CN1239720C - Method for producing high purity metal zinc from zinc oxide ore - Google Patents
Method for producing high purity metal zinc from zinc oxide ore Download PDFInfo
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- CN1239720C CN1239720C CNB031167543A CN03116754A CN1239720C CN 1239720 C CN1239720 C CN 1239720C CN B031167543 A CNB031167543 A CN B031167543A CN 03116754 A CN03116754 A CN 03116754A CN 1239720 C CN1239720 C CN 1239720C
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- oxide ore
- zinc oxide
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Abstract
The present invention discloses a method for producing high-purity metal zinc from zinc oxide ore, which relates to a technique for producing the high-purity metal zinc by using the zinc oxide ore with low grade as a raw material. Firstly, the zinc oxide ore is pulverized to 0.1 to 1mm, then the zinc oxide ore is leached by strong alkali solution, and the zinc and lead in the zinc oxide ore are leached out at 10 to 100 DEG C by slow stir for 60 to 100 minutes; then, leached liquid is filtered, filter residue is discharged and used for making bricks or being buried, and filter liquor containing the zinc and the lead is left; then, a separating agent as 0.1 to 5 times (molar ratio) as the content of the lead is added in the filter liquor, the filter liquor is stirred for 60 to 100 minutes, and the filter liquor containing zinc is electrolyzed directly after precipitate containing the lead is separated by filtration; finally, metal zinc with the purity above 99.95 percent deposits on a cathode and is obtained, and the solution is returned to the procedure of leaching by the alkali solution after electrolysis ends. The present invention has the advantages of simple and controllable process, wide source of raw materials, low cost and low energy consumption; the production cost of the present invention is less than half of the cost of the prior art, no environment pollution is generated, and comprehensive utilization can be realized; thereby, the present invention has large economical benefits and social benefits.
Description
Technical field
The present invention relates to a kind of technology that adopts low-grade zinc oxide ore as raw material production high purity metal zinc.
Technical background
High purity metal zinc is of many uses, can be used for alloyage (as brass, bronze, zinc alloy for die casting etc.), galvanized iron, drying battery, pyrotechnics, zine plate, chemical reagent etc.The zinc powder that makes with high purity metal zinc is a strong reductant, can be used for the smelting of organic synthesis, dyestuff preparation and gold and silver etc.At present, the production of traditional both at home and abroad high purity metal zinc all is to adopt that to contain the high-grade zink sulphide (sphalerite) of zinc 40% or more be raw material, by comprising these steps acquisitions of zink sulphide roasting-acidleach-removal of impurities-sour electrolysis, is commonly called as acid system production zinc.But on the one hand, this high-grade zink sulphide (being zinc sulfide ore) reserves are fewer and feweri, belong to deficient mineral products.On the other hand, though above-mentioned zink sulphide roasting-acidleach-removal of impurities-sour electrolysis process, finally can obtain purity at negative electrode is metallic zinc more than 99.95%.But there are many problems in this technology.At first be to produce a large amount of sulfurous gas in the roasting process, even adopt the partially recycled sulfurous gas of relieving haperacidity method, the environmental pollution that causes in roasting process also is quite serious.The secondth, the pickling liquor removal of impurities stage: after the mining vitriol oil leaching of roasting, the impurity in the ore deposit comprises that lead, copper, iron, calcium etc. enter in the solution with zinc basically.Separate these impurity from leaching liquid, flow process is extremely complicated, and process is restive, needs to consume a large amount of zinc powders and other compound simultaneously.In and during deironing because the carrying secretly of ironic hydroxide, the loss of zinc also is quite big.The 3rd is electrolysis stage.In this stage, necessary strict control current density allow outage anything but, otherwise the metallic zinc that electrolysis is come out can be dissolved in the electrolytic solution again.In addition, electrolytic solution can not chloride ion-containing, otherwise negative plate is very easily burnt plate, makes it to scrap.In addition,, contain 7800 yuans/ton of No. two metallic zinc prices of zinc more than 99.95% on the world market at present from cost value, and the zinc that adopts above-mentioned traditional acid system to produce, single production cost just reaches 8200 yuans/ton.More seriously, traditional acid system can only adopt and contain the zink sulphide of zinc more than 40% and make raw material, otherwise cost is higher.Yet the reserves of this higher-grade zink sulphide are quite deficient, and the difficulty of purchasing on the market is increasing at home, causes many zinc smeltery to close down.
