CN114107660A - High-germanium raw material zinc hydrometallurgy process - Google Patents
High-germanium raw material zinc hydrometallurgy process Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 76
- 239000011701 zinc Substances 0.000 title claims abstract description 43
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 40
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 238000009854 hydrometallurgy Methods 0.000 title claims abstract description 15
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 61
- 239000010941 cobalt Substances 0.000 claims abstract description 61
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 47
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000746 purification Methods 0.000 claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 27
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 239000012141 concentrate Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 239000002699 waste material Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims description 26
- 229910045601 alloy Inorganic materials 0.000 claims description 26
- 239000003153 chemical reaction reagent Substances 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 8
- 229940037003 alum Drugs 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 16
- 230000004913 activation Effects 0.000 abstract 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 14
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- CZJCMXPZSYNVLP-UHFFFAOYSA-N antimony zinc Chemical compound [Zn].[Sb] CZJCMXPZSYNVLP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052986 germanium hydride Inorganic materials 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- VDNSGQQAZRMTCI-UHFFFAOYSA-N sulfanylidenegermanium Chemical compound [Ge]=S VDNSGQQAZRMTCI-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- -1 germanium ions Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 208000006558 Dental Calculus Diseases 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001462 antimony Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- MRZMQYCKIIJOSW-UHFFFAOYSA-N germanium zinc Chemical compound [Zn].[Ge] MRZMQYCKIIJOSW-UHFFFAOYSA-N 0.000 description 2
- GGQZVHANTCDJCX-UHFFFAOYSA-N germanium;tetrahydrate Chemical compound O.O.O.O.[Ge] GGQZVHANTCDJCX-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- DFIYWQBRYUCBMH-UHFFFAOYSA-N oxogermane Chemical compound [GeH2]=O DFIYWQBRYUCBMH-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
Classifications
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- 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
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/02—Preliminary treatment of ores; Preliminary refining of zinc oxide
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention discloses a high germanium raw material zinc hydrometallurgy process, which relates to the technical field of zinc hydrometallurgy and comprises the following steps: step one, blending ores by a roasting system to enable zinc concentrate to enter a furnace; step two, controlling the pH value of the intermediate leaching by a leaching system; step three, optimizing a copper and cadmium removal process by a purification system; step four, optimizing a cobalt removal process by a purification system; fifthly, controlling the acidity of the waste electrolyte of the electrolysis system and increasing the electrolysis circulation flow; the invention realizes the deep purification of impurities such as copper, cobalt and the like in the new liquid, avoids the activation of harmful impurities such as cobalt and the like when the germanium in the new liquid exceeds the standard, and avoids the impurity burning caused by overhigh temperature of the electrolytic bath by reducing the temperature of the electrolytic bath.
Description
Technical Field
The invention relates to the technical field of zinc hydrometallurgy, in particular to a zinc hydrometallurgy process for a high-germanium raw material.
Background
In recent years, aiming at various defects of the traditional purification cobalt-removing process of zinc hydrometallurgy, a novel cobalt-removing agent for zinc hydrometallurgy purification is developed through domestic research. The cobalt remover is a DTC broad-spectrum heavy metal chelating agent, and can react with various heavy metal ions at normal temperature to generate water-insoluble chelate salt to form precipitate, so that the aim of removing the heavy metal ions is fulfilled. At present, a part of domestic zinc hydrometallurgy enterprises adopt a novel reagent cobalt removal process successively, the process solves the problems of instability, high consumption, easy reverse dissolution of cobalt and cadmium, poor system stability and the like of the traditional zinc powder cobalt removal process, the cobalt removal effect is good, and the purpose of deep purification is achieved. But the cobalt removal process has poor adaptability to high-germanium raw materials and unsatisfactory purification effect of germanium, and restricts the popularization and application of the cobalt removal process of the novel reagent.
