CN115896474A - Leaching process of zinc roasted ore - Google Patents
Leaching process of zinc roasted ore Download PDFInfo
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- CN115896474A CN115896474A CN202211315283.XA CN202211315283A CN115896474A CN 115896474 A CN115896474 A CN 115896474A CN 202211315283 A CN202211315283 A CN 202211315283A CN 115896474 A CN115896474 A CN 115896474A
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- copper
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- zinc
- slag
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- 238000002386 leaching Methods 0.000 title claims abstract description 99
- 239000011701 zinc Substances 0.000 title claims abstract description 72
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000010949 copper Substances 0.000 claims abstract description 101
- 229910052802 copper Inorganic materials 0.000 claims abstract description 100
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000002893 slag Substances 0.000 claims abstract description 62
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 58
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052742 iron Inorganic materials 0.000 claims abstract description 40
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 30
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229910052598 goethite Inorganic materials 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims description 94
- 239000006228 supernatant Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052793 cadmium Inorganic materials 0.000 claims description 13
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001556 precipitation Methods 0.000 abstract description 6
- 229910052785 arsenic Inorganic materials 0.000 description 16
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 15
- 239000013049 sediment Substances 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000000746 purification Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- ONJMCYREMREKSA-UHFFFAOYSA-N [Cu].[Ge] Chemical compound [Cu].[Ge] ONJMCYREMREKSA-UHFFFAOYSA-N 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- RBFDCQDDCJFGIK-UHFFFAOYSA-N arsenic germanium Chemical compound [Ge].[As] RBFDCQDDCJFGIK-UHFFFAOYSA-N 0.000 description 1
- -1 arsenic ions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- GDPKWKCLDUOTMP-UHFFFAOYSA-B iron(3+);dihydroxide;pentasulfate Chemical compound [OH-].[OH-].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GDPKWKCLDUOTMP-UHFFFAOYSA-B 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- 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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a leaching process of zinc roasted ore, belonging to the technical field of zinc roasted ore leaching; according to the invention, traditional neutral leaching is replaced by iron removal and neutralization, and the iron precipitation form during iron removal and neutralization is goethite by controlling the conditions of iron removal and neutralization, so that the slag entering of germanium and the leaching of copper are realized, the leaching rate of copper is improved, the germanium and the copper are separated more thoroughly, and the produced copper slag does not need to be separated from copper and germanium; the process of the invention also does not need iron powder to replace copper, thereby reducing the consumption of manganese powder or hydrogen peroxide.
Description
Technical Field
The invention belongs to the technical field of zinc roasted ore leaching, and particularly relates to zinc roasted ore leaching rich in copper and germanium.
Background
At present, zinc roasted ore leaching is mainly divided into a conventional leaching method and a hot acid leaching method. The conventional leaching process includes two main processes, neutral leaching and weak acid leaching. The hot acid leaching method comprises three main processes of neutral leaching, weak acid leaching and hot acid leaching. In the two leaching methods, in addition to leaching zinc in roasted ore, impurities such as iron, arsenic, germanium and the like in the solution need to be hydrolyzed into slag in neutral leaching to reduce the purification impurity removal pressure.
When the zinc roasted ore is rich in copper and germanium, the purification operation is facilitated by ensuring that Ge in neutral leachate (hereinafter referred to as supernatant) is less than or equal to 0.30mg/L, and the pH value of ore pulp is increased to 5.2-5.4 for adding germanium into slag. While copper has poor stability in solution and is easy to hydrolyze (the pH value of copper hydrolysis is 4.604 at 25 ℃), and when copper is leached at a neutral pH value of 5.2-5.4, the leaching rate of copper is only 30-40%, and the rest acid leaching residue is finally lost in water-quenched slag or kiln slag of a fuming furnace. Due to Cu 2+ And Ge 4+ The hydrolysis pH value of the copper-germanium-rich zinc roasted ore is close, when the zinc roasted ore rich in copper and germanium is leached, the germanium is difficult to enter the slag and the copper is difficult to enter the solution, because the germanium is required to enter the slag with a higher pH value and the copper is required to enter the solution with a lower pH value, the two are difficult to take into account. Meanwhile, germanium in the supernatant fluid is the element which is most difficult to remove in a purification mode and has the greatest influence on zinc electrodeposition, and in order to ensure normal operation of production, production enterprises intentionally increase the pH value of ore pulp to reduce the content of germanium in the supernatant fluid, but a large amount of copper is hydrolyzed and enters acid leaching residue to be lost, and the copper recovery rate is less than 40%.
