CN112410584A - Method for recovering germanium from zinc leaching residues - Google Patents
Method for recovering germanium from zinc leaching residues Download PDFInfo
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- CN112410584A CN112410584A CN202011247360.3A CN202011247360A CN112410584A CN 112410584 A CN112410584 A CN 112410584A CN 202011247360 A CN202011247360 A CN 202011247360A CN 112410584 A CN112410584 A CN 112410584A
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- germanium
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- leaching
- alkali
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 172
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 238000002386 leaching Methods 0.000 title claims abstract description 155
- 238000000034 method Methods 0.000 title claims abstract description 54
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011701 zinc Substances 0.000 title claims abstract description 40
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 88
- 239000003513 alkali Substances 0.000 claims abstract description 80
- 238000001556 precipitation Methods 0.000 claims abstract description 52
- 238000000605 extraction Methods 0.000 claims abstract description 51
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000002893 slag Substances 0.000 claims abstract description 35
- 239000012141 concentrate Substances 0.000 claims abstract description 34
- 239000012074 organic phase Substances 0.000 claims abstract description 31
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 108010010803 Gelatin Proteins 0.000 claims abstract description 20
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000159 gelatin Polymers 0.000 claims abstract description 20
- 239000008273 gelatin Substances 0.000 claims abstract description 20
- 235000019322 gelatine Nutrition 0.000 claims abstract description 20
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 20
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 20
- 239000011975 tartaric acid Substances 0.000 claims abstract description 20
- 238000001179 sorption measurement Methods 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 17
- 229940119177 germanium dioxide Drugs 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000003795 desorption Methods 0.000 claims abstract description 12
- 150000002505 iron Chemical class 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 238000012546 transfer Methods 0.000 claims abstract 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000005660 chlorination reaction Methods 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 238000001784 detoxification Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 230000026676 system process Effects 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 71
- 238000011084 recovery Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000004321 preservation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910006113 GeCl4 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 230000004304 visual acuity Effects 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
- C22B41/00—Obtaining germanium
-
- 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
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
本公开提供一种从锌浸出渣中回收锗的方法，其包括步骤：步骤一：将水与锌浸出渣加入酸浸出槽内，将酸浸出液与酸浸出渣分离；步骤二：酸浸出液转入搅拌槽，加入明胶和酒石酸，反应过滤后，转入萃取工序；步骤三：锗萃取至有机相中，有机相处理后获得碱反萃液和贫有机相，贫有机相返回循环使用，碱反萃液中加入铁盐，反应后，将沉锗渣与沉锗液分离，沉锗渣烘干得到锗精矿，锗精矿处理后得到二氧化锗；步骤四：将水与酸浸出渣加入碱浸出槽，反应后，将碱浸出液与碱浸出渣分离；步骤五：碱浸出液转入离子交换系统，进行树酯吸附后，获得解析液，树酯活化后循环使用，往解析液中加铁盐，沉锗完成后，沉锗渣烘干得到锗精矿，锗精矿经处理得到二氧化锗。The present disclosure provides a method for recovering germanium from zinc leaching residue, which comprises the following steps: step 1: adding water and zinc leaching residue into an acid leaching tank, and separating the acid leaching solution from the acid leaching residue; step 2: transferring the acid leaching solution into Stirring tank, add gelatin and tartaric acid, after reaction and filtration, transfer to extraction process; step 3: extract germanium into organic phase, obtain alkaline stripping liquid and lean organic phase after organic phase treatment, lean organic phase is returned for recycling, alkaline reversed Iron salt is added to the extraction solution, after the reaction, the germanium precipitation slag is separated from the germanium precipitation solution, the germanium precipitation slag is dried to obtain germanium concentrate, and germanium concentrate is treated to obtain germanium dioxide; step 4: adding water and acid leaching residue Alkali leaching tank, after the reaction, the alkali leaching solution and the alkali leaching residue are separated; Step 5: The alkali leaching solution is transferred to the ion exchange system, and after resin adsorption, a desorption solution is obtained, the resin is activated and recycled, and iron is added to the desorption solution. After the germanium precipitation is completed, the germanium precipitation slag is dried to obtain germanium concentrate, and the germanium concentrate is processed to obtain germanium dioxide.