Table 1 new liquid quality comparison summary
Germanium is the most hazardous impurity, which precipitates on the cathode during electrolysis and causes a violent back-dissolution of the zinc of the cathode (burning of the plate). Because germanium ions react with hydrogen to produce germanium hydride after being separated out from the cathode, and the germanium hydride reacts with the hydrogen ions to produce germanium ions, the electric energy is uselessly consumed and the germanium is oxidized and reduced: ge (germanium) oxide4++4e＝GeGe+4H＝GeH4GeH4+4H+＝Ge4++4H2(ii) a The germanium-induced sintered plate is characterized in that the sintered plate is sintered from the back surface to the surface and forms a black ring, and when the sintered plate is serious, large-area needle-shaped small holes are formed. The method has the advantages that the current efficiency is sharply reduced, the direct current is high, the electrolytic cathode zinc is frequently burnt and reversely dissolved, and the production is seriously influenced. In addition, during the electrolysis process, the repeated oxidation-reduction reaction of germanium causes the continuous rise of the bath temperature, and other impurities such as Co are added2+、Cu2 +The reverse dissolution probability of the sintered plate greatly influences the production.
Disclosure of Invention
The invention aims to: in order to solve the technical problems, the invention provides the high-germanium raw material zinc hydrometallurgy process, which can reduce the content of new liquid germanium, meet the requirements of electrolysis production and lay a foundation for stable and long-term operation of a cobalt removal process.
Distribution and behavior of germanium:
roasting: GeS of germanium in zinc concentrate2And GeS morphology. In the process of roasting, germanium oxide (GeO), germanium oxide with high valence Ge02And germanate salt forms remain in the calcine, with small amounts still present in the form of germanium sulfide.
Leaching: germanium sulfide and germanate do not dissolve into the slag, and germanium dioxide enters into the solution during acid leaching. In neutral leaching, germanium is precipitated by hydrolysis and precipitation of germanium hydroxide, the reactions of which mainly occur during the whole leaching process are as follows:
(1)GeO2leaching: GeO2+4H+＝Ge4++2H2O, simple chemical dissolution without valence changes, a diffusion-controlled process with a faster leaching rate.
(2)Ge4+Hydrolysis and co-precipitation of (a): ge (germanium) oxide4++4OH-＝Ge(OH)4↓，Ge(OH)4Easily react with Al (OH)3、Fe(OH)3And Cd2+、Cu2+The heavy metal ions are co-precipitated.
The removal rate of germanium in the leaching stage reaches about 85 percent. The content of the middle-supernatant germanium is generally controlled to be 0.05-0.6 mg/l.
Purifying: the novel reagent cobalt-removing purification process is different from the three-section reverse antimony-zinc powder replacement process and comprisesOne of the two processes is a process of replacing copper and cadmium by metal zinc powder, namely replacing impurity metal ions with more positive electric property by zinc with more negative electric property, wherein the standard electrode potential of germanium is greater than that of zinc and can be replaced by zinc theoretically, and Ge4++2Zn＝2Zn2++ Ge. Secondly, a novel cobalt removing process of the reagent, namely, the cobalt removing agent reacts with germanium to generate chelate sediment of the germanium.
(II) comparison of germanium removal capacities of different purification processes
The comparison between the novel reagent cobalt-removing purification process and the three-stage reverse antimony-zinc powder replacement process is shown in Table 2:
TABLE 2 comparative summary of cleaning process
Three-stage reverse antimony zinc powder replacement process: in the process of removing cobalt and nickel from alloy zinc powder at high temperature, the purification temperature is high, the reaction time is long, antimony-containing additives such as antimony salt and tartar are added in the reaction process, the granularity of the alloy zinc powder is smaller than that of metal zinc powder, the finer the granularity is, the quicker and thorough the replacement reaction is carried out, the replacement effect is good, and the requirement of deeply purifying germanium is met.
The novel cobalt removal and purification process of the reagent comprises the following steps: although the zinc powder replacement process is carried out on the first section and the second section of the process, the temperature is controlled to be low (55-60 ℃), the reaction time is short (about 40 min), and any antimony-containing additive is not added, so that the requirement of replacing germanium by zinc powder cannot be met. In the cobalt removing process of the reagent, the germanium removing effect is not ideal due to the low germanium content. Therefore, the three-stage reverse antimony purification process can achieve the purpose of deeply purifying germanium and has strong adaptability to high-germanium raw materials. The novel reagent cobalt-removing purification process has weak adaptability to germanium. Following long-term production practice, the applicability of the two purification processes to system germanium is shown in table 3:
TABLE 3 summary of germanium suitability of different cobalt removal process systems
| Item | Germanium content (ppm) of zinc concentrate | Germanium content of the supernatant (mg/l) | Germanium content (mg/l) of new liquid |
| Novel reagent cobalt removal process | ＜20 | ＜0.15 | 0.08-0.12 |
| Cobalt removing process for alloy zinc powder | ＜50 | ＜0.50 | ＜0.05 |
According to the behavior analysis of wet zinc-germanium smelting, the key point of germanium removal is leaching, and the core point is purification.