CN113088698A discloses a method for improving copper recovery rate in conventional leaching of high-copper high-germanium roasted ore, wherein 1-3g/L of pickle liquor containing sulfuric acid is firstly replaced by copper by iron powder, and the pickle liquor after copper replacement is returned to neutral leaching, so that the recovery rate of copper is improved, but the pickle liquor still contains Fe 3+ And Ge 4+ When copper is replaced by iron powder, fe will be mixed 3+ And Ge 4+ The reaction not only causes high consumption of iron powder, but also generates Fe during replacement 2+ Reoxidation to Fe 3+ Requires large amounts of oxidizing agent and also causes Ge to be consumed 4+ The copper slag is replaced and the copper is replacedThe problem of copper and germanium separation is also involved in the subsequent treatment of the slag. CN115011810A discloses a leaching process for improving copper recovery rate in zinc roasted ore, which adopts low-acid reinforced copper leaching to improve the leaching rate of copper, and uses weak acid to leach copper for iron precipitation and directly recover copper, but like CN113088698A, when replacing copper with iron powder, the iron powder can be replaced with Fe 3+ And Ge 4+ The reaction and the subsequent consumption of a large amount of oxidant and the replacement of copper slag still involve the problem of copper-germanium separation. CN115029562A discloses a method for separating copper and germanium in a wet zinc smelting process, wherein a weak immersion liquid with the pH of 3.0 to 4.0 is replaced by iron powder to precipitate copper, and the weak acid residue is subjected to low-acid reinforced copper immersion, but the iron powder and Fe can be mixed when replacing copper 3+ And Ge 4+ Reaction, only reduction of Fe 3+ And Ge 4+ The problems of copper-germanium separation, high iron powder consumption, large oxidant consumption and the like cannot be thoroughly solved.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a leaching process of zinc roasted ore, which controls the leaching process to ensure that Fe is contained 3+ Go into the sediment with goethite form, germanium is along with going into the sediment when iron goes into the sediment, and because iron goes into the sediment with goethite form, the ability reinforce of goethite absorption impurities such as arsenic germanium, germanium can be along with the sediment of goethite income sediment under lower pH value, has improved the leaching rate of copper when the sediment is gone into to the germanium sediment, copper and germanium separation is thorough, copper obtains high-efficient leaching, and does not increase manganese powder or hydrogen peroxide consumption among the recovery copper process, the copper sediment of output need not to carry out the copper and germanium separation again.
In order to realize the purpose, the invention is realized by the following technical scheme:
the leaching process of the zinc roasted ore comprises the following implementation steps:
(1) iron removal
Adding the acid liquor, the low-acid leaching liquor and the zinc roasted ore into a reaction tank continuously and simultaneously, and controlling the Fe in the leached ore pulp 3+ The maximum concentration of Fe, and controlling the reaction temperature and pH value to reduce Fe brought in the acid liquor 3+ Precipitating into slag.
(2) Neutralization
Adding zinc roasted ore into the iron-removed ore pulp, and up-regulating the orepH value of the pulp to ensure that residual Fe in the pulp 3+ Precipitating and feeding slag; after the neutralized ore pulp is settled and separated, copper enters the middle supernatant, the middle supernatant is purified, the copper in the middle supernatant enters the purified copper-cadmium slag during purification, the copper-cadmium slag is leached with zinc and cadmium, the copper enters the copper slag, and the neutralized bottom stream is subjected to low-acid leaching.
