CN1125883C - High-purity zinc and its preparing process - Google Patents
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Abstract
The present invention relates to high purity zinc and a preparation method thereof. The high purity zinc comprises at least 99.998% of Zn, at most 0.0001% of impurities of Cu, Cd, Co, Ni, As, Sb, Cr and Hg, at most 0.0002% of Fe and at most 0.0010% of Pb. The high purity zinc uses various zinc minerals, such as ZnO, Zn (OH)2, ZnCO3, etc., which exist in a soluble zinc state and industrial zinc containing by-product materials as raw materials. The raw materials are leached in an ammonium-ammonia-water system and then are added with zinc powder for purification and impurity removal, and the purified liquid is electrodeposited by using inert pollution free product materials as anodes to prepare the high purity zinc. The whole technical process is carried out at normal temperature, and the high purity zinc has the advantages of simple technology, low energy consumption and good product quality.
Description
The invention relates to a method for preparing high-purity zinc metal by using zinc-containing minerals or zinc-containing materials of various industrial byproducts.
The high-purity zinc metal is mainly used for preparing mercury-free zinc powder for batteries and fluorescent materials for color kinescope, and has wide application prospect. But the zinc sulfate electrodeposition method generally adopted in the industrial production of various countries in the world can not produce high-purity zinc metal. Therefore, some people adopt the metal zinc produced in the current industry as the raw material and prepare the high-purity zinc metal by a vacuum distillation method, and the method has high energy consumption and high cost. Chinese patents 93104303.4 and 89102917.6 propose a process for preparing zinc by complex electrolysis using zinc-containing minerals or various industrial by-products, which comprises leaching zinc with ammonia chloride hot solution, purifying and electrodepositing, wherein the leaching temperature is 50-80 ℃, even 60-100 ℃, the whole process must be heated, the process is complex, the energy consumption is high, and the product contains only 99.90-99.98% of Zn (the 89102917.6 patent is only 99-99.3%), the total amount of impurities is more than 0.020%, wherein: 0.001-0.003 percent of Fe, 0.017 percent of Pb0.017 percent of Cu and 0.0002 percent of Cd and 0.0004 percent of Cu, which only meet the quality requirement of electrolytic metal zinc in general industrial production and can not be used for preparing mercury-free zinc powder for batteries and fluorescent materials for color kinescope at all.
The invention aims to provide a method for preparing high-purity zinc metal for preparing mercury-free zinc powder for batteries and fluorescent materials for color kinescope, in particular to a process method for preparing high-purity zinc metal by using zinc-containing minerals or zinc-containing materials of various industrial byproducts, and the process method has the advantages of short process flow, easy operation and control, low energy consumption, low cost and small environmental pollution.
In order to realize the purpose, the method adopts the technical scheme that: leaching zinc-containing material in ammonium-ammonia-water system with leaching agent (mol/L) of [ NH4 +]＝3～7，[NH3]1-4, wherein the liquid-solid ratio (weight) is 2-10: 1, the leaching temperature is 20-50 ℃, and the leaching time is 0.5-4 h; purifying the filtered leachate by using zinc powder, wherein the using amount of the zinc powder is 1.5-30 times of the theoretical amount, the purification temperature is 10-50 ℃, and the stirring purification time is 0.5-5 h; the purified liquid is subjected to electrodeposition to produce high-purity zinc metal, the voltage of an electrolytic cell is 2.5-3.5 v, the homopolar distance is 6-12 cm, and the cathode current density is 200-1000A/m2The electrodeposition temperature is 20-50 ℃, and the anode is made of inert material and does not pollute the product.
The ammonium-ammonia-water system adopted by the leaching method comprises an ammonium chloride-ammonia-water system, an ammonium sulfate-ammonia-water system or an ammonium carbonate-ammonia-water system.
The method adopts two-stage countercurrent purification for purifying and removing impurities by adding zinc powder, and filter residue obtained in the second stage of purification returns to the first stage of purification.
The anode material adopted in the electrodeposition of the method is high-purity graphite or a ruthenium-coated titanium plate.