Description
Technical Field
The disclosure relates to the technical field of metallurgy, in particular to a method for recovering germanium from zinc leaching residues produced by a wet method.
Background
At present, the method mainly adopted for comprehensively recovering germanium and other valuable metals from the germanium-containing zinc slag is to make the valuable metals such as germanium, indium and the like in the slag enter a solution system. Comprehensive recovery of valuable metals is intensively studied at home and abroad, and a series of methods for comprehensively recovering germanium, such as an acid leaching method, an oxidizing roasting-chloridizing distillation method, a dressing and smelting combined method, an alkali dissolution-neutralization method, a fuming method and the like, are tried. But the recovery of germanium is of great concern and various attempts have been made to improve the recovery of germanium.
Disclosure of Invention
In view of the problems in the background art, it is an object of the present disclosure to provide a method for recovering germanium from zinc leach residues, which can improve the recovery rate of germanium. In order to achieve the above object, the present disclosure provides a method for recovering germanium from zinc leaching residue, comprising the steps of: step one, acid leaching, namely adding water and zinc leaching residues into an acid leaching tank according to a liquid-solid ratio of 5:1, then adding acid to adjust acidity, carrying out heat preservation reaction for 1-3 h, adding an oxidant after the reaction is finished, heating to 88-92 ℃ after the oxidant is added, reacting for 3-5 h, separating acid leaching liquid and acid leaching residues through solid-liquid separation equipment after the reaction is finished, transferring the acid leaching liquid to the next process, and transferring the acid leaching residues to an alkali leaching process; step two, transferring the acid leaching solution into a stirring tank, adding gelatin and tartaric acid, adjusting the pH value, reacting for 2-4 h under heat preservation, filtering by a filter, and transferring into an extraction process; step three, after the acid leaching solution is pretreated in the step two, continuous countercurrent extraction is adopted, germanium in the acid leaching solution is extracted into an organic phase, the organic phase is washed, subjected to alkali back extraction and detoxication to obtain an alkali back extraction solution and a poor organic phase, the poor organic phase is returned for recycling, an iron salt is added into the alkali back extraction solution, the pH value is adjusted to be 7-9, the germanium content is controlled to be less than 3ppm, after germanium precipitation is finished, germanium precipitation slag and germanium precipitation solution are separated through solid-liquid separation equipment, germanium concentrate is obtained after the germanium precipitation slag is dried, and germanium dioxide is obtained after the germanium concentrate is subjected to chlorination distillation, hydrolysis and drying; adding water and the acid leaching residue obtained in the first step into an alkali leaching tank according to a liquid-solid ratio of 6:1, adding alkali to adjust the alkalinity to 180-200 g/L, heating to 75-80 ℃, keeping the temperature, stirring and reacting for 2-4 h, separating the alkali leaching solution from the alkali leaching residue by solid-liquid separation equipment after the reaction is finished, and transferring the alkali leaching solution into an ion exchange system; and step five, after the alkali leaching solution is transferred to an ion exchange system, carrying out resin adsorption on the alkali leaching solution by the ion exchange system, after the resin is saturated by adsorption, carrying out acid analysis on the resin to obtain an analysis solution, activating the resin for recycling, adding iron salt into the analysis solution after the analysis is finished, then adding alkali to adjust the pH value to be 8-9, continuously reacting for 0.5-2.5 hours, controlling the germanium content to be less than 3ppm, separating the germanium precipitation slag from the germanium precipitation solution by solid-liquid separation equipment after the germanium precipitation is finished, drying the germanium precipitation slag to obtain germanium concentrate, and carrying out chlorination distillation, hydrolysis and drying on the germanium concentrate to obtain germanium dioxide.