The invention replaces the currently common neutral leaching with iron removal and neutralization, and in steps (1) and (2), fe 3+ The form of the precipitated slag is goethite.
Preferably, the Fe in the ore pulp is leached in the step (1) in a control way 3+ The maximum concentration of the sodium hypochlorite is less than or equal to 1000mg/L.
Preferably, in the step (1), the reaction temperature is controlled to be 80-85 ℃, and the pH value of the leached ore pulp is controlled to be 3.0-4.0.
Preferably, the pH of the ore pulp is adjusted to 4.5-4.8 in step (2).
Through the steps (1) and (2), the separation of germanium and copper is realized.
Preferably, the neutralized underflow is subjected to the low acid leaching treatment in step (3), specifically: adding zinc electrodeposition waste liquid into the neutralization bottom flow, adding manganese powder, controlling leaching conditions to leach zinc and copper in the neutralization bottom flow, leaving germanium in slag, settling and separating low-acid leaching ore pulp, filtering the bottom flow, and returning filtrate and low-acid supernatant to remove iron.
Preferably, the leaching conditions controlled in step (3) are: the pH value of the process and the end point is 0.6-1.0, the temperature is 75-80 ℃, and the time is 2-4 h.
Preferably, the low-acid filter residue in the step (3) is sent to a kiln for treatment by a pyrogenic process.
Preferably, the acid solution in the step (1) is one or two of dilute sulfuric acid and zinc electrodeposition waste liquid.
Preferably, in the step (3), the supernatant is purified, copper in the supernatant enters purified copper-cadmium slag, and the copper-cadmium slag is leached out of zinc and cadmium and then enters the copper slag.
Preferably, the zinc roasted ore fraction in steps (1) and (2) is calculated by the following steps, zn 52-58% by weight, fe7-11% by weight, cu0.4-0.8% by weight, ge0.01-0.03% by weight.
The invention has the beneficial effects that:
the invention controls the leaching process to lead Fe 3+ The slag is added in a goethite form, the germanium enters the slag along with the slag, and the germanium can be precipitated into the slag at a lower pH value due to the slag entering of the goethite, so that the leaching rate of copper is improved while the germanium is precipitated, the copper and the germanium are thoroughly separated, the copper is efficiently leached, the consumption of manganese powder or hydrogen peroxide is not increased in the copper precipitation process, and the copper slag produced does not need to be separated into copper and germanium.
In the steps of removing iron and neutralizing, the low-valence iron is not leached out, and is leached out into Fe in the low-acid leaching process 2+ And then oxidized into ferric iron by manganese powder, and when the low-acid leachate returns to the step of removing iron, goethite is precipitated into slag to play a role in adsorbing germanium and arsenic.
In the invention, copper enters the supernatant without replacing copper with iron powder, thereby reducing the consumption of manganese powder or hydrogen peroxide and not increasing a replacement tank and a filter press.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Other embodiments that can be derived by those skilled in the art from the embodiments of the present invention without any creative effort are within the protection scope of the present invention.
The leaching process of the zinc roasted ore comprises the following steps:
(1) iron removal
Adding acid liquor, low-acid leachate and zinc roasted ore into a reaction tank continuously and simultaneously, wherein the acid liquor is 1 or 2 of dilute sulfuric acid and zinc electrodeposition waste liquor. The acid liquor, the low-acid leaching liquor and the zinc roasted ore are continuously and simultaneously added into a leaching tank, and the purpose is to control and stably leach Fe in ore pulp 3+ The maximum concentration and the pH value of (1). Controlling Fe in leached ore pulp 3+ The maximum concentration is less than or equal to 1000mg/L, the reaction temperature is controlled to be 80-85 ℃, and the pH value is controlled to be 3.0-4.0, the method for precipitating iron is changed from the neutralization hydrolysis method in the prior art to E.Z method, so that Fe brought in by low acid liquor 3+ Is precipitated in the form of goethiteThe slag is precipitated rather than the ferric hydroxide form of the prior art.