The method of the invention has the advantages that the method does not use metal zinc as raw material, but uses industrial byproduct complex zinc material with high content of iron, chlorine (fluorine) or antimony (arsenic) and ZnO and Zn (OH)2、ZnCl2、ZnSO4、ZnCO3Zinc-containing materials in the form, such as: the zinc smelting plant fluidized bed furnace, rotary kiln soot, lead smelting plant by-product zinc oxide, iron (manganese) smelting blast furnace gas mud, zinc calcine, zinc oxide ore, and roasted hot galvanizing slag ash and zinc casting slag ash and the like directly prepare high-purity zinc metal, and the product quality reaches: zn is more than 99.998 percent, impurities of Cu, Cd, Co, Ni, As, Sb, Cr and Hg are less than 0.0001 percent, Fe is less than 0.0002 percent, and Pb is less than 0.0010 percent. The whole process of leaching, purification and electrodeposition is basically carried out at normal temperature, heating is not needed, the process flow is short and simple, the operation and control are easy, the energy consumption is low, the cost is low, the benefit is high, the environmental pollution is small, the product quality is good, and the high-purity zinc metal quality requirements of mercury-free zinc powder for producing green alkaline manganese batteries and fluorescent materials for color kinescopes can be met.
The technological process and the reaction principle of the invention are as follows:
firstly, leaching:
firstly, according to the requirements, the ammonium salt and ammonia are made into the aqueous solution of leaching agent, then the zinc-containing material is added into said ammonium-ammonia-water system solution to make leaching, and the zinc in the zinc-containing material is ZnO and Zn (OH)2、ZnCl2、ZnSO4、ZnCO3If the zinc in the zinc-containing material exists in the form of metallic zinc, the material is firstly roasted to convert the metallic zinc into soluble zinc compounds such as zinc oxide and the like, and then the soluble zinc compounds are added into a leaching agent solution for leaching. During leaching, zinc in the raw materialDissolving zinc with Zn (NH)3)i2+(i-4 is the main) complex ion form enters the solution (leachate), and impurities such as Cu, Cd, Co, Ni and the like are also Me (NH)3)j 2+(Me represents Cu, Cd, Co and Ni) complex ions enter the leaching solution, Fe, Mn, Cr, As, Sb, Hg, Sn, Pb, Bi and the like are not leached, and are left in residues to be removed by filtration. The leaching reaction is as follows:
during leaching, depending on the impurity content of the material, it is sometimes necessary to add oxidizing agents, such as: h2O2，KMnO4Will contain Fe2+Fe in the material2+To Fe3+For removal, the oxidizing agent is generally used in an amount of H2O20 to 50kg/t zinc, KMnO40 to 30kg/t zinc.
Secondly, a purification process:
the leaching solution also contains coordination ions Me (NH) of Cu, Cd, Co and Ni3)j 2+Therefore, zinc powdermust be added for replacement removal, and the chemical reaction formula is as follows:
during leaching of ammonium chloride-ammonia-water systems, part of Pb is present2+Formation of PbClk 2-kThe complex ions enter the leaching solution, and during purification, the Pb part enters the leaching solution2+Can be replaced by Zn and enters copper-cadmium slag to be removed, and the chemical reaction formula is as follows:
according to the amount of impurities in the raw materials, the adding amount of the zinc powder is 1.5-30 times of the theoretical amount of the reaction formula, and the granularity of the zinc powder is generally 0.175-0.104 mm. The purification process generally adopts multi-section purification, so that the two-section countercurrent purification has the best impurity removal effect, the first section of purification is followed by filtration, the purified liquid with copper and cadmium (lead) residues removed enters the second section of purification, and the filter residues of the second section of purification return to the first section of purification, so that the zinc powder can be saved. After purification, the content of impurity elements can be mostly reduced to below 1mg/L, and after filtration, the purified liquid is sent to electrodeposition.
Thirdly, an electrodeposition process:
during electrodeposition of the purified solution, the cathode material can be a conventional aluminum plate, or a stainless steel plate, or a titanium plate, and the anode material can be an inert material which does not pollute the product, such as: high-purity graphite is coated with insoluble materials such as ruthenium-titanium plates and the like so as to ensure the quality of high-purity zinc. The electrodeposition process reaction is as follows:
and (3) cathode reaction:
and (3) anode reaction:
(1) when an ammonium chloride-ammonia-water solution system is adopted, the reaction is as follows:
(2) when an ammonium sulfate (ammonium carbonate) -ammonia-water solution system is adopted, the reaction is as follows:
the current efficiency of the method is more than 90 percent, generally about 96 percent, and the concentration of zinc ions ([ Zn]in the electrolytic waste liquid2+]) And when the concentration is more than 10g/L, the electrodeposition waste liquid is returned to the leaching process after ammonia is supplemented.