The invention specifically adopts the following technical scheme for realizing the purpose: the zinc hydrometallurgy process for the high-germanium raw material is characterized by comprising the following steps of:
step one, blending ores by a roasting system to enable zinc concentrate to enter a furnace;
step two, controlling the pH value of the intermediate leaching to be 5.0-5.2 by a leaching system, controlling the iron concentration in the supernatant of the precipitated alum to be not lower than 5g/l, and controlling the zinc ion concentration in the supernatant of the intermediate leaching to be between 150 and 160 g/l;
step three, optimizing the copper and cadmium removal process by a purification system: the alloy zinc powder has the advantages of fine granularity (-300 meshes is more than 90%) and good activity and is used for replacing metal zinc powder to remove residual cadmium, namely, the metal zinc powder at low temperature (55-60 ℃) for removing copper and cadmium is purified at one stage, and the controlled Ge is less than or equal to 200mg/l after one time; removing residual cadmium by using the two-stage purified alloy zinc powder, increasing the adding amount of the alloy zinc powder, adding the alloy zinc powder in an excessive amount which is 2.3-2.5 times of the cadmium content of the primary post-liquid, increasing the temperature of the primary post-liquid to 65-70 ℃, and obtaining secondary post-liquid Cd which is less than or equal to 10mg/l and Ge which is less than or equal to 0.07mg/l after the two-stage purification;
step four, optimizing the cobalt removal process by the purification system: raising the temperature of the secondary liquid by 85-90 ℃, adding a novel cobalt removal reagent according to 2.2-2.4 times of the content of cadmium and cobalt in the secondary liquid, deeply purifying the cobalt, cadmium and germanium in the new liquid, and controlling Co in the new liquid to be less than or equal to 0.6mg/l and Ge to be less than or equal to 0.05 mg/l;
step five, controlling the acidity of the waste electrolyte of the electrolysis system within 180g/l, increasing the electrolysis circulation flow from 80-120l/min to 120-160l/min, and controlling the temperature of the electrolytic bath.
Preferably, Ge in the zinc concentrate fed into the furnace in the first step is less than or equal to 20ppm, and the zinc concentrate contains 10-11% of iron.
Preferably, the second purification time in the third step is 60-75 min.
Preferably, the temperature of the electrolytic bath in the fifth step is controlled to be 36-40 ℃.
The invention has the following beneficial effects:
1. in the purification system optimization cobalt-removing process, the temperature of the secondary liquid is increased by 85-90 ℃, the addition amount of a novel cobalt-removing reagent is increased, the content of cadmium and cobalt in the secondary liquid is increased to 2.2-2.4 times according to 1.8-2.2 times, the new liquid cobalt, cadmium and germanium are deeply purified, the cobalt content in the new liquid is controlled to be less than or equal to 0.6mg/l, and the Ge content in the new liquid is controlled to be less than or equal to 0.05mg/l, so that the impurities such as copper and cobalt in the new liquid are deeply purified, and the harmful impurities such as cobalt are prevented from being activated when the germanium content in the new liquid exceeds the standard.
2. The acidity of the waste electrolyte of the electrolysis system is controlled within 180g/l, the electrolysis circulation flow is increased from 80-120l/min to 120-160l/min, the temperature of the electrolysis bath is controlled at 36-40 ℃, the impurity burning caused by overhigh bath temperature is avoided, and the plate sticking phenomenon caused by the fact that a cathode plate which is not completely pulled out is put into the bath is avoided in the process of electrolysis discharging and loading.
Detailed Description
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Distribution and behavior of germanium:
roasting: GeS of germanium in zinc concentrate2And GeS morphology. In the process of roasting, germanium oxide (GeO), germanium oxide with high valence Ge02And germanate salt forms remain in the calcine, with small amounts still present in the form of germanium sulfide.