Controlled leaching of Fe from pulp 3+ The maximum concentration of (b) is particularly important when Fe 3+ At a maximum concentration of > 1000mg/L, fe 3+ Will precipitate as ferric hydroxide rather than goethite.
The E.Z method for precipitating iron is to use high-concentration Fe 3+ The solution is continuously added to the solution containing Fe 3+ Controlling Fe in ore pulp of reaction tank in ore pulp of low reaction tank 3+ Not more than 1000mg/L, and continuously feeding a neutralizing agent such as zinc roasted ore to neutralize acid released during iron removal, fe at a suitable temperature and pH value 3+ Precipitated as goethite. The reaction formula is as follows:
Fe 3+ +2H 2 O=FeO.OH↓+3H +
the goethite has strong adsorption capacity to germanium, arsenic and other ions in the solution, and a large amount of germanium, arsenic and other ions are adsorbed into slag by the goethite during iron removal, so that the aims of removing iron and impurities are fulfilled, and the pressure for removing germanium and arsenic during the neutralization step is reduced.
(2) Neutralization
Adding zinc roasted ore into the iron-removed ore pulp, and adjusting the pH value of the ore pulp to 4.5-4.8 to ensure that the residual Fe in the ore pulp 3+ Precipitating into slag. Because of Fe in ore pulp during iron removal 3+ Less than 1000mg/L, so that during neutralization, residual Fe in ore pulp 3+ Mainly precipitated in the form of goethite; because a large amount of germanium and arsenic ions are adsorbed into slag during iron removal, the pressure for removing germanium and arsenic during neutralization is reduced, when the pH value of ore pulp is controlled to be 4.5-4.8, the middle supernatant which meets the purification requirement can be produced, and when the pH value is controlled to be 4.5-4.8, copper in the middle supernatant can be kept at 1000mg/L, so that the purposes of precipitating germanium into slag and leading copper to enter the middle supernatant are achieved, and the copper and germanium in zinc roasting ore are thoroughly separated.
After the neutralized ore pulp is settled and separated, copper enters the middle supernatant, the middle supernatant is purified, the copper in the middle supernatant enters the purified copper-cadmium slag during purification, the copper-cadmium slag is leached out of zinc and cadmium by acid liquor, the copper is left in the slag, which is called copper slag, and the copper is recovered.
And the neutralization bottom flow is subjected to low-acid leaching. Because the germanium almost enters the bottom flow slag and the germanium content in the copper slag is only about 100-200 g/t, the copper slag does not need to be separated from the germanium, and the copper slag is sold or utilized by self.
The invention replaces the neutral leaching in the prior art with the steps of iron removal and neutralization, and the neutral leaching in the prior art is used for leaching Fe 3+ The precipitated form of (A) is changed from iron hydroxide to goethite, the goethite has a strong ability to adsorb impurities, and in step (B), the step (A) is performed
When iron is removed, a large amount of germanium and arsenic plasma precipitates can be adsorbed, so that the load of removing germanium and arsenic during neutralization is reduced, the middle supernatant meeting the purification requirement can be produced when the pH value at the end point of neutralization is 4.5-4.8, the germanium hydrolysis precipitation can be completed without controlling the pH value of the middle leaching to be 5.2-5.4 in the prior art, when the pH value at the end point of neutralization is 4.5-4.8, the copper in the middle supernatant can be kept at-1000 mg/L, the copper hydrolysis precipitation amount in the solution is small, and favorable conditions are created for effectively separating copper and germanium in zinc roasting ores.
(3) Low acid leaching
Adding zinc electrodeposition waste liquid into the neutralization bottom flow, adding manganese powder, controlling the process and the end point pH value to be 0.6-1.0, controlling the temperature to be 75-80 ℃, and controlling the time to be 2-4 h, so that zinc and copper in the neutralization bottom flow are leached, a large amount of germanium is left in the slag, after the low-acid leached ore pulp is settled and separated, filtering the bottom flow, returning the filtrate and the low-acid supernatant to the iron removal step, and sending the low-acid filter residue to a pyrometallurgical furnace kiln for treatment so as to recover the zinc and the germanium in the slag.