In some embodiments, in the first step, the acid is sulfuric acid or hydrochloric acid, the acid adding speed is 1000-1500L/h, and the acidity is adjusted to 150-160 g/L.
In some embodiments, in the first step, the temperature is maintained at 60-70 ℃, the oxidant is hydrogen peroxide or potassium permanganate, and the adding speed of the oxidant is 100-120 kg/h.
In some embodiments, in step two, the gelatin and tartaric acid are added in the following ratio: according to the weight ratio, the germanium, the tartaric acid and the gelatin are 1 (4-6) and 0.1-0.3, and the pH value is 1.2-1.5.
In some embodiments, in step three, the organic phase is formulated with N235, sec-octanol, and sulfonated kerosene in a volume ratio of 1:2: 6.
In some embodiments, in step three, the continuous countercurrent extraction is of 5-8 stages, the water washing is of 1-4 stages, the alkali back extraction is of 3-6 stages, and the detoxification is of 2-4 stages.
In some embodiments, in step three, the iron salt is ferric chloride.
In some embodiments, in step four, the base added is sodium hydroxide or potassium hydroxide.
In some embodiments, in step five, the iron salt is ferric chloride or ferric sulfate, and the base is sodium hydroxide or potassium hydroxide.
In some embodiments, in the fifth step, the resin is LSC-800, and the acid desorption is performed by using dilute sulfuric acid or dilute hydrochloric acid with a concentration ranging from 1mol/L to 2 mol/L.
The beneficial effects of this disclosure are as follows:
the zinc leaching residue is subjected to two-stage leaching by combining an acid method and an alkaline method, and then germanium in the leaching solution is enriched by an extraction method and an ion exchange method respectively, so that the recovery of germanium is efficiently realized, and the recovery rate of germanium is improved.
Detailed Description
The process for recovering germanium from zinc leach residue according to the present disclosure is described in detail below.
The method for recovering germanium from zinc leaching residues according to the present disclosure comprises the steps of: the method comprises the following steps: acid leaching, namely adding water and zinc leaching residues into an acid leaching tank according to a liquid-solid ratio of 5:1, then adding acid to adjust acidity, carrying out heat preservation reaction for 1-3 h, adding an oxidant after the reaction is finished, heating to 88-92 ℃ after the oxidant is added, carrying out reaction for 3-5 h, separating acid leaching liquid from acid leaching residues through solid-liquid separation equipment after the reaction is finished, transferring the acid leaching liquid to the next process, and transferring the acid leaching residues to an alkali leaching process; step two: transferring the acid leaching solution into a stirring tank, adding gelatin and tartaric acid, adjusting the pH value, carrying out heat preservation reaction for 2-4 h, filtering through a filter, and transferring into an extraction process; step three: after the acid leaching solution is pretreated in the second step, continuous countercurrent extraction is adopted, germanium in the acid leaching solution is extracted into an organic phase, the organic phase is washed, subjected to alkali back extraction and detoxication to obtain an alkali back extraction solution and a poor organic phase, the poor organic phase is returned for recycling, an iron salt is added into the alkali back extraction solution, the pH value is adjusted to be 7-9, the content of germanium is controlled to be less than 3ppm, after germanium precipitation is finished, germanium precipitation slag is separated from the germanium precipitation solution through solid-liquid separation equipment, germanium concentrate is obtained after the germanium precipitation slag is dried, and the germanium dioxide is obtained after the germanium concentrate is subjected to chlorination distillation, hydrolysis and drying; step four: adding water into the acid leaching residue obtained in the first step according to a liquid-solid ratio of 6:1, adding alkali into an alkali leaching tank, adding the alkali to adjust the alkalinity to 180-220 g/L, heating to 75-80 ℃, keeping the temperature, stirring and reacting for 2-4 hours, separating alkali leaching liquid from alkali leaching residues by solid-liquid separation equipment after the reaction is finished, and transferring the alkali leaching liquid to an ion exchange system; step five: after the alkali leaching solution is transferred to an ion exchange system, the ion exchange system performs resin adsorption on the alkali leaching solution, after the resin is saturated by adsorption, the resin is subjected to acidic resolution to obtain a resolution solution, the resin is activated and then recycled, when resolution is completed, ferric salt is added into the desorption solution, then alkali is added to adjust the pH value to be 8-9, reaction is continued for 0.5-2.5 hours, the germanium content is controlled to be less than 3ppm, after germanium precipitation is completed, germanium precipitation slag and the germanium precipitation solution are separated through solid-liquid separation equipment, germanium concentrate is obtained after the germanium precipitation slag is dried, and germanium dioxide is obtained after the germanium concentrate is subjected to chlorination distillation, hydrolysis and drying. Wherein the zinc leaching residue at least contains germanium, copper and iron.
In the first step, the action of adding acid in the acid leaching tank not only adjusts the acidity, but also dissolves germanium in the solid in the acid, and the principle is as follows:
Ge(OH)4+2H2SO4＝Ge(SO4)2+4H2O
in the first step, because germanium is easily dissolved in hot acid added with an oxidant, the oxidant is added to improve the solubility of germanium in acid, which is beneficial to improving the leaching rate of germanium.
In the first step, in some embodiments, the acid is sulfuric acid or hydrochloric acid, and both the sulfuric acid and hydrochloric acid are strong acids, so that under the condition of the oxidizing agent, the solubility of germanium in the strong acid can be increased, and the leaching rate of germanium can be improved.
In step one, in some embodiments, the acid is added at a rate of 1000 to 1500L/h. When the acid adding speed is less than 1000L/h, the time of the whole recovery process is prolonged, and the recovery efficiency is reduced; when the adding speed is more than 1500L/h, the reaction is too violent, and potential safety hazards are caused to operators.
In step one, in some embodiments, the acidity is adjusted to 150 to 160 g/L. When the acidity is less than 150g/L, the solubility of germanium is reduced; when the acidity is more than 160g/L, waste of acid is caused and the workload of subsequent treatment is increased.
In step one, in some embodiments, the reaction temperature is maintained at 60-70 ℃. When the heat preservation temperature is less than 60 ℃, the reaction cannot be accelerated well; when the temperature is higher than 70 ℃, the reaction is too violent, and potential safety hazards are caused to operators.
In step one, in some embodiments, the oxidizing agent is hydrogen peroxide or potassium permanganate. The hydrogen peroxide is light blue viscous liquid, can be mixed and dissolved with water in any proportion, is a strong oxidant, and is a colorless transparent liquid, and the aqueous solution is commonly called hydrogen peroxide. The hydrogen peroxide has the characteristic of almost no pollution, is called as the cleanest chemical product, can oxidize metal ions in zinc leaching residues, and can not cause new pollution because the product after reaction is water; potassium permanganate is a strong oxidant, is one of the strongest oxidants, is greatly influenced by pH when used as the oxidant, has the strongest oxidizing capability in an acidic solution, and is used as the oxidant to oxidize metal ions in zinc leaching residues under the acidic condition after the acidity of the solution is adjusted.
In step one, in some embodiments, the oxidant is added at a rate of 100 to 120 kg/h. When the adding speed of the oxidant is less than 100kg/h, the concentration of the oxidant in the solution is too low, and the reaction is slow; when the adding speed of the oxidant is more than 120kg/h, the concentration of the oxidant in the solution is too high, the reaction is violent, and potential safety hazards are caused to operators.
In the second step, the gelatin is used for removing iron, so that the influence of iron on extraction is reduced, and the tartaric acid is used as a co-extraction agent, so that the extraction rate is improved.
In step two, in some embodiments, the gelatin and tartaric acid are added in the following proportions: according to the weight ratio, the germanium, the tartaric acid and the gelatin are 1, (4-6) and (0.1-0.3). When the amount of tartaric acid is less than 4 times of that of germanium, the maximum synergistic extraction coefficient cannot be reached, and the synergistic extraction effect is not obvious; when the amount of tartaric acid is 6 times larger than that of germanium, the tartaric acid is excessive, and the resource waste is caused. When the amount of the gelatin is less than 0.1 time of that of the germanium, the content of residual iron is excessive, and the extraction of the germanium is influenced; when the amount of gelatin is more than 0.3 times of that of germanium, the gelatin is excessive, so that resource waste is caused, and the workload of subsequent treatment is increased.
In step two, in some embodiments, the pH is 1.2 to 1.5. When the pH is less than 1.2, the addition of acid is excessive, the burden of subsequent treatment is increased, and the waste of alkali liquor is caused when the pH is increased in the subsequent treatment; when the pH is more than 1.5, the optimum conditions for the reaction are not achieved, and the reaction does not proceed completely.
In step three, in some embodiments, the organic phase is formulated with N235, sec-octanol, and sulfonated kerosene in a volume ratio of 1:2: 6. The organic phase with the proportion ensures that the subsequent processes of water washing, alkali back extraction and detoxification achieve the best effect.
In step three, in some embodiments, the continuous countercurrent extraction is of 5-8 grades, the water washing is of 1-4 grades, the alkali back extraction is of 3-6 grades, and the detoxification is of 2-4 grades. When the continuous countercurrent extraction is less than 5 grades, the solute and the solvent are not thoroughly mixed, and the separation effect is poor; when the continuous countercurrent extraction is more than 8 grades, the time of the whole extraction process is increased, and the working efficiency is reduced. When the water washing is more than 4 grades, the waste of water resources is caused. When the alkali back extraction is less than 3 grades, each extracted component in the organic phase cannot be back extracted to the water phase, and the separated components cannot be fully separated; when the alkali back extraction is more than 6 grades, the period of the whole process is increased, and the recovery efficiency is reduced. When the detoxification is less than grade 2, the organic phase can not be sufficiently detoxified, and the extraction capacity is reduced; when detoxification is more than level 4, investment cost is high, and investment cost of the whole recovery process is increased.
In step three, in some embodiments, the iron salt is ferric chloride. Ferric chloride forms precipitated ferric hydroxide in an alkaline environment, and because of the iron affinity of germanium, the ferric hydroxide adsorbs germanium during precipitation, and the germanium enters the iron slag.
In the third step, the principle of chlorination distillation is as follows:
GeO2+4HCl＝GeCl4+2H2O
in step four, in some embodiments, the base added is sodium hydroxide or potassium hydroxide. Sodium hydroxide and potassium hydroxide are both strong bases, are completely ionized in water, and are easy to calculate the dosage when the pH is adjusted.
In step five, in some embodiments, the iron salt is ferric chloride or ferric sulfate. Ferric trichloride and ferric sulfate are precipitated into ferric hydroxide in an alkaline environment, and the ferric hydroxide is used for secondary germanium precipitation by utilizing the siderophilic characteristic of germanium.
In step five, in some embodiments, the base added is sodium hydroxide or potassium hydroxide. The addition of alkali is also used for adjusting the pH of the solution, and the alkali is completely ionized in water, so that the dosage can be easily calculated when the pH is adjusted.
In step five, in some embodiments, the resin used for adsorption is LSC-800. The LSC-800 resin has strong selectivity, can selectively adsorb germanium, and is not influenced by other impurities.
In step five, in some embodiments, the acid desorption is performed by using dilute sulfuric acid or dilute hydrochloric acid with a concentration ranging from 1 to 2 mol/L. When the concentration is less than 1mol/L, the resolving power is insufficient, and the germanium can not be fully resolved; when the concentration is more than 2mol/L, the waste of resources is caused, and in addition, the alkali dosage is increased when the resin is activated.
In the method for recovering germanium from zinc leaching residues, the recovery rate of germanium can reach 92-95%.
Finally, a test process is given.
Example 1
First, acid leaching
Adding water and zinc leaching residues (in the zinc leaching residues, the content of each component is 0.38 percent of germanium, 10.2 percent of copper and 6.5 percent of iron in terms of weight) into a leaching tank according to the liquid-solid ratio of 5:1, adding sulfuric acid for regulating the acidity to 155g/L in an amount of 1150-1250L/h, and carrying out heat preservation reaction for 2h at the temperature of 60-70 ℃. After the reaction is finished, adding hydrogen peroxide at the speed of 110-120 kg/h, heating to 88-92 ℃ after the hydrogen peroxide is added, reacting for 4h, separating acid leaching liquid from acid leaching slag through solid-liquid separation equipment after the reaction is finished, transferring the acid leaching liquid to the next process, and transferring the acid leaching slag to an alkali leaching process.
Second, pretreatment of germanium extraction
And transferring the acid leaching solution into a stirring tank, adding gelatin and tartaric acid according to a weight ratio of 1:4:0.1 of germanium to tartaric acid to gelatin, adjusting the pH value to 1.3, reacting for 3 hours at a constant temperature, filtering by a filter, and transferring into an extraction process.
Extraction of germanium
And (2) pretreating the acid leaching solution in the second step, extracting germanium in the acid leaching solution into an organic phase by adopting 6-stage continuous countercurrent extraction (the organic phase is prepared by adopting N235, sec-octanol and sulfonated kerosene according to the volume ratio of 1:2: 6), washing the organic phase by 2-stage water, carrying out 4-stage alkali back extraction and carrying out 3-stage detoxification to obtain alkali back extraction solution and an organic poor phase, and returning the organic poor phase for recycling.
Adding ferric trichloride into the alkali stripping solution, adjusting the pH value to be 8.1, controlling the germanium content to be less than 3ppm, separating the germanium precipitation slag from the germanium precipitation solution through solid-liquid separation equipment after the germanium precipitation is finished, drying the germanium precipitation slag to obtain germanium concentrate, and performing chlorination distillation, hydrolysis and drying on the germanium concentrate to obtain germanium dioxide.
Fourthly, alkaline leaching procedure
Adding water and the acid leaching residue in the first step into an alkali leaching tank according to the liquid-solid ratio of 6:1, adding sodium hydroxide to the alkalinity of 200g/L, heating to 75-80 ℃, keeping the temperature, stirring and reacting for 3 hours, separating the alkali leaching solution from the alkali leaching residue by solid-liquid separation equipment after the reaction is finished, and transferring the alkali leaching solution to a resin adsorption process.
Adsorption of resin
After the alkali leaching solution is transferred into an ion exchange system, the ion exchange system carries out resin adsorption on the alkali leaching solution, the resin adopts LSC-800, after resin LSC-800 is adsorbed and saturated, the resin is subjected to acid resolution by 1.5mol/L sulfuric acid to obtain resolution solution, and the resin is recycled after being activated by the resin.
And when the analysis is finished, adding ferric trichloride into the desorption solution, then adding sodium hydroxide to adjust the pH value to be 8.6, continuously reacting for 1 hour, controlling the germanium content in the solution to be less than 3ppm, separating the germanium precipitation slag from the germanium precipitation solution through solid-liquid separation equipment after the germanium precipitation is finished, drying the germanium precipitation slag to obtain germanium concentrate, and performing chlorination distillation, hydrolysis and drying on the germanium concentrate to obtain germanium dioxide.