Except zink sulphide, another zinc resource is a zinc oxide ore.According to the preliminary investigation of this seminar with Yunnan Province relevant department, the zinc oxide ore storage capacity in Shekinah south is at least in 1,000,000 tons of metallic zinc, in addition the zinc oxide ore storage capacity on ground such as Guizhou, Sichuan is also very abundant in addition.So the Application and Development zinc oxide ore is significant.Yet, because below, make the utilization of zinc oxide ore both domestic and external (comprising zincite, smithsonite) fail for a long time to implement.In general, zinc oxide ore is siliceous very high, produces colloid silicic acid during the acid dissolving, and leaching liquid can't effectively be separated with the leaching slag.In addition, the main mineral of zinc oxide ore are smithsonite.This ore deposit one runs into acid, produces a large amount of carbon dioxides immediately, and leaching can't be gone on.Simultaneously, it is lower that zinc oxide ore contains zinc, and generally about 30%, the overwhelming majority adopts the acid system leaching between 10-20%, and acid consumption is too big, and production cost is high.Can think that acid system should not be applied to the smelting of zinc oxide ore.
For this reason, the domestic zinc vertical retorting method that has many zinc smeltery to adopt country to prohibite is smelted zinc oxide ore.Even like this, the zinc content of the zinc oxide ore that is adopted is at least more than 30%, otherwise production cost is too high.The principle of zinc vertical retorting is that zinc oxide ore and coke are mixed together, and at high temperature makes zn cpds be reduced into metallic zinc, and zinc just is evaporated with the lower metallic zinc form of boiling point.The metallic zinc that is evaporated is oxidized to zinc oxide fumes again in cooling, collection process.Also has iron etc. with what metallic zinc was evaporated.Therefore, in the zinc oxide fumes of collecting, contain zinc and be about 60-80%.Then, with the raw material production high purity metal zinc of this zinc oxide fumes as acid system zinc metallurgy.In this production process, the total yield of zinc is lower than 60%, and the wasting of resources, environmental pollution are quite serious.
Summary of the invention
The objective of the invention is to disclose the method for a kind of technology usefulness low-grade zinc oxide ore simple, with low cost as raw material production high purity metal zinc.
In order to achieve the above object, the present invention is performed such.The contriver finds that through studying for a long period of time zinc has very high-dissolvability in strong base solution.Designed a kind of production method of brand-new high purity metal zinc for this reason.At first, select cheap, resourceful zinc content at the low-grade zinc oxide ore below 30% as raw material.This zinc oxide ore mainly comprises smithsonite and zincite.The main component in these two kinds of ore deposits is respectively zinc carbonate and zinc oxide, and they all are soluble in the strong base solution.Concrete steps are as follows: at first, the raw material zinc oxide ore is crushed to 0.1-1mm.Then, leach with strong base solution: above-mentioned raw materials is immersed in the strong base solution that concentration is 1-10mol/L, and its proportioning is that 1 ton of ore deposit needs 1-10 cubic meter strong base solution, and (120 rev/mins) stirred after 60-100 minute at a slow speed, the zinc in the zinc oxide ore and plumbous dissolved.Then, filter, the filter residue discharging stays the filtrate of containing zinc, lead.Subsequent again, in filtrate, add separating agent, the add-on of separating agent is 0.1-5 times (mol ratio) of lead content in the filtrate, separating agent is sodium sulphite, sulfuration ammonia, sulfurated lime, hydrogen sulfide, magnesium sulfide sulfides and thiosulphate, can be singly with also using by a plurality of mixing of arbitrary proportion.Stirring reaction 60-100 minute, filter, isolate post precipitation, the remaining zinc filtrate that contains is directly carried out electrolysis, be characterized in: the temperature with the strong base solution leaching is 95-100 ℃; Last on negative electrode deposition to obtain purity be 99.95% metallic zinc.After electrolysis finished, remaining solution directly was circulated in next leaching flow process.
The present invention has following advantage:
1. because the present invention is dissolved in filtrate with strong base solution with the zinc in the raw material zinc oxide ore, plumbous leaching earlier, with separating agent the zinc in the filtrate, lead are separated then, only zinciferous filtrate makes high purity metal zinc with electrolytic method at last, so-electrolysis molten with traditional high temperature evaporation-acid compared, this technology is very simple, also is easy to control.
2. the used raw material of technology of the present invention be the zinc content passed into disuse for a long time at the low-grade zinc oxide ore below 30%, wide material sources, cheap, make production cost reduce more than 50%.