When the pH value of the iron-removing ore pulp is 3.0-4.0 and the pH value of the neutralizing ore pulp is 4.5-4.8, the low-valent iron in the zinc roasted ore cannot be leached, but the low-acid leaching process is leached, and Fe is used for leaching 2+ The form enters the solution, so manganese powder is added in low acid leaching to oxidize Fe 2+ 。
The iron hydrated oxides comprise ferric hydroxide, goethite, iron vanadium, hematite and the like, and the stability sequence in a dilute sulfuric acid solution is as follows: the iron hydroxide is more than goethite and more than hematite and iron vanadium. It can be seen that the iron hydroxide in the dilute sulfuric acid solution is the least stable, inferior goethite. Through determination: at the temperature of 85 ℃ and the pH value of 2.5, the ferric hydroxide is completely dissolved; at a temperature of 85 deg.CThe pH value is 0.5, and about 50-60% of goethite is dissolved when the reaction is carried out for 3 hours. When goethite dissolves, fe 3+ And the adsorbed and precipitated germanium, arsenic and the like also enter the solution again and are gradually enriched, and the Fe in the zinc roasted ore leaching system can be only obtained by periodically opening a circuit and leaching the solution with low acid 3+ And germanium, arsenic plasma, and the like, are kept in balance, so that it is very important to control the low acid leaching process and the end point pH value. Through a great deal of research, when the pH value of the low-acid leaching process and the end point is controlled to be 0.6, the temperature is 80 ℃, and the time is 4 hours, goethite is hardly dissolved, only a small amount of ferric hydroxide and basic ferric sulfate in the goethite are dissolved, and only a small amount of adsorbed germanium, arsenic and the like are dissolved, so that the requirement of Fe in the system is completely met 3+ And germanium and arsenic, but the pH value is higher than 1.0, when the leaching time is lower than 2 hours, the zinc content of the low-acid residue is increased, the residue rate is increased, the pH value in the low-acid leaching process and the end point is controlled to be 0.6-1.0 by combining the leaching rate of zinc, the temperature is 75-80 ℃, and the time is preferably 2-4 hours.
The zinc roasted ore contains ZnS, and when the low-acid leaching process and the end point pH value are 0.6-1.0, part of zinc ferrite in the zinc roasted ore can be promoted to react with ZnS, so that the zinc content in the low-acid leaching slag is reduced, and part of iron in the zinc ferrite is Fe 2+ Form is leached out, fe 2+ Then oxidized into Fe by manganese powder 3+ And when the leached iron returns to the step of removing iron along with the low acid liquor, goethite is generated to adsorb impurity ions such as germanium, arsenic and the like to precipitate.
The iron removal step requires a certain amount of Fe 3+ In an amount to generate enough goethite to adsorb impurity ions such as germanium, arsenic and the like for precipitation. Low acid leaching step Fe 3+ The amount of Fe produced is related to the content of Fe in the roasted zinc ore and the pH value, and Fe is produced when the content of Fe in the roasted zinc ore is high 3+ Much, fe generated when the pH is low 3+ And (4) a plurality of methods. Therefore, the Fe can be controlled by adjusting the pH value of low-acid leaching through the iron content of the zinc roasted ore 3+ The amount of the produced (A) is such that the amount of goethite required for adsorbing impurity ions such as germanium and arsenic during iron removal is satisfied.
In order to illustrate the present invention more clearly, the following examples are given for the purpose of illustration.
Example 1
The zinc roasted ore used in the present example mainly comprises the following components: zn52.31% wt, fe10.69% wt, cu0.78% wt, ge0.01% wt.
