CN110607453B - Method for improving germanium leaching rate of germanium-rich secondary zinc oxide smoke dust - Google Patents
Method for improving germanium leaching rate of germanium-rich secondary zinc oxide smoke dust Download PDFInfo
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- CN110607453B CN110607453B CN201910922237.8A CN201910922237A CN110607453B CN 110607453 B CN110607453 B CN 110607453B CN 201910922237 A CN201910922237 A CN 201910922237A CN 110607453 B CN110607453 B CN 110607453B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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- 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
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/02—Working-up flue dust
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- 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
Abstract
The invention relates to a method for improving germanium leaching rate of germanium-rich secondary zinc oxide smoke dust, which belongs to the technical field of non-ferrous metal hydrometallurgy, and mainly comprises five steps of slurrying, first-stage leaching, second-stage leaching, third-stage leaching and filtering, wherein zinc, silicate and germanium are selectively leached in sequence by adjusting and controlling the pH value of slurry, so that the silicate is leached before the germanium, and the generated orthosilicic acid is precipitated into slag in a hydrated silicatein form, thereby effectively solving the influence of synchronous dissolution and coprecipitation of the silicate and the germanium on the germanium yield; after the liquid-solid separation of the leached ore pulp, the germanium and the zinc are recovered from the filtrate. The method solves the technical problem of low germanium leaching caused by silicon and germanium coprecipitation during leaching, and improves the germanium leaching rate by 15-22%.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal hydrometallurgy, and particularly relates to a method for improving germanium leaching rate of germanium-rich secondary zinc oxide smoke dust.
Background
Germanium is an associated element of zinc concentrate, germanium associated in the zinc concentrate is enriched in acid leaching slag after fluidized bed roasting desulfurization and zinc calcine leaching by a conventional method, and germanium is enriched again in the form of germanium-rich secondary zinc oxide smoke dust after the acid leaching slag is reduced and volatilized by a pyrogenic process.
At present, the recovery of germanium in germanium-rich zinc hypoxide smoke dust is carried out by taking sulfuric acid as leaching medium for industrial application, carrying out two-stage leaching on the germanium-rich zinc hypoxide smoke dust, and recovering zinc from the obtained first-stage leaching solution after recovering germanium by tannin chelate precipitation method or extraction method. When the tannin chelate precipitation method is adopted to recover germanium, the acidity (pH value) in the first-stage leaching solution has great influence on the consumption of tannin. The design handbook of heavy nonferrous metal metallurgy- -volume of lead-zinc-bismuth (1994, publication of metallurgy industry, P368) shows the relationship between acidity of solution and consumption of tannin:
in the table, when the Ge content of the solution after germanium precipitation is controlled to be less than or equal to 0.8mg/L, the solution containing 1-2 g/L of tannin consumes 5 times more than the solution containing less than 1g/L of tannin. The tannin source is narrow and expensive, therefore, the tannin chelate precipitation method needs to strictly control the acid content of a leaching solution to be less than 1g/L (because of Fe in a production or test solution)3+About 0.3g/L, so the corresponding pH value is 2.5-3.0) to reduce the consumption of tannin and the production cost. However, under such an acidic condition, the dissolved silicate forms orthosilicic acid (H)4SiO4) The germanium is precipitated into slag in a hydrated silica protein form, meanwhile, dissolved germanium is precipitated into slag along with the hydrated silica protein, the precipitated germanium and the hydrated silica protein exist in a homogeneous structure and are stable in structure, and when the two-stage leaching method adopts normal pressure or even pressure leaching, the precipitated germanium is hardly dissolved out due to the stable structure of the hydrated silica protein, so that the leaching rate of the germanium is low and is only 50-70% (wt) when the tannin chelate precipitation method is adopted.
In the literature "sulfuric acid leaching process research of germanium-containing smoke (zhengdongsheng et al, yunnan chemical industry, 2 months 2012, vol 37, 6 th), the smoke components were studied: (wt%): zn41.7, Pb27.7, Ge0.045, SiO26.80, recovering germanium, wherein the germanium in the smoke mainly exists in the form of germanate and germanium oxide, the insoluble germanium is 9.88% (wt) of the total germanium content under the acidic condition, the insoluble germanium is mainly tetragonal germanium dioxide, and a one-stage acid leaching process is adopted, and the test conditions are as follows: the leaching temperature is 90 ℃, the initial acid is 120g/L, the liquid-solid ratio is 8ml/g, the leaching time is 2.5h, and when the final acid is 34.80g/L, the leaching rate of germanium is 87.61%, and after insoluble germanium is removed, the leaching rate of germanium can reach 97.21%. However, the acidity of the final acid is too high, the recovery of germanium entering the leachate is difficult, and if a neutralization method is adopted to reduce the acidity of the leachate, silicon dioxide and germanium entering the solution are subjected to coprecipitation, so that the actual leaching rate of germanium is reduced. Therefore, the research only proves the leaching rate of the germanium in the smoke dust, and cannot change the current situation that the leaching rate of the germanium is low in the existing industrial production。
Disclosure of Invention
The invention provides a novel germanium leaching treatment method for germanium-rich secondary zinc oxide smoke dust, which aims at overcoming the defects of the prior art, the germanium-rich secondary zinc oxide smoke dust is slurried by water, and zinc, silicate and germanium are selectively leached in sequence by controlling the pH value of leaching slurry in a segmented manner, so that most silicate in the smoke dust is leached and precipitated before the germanium, the problems that the silicate and the germanium are difficult to separate in a coprecipitation mode and partial germanium and silicon dioxide are coprecipitated when the pH value of ore pulp is adjusted in a later stage are solved, and the leaching rate of the germanium is effectively improved.
When the invention is not particularly described, the percentages are mass percentages.
In order to realize the purpose, the invention is realized by the following technical scheme:
the method for improving the germanium leaching rate of germanium-rich secondary zinc oxide smoke dust comprises the following steps:
(1) slurrying: pulping the germanium-rich zinc hypoxide smoke dust with water.
(2) First-stage leaching: adding acid liquor, and controlling the pH value of the slurry to be 4.0-4.5 to dissolve out zinc.
The main components of the germanium-rich secondary zinc oxide smoke dust are ZnO and PbO, and the added dilute sulfuric acid mainly reacts with zinc and lead oxides as follows:
ZnO+H2SO4=ZnSO4+H2O （1）
PbO+H2SO4=PbSO4↓+H2O （2）
because the granularity of the germanium-rich zinc hypoxide smoke is extremely fine and the zinc and lead contents are high, the reaction formulas (1) and (2) are fast to carry out, the added dilute sulfuric acid is quickly consumed by the reaction, and the zinc can be preferentially dissolved out.
(3) Secondary leaching: and continuously adding acid liquor, controlling the pH value of the slurry to be 3.5-4.0, dissolving out silicate, immediately resolving the silicon dioxide entering the solution with water, and discharging the silicon dioxide into slag, so that silicate in the zinc hypoxide smoke dust is dissolved out and precipitated before germanium.
After the first leaching, the silicate in the germanium-rich zinc hypoxide smoke and the dilute acid begin to react as follows:
ZnO.SiO2+ H2SO4+H2O=ZnSO4+ H4SiO4 （3）
PbO.SiO2+ H2SO4+H2O =PbSO4↓+H4SiO4 （4）
when the reaction formulas (3) and (4) are carried out, the pH value is controlled to be 3.5-4.0, a large amount of silicon dioxide can be dissolved, and only a small part of germanium is dissolved in the pH value range.
Silicic acid (H) formed by silica going into solution4SiO4) When the pH value of the ore pulp is 3.5-4.0, generating hydrated silicatein:
H4SiO4+(n-2)H2O= SiO2.nH2O↓ （5）
the silicon dioxide entering the solution generates hydrated silica protein to be separated out, so that the separation of the silicon dioxide and the germanium is realized, and the coprecipitation of the silicon dioxide and the germanium is avoided.
(4) Three-stage leaching: and continuously adding acid liquor, and controlling the pH value of the slurry to be 2.5-3.0 to dissolve germanium out.
The reaction equation that occurs at this stage is as follows:
GeO+ H2SO4=GeSO4+ H2O （6）
GeO2+2H2SO4=Ge(SO4)2+2 H2O （7）
ZnO.GeO2+3H2SO4= Ge(SO4)2+ ZnSO4+3H2O （8）
PbO.GeO2+3H2SO4= Ge(SO4)2+ PbSO4↓+3H2O （9）
thereby completing the dissolution of germanium and zinc.
(5) And (3) filtering: filtering to obtain filter residue and filtrate.
Further, in the one-to-three-stage leaching process, 3-5 points of acid liquor are added in a dispersing mode to prevent the local acidity of the slurry from being too high.
Further, the acid solution is one or a mixture of dilute sulfuric acid and zinc electrolysis waste liquid.
Further, the silicate in the step (3) is zinc silicate or lead silicate.
Further, the leaching time of the step (2) is 0.5-1.5 hours
Further, the leaching time of the step (3) is 0.5-1.5 hours.
Further, the leaching time in the step (4) is 0.5-1.0 hour.
Further, recovering germanium and zinc from the filtrate obtained in the step (5).
The invention has the beneficial effects that:
the invention uses water to slurry the germanium-rich secondary zinc oxide smoke dust, selectively leaches zinc, silicate and germanium step by step in sequence, so that the silicate is leached before the germanium, and the generated silicic acid is precipitated in the form of hydrated silica protein to be discharged and discharged as slag; after the silicate is leached and merged into the slag, the germanium is leached, the technical problems that the silicate and the germanium are easy to generate coprecipitation and are difficult to separate when coexisting are effectively solved, and the leaching rate of germanium in the germanium-rich zinc hypoxide smoke dust is improved by 15-22 percent through the step-by-step leaching of the silicate and the germanium.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.
Example 1
The germanium-rich zinc hypoxide smoke used in the embodiment mainly comprises the following components: zn: 45.39%, Pb: 18.43% of acid-soluble SiO2：2.87%，Ge：0.0741%。
(1) Slurrying: 500g of germanium-rich secondary zinc oxide smoke dust is taken and slurried by clear water.
(2) First-stage leaching: adding dilute sulfuric acid into the slurry at 3 acid adding points by using a metering pump with adjustable flow until the pH value of the slurry is approximately equal to 4.0, keeping the pH value to react for 0.5h, and dissolving out zinc.
(3) Secondary leaching: continuously adding dilute sulfuric acid at 3 points, controlling the pH value of the ore pulp to be approximately equal to 3.5, and keeping the pH value to react for 0.5 h; the silicate is dissolved out, and the silicon dioxide dissolved into the solution is hydrated with the Silicatein (SiO)2.nH2O) morphologically separating out the slag.
(4) Three-stage leaching: continuously adding dilute sulfuric acid at 3 points until the pH value of the slurry is approximately equal to 3.0, keeping the pH value to react for 0.5h to dissolve germanium
Thereby completing the dissolution of germanium and zinc.
(5) And (3) filtering: and filtering the slurry leached in the three stages, and sending the filtrate to other working procedures for recovering germanium and zinc. And (3) baking the filter residue at the constant temperature of 105 ℃ to constant weight to obtain 250.95g of dry weight of the filter residue, wherein the residue contains 0.0322% of Gem, and the leaching rate of the germanium is 78.19%.
Comparative example 1:
500g of germanium-rich secondary zinc oxide smoke dust in the same batch as that in the example 1 is taken, slurried by clear water, one-time addition of dilute sulfuric acid required by the reaction is carried out, so that zinc, silicate and germanium are leached together, the leaching time is controlled to be 1.5h, the end point pH value is approximately equal to 3.0, liquid-solid separation is carried out after leaching, the filter residue is baked at a constant temperature of 105 ℃ to constant weight, 255.15g of dry weight of the filter residue is obtained, the residue contains Ge0.0642%, and the germanium leaching rate is 55.79% in terms of the residue.
Example 2
The germanium-rich zinc hypoxide smoke used in the embodiment mainly comprises the following components: zn: 49.85%, Pb: 21.09% of acid-soluble SiO2：4.03%，Ge：0.0956%。
(1) Slurrying: 500g of germanium-rich secondary zinc oxide smoke dust is taken and slurried by clear water.
(2) First-stage leaching: adding dilute sulfuric acid into the slurry at 4 acid adding points by using a metering pump with adjustable flow until the pH value of the slurry is approximately equal to 4.5, keeping the pH value to react for 1.0h, and dissolving out zinc.
(3) Secondary leaching: continuously adding dilute sulfuric acid at 4 points, controlling the pH value of the ore pulp to be approximately equal to 4.0, and keeping the pH value to react for 1.0 h; the silicate is dissolved out, and the silicon dioxide dissolved into the solution is hydrated with the Silicatein (SiO)2.nH2O) morphologically separating out the slag.
(4) Three-stage leaching: continuously adding dilute sulfuric acid at 4 points until the pH value of the slurry is approximately equal to 2.5, keeping the pH value and reacting for 0.5h to dissolve germanium
Thereby completing the dissolution of germanium and zinc.
(5) And (3) filtering: and filtering the slurry leached in the three stages, and sending the filtrate to other working procedures for recovering germanium and zinc. And (3) baking the filter residue at the constant temperature of 105 ℃ to constant weight to obtain 211.70g of dry weight of the filter residue, wherein the residue contains Ge0.0397%, and the leaching rate of germanium is 82.42%.
Comparative example 2:
500g of germanium-rich zinc hypoxide smoke dust in the same batch as in example 2 is taken and slurried with clear water. And adding dilute sulfuric acid solution required by the reaction at one time after slurrying to leach the zinc, the silicate and the germanium together, reacting for 2.5 hours, wherein the end point pH value is approximately equal to 2.5, carrying out liquid-solid separation, baking the filter residue at a constant temperature of 105 ℃ to constant weight, wherein the dry weight of the filter residue is 214.55g, the content of Ge0.0734% in the residue is calculated, and the leaching rate of the germanium is 67.05% in terms of the residue.
Example 3
The germanium-rich zinc hypoxide smoke used in the embodiment mainly comprises the following components: zn: 55.26%, Pb: 13.38% of acid-soluble SiO2：5.31%，Ge：0.117%。
(1) Slurrying: 500g of germanium-rich secondary zinc oxide smoke dust is taken and slurried by clear water.
(2) First-stage leaching: adding zinc electrolysis waste liquid into the solution by 5 acid adding points with adjustable flow metering pump until the pH value of the slurry is approximately equal to 4.0, keeping the pH value to react for 1.5h, and dissolving out zinc.
(3) Secondary leaching: continuously adding zinc electrolysis waste liquid at 5 points, controlling the pH value of ore pulp to be approximately equal to 3.5, and keeping the pH value to react for 1.5 h; the silicate is dissolved out, and the silicon dioxide dissolved into the solution is hydrated with the Silicatein (SiO)2.nH2O) morphologically separating out the slag.
(4) Three-stage leaching: continuously adding zinc electrolysis waste liquid at 5 points until the pH value of the slurry is approximately equal to 2.5, keeping the pH value to react for 1.0h, and dissolving out germanium
Thereby completing the dissolution of germanium and zinc.
(5) And (3) filtering: and filtering the slurry subjected to three-stage leaching, and baking the filter residue at the constant temperature of 105 ℃ to constant weight to obtain 176.50g of dry weight of the filter residue, wherein the residue contains 0.0437 percent of GeC, and the leaching rate of Ge is 86.82 percent in terms of residue.
Comparative example 3:
500g of germanium-rich secondary zinc oxide smoke dust in the same batch as that in the embodiment 3 is taken, slurried by clear water, added with zinc electrolysis waste liquid required by the reaction at one time to leach zinc, silicate and germanium together, the reaction time is controlled to be 4.0h, the end point pH value is approximately equal to 2.5, liquid-solid separation is carried out, filter residue is baked at the constant temperature of 105 ℃ to constant weight, the dry weight of the filter residue is 180.20g, the content of Ge0.0969% in the residue is measured, and the leaching rate of germanium calculated by the residue is 70.15%.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. A method for improving germanium leaching rate of germanium-rich secondary zinc oxide smoke dust is characterized by comprising the following steps: the method for improving the germanium leaching rate of germanium-rich secondary zinc oxide smoke dust comprises the following steps:
(1) slurrying: pulping the germanium-rich zinc hypoxide smoke dust with water;
(2) first-stage leaching: adding acid liquor, and controlling the pH value of the slurry to be 4.0-4.5 to dissolve out zinc;
(3) secondary leaching: continuously adding acid liquor, controlling the pH value of the slurry to be 3.5-4.0, dissolving out silicate, and immediately hydrolyzing the silicon dioxide entering the solution into slag;
(4) three-stage leaching: continuously adding acid liquor, and controlling the pH value of the slurry to be 2.5-3.0 to dissolve germanium out;
(5) and (3) filtering: filtering to obtain filter residue and filtrate;
wherein, the acid solution in the steps (2) to (4) is one or a mixture of dilute sulfuric acid and zinc electrolysis waste liquid.
2. The method for improving the germanium leaching rate of germanium-rich zinc hypoxide smoke dust according to claim 1, which is characterized in that: in the first-stage to third-stage leaching process, the acid liquor is added in a dispersing way by 3-5 acid adding points so as to prevent the local acidity of the slurry from being overlarge.
3. The method for improving the germanium leaching rate of germanium-rich zinc hypoxide smoke dust according to claim 1, which is characterized in that: the silicate in the step (3) is zinc silicate or lead silicate.
4. The method for improving the germanium leaching rate of germanium-rich zinc hypoxide smoke dust according to claim 1, which is characterized in that: the leaching time in the step (2) is 0.5-1.5 hours.
5. The method for improving the germanium leaching rate of germanium-rich zinc hypoxide smoke dust according to claim 1, which is characterized in that: the leaching time in the step (3) is 0.5-1.5 hours.
6. The method for improving the germanium leaching rate of germanium-rich zinc hypoxide smoke dust according to claim 5, wherein the method comprises the following steps: the leaching time in the step (4) is 0.5-1.0 hour.
7. The method for improving the germanium leaching rate of germanium-rich zinc hypoxide smoke dust according to claim 1, which is characterized in that: and (5) recovering germanium and zinc from the filtrate obtained in the step (5).
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| CN115874058B (en) * | 2023-03-02 | 2023-05-12 | 昆明理工大学 | Method for efficiently enriching germanium by pre-dezincification and germanium-containing zinc oxide smoke neutralization method |
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