Example 2
First, acid leaching
Adding water and zinc leaching residues (in the zinc leaching residues, the content of each component is 0.42 percent of germanium content, 11.3 percent of copper content and 4.7 percent of iron content in percentage by weight) into a leaching tank according to the liquid-solid ratio of 5:1, adding hydrochloric acid at the speed of 1150-1250L/h to adjust the acidity to 155g/L, and carrying out heat preservation reaction for 2h at the temperature of 60-70 ℃. After the reaction is finished, adding potassium permanganate at the speed of 120kg/h, heating to 88-92 ℃ after the addition is finished, reacting for 4h, separating acid leaching liquid from acid leaching residues through solid-liquid separation equipment after the reaction is finished, transferring the leaching liquid to the next process, and transferring the acid leaching residues to an alkali leaching process.
Second, pretreatment of germanium extraction
And transferring the acid leaching solution into a stirring tank, adding gelatin and tartaric acid according to a weight ratio of 1:4:0.1 of germanium to tartaric acid to gelatin, adjusting the pH value to 1.4, reacting for 3 hours at a constant temperature, filtering by a filter, and transferring into an extraction process.
Extraction of germanium
And (2) pretreating the acid leaching solution in the second step, extracting germanium in the acid leaching solution into an organic phase by adopting 6-stage continuous countercurrent extraction (the organic phase is prepared by adopting N235, sec-octanol and sulfonated kerosene according to the volume ratio of 1:2: 6), washing the organic phase by 2-stage water, carrying out 4-stage alkali back extraction and carrying out 3-stage detoxification to obtain alkali back extraction solution and an organic poor phase, and returning the organic poor phase for recycling.
Adding ferric trichloride into the alkali stripping solution, adjusting the pH value to be 8.3, controlling the germanium content to be less than 3ppm, separating the germanium precipitation slag from the germanium precipitation solution through solid-liquid separation equipment after the germanium precipitation is finished, drying the germanium precipitation slag to obtain germanium concentrate, and performing chlorination distillation, hydrolysis and drying on the germanium concentrate to obtain germanium dioxide.
Fourthly, alkaline leaching procedure
Adding water and the acid leaching residue in the first step into an alkali leaching tank according to the liquid-solid ratio of 6:1, adding potassium hydroxide to the alkalinity of 200g/L, heating to 75-80 ℃, keeping the temperature, stirring and reacting for 3 hours, separating the alkali leaching solution from the leaching residue by solid-liquid separation equipment after the reaction is finished, and transferring the leaching solution to a resin adsorption process.
Adsorption of resin
After the alkali leaching solution is transferred into an ion exchange system, the ion exchange system is subjected to resin adsorption, the resin adopts LSC-800, after the resin is subjected to adsorption saturation by the LSC-800, the resin is subjected to acid desorption by 1.5mol/L sulfuric acid to obtain desorption solution, and the resin is recycled after being activated by the resin.
And when the analysis is finished, adding ferric trichloride into the desorption solution, then adding sodium hydroxide to adjust the pH value to be 8.4, continuously reacting for 1 hour, controlling the germanium content in the solution to be less than 3ppm, separating the germanium precipitation slag from the germanium precipitation solution through solid-liquid separation equipment after the germanium precipitation is finished, drying the germanium precipitation slag to obtain germanium concentrate, and performing chlorination distillation, hydrolysis and drying on the germanium concentrate to obtain germanium dioxide.
Example 3
First, acid leaching
Adding water and zinc leaching residues (in the zinc leaching residues, the content of each component is 0.37 percent of germanium content, 11.6 percent of copper content and 4.9 percent of iron content in terms of weight) into a leaching tank according to the liquid-solid ratio of 5:1, adding sulfuric acid at the speed of 1150-150L/h to adjust the acidity to 155g/L, and carrying out heat preservation reaction for 2h at the temperature of 60-70 ℃. After the reaction is finished, adding hydrogen peroxide at a speed of 110-120 kg/h, heating to 88-92 ℃ after the hydrogen peroxide is added, reacting for 4h, separating acid leaching liquid from acid leaching slag through solid-liquid separation equipment after the reaction is finished, transferring the acid leaching liquid to the next process, and transferring the acid leaching slag to an alkali leaching process.