(1) Iron removal
Get and contain H 2 SO 4 230g/L dilute sulfuric acid, electrodeposition waste liquid, fe-containing 3+ After being uniformly mixed, 8.3g/L of low acid liquid is placed in a high-level bottle with an outlet valve; preparing a solution containing Zn160g/L, PH with the value of 3.0 by using industrial-grade zinc sulfate, placing the solution into a reaction tank to serve as a leached base solution, opening a high-position bottle valve to continuously add the prepared acid solution into the reaction tank after stirring, reacting at the temperature of 85 ℃, continuously adding zinc roasted ore according to the pH value of the leached ore pulp of 3.0, controlling the adding speed of the acid solution prepared in the high-position bottle, taking a small amount of ore pulp after adding the acid solution, filtering, and measuring Fe in the filtrate 3+ 550mg/L、Ge1.2mg/L、As3.2mg/L。
(2) Neutralization
Adding zinc roasted ore into the iron-removed ore pulp, adjusting the pH value to 4.5, wherein the neutralization time is 60min, and siphoning out supernatant after settling separation of the neutralized ore pulp, wherein the supernatant comprises the following components: zn155g/L, cu960mg/L, ge0.25mg/L and As0.2mg/L, purifying the middle supernatant, purifying copper and cadmium slag, leaching zinc and cadmium in the copper and cadmium slag by acid liquor to prepare copper slag, wherein the copper slag comprises the following components: cu60.52% wt, ge105g/t; the neutralization bottom stream is subjected to low-acid leaching.
(3) Low acid leaching
Adding zinc electrodeposition waste liquid and manganese powder into the neutralized underflow, controlling the pH value of the process and the end point to be 1.0, the temperature to be 75 ℃, the time to be 2 hours, leaching zinc and copper in the neutralized underflow, settling and separating low-acid leached ore pulp, siphoning out low-acid supernatant, filtering the underflow, wherein the components of filtrate and low-acid supernatant are Cu360mg/L and Fe 360mg/L, and the 3+ 8.6g/L, ge3.5mg/L, and returning to remove iron; the low-acid filter residue comprises 15.68 wt% of Zns, 25.79 wt% of Fes, 0.42 wt% of Cus and 0.0246 wt% of Ges, and is sent to a furnace kiln for treatment by a fire method. The leaching rate of copper is 79.06 percent by low acid filter residue, the rate of germanium entering the low acid filter residue is 98.22 percent, and the copper and the germanium are thoroughly separated.
Example 2
The zinc roasted ore used in the present example mainly comprises the following components: zn57.68% wt, fe7.23% wt, cu0.42% wt, ge0.028% wt.
(1) Iron removal
Get the product containing H 2 SO 4 230g/L dilute sulfuric acid containing Fe 3+ 7.8g/L of low acid liquid is prepared, mixed evenly and then placed in a high-level bottle with an outlet valve; preparing a solution containing Zn160g/L and PH4.0 by using industrial-grade zinc sulfate, placing the solution in a reaction tank as a leaching base solution, starting stirring, then opening a high-position bottle valve to continuously add the prepared acid solution into the reaction tank, reacting at 85 ℃, continuously adding zinc roasted ore according to the pH4.0 of leaching ore pulp, wherein the adding speed of the acid solution in the high-position bottle is 23mL/min, taking a small amount of ore pulp after adding the acid solution, filtering, and measuring Fe in the filtrate 3+ 320mg/L、Ge1.8mg/L、As3.9mg/L。
(2) Neutralization
Adding zinc roasted ore into the iron-removed ore pulp, adjusting the pH value to 4.8, wherein the neutralization time is 40min, and siphoning out the supernatant after settling separation of the neutralized ore pulp, wherein the supernatant comprises the following components: zn146g/L, cu570mg/L, ge0.28mg/L and As0.3mg/L, purifying the supernatant, purifying copper and cadmium slag, leaching zinc and cadmium in the copper and cadmium slag by acid liquor to prepare copper slag, wherein the copper slag comprises the following components: cu52.61% wt, ge192g/t; the neutralization bottom stream is subjected to low-acid leaching.
