain gallium-containing solid slag and germanium-containing leaching solution.
2. A method for the separation of gallium germanium from sulfuric acid leach liquor by pressure oxidation according to claim 1, wherein: in the step S2, before the pressurized oxidation reaction of the turbid leaching solution, adding a neutralizing agent, wherein 0.05-5 g of the neutralizing agent is added to 1L of the turbid leaching solution.
3. A method for the separation of gallium germanium from sulfuric acid leach liquor by pressure oxidation according to claim 1, wherein: and (3) washing the gallium-containing solid slag obtained in the step (S3) by slurrying water, wherein the solid ratio of slurrying liquid to solid is 4-8:1, the reaction time is 1-2 h, and the reaction temperature is 60-80 ℃ to obtain gallium-containing enriched slag.
4. A method for the separation of gallium germanium from sulfuric acid leach liquor by pressure oxidation according to claim 1, wherein: the neutralizer is sodium carbonate.
5. A method for the separation of gallium germanium from sulfuric acid leach liquor by pressure oxidation according to claim 1, wherein: and the oxygen introduced in the step S2 is oxygen with the oxygen concentration of more than 93%.
6. A method for the separation of gallium germanium from sulfuric acid leach liquor by pressure oxidation according to claim 3, wherein: the gallium grade of the gallium-containing enriched slag is more than 1%, and the germanium grade is less than 0.05%, so that the gallium-containing enriched slag can be used for recycling gallium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011473242.4A CN112795795B (en) | 2020-12-15 | 2020-12-15 | Method for separating gallium and germanium in sulfuric acid leaching solution through pressurized oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011473242.4A CN112795795B (en) | 2020-12-15 | 2020-12-15 | Method for separating gallium and germanium in sulfuric acid leaching solution through pressurized oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112795795A CN112795795A (en) | 2021-05-14 |
| CN112795795B true CN112795795B (en) | 2023-10-03 |
Family
ID=75806730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011473242.4A Active CN112795795B (en) | 2020-12-15 | 2020-12-15 | Method for separating gallium and germanium in sulfuric acid leaching solution through pressurized oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112795795B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345981A (en) * | 2000-09-25 | 2002-04-24 | 中南大学 | Process for enriching germanium and silver in zinc smelting process of heat acid leaching-ferro-alum method |
| CN1479793A (en) * | 2000-12-08 | 2004-03-03 | ���п�ķ�����Ϲɷݹ�˾ | Mtehod for hydrolytic precitpitation of iron |
| CN108130431A (en) * | 2017-12-04 | 2018-06-08 | 云南驰宏资源综合利用有限公司 | A kind of richness germanium zinc concentrate oxygen leaching inhibits the method that germanium leaches |
| CN111041227A (en) * | 2019-11-27 | 2020-04-21 | 曲靖师范学院 | Method for removing arsenic, iron and organic matters from zinc sulfate solution obtained after germanium precipitation of zinc oxide smoke leachate |
| CN111996382A (en) * | 2020-09-03 | 2020-11-27 | 昆明理工大学 | Method for separating germanium from zinc hydrometallurgy solution by inorganic precipitation |
-
2020
- 2020-12-15 CN CN202011473242.4A patent/CN112795795B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1345981A (en) * | 2000-09-25 | 2002-04-24 | 中南大学 | Process for enriching germanium and silver in zinc smelting process of heat acid leaching-ferro-alum method |
| CN1479793A (en) * | 2000-12-08 | 2004-03-03 | ���п�ķ�����Ϲɷݹ�˾ | Mtehod for hydrolytic precitpitation of iron |
| CN108130431A (en) * | 2017-12-04 | 2018-06-08 | 云南驰宏资源综合利用有限公司 | A kind of richness germanium zinc concentrate oxygen leaching inhibits the method that germanium leaches |
| CN111041227A (en) * | 2019-11-27 | 2020-04-21 | 曲靖师范学院 | Method for removing arsenic, iron and organic matters from zinc sulfate solution obtained after germanium precipitation of zinc oxide smoke leachate |
| CN111996382A (en) * | 2020-09-03 | 2020-11-27 | 昆明理工大学 | Method for separating germanium from zinc hydrometallurgy solution by inorganic precipitation |
Non-Patent Citations (1)
| Title |
|---|
| 铅锌冶炼渣浸出液提取镓的研究;王艳 等;《稀有金属与硬质合金》;20011231(第4期);第7-9、17页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112795795A (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3208352A1 (en) | Method for recovering high-purity scandium | |
| CN108467942B (en) | Method for selectively leaching zinc, lead, gallium and germanium from zinc replacement slag | |
| JPS5919976B2 (en) | Method for extracting metals, especially nickel and copper, contained in nodules on the deep sea bed | |
| DE1114794B (en) | Process for the extraction of uranium by the alkaline treatment of uranium ores | |
| WO2011132729A1 (en) | Method for producing crystalline iron arsenate starting material liquid from smoke and ash | |
| CN111996373A (en) | Process for synergistically extracting cobalt from copper-cobalt ore pretreatment leachate | |
| CN101619390B (en) | Method for reducing arsenic in amine extracted germanium organic phase | |
| CN105274352B (en) | A kind of method that copper cobalt manganese is separated in the manganese cobalt calcium zinc mixture from copper carbonate | |
| CN103160688A (en) | Method for preparing germanium concentrate from germanium-containing leachate through utilizing zinc powder replacement method | |
| CN110983044B (en) | Method for recycling scandium and vanadium from titanium white wastewater produced by chlorination process | |
| US20210254193A1 (en) | Method for recovering scandium | |
| CN103154283A (en) | Method for treating a solution containing zinc sulphate | |
| CN108130431A (en) | A kind of richness germanium zinc concentrate oxygen leaching inhibits the method that germanium leaches | |
| CN115976347A (en) | Rare earth concentrate defluorination method | |
| CN114592129A (en) | Method for comprehensively recovering valuable metals in high-copper-content smelting smoke dust | |
| CN112795795B (en) | Method for separating gallium and germanium in sulfuric acid leaching solution through pressurized oxidation | |
| CN108441649B (en) | Method for extracting nickel from chemical precipitation nickel sulfide material | |
| CN109266870A (en) | The method for extracting scandium oxide | |
| JP4109501B2 (en) | Zinc hydrometallurgical process | |
| CN116002745A (en) | Method for preparing mixed rare earth oxide from rare earth film enriched liquid | |
| CN113355517B (en) | Method for harmlessly treating and recycling magnesium fluoride waste acid in zinc smelting process | |
| CN113881857A (en) | Method for treating cobalt-containing solution produced in wet zinc smelting cadmium recovery process | |
| CN114737064A (en) | Zinc jarosite hydrometallurgy method | |
| CN108754179B (en) | Method for oxidizing pretreatment of zinc-containing secondary material | |
| CN110819806A (en) | Preparation method for preparing zinc iron sulfate flocculating agent from germanium extraction liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |