CN115109929A - Method for directly preparing coarse germanium dioxide from tannin germanium slag - Google Patents
Method for directly preparing coarse germanium dioxide from tannin germanium slag Download PDFInfo
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- CN115109929A CN115109929A CN202210073994.4A CN202210073994A CN115109929A CN 115109929 A CN115109929 A CN 115109929A CN 202210073994 A CN202210073994 A CN 202210073994A CN 115109929 A CN115109929 A CN 115109929A
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- 239000002893 slag Substances 0.000 title claims abstract description 99
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 90
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 235000018553 tannin Nutrition 0.000 title claims abstract description 56
- 229920001864 tannin Polymers 0.000 title claims abstract description 56
- 239000001648 tannin Substances 0.000 title claims abstract description 56
- 229940119177 germanium dioxide Drugs 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000002386 leaching Methods 0.000 claims abstract description 46
- 238000005406 washing Methods 0.000 claims abstract description 44
- 239000011701 zinc Substances 0.000 claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012141 concentrate Substances 0.000 claims abstract description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005554 pickling Methods 0.000 claims abstract description 20
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004471 Glycine Substances 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 104
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000003929 acidic solution Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/02—Germanium dioxide
-
- 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
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- 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
-
- 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
Abstract
The invention relates to a method for directly preparing coarse germanium dioxide from tannin germanium slag, and belongs to the technical field of comprehensive utilization of valuable metals. The invention adopts a coordination agent to prepare a coordination solution, and the pH value of the coordination solution is adjusted to be not more than 4; wherein the complexing agent is NH 3 One or more of oxalic acid, citric acid, ethylenediamine, glycine, nitrilotriacetic acid, and oxalic acid; leaching tannin germanium slag by using a coordination solution, performing solid-liquid separation to obtain coordination slag and a leaching solution, and washing the coordination slag by using an acid solution to obtain acid washing slag and an acid washing solution; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; leaching outWhen the total concentration of zinc and iron in the solution and the pickling solution is 80-150 g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate; distilling the acid washing slag to remove the coordination agent to obtain distilled slag and distillate, and returning the distillate to prepare a coordination solution; and roasting the distillation slag to obtain coarse germanium dioxide. The invention can deeply separate zinc and iron impurity elements from germanium, improve the grade of germanium concentrate and realize the recycling of the iron and zinc impurity elements.
Description
Technical Field
The invention relates to a method for directly preparing coarse germanium dioxide from tannin germanium slag, and belongs to the technical field of comprehensive utilization of valuable metals.
Background
With the increasingly deep and wide research of high and new technical materials and scientific technologies, the application field of germanium materials is increasingly expanded, the value of recovering germanium from germanium semi-crude ore and germanium secondary resources is increasingly highlighted in the face of the situation that the germanium consumption is increased and the germanium resources are relatively lacked, the grade of the produced final germanium concentrate directly influences the comprehensive recovery value of the germanium resources, and in order to reduce subsequent processing procedures and improve the quality of germanium products, high-grade germanium concentrate needs to be produced and even coarse germanium dioxide is prepared in one step.
Germanium is recovered from the brown ore of germanium and the secondary resource of germanium, a tannin germanium precipitation method is mainly utilized, the germanium content reaches about 2% after the tannin germanium precipitation, and the total amount of zinc and iron is also about 3%, so that the germanium concentrate grade is low. In the prior art, hydrochloric acid + salt leaching impurity removal-three-stage water countercurrent washing is adopted to remove calcium and zincAnd iron, wherein the grade of the obtained germanium concentrate is 27%; the zinc in the tannin germanium slag is leached at low temperature by ammonium chloride, and then the tannin is recovered by adding oxalic acid, the zinc recovery rate reaches 92 percent, the lead recovery rate reaches 93 percent, the germanium grade is improved by more than 5 times, but a large amount of Cl - The introduction of a main system seriously affects the zinc electrolysis, and has large hydrochloric acid consumption and high cost.
Carrying out 2-4-stage countercurrent washing on the tannin germanium slag by adopting a sulfuric acid solution, and then roasting for 3-5 hours to prepare black germanium concentrate, wherein the germanium concentrate contains 35.0% of germanium and 1.0% of arsenic; the removal of iron in the germanium concentrate is enhanced by enhancing the pulping and washing process of the tannin slag and adjusting the pulping and stirring mode, so that the germanium concentrate is improved; preparing dilute sulfuric acid solution with pH value of 2 with water and a small amount of industrial sulfuric acid, heating to 60 deg.C, adding tannin germanium, keeping the temperature at 70 deg.C, stirring for 30min, filtering, washing once or twice under the same conditions to obtain germanium concentrate with germanium content of 24-30%. The germanium concentrate grade in the process is improved, but the zinc separation efficiency is low, and the comprehensive utilization efficiency of valuable metals is low.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for directly preparing crude germanium dioxide from tannin germanium slag, which separates zinc in the tannin germanium slag through coordination leaching and washing, directly bakes the tannin germanium slag to generate crude germanium dioxide, simultaneously returns residual complexing agent in the germanium slag for utilization through low-temperature pre-distillation before a baking section, and precipitates and returns the washing liquid after zinc is enriched to a certain degree.
A method for directly preparing coarse germanium dioxide from tannin germanium slag comprises the following specific steps:
(1) preparing a coordination solution by adopting a coordination agent, and adjusting the pH value of the coordination solution to be not more than 4; wherein the complexing agent is NH 3 One or more of oxalic acid, citric acid, ethylenediamine, glycine, nitrilotriacetic acid, and oxalic acid;
(2) leaching tannin germanium slag by using the coordination solution obtained in the step (1), performing solid-liquid separation to obtain coordination slag and leaching solution, and washing the coordination slag by using an acid solution to obtain acid washing slag and acid washing solution; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; when the total concentration of zinc and iron in the leaching solution and the pickling solution is 80-150 g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate;
(3) distilling the acid washing slag obtained in the step (2) to remove the coordination agent to obtain distilled slag and distillate, and returning the distillate to the step (1) to prepare a coordination solution;
(4) roasting the distillation slag obtained in the step (3) to obtain coarse germanium dioxide;
the concentration of the coordination solution in the step (1) is 10-200 g/L:
the liquid-solid ratio L: g of the coordination solution and the tannin germanium slag in the step (2) is 1: 1-6: 1, and the washing temperature of the coordination solution is not higher than 40 ℃;
the acidity of the acidic solution in the step (2) is 1-5%, and the washing temperature of the acidic solution is not higher than 40 ℃;
the distillation temperature in the step (3) is 80-300 ℃, and the distillation time is 30-60 min;
in the step (4), the roasting temperature in the step (4) is 600-800 ℃, the roasting time is 8-15 h, and the roasting atmosphere is oxygen-enriched or air atmosphere;
the zinc grade of the zinc oxide concentrate can reach more than 50%.
The preparation process of the coarse germanium dioxide comprises the following steps: the method comprises the steps of performing coordination leaching on iron tannin, zinc tannin, an inorganic zinc compound, an inorganic iron compound and a coordination reagent to obtain residual germanium tannin, then roasting the germanium tannin to decompose the residual germanium tannin to generate crude germanium dioxide, reacting in a washing process,
m[TA-Fe(III)]+nL→Fe m L n +TA (a)
x[TA-Zn(II)]+yL→Zn x L y +TA (b)
m/2Fe 2 (SO 4 ) 3 +nL→Fe m L n +3m/2SO 4 2- (c)
mFeSO 4 +nL→Fe m L n +SO 4 2- (c)
xZnSO 4 +yL→Zn x L y +SO 4 2- (d)
wherein TA represents tannin and L represents ligand.
The invention has the beneficial effects that:
(1) the tannin germanium slag mainly comprises tannin germanium, tannin iron, tannin zinc, inorganic zinc compounds and inorganic iron compounds, so that germanium concentrate roasted by the tannin germanium slag contains a large amount of zinc, iron and the like, and the grade of the germanium concentrate is only 10-25%; according to the invention, through coordination leaching of a coordination solution and washing of an acidic solution, zinc and iron are removed by more than 90%, germanium is not lost completely, zinc and iron coordinate to enter a leaching solution and a pickling solution, effective recovery of zinc and iron in tannin germanium slag is realized, and the pickling slag is roasted to directly prepare crude germanium dioxide with the germanium grade of more than 50%;
(2) the invention realizes the recycling of the coordination agent by low-temperature distillation, and has simple process operation and low separation cost;
(3) the invention can deeply separate zinc and iron impurity elements and germanium, realize the recycling of the iron and zinc impurity elements while improving the grade of germanium concentrate, and improve the additional benefit of germanium production.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for directly preparing coarse germanium dioxide from tannin germanium slag (see figure 1) comprises the following specific steps:
(1) preparing a coordination solution (citric acid solution) with the concentration of 10g/L, and adjusting the pH value of the citric acid solution to be 4 by adopting 25% ammonia water;
(2) leaching the tannin germanium slag by using the citric acid solution obtained in the step (1), wherein the liquid-solid ratio L: g of the citric acid solution to the tannin germanium slag is 1:1, the leaching temperature is 40 ℃, the leaching time is 1h, performing solid-liquid separation to obtain coordination slag and leachate, and flushing the coordination slag by using an acid solution with the acidity of 1% at the temperature of 40 ℃ to obtain acid washing slag and acid washing liquid; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; when the total concentration of zinc and iron in the leaching solution and the pickling solution is about 85g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate;
(3) distilling the acid washing slag obtained in the step (2) at the temperature of 150 ℃ for 30min to remove a coordination agent (citric acid) to obtain distilled slag and a distillate, and returning the distillate to the step (1) to prepare a coordination solution;
(4) roasting the distillation slag obtained in the step (3) for 8 hours in an oxygen-rich atmosphere at the temperature of 600 ℃ to obtain crude germanium dioxide;
in this example, the grade of zinc oxide concentrate is 50%, and the germanium content in the coarse germanium dioxide is 50%.
Example 2: a method for directly preparing coarse germanium dioxide from tannin germanium slag (see figure 1) comprises the following specific steps:
(1) preparing a coordination solution (glycine solution) with the concentration of 100g/L, and adjusting the pH value of the glycine solution to be 0.5 by adopting 200g/L sulfuric acid;
(2) leaching the tannin germanium slag by using the glycine solution obtained in the step (1), wherein the liquid-solid ratio L of the glycine solution to the tannin germanium slag is 3:1, the leaching temperature is 30 ℃, the leaching time is 45min, performing solid-liquid separation to obtain coordination slag and leachate, and washing the coordination slag by using an acid solution with the acidity of 2.5% at the temperature of 30 ℃ to obtain acid washing slag and an acid washing solution; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; when the total concentration of zinc and iron in the leaching solution and the pickling solution is about 100g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate;
(3) distilling the acid washing slag obtained in the step (2) at 250 ℃ for 45min to remove a coordination agent (glycine) to obtain distilled slag and distillate, and returning the distillate to the step (1) to prepare a coordination solution;
(4) roasting the distillation slag obtained in the step (3) for 10 hours in an oxygen-rich atmosphere at the temperature of 700 ℃ to obtain crude germanium dioxide;
in this example, the grade of zinc oxide concentrate is 60%, and the germanium content in the coarse germanium dioxide is 55%.
Example 3: a method for directly preparing coarse germanium dioxide from tannin germanium slag (see figure 1) comprises the following specific steps:
(1) preparing a coordination solution (ammonium sulfate solution) with the concentration of 200g/L, and adjusting the pH value of the ammonium sulfate solution to 2 by adopting 200g/L sulfuric acid;
(2) leaching the tannin germanium slag by using the ammonium sulfate solution obtained in the step (1), wherein the liquid-solid ratio L: g of the ammonium sulfate solution to the tannin germanium slag is 6:1, the leaching temperature is 25 ℃, the leaching time is 30min, solid-liquid separation is performed to obtain coordination slag and leachate, and then at the temperature of 25 ℃, the coordination slag is washed by using an acid solution with the acidity of 5% to obtain acid washing slag and acid washing liquid; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; when the total concentration of zinc and iron in the leaching solution and the pickling solution is about 150g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate;
(3) distilling the acid washing slag obtained in the step (2) at the temperature of 300 ℃ for 60min to remove a coordination agent (ammonium sulfate) to obtain distilled slag and distillate, and returning the distillate to the step (1) to prepare a coordination solution;
(4) roasting the distillation slag obtained in the step (3) for 12 hours in an oxygen-rich atmosphere at the temperature of 650 ℃ to obtain crude germanium dioxide;
in the embodiment, the grade of the zinc oxide concentrate is 65%, and the content of germanium in the coarse germanium dioxide is 60%.
Example 4: a method for directly preparing crude germanium dioxide from tannin germanium slag (see figure 1) comprises the following specific steps:
(1) preparing a coordination solution (ammonia solution) with the concentration of 80g/L, and adjusting the pH value of the ammonia solution to 2 by adopting 200g/L sulfuric acid;
(2) leaching the tannin germanium slag by using the ammonia water solution obtained in the step (1), wherein the liquid-solid ratio L: g of the ammonia water solution to the tannin germanium slag is 4:1, the leaching temperature is 25 ℃, the leaching time is 30min, solid-liquid separation is carried out to obtain coordination slag and leachate, and then at the temperature of 25 ℃, the coordination slag is washed by using an acid solution with the acidity of 2% to obtain acid washing slag and acid washing liquid; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; when the total concentration of zinc and iron in the leaching solution and the pickling solution is about 100g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate;
(3) distilling the acid washing slag obtained in the step (2) at the temperature of 100 ℃ for 30min to remove a coordination agent (ammonia water) to obtain distilled slag and distillate, and returning the distillate to the step (1) to prepare a coordination solution;
(4) roasting the distillation slag obtained in the step (3) for 12 hours in an oxygen-rich atmosphere at the temperature of 650 ℃ to obtain crude germanium dioxide;
in the embodiment, the grade of the zinc oxide concentrate is 65%, and the content of germanium in the coarse germanium dioxide is 58%.
Example 5: a method for directly preparing coarse germanium dioxide from tannin germanium slag (see figure 1) comprises the following specific steps:
(1) preparing a coordination solution (ethylenediamine solution) with the concentration of 120g/L, and adjusting the pH value of the ethylenediamine solution to 2 by adopting 200g/L sulfuric acid;
(2) leaching tannin germanium slag by using the ethylenediamine solution obtained in the step (1), wherein the liquid-solid ratio L: g of the ethylenediamine solution to the tannin germanium slag is 5:1, the leaching temperature is 25 ℃, the leaching time is 40min, performing solid-liquid separation to obtain coordination slag and leachate, and flushing the coordination slag by using an acid solution with the acidity of 2% at the temperature of 25 ℃ to obtain acid washing slag and acid washing liquid; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; when the total concentration of zinc and iron in the leaching solution and the pickling solution is about 100g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate;
(3) distilling the acid washing slag obtained in the step (2) at the temperature of 120 ℃ for 30min to remove a coordination agent (ethylenediamine) to obtain distilled slag and distillate, and returning the distillate to the step (1) to prepare a coordination solution;
(4) roasting the distillation slag obtained in the step (3) for 12 hours in an oxygen-rich atmosphere at the temperature of 650 ℃ to obtain crude germanium dioxide;
in this example, the grade of the zinc oxide concentrate is 61%, and the germanium content in the coarse germanium dioxide is 55%.
Example 6: a method for directly preparing coarse germanium dioxide from tannin germanium slag (see figure 1) comprises the following specific steps:
(1) preparing a coordination solution (ammonia water-ammonium sulfate solution) with the total ammonia concentration of 60g/L, wherein the mixing molar ratio of ammonium sulfate to ammonia water is 2:1, and the pH value of the ammonia water-ammonium sulfate solution is adjusted to 2 by adopting 200g/L sulfuric acid;
(2) leaching the tannin germanium slag by using the ammonia water-ammonium sulfate solution obtained in the step (1), wherein the liquid-solid ratio L of the ammonia water-ammonium sulfate solution to the tannin germanium slag is 5:1, the leaching temperature is 25 ℃, the leaching time is 40min, performing solid-liquid separation to obtain coordination slag and leachate, and washing the coordination slag by using an acidic solution with the acidity of 2% at the temperature of 25 ℃ to obtain acid washing slag and acid washing liquid; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; when the total concentration of zinc and iron in the leaching solution and the pickling solution is about 100g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate;
(3) distilling the acid washing slag obtained in the step (2) at the temperature of 100 ℃ for 30min to remove a coordination agent (ammonia water-ammonium sulfate) to obtain distilled slag and distillate, and returning the distillate to the step (1) to prepare a coordination solution;
(4) roasting the distillation slag obtained in the step (3) for 12 hours in an oxygen-rich atmosphere at the temperature of 650 ℃ to obtain crude germanium dioxide;
in the embodiment, the grade of the zinc oxide concentrate is 65%, and the content of germanium in the coarse germanium dioxide is 60%.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (6)
1. A method for directly preparing coarse germanium dioxide from tannin germanium slag is characterized by comprising the following specific steps:
(1) preparing a coordination solution by adopting a coordination agent, and adjusting the pH value of the coordination solution to be not more than 4; wherein the complexing agent is NH 3 One or more of oxalic acid, citric acid, ethylenediamine, glycine, nitrilotriacetic acid, and oxalic acid;
(2) leaching tannin germanium slag by using the coordination solution obtained in the step (1), performing solid-liquid separation to obtain coordination slag and leachate, and washing the coordination slag by using an acid solution to obtain acid washing slag and an acid washing solution; adding a coordination agent into the leaching solution and the pickling solution to prepare a coordination solution; when the total concentration of zinc and iron in the leaching solution and the pickling solution is 80-150 g/L, performing zinc precipitation treatment to obtain zinc oxide concentrate;
(3) distilling the acid washing slag obtained in the step (2) to remove the coordination agent to obtain distilled slag and distillate, and returning the distillate to the step (1) to prepare a coordination solution;
(4) and (4) roasting the distillation slag obtained in the step (3) to obtain crude germanium dioxide.
2. The method for directly preparing crude germanium dioxide from the tannin germanium slag according to claim 1, which is characterized by comprising the following steps: the concentration of the coordination solution in the step (1) is 10-200 g/L.
3. The method for directly preparing crude germanium dioxide from the tannin germanium slag as claimed in claim 2, which is characterized in that: the liquid-solid ratio L: g of the coordination solution to the tannin germanium slag in the step (2) is 1: 1-6: 1, and the washing temperature of the coordination solution is not higher than 40 ℃.
4. The method for directly preparing crude germanium dioxide from the tannin germanium slag as claimed in claim 1, which is characterized in that: the acidity of the acidic solution in the step (2) is 1-5%, and the washing temperature of the acidic solution is not higher than 40 ℃.
5. The method for directly preparing crude germanium dioxide from the tannin germanium slag according to claim 1, which is characterized by comprising the following steps: and (3) distilling at 80-300 ℃ for 30-60 min.
6. The method for directly preparing crude germanium dioxide from the tannin germanium slag according to claim 1, which is characterized by comprising the following steps: and (4) roasting at the roasting temperature of 600-800 ℃ for 8-15 h in the step (4), wherein the roasting atmosphere is oxygen-enriched or air.
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