(3) Low acid leaching
Adding zinc electrodeposition waste liquid and manganese powder into the neutralized underflow, controlling the process and the end point pH value to be 0.6, the temperature to be 80 ℃, and the time to be 4 hours, leaching zinc and copper in the neutralized underflow, settling and separating low-acid leached ore pulp, siphoning out low-acid supernatant, filtering the underflow, wherein the components of filtrate and low-acid supernatant are Cu260mg/L, fe is 260mg/L, and 3+ 7.5g/L and Ge7.6mg/L, and returning to remove iron; the low-acid filter residue comprises Zn12.56 wt%, fe21.96 wt%, cu0.29 wt% and Ge0.083%, and is treated by a fire method and a kiln. The leaching rate of copper is 74.63 percent by the low-acid filter residue, the rate of germanium entering the low-acid filter residue is 97.96 percent, and the copper and germanium are completely separated.
Example 3
The zinc roasted ore used in the present example mainly comprises the following components: zn55.38 percent wt, fe8.29 percent wt, cu0.58 percent wt and Ge0.019 percent wt.
(1) Iron removal
Taking out of the accumulated waste liquid containing Fe 3+ 7.6g/L of low acid liquid is prepared, mixed evenly and then placed in a high-level bottle with an outlet valve; preparing a solution containing Zn of 160g/L and pH3.5 by using industrial-grade zinc sulfate, and placing the solution into a reaction tank to be used as a solutionStarting the leached bottom liquid, stirring, opening a valve of a high-position bottle, continuously adding the prepared acid liquid into the reaction tank, reacting at 80 ℃, continuously adding zinc roasted ore according to the pH value of leached ore pulp of 3.5, wherein the adding speed of the acid liquid prepared in the high-position bottle is 18mL/min, filtering a small amount of ore pulp after adding the acid liquid, and measuring Fe in the filtrate 3+ 420mg/L、Ge1.6mg/L、As2.1mg/L。
(2) Neutralization
Adding zinc roasted ore into the iron-removed ore pulp, adjusting the pH value to 4.6, neutralizing for 50min, settling and separating the neutralized ore pulp, and siphoning to obtain supernatant, wherein the supernatant comprises the following components: zn150g/L, cu740mg/L, ge0.22mg/L and As0.3mg/L, purifying the supernatant, purifying copper and cadmium slag, leaching zinc and cadmium in the copper and cadmium slag by acid liquor to prepare copper slag, wherein the copper slag comprises the following components: cu57.96% wt, ge136g/t; the neutralization bottom stream is subjected to low-acid leaching.
(3) Low acid leaching
Adding zinc electrodeposition waste liquid and manganese powder into the neutralized underflow, controlling the pH value of the process and the end point to be 0.8, the temperature to be 80 ℃, and the time to be 3 hours, leaching zinc and copper in the neutralized underflow, settling and separating low-acid leached ore pulp, siphoning out low-acid supernatant, filtering the underflow, wherein the components of filtrate and low-acid supernatant are Cu330mg/L and Fe 330mg/L 3+ 7.8g/L and Ge5.9mg/L, and returning to remove iron; the low-acid filter residue comprises 13.33 wt% of Zns, 23.05 wt% of Fes, 0.41 wt% of Cus and 0.0516% of Ges, and is sent to a furnace kiln for treatment. The leaching rate of copper is 75.86 percent by low-acid filter residue, the rate of germanium entering the low-acid filter residue is 98.04 percent, and the copper and the germanium are completely separated.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The leaching process of the zinc roasted ore is characterized by comprising the following implementation steps of:
iron removal
Acid liquor, low-acid leachate and zinc roasted oreContinuously and simultaneously adding the mixture into a reaction tank to control and leach Fe in ore pulp 3+ The maximum concentration of Fe, and controlling the reaction temperature and pH value to reduce Fe brought in the acid liquor 3+ Precipitating and adding slag;
neutralization
Adding zinc roasted ore into the iron-removed ore pulp, and adjusting the pH value of the ore pulp to ensure that residual Fe in the ore pulp 3+ Precipitating and feeding slag; and settling and separating the neutralized ore pulp to obtain a supernatant and a neutralized underflow, wherein copper enters the supernatant.
