CN110079676B - Germanium-rich zinc oxide smoke dust gradient leaching process - Google Patents
Germanium-rich zinc oxide smoke dust gradient leaching process Download PDFInfo
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Abstract
The invention discloses a gradient leaching process of germanium-rich zinc oxide smoke dust, which relates to a process for efficiently leaching zinc and germanium from the germanium-rich zinc oxide smoke dust and synchronously controlling the iron valence state in a solution.
Description
Technical Field
The invention belongs to the technical field of wet metallurgy, relates to a gradient leaching process of germanium-rich zinc oxide smoke dust, and particularly relates to a process for efficiently leaching zinc and germanium from the germanium-rich zinc oxide smoke dust and synchronously controlling the iron valence state in a solution.
Background
Germanium is widely applied to the high-tech field due to unique physical and chemical properties, a germanium ore deposit which can be independently exploited exists in nature, at present, the recovery of germanium mainly comes from zinc smelting industry, germanium can be enriched in zinc leaching slag in the hydrometallurgical process of zinc blende, and the zinc leaching slag becomes an important resource for recovering gallium and germanium. The method for recovering germanium from the germanium-containing zinc leaching residue mainly comprises a pyrogenic reduction volatilization method and wet high-temperature high-acid leaching, and also comprises direct oxygen pressure leaching of germanium-containing zinc concentrate. For example, Yunnan Chihong zinc germanium GmbH adopts a conventional zinc smelting process and a fuming furnace zinc oxide process for volatilizing germanium; the method is characterized in that gallium and germanium in the slag are leached by a liquid sulfur dioxide reduction acid leaching method in Japan Millettia smelting plants, research work of sulfur dioxide high-pressure reduction leaching is carried out by Beijing mining and metallurgy research institute (research on high-pressure leaching of gallium and germanium from zinc leaching slag, nonferrous metals (smelting part), 2012 and 8 th), and a smelting process of sulfur dioxide high-pressure reduction leaching zinc leaching slag is established for effectively recovering valuable metals in zinc leaching slag by Yunnan Hualian zinc-indium limited company; the Guangdong Shaoguan Danxia smeltery adopts a direct two-end high-temperature acid leaching process of zinc sulfide concentrate (comprehensively recovering gallium, germanium and nonferrous metals from zinc leaching slag of the Danxia smeltery, 4 th stage in 2009).
However, because the prior zinc smelting process in China is mainly the conventional process, the raw material for extracting germanium is mainly germanium-containing zinc oxide smoke dust. The method for treating zinc oxide smoke dust containing germanium is an intermediate raw material mainly containing valuable metals such as zinc, lead, germanium, silver and the like, which is produced after zinc hydrometallurgy and lead pyrometallurgy slag are treated by a pyrogenic fuming volatilization method. However, long-term production practice shows that the recovery flow of germanium is long in the conventional zinc smelting process, the recovery rate of zinc and germanium in the zinc oxide containing germanium is low, and the zinc content is only about 85%; less than 60% of germanium. The low recovery rate of zinc and germanium mainly comprises the main existing forms of zinc in the germanium-containing zinc oxide smoke dust, such as zinc oxide, zinc sulfate, zinc sulfide and the like, more insoluble sulfides are present, the zinc oxide smoke dust has larger particles and uneven particle size, and the leaching rate of zinc and germanium is low by adopting a conventional treatment process. Therefore, how to improve the leaching rate of zinc and germanium and reduce the content of zinc and germanium in the final leaching residue (lead-silver residue) is a key link for restricting the recovery rate of zinc and germanium.