3. technology of the present invention does not need high-temperature roasting, extracts metallic zinc by leaching-removal of impurities in alkaline solution-electrolytic method from zinc oxide ore.Zinc in the alkaline solution very easily extracts by electrolysis again, and circulation of elecrolyte is used.The current consumption of electrolytic metal zinc is lower by 20% than acid system in the alkaline solution, and both additions make production cost reduce by 30%, have great economic benefit.
4. owing to twice filter residue in the technological process of the present invention can both utilize, the former can be used for brickmaking etc. after using alkali lye and water washing, or landfill.Through toxicity leaching test, the filter residue nontoxicity can be used as Ordinary solid waste and handles.The latter can sell.So both protected environment, accomplished comprehensive utilization again, economic and social benefit is all good.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
Embodiment
Embodiment 1
See also accompanying drawing 1.At first, the zinc oxide ore that mainly comprises smithsonite and zincite of selecting Kunming, Yunnan to produce, the main component in these two kinds of ore deposits is respectively zinc carbonate, zinc silicate and zinc oxide (ZnCO
3, Zn
2SiO
4, 2ZnCO
33Zn (OH)
2, ZnO, Zn
2SiO
3H
2O) and plumbous, they all are soluble in the strong base solution.Then zinc oxide ore is crushed to 0.1-0.8mm.Then, leach with industrial caustic soda solution: immerse 3-10 cubic meter industrial caustic soda solution by 1 ton of zinc oxide ore and feed intake, leaching temperature is controlled at 95 ℃, the concentration of industrial caustic soda solution is 5-10M, after 90 minutes, zinc and plumbous extraction yield are respectively 98% and 93% in the mineral in reaction under 120 rev/mins the agitation condition at a slow speed.Filter, the filter residue discharging adds separating agent in the filtrate.Separating agent is a sodium sulphite, and add-on is 3 times (mol ratios) of lead content in the filtrate, stirs filtration in 60 minutes, and leaded filter residue is sold, and (content of Zn is 24-30Kg/m to contain zinc filtrate
3) directly carry out electrolysis: with voltage control is 2.4-2.7V.At last, obtaining purity in deposition on the negative electrode is metallic zinc more than 99.95%.After electrolysis finished, caustic soda soln directly was circulated in next leaching flow process.The loss of caustic soda is not more than 50g NaOH/kgZn (metal) in the whole flow process.Power consumption (Kwh/kgZn) is 2.5-2.6.
Embodiment 2
At first, select the zinc oxide ore that comprises smithsonite and zincite in Kweiyang, the main component in these two kinds of ore deposits is respectively zinc carbonate, zinc silicate and zinc oxide (ZnCO
3, Zn
SIO
4, 2ZnCO
33Zn (OH)
2, ZnO, Zn
2SiO
3H
2O) and copper, iron plumbous and trace, they all are soluble in the strong base solution.Then, zinc oxide ore is crushed to 0.5-1mm.Then, leach with aqua calcis: immerse 3 cubic metres of aqua calcises by 1 ton of zinc oxide ore and feed intake, leaching temperature is controlled at 100 ℃, the concentration of aqua calcis is 10M, reaction is after 100 minutes down with 120 rev/mins agitation conditions at a slow speed, and zinc and plumbous extraction yield are 100% in the mineral.Subsequent again, the zinc in zinc oxide ore and plumbous by after the leaching, filtered while hot, filter residue with the calcium hydroxide of above-mentioned concentration and water washing after discharging brickmaking or landfill, but washings recirculation is as leaching zinc oxide ore.Subsequent again, add separating agent in the filtrate of containing zinc, lead that after filtration, obtains, separating agent is an ammonium sulfide, the add-on of separating agent adds by 1.5 times (mol ratio) of lead content in the filtrate, through stirring reaction, filter to isolate high purity lead compound filter residue, be sold to plumbous smeltery after, stay and contain zinc filtrate and directly carry out electrolysis, voltage is 2.4-2.7V.At last, obtaining purity in deposition on the negative electrode is metallic zinc more than 99.95%.After electrolysis finished, remaining solution directly was circulated in next alkali leaching operation.The loss of alkali is not more than 50g CaOH/kgZn (metal) in the whole flow process.Power consumption (Kwh/kgZn) is 2.5-2.6.Twice filtering filter residue all can be used again.