Second, pretreatment of germanium extraction
And transferring the acid leaching solution into a stirring tank, adding gelatin and tartaric acid materials according to a weight ratio of 1:4:0.1 of germanium to tartaric acid to gelatin, adjusting the pH value to 1.3, reacting for 3 hours at a constant temperature, filtering by a filter, and transferring into an extraction process.
Extraction of germanium
And (2) pretreating the acid leaching solution in the second step, extracting germanium in the acid leaching solution into an organic phase by adopting 6-stage continuous countercurrent extraction (the organic phase is prepared by adopting N235, sec-octanol and sulfonated kerosene according to the volume ratio of 1:2: 6), washing the organic phase by 2-stage water, carrying out 4-stage alkali back extraction and carrying out 3-stage detoxification to obtain alkali back extraction solution and an organic poor phase, and returning the organic poor phase for recycling.
Adding ferric trichloride into the alkali stripping solution, adjusting the pH value to be 7.5, controlling the germanium content to be less than 3ppm, separating the germanium precipitation slag from the germanium precipitation solution through solid-liquid separation equipment after the germanium precipitation is finished, drying the germanium precipitation slag to obtain germanium concentrate, and performing chlorination distillation, hydrolysis and drying on the germanium concentrate to obtain germanium dioxide.
Fourthly, alkaline leaching procedure
Adding water and the acid leaching residue in the first step into an alkali leaching tank according to the liquid-solid ratio of 6:1, adding potassium hydroxide to the alkalinity of 200g/L, heating to 75-80 ℃, keeping the temperature, stirring and reacting for 3 hours, separating the alkali leaching solution from the alkali leaching residue by solid-liquid separation equipment after the reaction is finished, and transferring the alkali leaching solution to a resin adsorption process.
Adsorption of resin
After the alkali leaching solution is transferred into an ion exchange system, the ion exchange system performs resin adsorption on the alkali leaching solution, the resin adopts LSC-800, after the resin is adsorbed and saturated by LSC-800, the resin is subjected to acidic resolution to obtain a resolution solution, and the resin is recycled after being activated.
And when the analysis is finished, adding ferric sulfate into the desorption solution, then adding potassium hydroxide to adjust the pH value to be 8.5, continuously reacting for 1 hour, controlling the content of germanium in the solution to be less than 3ppm, separating the germanium precipitation slag from the germanium precipitation solution through solid-liquid separation equipment after the germanium precipitation is finished, obtaining germanium concentrate after the germanium precipitation is dried, and performing chlorination distillation, hydrolysis and other steps on the germanium concentrate to obtain germanium dioxide.
Comparative example 1
Example 1 was repeated except that step four and step five of example 1 were not used and the zinc leaching residue in the steps was adjusted (in the zinc leaching residue, the contents of the respective components by weight: germanium content 0.39%, copper content 9.8%, and iron content 7.3%).
Comparative example 2
The procedure of example 1 was repeated, except that the second and third steps of example 1 were not employed and the zinc leaching residue in the first step was adjusted (in the zinc leaching residue, the contents of the respective components: germanium content 0.40%, copper content 10.6%, and iron content 5.8% by weight).
Comparative example 3
Example 1 was followed except that the weight of the zinc-leached residue in step one was adjusted and the LSC-800 in step five was replaced with a D201 styrene-based anion exchange resin.
TABLE 1 parameters and results for examples 1-3 and comparative examples 1-3
Note that in examples 1-3 and comparative example 3, the weight of the produced germanium concentrate was the total amount of germanium concentrate obtained in step three and step five; in comparative example 1, the weight of the produced germanium concentrate was only the amount of germanium concentrate of step three; in comparative example 2, the weight of the produced germanium concentrate was only the amount of germanium concentrate of step five.
The above-disclosed features are not intended to limit the scope of practice of the present disclosure, and therefore, all equivalent variations that are described in the claims of the present disclosure are intended to be included within the scope of the claims of the present disclosure.
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