In order to improve the leaching rate of zinc and germanium, oxygen pressure leaching is an effective method, Chinese patent application No. 201711216573.8 discloses a method for recovering germanium from zinc oxide smoke dust, provides a two-stage countercurrent leaching process of I-stage normal-pressure low-temperature acid leaching and II-stage high-temperature oxygen pressure leaching, and simultaneously reduces the leaching solution by adopting sodium sulfite; the Chinese patent application number of 201810417628.X discloses a method for efficiently extracting zinc and germanium from zinc oxide smoke dust, provides a two-stage countercurrent leaching process of I-stage normal-pressure low-temperature acid leaching and II-stage oxygen-pressure low-temperature high-acid leaching, and reduces the temperature of II-stage oxygen-pressure leaching in comparison. The leaching rate of zinc and germanium can be greatly improved by oxygen pressure leaching, but compared with the normal pressure leaching process, the required equipment requirement is high, the concentration of ferric iron in the leaching solution is difficult to control, the influence of high-concentration ferric iron on the subsequent recovery of germanium from the leaching solution is large, and a special reduction process needs to be added to ensure that iron in the leaching solution is ferrous iron.
Therefore, how to realize the high-efficiency leaching of zinc and germanium from the germanium-rich zinc oxide smoke dust under a normal pressure system and synchronously control the iron valence state in the solution, and the method has important significance for simplifying the production process.
Disclosure of Invention
The invention aims to provide a germanium-rich zinc oxide smoke dust step leaching process aiming at the problem of low leaching rate of the traditional two-stage countercurrent leaching process flow, the traditional multi-stage leaching is adjusted to single-stage continuous step leaching, the leaching rate of zinc and germanium, the reduction of iron ions and the terminal acidity of a leaching solution are controlled step by step, the problems of high-efficiency leaching of zinc and germanium, control of ferric iron in the leaching solution and the like in the smelting process are solved, the process flow is simple, the energy consumption is low, the process is clean and environment-friendly, and the comprehensive recycling of resources is facilitated.
The process flow and the steps adopted for realizing the invention are as follows:
mixing germanium-rich zinc oxide smoke dust with a sulfur dispersant, adding water or washing liquor produced in the fifth step, performing size mixing, and performing mechanical activation through a wet ball mill to obtain finely ground ore pulp with the smoke dust granularity being less than 0.074 mm;
the known conventional zinc slag and lead slag containing rich germanium in zinc oxide are treated by a pyrogenic fuming volatilization method to obtain zinc-containing smoke dust, wherein the zinc-containing smoke dust contains 0.05-0.20 wt% of germanium and 2-8 wt% of sulfur except zinc and iron; the zinc hydrometallurgy electrolytic waste liquid is zinc sulfate aqueous solution which is produced by a known conventional zinc hydrometallurgy electrolytic process and contains 155-185 g/L sulfuric acid;
wherein the germanium-rich zinc oxide smoke dust is water or washing liquid = 1kg: 1.5-2.5L;
the sulfur dispersant is sodium lignosulfonate or calcium lignosulfonate; the mass ratio of the germanium-rich zinc oxide smoke dust to the sulfur dispersing agent is 1: 0.001-0.003;
secondly, mixing the finely ground ore pulp with the zinc hydrometallurgy electrolytic waste liquid, controlling the end point acidity to be 80-100 g/L and the reaction temperature to be 80-90 ℃, performing primary high-acid leaching, and overflowing the high-acid leaching ore pulp to a No. 1 oxidation leaching tank after reacting for 1-2 hours;
finely grinding ore pulp dry base, namely, zinc hydrometallurgy electrolysis waste liquid = 1kg: 9-11L;
adding the finely ground ore pulp into a No. 1 oxidation leaching tank, introducing oxygen with the volume concentration of 80-99.9%, and simultaneously adding the wet zinc smelting electrolytic waste liquid into a No. 2 oxidation leaching tank at a constant speed through a metering pump so as to maintain the acidity of the reaction in the No. 1 and No. 2 oxidation leaching tanks at 30-40 g/L and the reaction temperature of 80-90 ℃; performing secondary oxidation leaching on the high-acid leached ore pulp in a No. 1 oxidation leaching tank and a No. 2 oxidation leaching tank which are connected in series, and overflowing the oxidation leached ore pulp to a No. 1 neutralization leaching tank after reacting for 1.5-2.5 h;
finely grinding ore pulp dry base, namely 9-11L of peracid leaching ore pulp = 0.70-0.80 kg;