Claims (1)
1. method of producing high purity metal zinc with zinc oxide ore, at first, select zinc content at the low-grade zinc oxide ore below 30% as raw material, be crushed to 0.1-1mm; Then, leach with strong base solution: above-mentioned raw materials is immersed in the strong base solution that concentration is 1-10mol/L, and its proportioning is that 1 ton of ore deposit needs 1-7 cubic meter strong base solution, stir 60-100 minute at a slow speed after, the zinc in the zinc oxide ore and plumbous dissolved; Then, filter, the filter residue discharging stays the filtrate of containing zinc, lead; Subsequent again, in filtrate, add separating agent, the add-on of separating agent is a 0.1-5 times of mol ratio of lead content in the filtrate, separating agent is a sulfide, and restir reaction 60-100 minute is filtered, isolate plumbiferous precipitation and sell, stay and contain zinc filtrate and directly carry out electrolysis; It is characterized in that: the temperature with the strong base solution leaching is 95-100 ℃, and is last, and deposition acquisition purity is 99.95% metallic zinc on negative electrode, and after electrolysis finished, remaining solution directly was circulated in next alkali leaching flow process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031167543A CN1239720C (en) | 2003-05-07 | 2003-05-07 | Method for producing high purity metal zinc from zinc oxide ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031167543A CN1239720C (en) | 2003-05-07 | 2003-05-07 | Method for producing high purity metal zinc from zinc oxide ore |
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| Publication Number | Publication Date |
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| CN1450182A CN1450182A (en) | 2003-10-22 |
| CN1239720C true CN1239720C (en) | 2006-02-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031167543A Expired - Lifetime CN1239720C (en) | 2003-05-07 | 2003-05-07 | Method for producing high purity metal zinc from zinc oxide ore |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417475C (en) * | 2006-03-10 | 2008-09-10 | 同济大学 | Production of metal zinc powder from zinc dust and zinc dross |
| CN100410394C (en) * | 2006-06-07 | 2008-08-13 | 同济大学 | Mehtod for producing zinc concentrate and lead concentrate using zinc oxide ore and zinc slag |
| CN100400683C (en) * | 2006-12-30 | 2008-07-09 | 同济大学 | Method for producing metallic lead and zinc by using lead-zinc containing waste slag or lead-zinc monoxide mine |
| CN101457293B (en) * | 2009-01-05 | 2010-12-01 | 同济大学 | Method for chlorides from zinc alkali solution |
| US8524177B2 (en) * | 2011-09-09 | 2013-09-03 | Canadus Chemical LLC | Process for purifying zinc oxide |
| CN103255442B (en) * | 2012-02-16 | 2015-07-29 | 同济大学 | A kind of method of adding lead-containing compounds alkali lye electrolytic preparation super-fine zinc dust |
| CN102776368B (en) * | 2012-06-29 | 2014-03-19 | 张晋敏 | Lead and zinc tailing recycling method |
| PE20210787A1 (en) | 2014-05-12 | 2021-04-22 | Summit Mining Int Inc | BRINE LEACHING PROCESS FOR THE RECOVERY OF VALUABLE METALS FROM OXIDE MATERIALS |
| CN105645706B (en) * | 2016-03-02 | 2019-02-15 | 环境保护部南京环境科学研究所 | A method of containing high zinc, the processing of lead sewage sludge harmlessness |
| CN106337123A (en) * | 2016-08-09 | 2017-01-18 | 四川师范大学 | Willemite leaching method |
| CN107058776B (en) * | 2017-04-05 | 2019-12-10 | 江苏宏德特种部件股份有限公司 | Method for modifying and microalloying hypoeutectic cast aluminum-silicon alloy |
| CN109055739A (en) * | 2018-08-20 | 2018-12-21 | 云南宏景科创锌业有限公司 | Alkali soaks electrolysis method from low-grade containing the method for producing zinc powder in zinc ore |
| CN109321762A (en) * | 2018-10-18 | 2019-02-12 | 云南宏景科创锌业有限公司 | A kind of energy conservation and environmental protection zinc hydrometallurgy production technology |
| US11319613B2 (en) | 2020-08-18 | 2022-05-03 | Enviro Metals, LLC | Metal refinement |
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2003
- 2003-05-07 CN CNB031167543A patent/CN1239720C/en not_active Expired - Lifetime
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| CN1450182A (en) | 2003-10-22 |
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Effective date of registration: 20110914 Address after: Baiyun road 650224 Yunnan city of Kunming province No. 548 Dan Tong modern city 18 building B8 room Patentee after: KUNMING TONGYUE TECHNOLOGY DEVELOPMENT CO.,LTD. Address before: 1239 Siping Road, Shanghai, No. 200092 Patentee before: Tongji University |
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