Examples of the process of the present invention are as follows (the impurity content 1PPm in the examples is 0.0001%.
The zinc-containing material in example 1 is zinc oxide which is a byproduct of lead smelting, and the material comprises the following components (%), namely Zn 62.05, Pb 10.73, Cu 0.025, Sb 0.85, As 0.38 and Cd<0.001.
Ammonium chloride-ammonia-water system is adopted for leaching, and the leaching agent comprises the following components (mol/L): [ NH]4 +]＝5，[NH3]Weighing leaching agent 4L (2.7), weighing lead smelting byproduct zinc oxide 600g (6.67: 1), leaching for 2 hours at 30-40 deg.C for 1 hr, and adding H2O2(content: 30%) 10ml of the iron oxide contained therein. The leaching rate of zinc is 96.23 percent, and the leaching solution comprises the following components (g/L): zn 81.91, Cu 0.0043, Cd 0.0021, Pb 0.56, Co less than 0.001, Fe 0.00013, Ni less than 0.001. Purifying, namely adding zinc powder into 17 times (3g of zinc powder/L of leachate) of the theoretical amount of lead, and performing two-stage countercurrent purification, wherein the stirring time is 1h, and the temperature is 30-40 ℃, and the impurity content (mg/L) of the purification solution is as follows: cu 0.06, Cd 0.04, Co 0.08 and Ni 0.1. The purified liquid is electrodeposited by taking graphite as an anode, and the current density is 400A/m2The homopolar distance is 7cm, the electrodeposition temperature is 30-43 ℃, the cell voltage is 3.1v, and the waste electrolyte [ Zn]2+]12.03g/L, current efficiency 94.53%. Zinc content of zinc is more than 99.998%, impurity component (ppm): cu 0.87, Cd 0.080, Co 0.19, Pb 1.9, Ni 0.20, As 0.58, Cr 0.23, Fe 1.6, and the rest of Sb, Mn and Hg are all less than 1.
Example 2 the zinc-containing material is hot galvanizing slag ash, and the material components (%) are Zn 67.65, Cl 4.82, Pb 4.2 and Fe 2.5.
Most of zinc in the hot galvanizing slag ash exists in the form of metallic zinc, and the zinc is roasted at the temperature of 200-350 ℃ for 0.5-3 h and then leached. Ammonium chloride-ammonia-water system is adopted for leaching, and the leaching agent comprises the following components (mol/L): [ NH]4 +]＝7.0、[NH3]Weighing 1L of leaching agent, taking 160g ofroasting hot galvanizing slag ash, wherein the liquid-solid ratio is 6.25: 1, the leaching time is 0.5h, the temperature is 40-50 ℃, the leaching rate of zinc is 96.78%, and the leaching solution components (g/L): zn 95.87, Cu 0.0018, Cd 0.001, Pb 0.52, Co 0.0020 and Fe 0.00011. Purification 18 times the theoretical amount of lead (3g zinc powder/L leaching)Discharging liquid), adding zinc powder, stirring for 0.5h at 20-30 ℃, purifying in two sections, and then electrodepositing by taking a ruthenium-coated titanium plate as an anode with the current density of 1000A/m2The same polar distance is 10cm, the electrodeposition temperature is 28-40 ℃, the cell voltage is 3.5V, and the waste electrolyte [ Zn]2+]10.85g/L, current efficiency 96.17%. The total zinc content is more than 99.998 percent, and the impurity components (ppm): cu, Cd,Co, Ni, As, Sb, Bi, Mn, Cr and Hg are all less than 1, Fe1.7 and Pb is less than 5.
Example 3 the zinc containing material was zinc calcine, material composition (%): zn 52.56, Pb 1.84, Cu 0.82Fe 12.2. Ammonium chloride-ammonia-water system is adopted for leaching, and the leaching agent comprises the following components (mol/L): [ NH]4 +]＝3、[NH3]Weighing 1L of leaching agent and 200g of zinc calcine with the liquid-solid ratio of 5: 1 at 20-30 ℃, leaching for 4h, wherein the leaching rate of zinc is 89.7%, and the leaching solution comprises the following components (g/L): zn 87.02, Cu 1.37, Pb 0.029, Cd 0.12, Fe 0.00012. Adding zinc powder (3g/L of leaching solution) with the theoretical amount of 2.1 times of that of the copper and cadmium for purification, and stirring for 1.5 hours at the temperature of 35-45 ℃. The two-section purified liquid is electrodeposited by taking a ruthenium-coated titanium plate as an anode, and the current density is 400A/m2The same polar distance is 6cm, the electrodeposition temperature is 20-32 ℃, and the cell voltage is 3.0V. Waste electrolyte [ Zn2+]10.87g/L, the current efficiency is 97.12%. Zinc content of zinc is more than 99.998%, impurity component (ppm): cu 0.17Cd 0.087, Co 0.17, Pb 3.7, Ni 0.24, As 0.63, Sb 0.95, Fe 0.1, and the rest of Bi, Mn, Cr and Hg are all less than 0.05.