Leaching: germanium sulfide and germanate do not dissolve into the slag, and germanium dioxide enters into the solution during acid leaching. In neutral leaching, germanium is precipitated by hydrolysis and precipitation of germanium hydroxide, the reactions of which mainly occur during the whole leaching process are as follows:
(1)GeO2leaching: GeO2+4H+＝Ge4++2H2O, simple chemical dissolution without valence changes, a diffusion-controlled process with a faster leaching rate.
(2)Ge4+Hydrolysis and co-precipitation of (a): ge (germanium) oxide4++4OH-＝Ge(OH)4↓，Ge(OH)4Easily react with Al (OH)3、Fe(OH)3And Cd2+、Cu2+The heavy metal ions are co-precipitated.
The removal rate of germanium in the leaching stage reaches about 85 percent. The content of the middle-supernatant germanium is generally controlled to be 0.05-0.6 mg/l.
Purifying: the novel reagent cobalt-removing purification process is different from a three-section reverse antimony-zinc powder replacement process, and comprises two processes, namely, a process of replacing copper and cadmium by using metal zinc powder, namely replacing impurity metal ions with positive electrical property by using zinc with negative electrical property, wherein the standard electrode potential of germanium is greater than that of zinc, and can be theoretically replaced by zinc, and Ge can be replaced by4++2Zn＝2Zn2++ Ge. Secondly, a novel cobalt removing process of the reagent, namely, the cobalt removing agent reacts with germanium to generate chelate sediment of the germanium.
(II) comparison of germanium removal capacities of different purification processes
The comparison between the novel reagent cobalt-removing purification process and the three-stage reverse antimony-zinc powder replacement process is shown in Table 2:
TABLE 2 comparative summary of cleaning process
Three-stage reverse antimony zinc powder replacement process: in the process of removing cobalt and nickel from alloy zinc powder at high temperature, the purification temperature is high, the reaction time is long, antimony-containing additives such as antimony salt and tartar are added in the reaction process, the granularity of the alloy zinc powder is smaller than that of metal zinc powder, the finer the granularity is, the quicker and thorough the replacement reaction is carried out, the replacement effect is good, and the requirement of deeply purifying germanium is met.
The novel cobalt removal and purification process of the reagent comprises the following steps: although the zinc powder replacement process is carried out on the first section and the second section of the process, the temperature is controlled to be low (55-60 ℃), the reaction time is short (about 40 min), and any antimony-containing additive is not added, so that the requirement of replacing germanium by zinc powder cannot be met. In the cobalt removing process of the reagent, the germanium removing effect is not ideal due to the low germanium content. Therefore, the three-stage reverse antimony purification process can achieve the purpose of deeply purifying germanium and has strong adaptability to high-germanium raw materials. The novel reagent cobalt-removing purification process has weak adaptability to germanium. Following long-term production practice, the applicability of the two purification processes to system germanium is shown in table 3:
TABLE 3 summary of germanium suitability of different cobalt removal process systems
| Item | Germanium content (ppm) of zinc concentrate | Germanium content of the supernatant (mg/l) | Germanium content (mg/l) of new liquid |
| Novel reagent cobalt removal process | ＜20 | ＜0.15 | 0.08-0.12 |
| Cobalt removing process for alloy zinc powder | ＜50 | ＜0.50 | ＜0.05 |
According to the behavior analysis of wet zinc-germanium smelting, the key point of germanium removal is leaching, and the core point is purification.
Example 1
The embodiment provides a zinc hydrometallurgy process for a high germanium raw material, which comprises the following steps:
the method comprises the following steps: reasonably proportioning ores by a roasting system, wherein the zinc concentrate fed into the furnace contains 15ppm of germanium and 10.5% of iron;
step two: the pH value of the leaching system is controlled to be 5.2, the iron of the supernatant of the alum is precipitated to be 5.8g/l, and the Zn of the supernatant of the medium is precipitated2+Controlling the concentration at 156 g/l;
step three: the purification system optimizes the copper and cadmium removal process, and alloy zinc powder with fine granularity is used for replacing metal zinc powder to remove residual cadmium, namely the metal zinc powder at low temperature (58 ℃) is purified for removing copper and cadmium in one section, and the liquid cadmium is 152mg/l after one time; removing residual cadmium by using the two-stage purified alloy zinc powder, increasing the adding amount of the alloy zinc powder, adding the alloy zinc powder in an excessive amount which is 2.3 times of the content of the cadmium in the primary post-liquid, increasing the temperature of the primary post-liquid to 68 ℃, purifying for 60min, and increasing the removal efficiency of germanium, wherein the content of the cadmium in the secondary post-liquid is 7.8 mg/l;
step four: the purification system optimizes the cobalt removal process, improves the secondary post-liquid temperature by 89 ℃, increases the addition amount of a novel cobalt removal reagent, and adds the novel cobalt removal reagent according to 2.2 times of the content of cadmium and cobalt in the secondary post-liquid, deeply purifies the novel liquid cobalt and cadmium, controls 0.45mg/l of the novel liquid cobalt, and avoids the situation that harmful impurities such as cobalt and the like are active when the content of germanium in the novel liquid exceeds the standard;
step five: the acidity of the waste electrolyte of the electrolysis system is within 175g/l, the electrolysis circulation flow is increased to 150l/min, the temperature of the electrolytic bath is reduced and controlled at 37 ℃, and the phenomenon that the bath temperature is too high and impurities are easy to burn is avoided. Meanwhile, during the process of electrolytic discharging and tank loading, the phenomenon that the cathode plate which is not completely pulled is put into the tank to cause plate sticking and the like is avoided.
Example 2
The embodiment provides a zinc hydrometallurgy process for a high germanium raw material, which comprises the following steps:
the method comprises the following steps: reasonably proportioning ores by a roasting system, wherein the zinc concentrate fed into the furnace contains 18ppm of germanium and 10.8% of iron;
step two: the pH value of the leaching system is controlled to be 5.1, the iron of the supernatant of the alum is 6.1g/l, and the Zn of the supernatant of the medium is controlled to be2+Controlling the concentration at 155 g/l;
step three: the purification system optimizes the copper and cadmium removal process, and utilizes alloy zinc powder to replace metal zinc powder to remove residual cadmium, namely, the metal zinc powder at low temperature (57 ℃) is purified for removing copper and cadmium, and the liquid cadmium is 149mg/l after one time; removing residual cadmium by using the two-stage purified alloy zinc powder, increasing the adding amount of the alloy zinc powder, adding the alloy zinc powder in an excessive amount which is 2.4 times of the content of the cadmium in the primary post-liquid, increasing the temperature of the primary post-liquid to 69 ℃, purifying for 70min, and increasing the removal efficiency of germanium, wherein the content of the cadmium in the secondary post-liquid is 5.8 mg/l;
step four: the purification system optimizes the cobalt removal process, improves the secondary post-liquid temperature by 88 ℃, increases the addition amount of a novel cobalt removal reagent, adds the novel cobalt removal reagent according to 2.3 times of the content of cadmium and cobalt in the secondary post-liquid, deeply purifies the new liquid cobalt and cadmium, controls the cobalt content of the new liquid to be 0.58mg/l, and avoids the situation that harmful impurities such as cobalt and the like are activated when the germanium content of the new liquid exceeds the standard;
step five: the acidity of the waste electrolyte of the electrolysis system is 172g/l, the electrolysis circulation flow is increased to 145l/min, the temperature of the electrolytic cell is reduced, the temperature is controlled at 38 ℃, the phenomenon that the temperature of the electrolytic cell is too high and the impurity burning is easily caused is avoided, and meanwhile, the phenomenon that the cathode plate which is not pulled clean is put into the electrolytic cell to cause plate sticking and the like is avoided in the process of electrolyzing out of the electrolytic cell.