2. The process of leaching according to claim 1, wherein in steps (1) and (2), fe 3+ The form of the precipitated slag is goethite.
3. The process of claim 1, wherein the step (1) includes controlling the Fe in the leach pulp 3+ The maximum concentration is less than or equal to 1000mg/L.
4. The leaching process according to claim 1, wherein in the step (1), the reaction temperature is 80-85 ℃, and the pH value of the leaching ore pulp is 3.0-4.0.
5. The process of leaching according to claim 1, wherein in step (2), the pH of the pulp is adjusted up to 4.5-4.8.
6. The leaching process according to any one of claims 1 to 5, further comprising the step of
Low acid leach, go to step>
Adding zinc electrodeposition waste liquid into the neutralization underflow, adding manganese powder, controlling leaching conditions to leach zinc and copper in the neutralization underflow, leaving germanium in residues, settling and separating low-acid leaching ore pulp, filtering the underflow, returning filtrate and low-acid supernatant to the step of & lt/EN & gt>
。
7. The process of leaching according to claim 6, wherein in step (3), the leaching conditions are: the pH value of the process and the end point is 0.6-1.0, the temperature is 75-80 ℃, and the time is 2-4 h.
8. A leaching process according to claim 6, wherein in step (3), the low acid residue is sent to a pyro-kiln for treatment.
9. The leaching process according to claim 1, wherein in the step (3), the supernatant is purified, copper in the supernatant enters purified copper-cadmium slag, and the copper-cadmium slag is leached with zinc and cadmium, and then the copper enters the copper slag.
10. The leaching process according to claim 1, wherein the acid liquor in step (1) is one or both of dilute sulfuric acid and zinc electrodeposition waste liquor.
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Citations (5)
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|---|---|---|---|---|
| US4128617A (en) * | 1977-07-11 | 1978-12-05 | Newmont Exploration Limited | Treatment of zinc calcines for zinc recovery |
| CN102010995A (en) * | 2010-12-29 | 2011-04-13 | 株洲冶炼集团股份有限公司 | Method for increasing copper recovery rate in zinc hydrometallurgy process |
| CN104745810A (en) * | 2015-04-01 | 2015-07-01 | 昆明理工大学科技产业经营管理有限公司 | Treatment technique of copper-containing high-indium high-iron zinc sulfide concentrate |
| CN110093506A (en) * | 2019-04-09 | 2019-08-06 | 云南驰宏锌锗股份有限公司 | Valuable metal high efficiency extraction and its minimizing processing method in germanic zinc leaching residue |
| CN115029562A (en) * | 2022-01-05 | 2022-09-09 | 昆明理工大学 | Method for separating copper and germanium in zinc hydrometallurgy process |
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2022
- 2022-10-26 CN CN202211315283.XA patent/CN115896474A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128617A (en) * | 1977-07-11 | 1978-12-05 | Newmont Exploration Limited | Treatment of zinc calcines for zinc recovery |
| CN102010995A (en) * | 2010-12-29 | 2011-04-13 | 株洲冶炼集团股份有限公司 | Method for increasing copper recovery rate in zinc hydrometallurgy process |
| CN104745810A (en) * | 2015-04-01 | 2015-07-01 | 昆明理工大学科技产业经营管理有限公司 | Treatment technique of copper-containing high-indium high-iron zinc sulfide concentrate |
| CN110093506A (en) * | 2019-04-09 | 2019-08-06 | 云南驰宏锌锗股份有限公司 | Valuable metal high efficiency extraction and its minimizing processing method in germanic zinc leaching residue |
| CN115029562A (en) * | 2022-01-05 | 2022-09-09 | 昆明理工大学 | Method for separating copper and germanium in zinc hydrometallurgy process |
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