Example 4 the zinc-containing material is a lead smelting by-product zinc oxide, and the material comprises the following components (%): zn 62.05, Pb 10.73Cu 0.025, Cd 0.064, Sb 0.56, As 0.25.
Leaching by adopting an ammonium sulfate-ammonia-water system to prepare [ NH]4 +]＝6mol/L[NH3]Weighing 150g of lead smelting byproduct zinc oxide in a liquid-solid ratio of 6.67: 1 at the leaching temperature of 30-40 ℃ in 1L of 3mol/L leaching agent, adding 3mL of H after leaching for 1H2O2(the content is 30%), leaching is carried out for 0.5h, then filtering is carried out, the leaching rate of zinc is 92.23%, and the leaching solution components (g/L): zn 78.6, Cu 0.0029, Cd 0.074, Pb 0.005, Co<0.001. Adding 30 times of theoretical amount (0.3g zinc powder/L leaching) based on the total amount of Cu, Cd, Pb and CoDischarging liquid) zinc powder, and carrying out two-stage purification, wherein the stirring time is 1h and the temperature is 30-40 ℃. The purified solution was subjected to electrodeposition under the same conditions as in example 1 to discard the electrolyte [ Zn]2+]11.50g/L, current efficiency 92.10%. Zinc content of zinc is more than 99.998%, impurity component (ppm): cu 0.18, Cd 0.069, Co 0.16, Pb 0.3, Ni 0.36, As 0.48, Cr 0.10Fe 0.11, Sb 0.90, Mn less than 0.05 and Hg less than 0.05.
Example 5 the zinc containing material is zinc hydroxide slag, the material composition (%): zn 67.21, Pb 0.030, Fe 0.084, Cd 0.053, Cu 0.18, SO4 2-7.8。
Leaching by adopting an ammonium sulfate-ammonia-water system to prepare [ NH]4 +]＝5mol/L，[NH3]Weighing 160g of zinc hydroxide slag with the liquid-solid ratio of 6.25: 1 in 1L of 3.5mol/L leaching agent, leaching for 2h at the leaching temperature of 30-40 ℃,the leaching rate of zinc is 94.43%, zinc powder is added according to the amount of 18 times of theoretical amount (0.5g zinc powder/L leaching solution) of the total amount of Cu, Cd and Pb, the stirring time is 1.5h, the purification temperature is 25-35 ℃, two-stage purification is carried out, electrodeposition is carried out after purification, the anode material is graphite, and the cathode current density is 200A/m2The same polar distance is 6cm, the electrodeposition temperature is 20-35 ℃, the cell voltage is 2.86V, and the waste electrolyte [ Zn]2+]12.05g/L, current efficiency 96.65%. Zinc content of zinc is more than 99.998%, impurity component (ppm): cu 0.093, Cd 0.080, Co 0.14, Pb 0.23Ni 0.36, As 0.36, Cr 0.25, Fe 0.11, Sb 0.87, Mn less than 0.05, Hg less than 0.05.
Example 6 the zinc containing material was zinc oxide ore, material composition (%): zn 21.88, Pb 1.74, Cu0.01, Cd 0.29, Co 0.038 and Fe 13.53.
Leaching with ammonium carbonate-ammonia-water system to obtain [ NH]4 +]＝4mol/L，[NH3]Weighing 333g of zinc oxide ore as 4.0mol/L of leaching agent 1L, leaching for 4h at the liquid-solid ratio of 3: 1, wherein the leaching temperature is 20-35 ℃, and the leaching rate of zinc is 85.38%. Leachate component (g/L): zn 59.68, Cu 0.02, Cd 0.71, Co 0.012 and Pb 0.08. Zinc powder was added in an amount 4 times the theoretical amount of the total amount of Cu, Cd, Co and Pb (3g zinc powder/L of the leachate). Stirring for 2h, purifying at 35-45 ℃, and purifying the solution in two stagesCarrying out electrodeposition at 30-40 ℃ under the same conditions as in example 1, using a waste electrolyte [ Zn]2+]10.76g/L, zinc content>99.998%, impurity content (ppm): cu 0.83, Cd 0.72, Co 0.21, Pb 3.8, Ni 0.24, As 0.45, Cr 0.03, Fe 0.51, Sb 0.09 and Hg<0.05.