adding the finely ground ore pulp into a 1# neutralization leaching tank and a 2# neutralization leaching tank at a constant speed through a metering pump respectively to maintain the reaction pH value of 2.5-3.5 in the 1# neutralization leaching tank, the 2# neutralization leaching tank and the 3# neutralization leaching tank at a reaction temperature of 80-90 ℃; carrying out three-stage neutralization leaching on the oxidized leached ore pulp in serially connected 1#, 2# and 3# neutralization leaching tanks, reacting for 2.0-3.0 h, and then overflowing the neutralized leached ore pulp to a thickener to produce zinc-germanium leachate containing ferric iron less than 30mg/L and underflow;
wherein, the dry basis of the finely ground ore pulp is that the oxidizing leaching ore pulp is = 0.60-0.70 kg and 9-11L;
fifthly, performing filter pressing on the underflow, performing low-temperature slurrying, acid washing and centrifugal filtration on filter pressing residues to produce zinc and germanium containing washing liquor, leaching final slag containing 6-10 wt% of zinc, 0.02-0.03 wt% of germanium and 1-3 wt% of iron, and returning the washing liquor after acid washing to the first step for mechanically activating, finely grinding and size mixing to leach the final slag, namely the traditional wet-process zinc-smelting lead-silver slag;
wherein the dry basis of the medium-pressure filter residue obtained by low-temperature slurrying and acid washing is washing liquid = 0.65-0.85 kg and 3-4L, and the washing liquid is sulfuric acid solution with pH = 1.5-2.5.
The invention has the beneficial effects that:
according to the invention, the high-efficiency leaching of the germanium-rich zinc oxide smoke dust is realized by a method of continuous step leaching and step-by-step control; ferric oxide is leached and decomposed by using peracid, and certain ferric ions are provided and used as an oxidant carrier required by sulfide oxidation; the method comprises the steps of decomposing sulfides by oxidative leaching, promoting oxygen transfer by means of iron ions provided by peracid leaching, improving the solution oxygen potential, oxidizing, converting and leaching indissolvable sulfides, and simultaneously adopting two-stage control in the oxidative leaching process, wherein firstly, oxygen is used for oxidizing iron into ferric iron in a No. 1 oxidative leaching tank, the sulfides in smoke are oxidized synchronously, secondly, the reaction of the ferric iron and the sulfides in the smoke is realized in a No. 2 oxidative leaching tank, and most of the ferric iron is reduced into ferrous iron synchronously; and (3) adjusting the end-point acidity of the leachate by utilizing neutralization leaching, and simultaneously precipitating the unreduced ferric iron in the solution in a goethite-like form, so as to ensure that the acidity and ion concentration of the produced solution meet the requirement of subsequent separation and recovery of germanium. Compared with the prior art, the method has the following advantages:
(1) the leaching rate of zinc and germanium is high. Adding the ore pulp obtained by finely grinding the zinc oxide smoke dust into a leaching system step by step in batches, wherein the smoke dust amount required in the early reaction stage is large, and the smoke dust amount required in the later reaction stage is small, so that most raw materials undergo the processes of high-acid leaching and oxidation leaching instead of the traditional process of firstly performing weak-acid (the end point pH is 1.5-3.5) leaching, thereby strengthening the leaching condition and being beneficial to the efficient leaching of zinc and germanium in the smoke dust; meanwhile, the amount of iron deposited is small due to the later-stage neutralization leaching, and the amount of smoke and dust required by the neutralization is small, so that the amount of slag is small, the content of zinc and germanium in the final leached slag is low, and compared with the traditional process that the weak acid (the end point pH is 1.5-3.5) leaching is firstly carried out in the first stage and then the high acid leaching is carried out, the leaching rate can be improved by about 10 percent;
(2) easy separation of zinc, germanium and iron. Reducing ferrous iron by a continuous cascade leaching method, and then performing neutralization leaching to gradually realize reduction of iron ions and control of pH of a leaching solution, wherein the amount of ferric iron in the neutralization process is small, so that the amount of leaching residues is reduced, the amount of zinc oxide smoke dust required by the neutralization leaching is reduced, the ferric iron in the obtained leaching solution is less than 30mg/L, the pH value is 2.5-3.5, and the subsequent precipitation and recovery of germanium from the leaching solution are facilitated;
(3) the process and the equipment are simple. The invention adopts the normal pressure leaching process, controls the leaching in a stage, does not need a pressurized reaction kettle, and simplifies the process compared with the normal pressure-pressurized combined process; compared with the traditional multistage countercurrent leaching process, the method saves the liquid-solid separation operation among the leaching processes of each stage, simplifies the flow and equipment, and has simple operation and easy process control.
Drawings
FIG. 1 is a process flow diagram of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the above-described examples.
Example 1:
the main components of the zinc oxide smoke dust rich in germanium provided by a certain factory are as follows: 45.33wt% of Zn, 3.22 wt% of Fe, 2.05 wt% of S, 13.89 wt% of Pb13, 1972g/t of Ge, and the electrolytic waste liquid of zinc hydrometallurgy comprises the following main components: h2SO4: 155g/L、Zn: 46g/L；
Mixing 1.67kg of germanium-rich zinc oxide smoke dust with 3g of sodium lignosulfonate, adding 3L of water, and mechanically activating by a wet ball mill to obtain finely ground ore pulp with the smoke dust granularity of less than 0.074 mm;
secondly, adding 11L of zinc hydrometallurgy electrolytic waste liquid into 1kg of finely ground ore pulp dry basis, mixing the finely ground ore pulp and the zinc hydrometallurgy electrolytic waste liquid, controlling the end point acidity to be 100g/L, controlling the reaction temperature to be 80 ℃, performing primary high-acid leaching, and overflowing the high-acid leaching ore pulp to a No. 1 oxidation leaching tank after reacting for 1.5 hours;
thirdly, according to the mixing ratio of 0.80kg of finely ground ore pulp dry basis and 11L of high-acid leaching ore pulp, adding the finely ground ore pulp into a No. 1 oxidation leaching tank, introducing oxygen with the oxygen volume concentration of 99.9%, simultaneously adding the zinc hydrometallurgy electrolysis waste liquid into a No. 2 oxidation leaching tank at a constant speed through a metering pump so as to maintain the acidity of the reaction in the No. 1 and No. 2 oxidation leaching tanks to be 40g/L, keeping the reaction temperature to be 90 ℃, carrying out secondary oxidation leaching on the high-acid leaching ore pulp, and overflowing the oxidation leaching ore pulp to a No. 1 neutralization leaching tank after reacting for 2 hours;
adding the finely ground ore pulp into 1# and 2# neutralizing leaching tanks at constant speed through a metering pump according to the mixing ratio of 0.67kg of finely ground ore pulp dry basis and 11L of oxidizing leaching ore pulp to maintain the reaction pH value in the 1#, 2# and 3# neutralizing leaching tanks to be 2.5, the reaction temperature is 85 ℃, performing three-stage neutralizing leaching on the oxidizing leaching ore pulp in the 1#, 2# and 3# neutralizing leaching tanks connected in series, overflowing the neutralizing leaching ore pulp to a thickener after reacting for 2 hours, and producing zinc-germanium leaching solution (sent to a subsequent germanium precipitation section) containing ferric iron of less than 30mg/L and underflow;
fifthly, performing pressure filtration on the underflow to obtain 0.65kg of filter-pressing residue (dry basis), mixing the filter-pressing residue with 3L of acid washing water with the pH =1.5, performing low-temperature slurrying, acid washing and centrifugal filtration to produce leaching final slag containing zinc and germanium washing liquor, 6.1wt% of zinc, 0.03wt% of germanium and 1.1wt% of iron, wherein the washing liquor is used for the first step of the example 2, and the leaching final slag is zinc-lead-silver slag (traditional wet smelting);
the leaching rate of zinc in the whole process is 94.1 percent, and the leaching rate of germanium is 93.3 percent.
Example 2:
the main components of the zinc oxide smoke dust rich in germanium provided by a certain factory are as follows: 47.26wt% of Zn, 5.03 wt% of Fe, 7.98wt% of S, 12.57 wt% of PbO, and 506g/t of Ge, wherein the electrolytic waste liquid from the zinc hydrometallurgy comprises the following main components: h2SO4: 185g/L、Zn: 53g/L；
Mixing 1.7kg of germanium-rich zinc oxide smoke dust with 5g of calcium lignosulfonate, adding 4L of washing liquor obtained in the step 1 for size mixing, and mechanically activating by a wet ball mill to obtain finely ground ore pulp with the smoke dust granularity of less than 0.074 mm;
secondly, adding 9L of zinc hydrometallurgy electrolytic waste liquid into 1kg of finely ground ore pulp dry basis, mixing the finely ground ore pulp and the zinc hydrometallurgy electrolytic waste liquid, controlling the end point acidity to be 90g/L, controlling the reaction temperature to be 90 ℃, performing primary high-acid leaching, and overflowing the high-acid leaching ore pulp to a No. 1 oxidation leaching tank after reacting for 1 h;
thirdly, according to the mixing ratio of 0.78kg of finely ground ore pulp dry basis and 9L of high-acid leaching ore pulp, adding the finely ground ore pulp into a No. 1 oxidation leaching tank, introducing oxygen with the oxygen volume concentration of 89%, simultaneously adding the zinc hydrometallurgy electrolytic waste liquid into a No. 2 oxidation leaching tank at a constant speed through a metering pump so as to maintain the acidity of the reaction in the No. 1 and No. 2 oxidation leaching tanks to be 34g/L, keeping the reaction temperature to be 85 ℃, performing secondary oxidation leaching on the high-acid leaching ore pulp in the No. 1 oxidation leaching tank and the No. 2 oxidation leaching tank which are connected in series, and overflowing the oxidation leaching ore pulp to the No. 1 neutralization leaching tank after reacting for 2.5 hours;
fourthly, according to the mixing proportion of 0.70kg of finely ground ore pulp dry basis and 9L of oxidation leaching ore pulp, uniformly adding the finely ground ore pulp into the 1# and 2# neutralization leaching tanks through a metering pump to maintain the reaction pH value in the 1# and 2# neutralization leaching tanks to be 3.5, the reaction temperature is 80 ℃, carrying out three-stage neutralization leaching on the oxidation leaching ore pulp in the 1# and 2# and 3# neutralization leaching tanks connected in series, overflowing the neutralization leaching ore pulp to a thickener after reacting for 3h, and producing leaching solution (a subsequent germanium precipitation section) containing trivalent iron less than 30mg/L of zinc and germanium and underflow;
fifthly, performing pressure filtration on the underflow to obtain 0.85kg of filter-pressing residues (dry basis), mixing the filter-pressing residues with 4L of acid washing water with the pH =2.5, performing low-temperature slurrying, acid washing and centrifugal filtration to produce leaching final residues containing zinc and germanium washing liquor, 9.91wt% of zinc, 0.02wt% of germanium and 1.7wt% of iron, wherein the washing liquor is used for the first step in the example 3, and the leaching final residues (traditional wet zinc-lead-silver smelting residues);
the leaching rate of zinc in the whole process is 90.5 percent, and the leaching rate of germanium is 82.2 percent.
Example 3:
the main components of the zinc oxide smoke dust rich in germanium provided by a certain factory are as follows: 47.17wt% of Zn, 4.03 wt% of Fe, 6.45 wt% of S, 11.96 wt% of Pb11, 721g/t of Ge and the main components of the zinc hydrometallurgy electrolytic waste liquid are as follows: h2SO4: 165g/L、Zn: 49g/L；
Mixing 1.6kg of germanium-rich zinc oxide smoke dust with 1.6g of sodium lignosulfonate, adding 3.4L of washing liquor obtained in the step 2, performing size mixing, and performing mechanical activation through a wet ball mill to obtain fine ground ore pulp with the smoke dust granularity of less than 0.074 mm;
secondly, adding 10L of zinc hydrometallurgy electrolytic waste liquid into 1kg of finely ground ore pulp dry basis, mixing the finely ground ore pulp and the zinc hydrometallurgy electrolytic waste liquid, controlling the end point acidity to be 80g/L, controlling the reaction temperature to be 85 ℃, performing primary high-acid leaching, and overflowing the high-acid leaching ore pulp to a No. 1 oxidation leaching tank after reacting for 2 hours;
thirdly, according to the mixing ratio of 0.70kg of finely ground ore pulp dry basis and 10L of high-acid leaching ore pulp, adding the finely ground ore pulp into a No. 1 oxidation leaching tank, introducing oxygen with the oxygen volume concentration of 80%, simultaneously adding the zinc hydrometallurgy electrolytic waste liquid into a No. 2 oxidation leaching tank at a constant speed through a metering pump so as to maintain the reaction acidity in the No. 1 and No. 2 oxidation leaching tanks at 30g/L and the reaction temperature of 80 ℃, performing secondary oxidation leaching on the high-acid leaching ore pulp in the No. 1 oxidation leaching tank and the No. 2 oxidation leaching tank which are connected in series, and overflowing the oxidation leaching ore pulp to the No. 1 neutralization leaching tank after reacting for 1.5 hours;
fourthly, according to the mixing proportion of 0.60kg of finely ground ore pulp dry basis and 10L of oxidation leaching ore pulp, uniformly adding the finely ground ore pulp into the 1# and 2# neutralization leaching tanks through a metering pump to maintain the reaction pH value in the 1# and 2# neutralization leaching tanks to be 3.1, the reaction temperature is 90 ℃, carrying out three-stage neutralization leaching on the oxidation leaching ore pulp in the 1# and 2# and 3# neutralization leaching tanks connected in series, reacting for 2.5 hours, and then overflowing the neutralization leaching ore pulp to a thickener to produce zinc-germanium leachate (sent to a subsequent germanium precipitation section) containing ferric iron of less than 30mg/L and underflow;
and fifthly, performing pressure filtration on the underflow to obtain 0.78kg of filter-pressing residue (dry basis), mixing the filter-pressing residue with 3.4L of acid washing water with the pH =2.1, performing low-temperature slurrying, acid washing and centrifugal filtration to produce leaching final slag containing zinc and germanium washing liquor, 8.9wt.% of zinc, 0.027wt.% of germanium and 2.9wt.% of iron, wherein the washing liquor is used in the next size mixing step, and the leaching final slag is traditional wet zinc-lead-silver smelting slag.
The leaching rate of zinc in the whole process is 91.2 percent, and the leaching rate of germanium is 84.3 percent.
Claims (2)
1. A gradient leaching process for germanium-rich zinc oxide smoke dust is characterized by comprising the following steps:
mixing germanium-rich zinc oxide smoke dust with a sulfur dispersant, adding water or washing liquor produced in the fifth step, performing size mixing, and performing mechanical activation through a wet ball mill to obtain finely ground ore pulp with the smoke dust granularity being less than 0.074 mm;
secondly, mixing the finely ground ore pulp with the zinc hydrometallurgy electrolytic waste liquid, controlling the end point acidity to be 80-100 g/L and the reaction temperature to be 80-90 ℃, performing primary high-acid leaching, and overflowing the high-acid leaching ore pulp into a No. 1 oxidation leaching tank after reacting for 1-2 hours;
adding finely ground ore pulp into a No. 1 oxidation leaching tank, introducing oxygen with the volume concentration of 80-99.9%, and simultaneously adding the wet zinc smelting electrolytic waste liquid into a No. 2 oxidation leaching tank at a constant speed through a metering pump so as to maintain the acidity of the reaction in the No. 1 and No. 2 oxidation leaching tanks at 30-40 g/L and the reaction temperature of 80-90 ℃; performing secondary oxidation leaching on the high-acid leached ore pulp in a No. 1 oxidation leaching tank and a No. 2 oxidation leaching tank which are connected in series, and overflowing the oxidation leached ore pulp to a No. 1 neutralization leaching tank after reacting for 1.5-2.5 h;
adding the finely ground ore pulp into a 1# neutralization leaching tank and a 2# neutralization leaching tank at a constant speed through a metering pump respectively to maintain the reaction pH value of 2.5-3.5 in the 1# neutralization leaching tank, the 2# neutralization leaching tank and the 3# neutralization leaching tank at a reaction temperature of 80-90 ℃; carrying out three-stage neutralization leaching on the oxidized leached ore pulp in serially connected 1#, 2# and 3# neutralization leaching tanks, reacting for 2.0-3.0 h, and then overflowing the neutralized leached ore pulp to a thickener to produce zinc-germanium leachate containing ferric iron less than 30mg/L and underflow;
fifthly, performing filter pressing on the underflow, performing low-temperature slurrying, acid washing and centrifugal filtration on filter pressing residues to produce zinc and germanium containing washing liquor, leaching final slag containing 6-10 wt% of zinc, 0.02-0.03 wt% of germanium and 1-3 wt% of iron, returning the washing liquor after acid washing to the step (I) for mechanical activation and fine grinding and size mixing, wherein the leaching final slag is the traditional wet zinc-lead-silver smelting slag
1.5-2.5L of water or washing liquid as the germanium-rich zinc oxide smoke dust in the step I, wherein the sulfur dispersing agent is sodium lignosulfonate or calcium lignosulfonate; the mass ratio of the germanium-rich zinc oxide smoke dust to the sulfur dispersing agent is 1: 0.001-0.003;
in the step II, finely ground ore pulp dry basis is 9-11L of wet zinc smelting electrolytic waste liquid 1 kg;
in the step III, the dry basis of the finely ground ore pulp is 0.70-0.80 kg of high-acid leached ore pulp and 9-11L;
in the step IV, oxidizing leached ore pulp is 0.60-0.70 kg and 9-11L as a dry basis of the finely ground ore pulp;
in the fifth step, the low-temperature slurrying and acid washing medium-pressure filter residue dry basis is that the washing liquid is 0.65-0.85 kg and 3-4L, and the washing liquid is sulfuric acid solution with the pH value of 1.5-2.5.
2. The germanium-rich zinc oxide soot step leach process of claim 1, wherein: the zinc oxide smoke dust rich in germanium is zinc-containing smoke dust obtained when zinc slag is smelted by a wet method and lead slag is smelted by a fire method and treated by a fire fuming volatilization method, wherein the zinc-containing smoke dust contains 0.05-0.20 wt% of germanium and 2-8 wt% of sulfur except zinc and iron; the zinc hydrometallurgy electrolytic waste liquid is zinc sulfate aqueous solution containing 155-185 g/L of sulfuric acid and produced by a zinc hydrometallurgy electrolytic process.
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| CN113621836B (en) * | 2021-08-13 | 2023-01-13 | 衢州华友钴新材料有限公司 | Method for selectively precipitating germanium from acidic solution containing cobalt, nickel, germanium and iron |
| CN113755699A (en) * | 2021-08-17 | 2021-12-07 | 西部矿业股份有限公司 | Method for opening circuit of surplus acid radicals in oxygen pressure leaching process by lead-containing smoke dust |
| CN113832346B (en) * | 2021-09-16 | 2023-07-21 | 云南驰宏资源综合利用有限公司 | Method for efficiently and simply treating germanium-containing zinc leaching residues |
| CN115216651A (en) * | 2022-09-06 | 2022-10-21 | 昆明冶金研究院有限公司 | Method for efficiently recycling zinc and germanium in zinc oxide smoke dust |
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