Example 3
The embodiment provides a zinc hydrometallurgy process for a high germanium raw material, which comprises the following steps:
the method comprises the following steps: reasonably proportioning ores by a roasting system, wherein the zinc concentrate fed into the furnace contains 16ppm of germanium and 10.7% of iron;
step two: the pH value of the leaching system is controlled to be 5.0, the iron of the supernatant of the alum is 5.5g/l, and the Zn of the supernatant of the medium is controlled to be2+154g/l；
Step three: the purification system optimizes the copper and cadmium removal process, and utilizes alloy zinc powder to replace metal zinc powder to remove residual cadmium, namely, the metal zinc powder at low temperature (59 ℃) is purified for removing copper and cadmium, and the liquid cadmium is 126mg/l after one time; removing residual cadmium by using the two-stage purified alloy zinc powder, increasing the adding amount of the alloy zinc powder, adding the alloy zinc powder in an excessive amount which is 2.5 times of the content of the cadmium in the primary post-liquid, increasing the temperature of the primary post-liquid to 70 ℃, purifying for 75min, and increasing the removal efficiency of germanium, wherein the content of the cadmium in the secondary post-liquid is 7.5 mg/l;
step four: the purification system optimizes the cobalt removal process, improves the temperature of the secondary post-liquid by 90 ℃, increases the addition amount of a novel cobalt removal reagent, adds the novel cobalt removal reagent according to 2.4 times of the content of cadmium and cobalt in the secondary post-liquid, deeply purifies the novel liquid cobalt and cadmium, controls the cobalt content of the novel liquid to be 0.44mg/l, and avoids the situation that harmful impurities such as cobalt and the like are activated when the germanium content of the novel liquid exceeds the standard;
step five: the acidity of the waste electrolyte of the electrolysis system is 177g/l, the electrolysis circulation flow is increased to 159l/min, the temperature of the electrolytic cell is reduced, the temperature is controlled at 37 ℃, the phenomenon that the temperature of the electrolytic cell is too high and the impurity burning is easily caused is avoided, and meanwhile, the phenomenon that the cathode plate which is not pulled clean is put into the electrolytic cell to cause plate sticking and the like is avoided in the process of electrolyzing out of the electrolytic cell.
Claims (4)
1. The zinc hydrometallurgy process for the high-germanium raw material is characterized by comprising the following steps of:
step one, blending ores by a roasting system to enable zinc concentrate to enter a furnace;
step two, controlling the pH value of the intermediate leaching to be 5.0-5.2 by a leaching system, controlling the iron concentration in the supernatant of the precipitated alum to be not lower than 5g/l, and controlling the zinc ion concentration in the supernatant of the intermediate leaching to be between 150 and 160 g/l;
step three, optimizing the copper and cadmium removal process by a purification system: the alloy zinc powder has the advantages of fine granularity (-300 meshes > 90%) and good activity and is used for replacing metal zinc powder to remove residual cadmium, namely, the metal zinc powder at low temperature (55-60 ℃) for removing copper and cadmium in a first section is purified, and the liquid control Ge is less than or equal to 200mg/l after one time; removing residual cadmium by using the two-stage purified alloy zinc powder, increasing the adding amount of the alloy zinc powder, adding the alloy zinc powder in an excessive amount which is 2.3-2.5 times of the cadmium content of the primary post-liquid, increasing the temperature of the primary post-liquid to 65-70 ℃, and obtaining secondary post-liquid Cd which is less than or equal to 10mg/l and Ge which is less than or equal to 0.07mg/l after the two-stage purification;
step four, optimizing the cobalt removal process by the purification system: raising the temperature of the secondary liquid by 85-90 ℃, adding a novel cobalt removal reagent according to 2.2-2.4 times of the content of cadmium and cobalt in the secondary liquid, deeply purifying the cobalt, cadmium and germanium in the new liquid, and controlling Co in the new liquid to be less than or equal to 0.6mg/l and Ge to be less than or equal to 0.05 mg/l;
step five, controlling the acidity of the waste electrolyte of the electrolysis system within 180g/l, increasing the electrolysis circulation flow from 80-120l/min to 120-160l/min, and controlling the temperature of the electrolytic bath.
2. The high germanium raw material hydrometallurgical zinc process of claim 1, wherein: and (3) Ge in the zinc concentrate fed into the furnace in the step one is less than or equal to 20ppm, and the zinc concentrate contains 10-11% of iron.
3. The high germanium raw material hydrometallurgical zinc process of claim 1, wherein: the second purification time in the third step is 60-75 min.
4. The high germanium raw material hydrometallurgical zinc process of claim 1, wherein: and in the fifth step, the temperature of the electrolytic bath is controlled to be 36-40 ℃.
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