Claims (4)
1. A process for preparing high-purity Zn metal from ZnO and Zn (OH)2、ZnCl2、ZnSO4、ZnCO3The method is characterized in that the zinc-containing material is leached in an ammonium-ammonia-water system, and the leaching agent component (mol/L) is [ NH]4 +]＝3～7，[NH3]1-4, wherein the liquid-solid ratio (weight) is 2-10: 1, the leaching temperature is 20-50 ℃, and the leaching time is 0.5-4 h; purifying the filtered leachate by using zinc powder, wherein the using amount of the zinc powder is 1.5-30 times of the theoretical amount, the purification temperature is 10-50 ℃, and the stirring purification time is 0.5-5 h; the purified liquid is subjected to electrodeposition to produce high-purity zinc metal, the voltage of an electrolytic cell is 2.5-3.5 v, the homopolar distance is 6-12 cm, and the cathode current density is 200-1000A/m2The electrodeposition temperature is 20-50 ℃, and the anode is made of inert material and does not pollute the product.
2. The method of claim 1, wherein the ammonium-ammonia-water system comprises ammonium chloride-ammonia-water system, ammonium sulfate-ammonia-water system, or ammonium carbonate-ammonia-water system.
3. The method for preparing high purity zinc metal according to claim 1 or 2, characterized in that the purification and impurity removal by adding zinc powder adopts two-stage countercurrent purification, and the filter residue of the second stage purification is returned to the first stage purification.
4. The method for producing high purity zinc metal according to claim 1 or 2, wherein the anode material for electrodeposition is high purity graphite or ruthenium-coated titanium plate.
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| WO2002066708A1 (en) * | 2001-02-16 | 2002-08-29 | Tecnicas Reunidas, S.A. | Method for electrolytic production of ultra-pure zinc or zinc compounds from zinc primary and secondary raw materials |
| CN101818248A (en) * | 2010-05-28 | 2010-09-01 | 中南大学 | Method for deeply purifying zinc-ammonia leaching solution |
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| CN102212700A (en) * | 2011-05-31 | 2011-10-12 | 新干县金山化工厂 | Production method of high-purity anhydrous zinc chloride |
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| CN105349800B (en) * | 2015-11-18 | 2017-11-17 | 来宾华锡冶炼有限公司 | A kind of method and its purification tank of solution of zinc sulfate displacement removal of impurities |
| CN105586496B (en) * | 2016-03-29 | 2019-01-01 | 河南国玺超纯金属材料有限公司 | The technique of industrialized production high purity zinc |
| CN106119556A (en) * | 2016-06-27 | 2016-11-16 | 李果 | A kind of Application way of steel plant zinc smoke ash |
| CN106853982A (en) * | 2017-01-20 | 2017-06-16 | 河北长力金属制品有限公司 | A kind of preparation method of high-purity zinc oxide |
| CN108300855B (en) * | 2018-02-05 | 2019-11-15 | 彭勃 | A kind of process of the joint of double-flow containing zinc oxide leaching and mixed liquid electrolytic zinc |
| CN110616442A (en) * | 2018-06-20 | 2019-12-27 | 云南远大金业有限公司 | Ammonia process electrolytic recovery of zinc |
| CN113186394B (en) * | 2020-12-15 | 2023-03-03 | 云南宇菲工程设计有限责任公司 | Method for producing metal zinc by treating high-lead zinc-containing material by ammonia-ammonium method |
| CN114540879A (en) * | 2022-01-24 | 2022-05-27 | 吉首市金湘资源科技开发有限公司 | Method for deeply purifying electrolytic zinc by ammonia-chlorine method |
| CN115536055B (en) * | 2022-09-27 | 2023-08-18 | 昆明理工大学 | Method for preparing germanium dioxide from zinc hydrometallurgy inorganic germanium slag |
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| CN1046761A (en) * | 1989-04-29 | 1990-11-07 | 化工部天津化工研究院 | Zinc hydrometallurgy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046761A (en) * | 1989-04-29 | 1990-11-07 | 化工部天津化工研究院 | Zinc hydrometallurgy |
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